KR20170080835A - Spinning device for two-component composited nanofiber and method of manufacturing two-component composited nanofiber thereby - Google Patents

Spinning device for two-component composited nanofiber and method of manufacturing two-component composited nanofiber thereby Download PDF

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KR20170080835A
KR20170080835A KR1020150190031A KR20150190031A KR20170080835A KR 20170080835 A KR20170080835 A KR 20170080835A KR 1020150190031 A KR1020150190031 A KR 1020150190031A KR 20150190031 A KR20150190031 A KR 20150190031A KR 20170080835 A KR20170080835 A KR 20170080835A
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South Korea
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tube
spinning
spinning solution
radiation
main body
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KR1020150190031A
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Korean (ko)
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KR101816733B1 (en
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김학용
김태우
채수형
박미라
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주식회사 우리나노
전북대학교산학협력단
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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
    • 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
    • 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
    • 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
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning

Abstract

The present invention provides a spinning device for producing a bicomponent composite nanofiber, comprising: (i) a spinning tube main body (Ta) having one shape selected from a cylindrical shape and a conical shape; A hollow portion Tb on the polygonal tube formed along the longitudinal direction of the radiation tube main body Ta and a lower portion of the radiation tube main body Ta from a position spaced a predetermined distance h downward from the upper surface of the radiation tube main body Ta And a plurality of nozzles Tc disposed at positions facing the respective corner portions of the hollow portion Tb on the polygonal tube along the longitudinal direction of the radiation tube main body Ta, A radial tube T having a structure in which the corner portions of the radial tube body Ta abut the outer peripheral surface of the radiation tube main body Ta; And (ii) a spinning liquid distribution tube (1) connected to the spinning tube (T) and having a shape selected from cylindrical and conical shapes of a double pipe structure.
The present invention relates to a process for producing a two-component composite nanofiber with high productivity (discharge amount) because it uses electrostatic force and centrifugal force at the same time, facilitates solvent volatilization and recovery, (Drop phenomenon) is effectively prevented, thereby improving the quality of the two-component composite nanofiber web.

Description

TECHNICAL FIELD The present invention relates to a spinning device for manufacturing a two-component composite nanofiber, and a method for manufacturing a two-component composite nanofiber using the spin-

TECHNICAL FIELD The present invention relates to a spinning device for producing a two-component composite nanofiber and a method for manufacturing a two-component composite nanofiber using the same, and more particularly, to a spinning device for producing a two- The present invention relates to a radiation tube, and more particularly, to a method for producing a high quality two-component composite nanofiber web using the radiation tube.

The term " two-component composite nanofiber "of the present invention is used to include both core-sheath type composite nanofiber and side-by-side type composite nanofiber, Is used to mean also an eccentric core-sheath type composite nanofiber.

As a conventional technique for producing core-sheath type composite nanofibers, a method of electrospinning a spray solution for forming a sheath and a spinning solution for forming a core through a nozzle of a sheath / core type (double pipe type) with electrostatic force has been widely used.

However, since the above-mentioned conventional method relies solely on the electrostatic force to perform electrospinning, the discharge amount per nozzle unit per unit time per unit time is extremely low to 0.01 g, which leads to a problem of productivity and difficulty in mass production.

In general, the production of nanofibers through electrospinning is 0.1 to 1 g per hour, and the solution discharge rate is very low, ranging from 1.0 to 5.0 mL per hour [D. H. H. Renecker et al., Nanotechnology 2006, Vo 17, 1123]

Specifically, Nano Letters, 2007, Vol. 7 (4) 1081 discloses another conventional art in which a single nozzle having an inner diameter of 0.4 mm among the composite nozzles in which two nozzles are arranged side by side is provided with SnO 2 The precursor solution was supplied, and the other nozzle having an inner diameter of 0.7 mm was charged with TiO 2 A method of producing TiO 2 / SnO 2 composite inorganic nanofibers in a side-by-side configuration is provided. However, since the conventional method depends on only the electrostatic force, the discharge amount per nozzle per unit time The productivity is deteriorated, and nozzle replacement and cleaning are difficult.

In Polymer, 2003, Vol. 44, 6353, a Teflon needle having an inner diameter of 0.7 mm and a thickness of 0.2 mm was used, and two kinds of solutions were simultaneously injected into a cylinder pump so that two kinds of solutions were combined at the needle part And a platinum electrode is placed in a solution to perform electrospinning to produce a side-by-side composite nanofiber. However, since the conventional method also depends only on the electrostatic force, the discharge amount per nozzle per unit time is very low, There is a problem that it is difficult to remove and replace the nozzle and clean it.

In addition, the above conventional methods have a problem that the phenomenon in which the spinning solution falls on the collector in a solution state not in the form of a fiber (hereinafter referred to as "droplet phenomenon") is severely generated, and the quality of the two-component composite nanofiber web deteriorates.

The object of the present invention is to minimize the risk of work due to the application of high voltage and to greatly improve the productivity of the two-component composite nanofiber and to prevent the droplet phenomenon in the production of the nanofiber, And to provide a spinning device for manufacturing a two-component complex nanofiber.

Another object of the present invention is to provide a method for producing high-quality two-component composite nanofibers with high productivity by using a radial tube for producing the two-component composite nanofibers.

In order to achieve the above object, the present invention provides a spinning device for manufacturing a bicomponent composite nanofiber, comprising: (i) a radiation tube main body (Ta) having one shape selected from a cylindrical shape and a conical shape; A hollow portion Tb on the polygonal tube formed along the longitudinal direction of the radiation tube main body Ta and a portion spaced a predetermined distance h downward from the upper surface of the radiation tube main body Ta, And a plurality of nozzles (Tc) provided at positions facing the respective corner portions of the hollow portion (Tb) on the polygonal tube along the longitudinal direction of the radiation tube main body (Ta) to the lower surface of the polygonal tube (Ta) (T) having a structure in which the corner portions of the tube-shaped hollow portion (Tb) are in contact with the outer peripheral surface of the radiation tube body (Ta) and (ii) the radiation tube (T) Cylindrical It is composed of a spinning solution distribution tube (1) having one shape of selected from the cone.

The present invention also relates to a method of controlling a radiation source of a radiation source, comprising the steps of: (i) applying a high voltage to the radiation tube (T) and the radiation liquid distribution tube (1) (Ii) supplying the first spinning solution into the outer tube 1c constituting the spinning solution distributing tube 1 of the double-tube structure, and supplying the first spinning solution to the inner side of the spinning solution distributing tube 1 of the double- (Iii) supplying the first spinning solution supplied into the outer tube (1c) of the spinning solution distribution tube to the nozzle (1b) constituting the spinning tube (T) The second spinning solution supplied into the inner tube 1b of the spinning solution distribution tube is supplied to the hollow portion Tb on the polygonal tube constituting the spinning tube T, Tc) and the second spinning solution supplied to the hollow portion (Tb) on the polygonal tube constituting the spinning tube (T) are subjected to centrifugal force and electric force, Component composite nanofibers are produced in the direction of the collector 2 in which a high voltage is applied by the voltage generator 6 through the corner portion of the hollow portion Tb on the polygonal tube constituting the yarn tube T.

The present invention relates to a process for producing a two-component composite nanofiber with high productivity (discharge amount) because it uses electrostatic force and centrifugal force at the same time, facilitates solvent volatilization and recovery, (Drop phenomenon) is effectively prevented, thereby improving the quality of the two-component composite nanofiber web.

1 is a schematic view of a process for producing a two-component composite nanofiber according to the present invention.
Fig. 2 is an enlarged schematic view of the radiation tube T in Fig. 1; Fig.
3 is a schematic view showing a mechanism of formation of a core-sheath type bicomponent composite nanofiber in a radial tube (T) for manufacturing a bicomponent composite nanofiber of the present invention.
4 to 5 are schematic views showing a state in which a nozzle Tc is formed on a corner portion of the hollow Tb on the polygonal tube formed in the spinning solution distribution tube 1 of the present invention.
6 is a scanning electron micrograph of the core-sheath type two-component composite nanofiber prepared in Example 1. Fig.
7 is a scanning electron microscope (SEM) image of the hollow carbon nanofibers prepared in Example 2. Fig.
8 is a scanning electron micrograph of the core-sheath type two-component composite nanofiber prepared in Example 3. Fig.
9 is a scanning electron microscope (SEM) image of the hollow carbon nanofibers prepared in Example 4. Fig.
10 is a scanning electron micrograph of the core-sheath type two-component composite nanofiber prepared in Example 5. Fig.
11 is a scanning electron microscope (SEM) image of the hollow carbon nanofiber prepared in Example 6. Fig.
12 is a scanning electron micrograph of the core-sheath type two-component composite nanofiber prepared in Comparative Example 1. Fig.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

As shown in FIG. 1, the spinning device for producing a bicomponent composite nanofiber according to the present invention comprises (i) a radiation tube main body Ta having one shape selected from a cylindrical shape and a conical shape, A polygonal tube-shaped hollow portion Tb formed along the longitudinal direction of the radiation tube main body Ta and a radially outer portion of the radiation tube main body Ta from a position spaced apart by a predetermined distance h downward from the upper surface of the radiation tube main body Ta, And a plurality of nozzles Tc provided at positions facing the respective corner portions of the hollow portion Tb on the polygonal tube along the longitudinal direction of the radiation tube main body Ta to the lower surface of the main body Ta, A radiation tube T having a structure in which the corner portions of the hollow portion Tb on the polygonal tube abuts the outer peripheral surface of the radiation tube main body Ta; And (ii) a spinning liquid distribution tube (1) connected to the spinning tube (T) and having a shape selected from cylindrical and conical shapes of a double pipe structure.

The radiation tube T is moved along the longitudinal direction of the radiation tube main body Ta from a position spaced a predetermined distance h downward from the upper surface of the radiation tube main body Ta to the lower surface of the radiation tube main body Ta One or two or more nozzles Tc are provided at positions facing the respective corner portions of the polygonal tube-shaped hollow portion Tb to be constituted.

The radiation tube (T) and the radiation liquid distribution tube (1) may be integrally formed or formed from the beginning, or may be separately manufactured and then connected to each other by assembly.

Next, as shown in FIG. 1, the method for manufacturing the two-component composite nanofibers according to the present invention will be described. (I) While rotating the spinning tube (T) and the spinning solution distribution tube (1) A high voltage is applied to the radiating tube T and the spinning solution distribution tube 1 by the first radiating tube 6 and then to the outer tube 1c constituting the spinning solution distributing tube 1 of the double- Supplying a spinning solution and supplying a second spinning solution different from the first spinning solution into the inner tube (1b) constituting the spinning solution distribution tube (1) of the double pipe structure, and (iii) The first spinning solution supplied into the outer tube 1c is supplied to the nozzle Tc constituting the spinning tube T and the second spinning solution supplied into the inner tube 1b of the spinning solution distribution tube is supplied to the spinning tube T (Iv) a first spinning solution supplied to the nozzle Tc and the spinning tube T constituting the spinning tube T, The second spinning liquid supplied to the polygonal tube-shaped hollow portion Tb is discharged by the voltage generator 6 through the corner portion of the polygonal tube-shaped hollow portion Tb constituting the radiation tube T by centrifugal force and electric force And radiates in the direction of the collector 2 having a high voltage to produce a two-component composite nanofiber.

At this time, the second spinning solution is supplied into the inner tube 1b constituting the spinning solution distribution tube by using the first spinning solution supply tube 3a, and the second spinning solution is supplied by using the second spinning solution supply tube 3b, The first spinning solution is supplied into the outer tube 1c and then the first spinning solution supplied into the outer tube 1c of the spinning solution distribution tube is supplied to the nozzle Tc constituting the spinning tube T, The second spinning solution supplied into the inner tube 1b of the distribution tube is supplied to the hollow portion Tb on the polygonal tube constituting the radiation tube T. [

Fig. 3 is a graph showing the relationship between a first spinning solution (A: spinning solution for forming a core) and a second spinning solution (B: sheathing solution) supplied to a corner portion Tb 'of a hollow portion Tb on a polygonal tube, And a mechanism of forming a core-sheath type two-component complex nanofiber.

As shown in FIG. 3, the first spinning solution (A: spinning liquid for forming a core) is passed through a nozzle Tc having a relatively small diameter making up the spinneret, at the corner portion of the hollow portion on the polygon tube And the second spinning liquid (B: spinning liquid for forming a sheath) is supplied through a polygonal tube-shaped hollow portion (Tb) of a radial tube having a relatively large diameter to a hollow portion of a polygonal tube- The cross-sectional shape of the two-component composite nanofiber can be precisely controlled since it is supplied at the corner portion (Tb ').

The manufacturing mechanism of the core-sheath type two-component composite nanofibers according to the present invention described above is completely different from the mechanism of manufacturing the core-sheath type two-component composite nanofibers by arranging the two nozzles in a core-sheath form .

Since the two-component composite nanofibers are simultaneously produced at the plurality of corner portions Tb ', the productivity is greatly improved as compared with the conventional nozzle type method. When the shape of the radiation tube T is changed, Component composite nanofiber can be produced.

Wherein the two-component composite nanofiber is a core-sheath type composite nanofiber or a side by side type composite nanofiber, and the core-sheath type composite fiber is an eccentric core- It may be a composite nanofiber.

As an example of implementation, a spinning solution for forming a core (first spinning solution) is supplied into a nozzle Tc constituting a spinning tube T, and into a hollow portion Tb on a polygonal tube constituting a spinning tube T Is supplied with a spinning solution for forming a sheath (second spinning solution) to prepare a core-sheath type composite nanofiber.

At this time, as shown in FIG. 2 and FIG. 5, the distance from the upper surface of the radiation tube main body Ta to the lower surface of the radiation tube main body Ta by a distance (h) Using a radial tube T provided with three nozzles Tc at positions facing the respective corner portions of the hollow portion Tb on the polygonal tube constituting the radiation tube T along the longitudinal direction of the core tube Three individual core-sheath type composite nanofibers can be produced.

4, when the distance d between the corner vertex of the hollow portion Tb on the polygonal tube and the nozzle Tc constituting the radiation tube T is appropriately adjusted, as shown in FIG. 4, Side composite nanofiber can be produced.

As one example of implementation, one of the two different polymer solutions is used as the first spinning solution supplied into the nozzle Tc constituting the spinning tube T, and the other one is used as the first spinning solution supplied to the nozzle Tc constituting the spinning tube T, Core-sheath type composite nanofiber or side-by-side type composite nanofiber is used as a second spinning solution supplied into the tube-shaped hollow portion (Tb).

The core part of the core-sheath type composite nanofiber thus prepared may be dissolved in an organic solvent or the like to produce a hollow fiber.

As another embodiment, one of two kinds of precursor solutions containing different minerals is used as a first spinning solution supplied into a nozzle Tc constituting a spinning tube T, Is supplied as a second spinning solution to be fed into the polygonal tube-shaped hollow portion (Tb) constituting the spinneret (T) to produce a bicomponent composite inorganic nanofiber.

The thus prepared two-component composite inorganic nanofiber is stabilized and carbonized to produce a single-component or two-component inorganic nanofiber.

As another embodiment, the polymer solution is used as the first spinning solution supplied into the nozzle Tc constituting the spinning tube T, and the precursor solution containing the inorganic substance is supplied to the polygonal tube T constituting the spinning tube T Is used as a second spinning solution to be fed into the upper hollow portion (Tb) to prepare a core-sheath type composite nanofiber in which the core component is a polymer and the sheath component is an inorganic substance.

When the core component of the core-sheath type composite nanofiber thus prepared is dissolved in an organic solvent or the like, or is removed by carbonization, an inorganic hollow fiber is produced.

As another example of implementation, a precursor solution containing an inorganic substance is used as a first spinning solution to be fed into a nozzle Tc constituting a spinning tube T, and the polymer solution is injected into a polygonal tube Is used as a second spinning solution supplied into the upper hollow portion (Tb) to prepare a core-sheath type composite nanofiber in which the core component is an inorganic substance and the sheath component is a polymer.

A water soluble polyvinyl alcohol solution is used as a first spinning solution to be fed into a nozzle Tc constituting a spinning tube T, and a polyvinyl alcohol solution of poly The acrylonitrile solution was used as a second spinning solution to be fed into the hollow portion Tb on the polygonal tube constituting the spinning tube T to prepare a core-sheath type composite nanofiber, and then a water-soluble polyvinyl The alcohol is removed with water to prepare a hollow polyacrylonitrile fiber, and the hollow polyacrylonitrile fiber thus prepared is stabilized and carbonized to produce a hollow carbon nanofiber.

At this time, if a radiation tube provided with two or more nozzles Tc in each of the corner portions of the hollow portion Tb on the polygonal tube constituting the radiation tube T is used, the porous carbon nanofibers are produced.

The hollow carbon nanofibers or the porous carbon nanofibers prepared as described above are useful as a filter material, a secondary battery membrane material, an electrode material, a highly functional garment material, and a drug delivery material.

Hereinafter, the present invention will be described in more detail with reference to Examples.

However, the scope of protection of the present invention is not limited by the following examples.

Example  One

Polymethylmethacrylate was dissolved in dimethylformamide as a solvent to prepare a polymethylmethacrylate solution (first spinning solution) having a solid content of 10% by weight.

Polyacrylonitrile was dissolved in dimethylformamide as a solvent to prepare a polyacrylonitrile solution (second spinning solution) having a solid content of 12% by weight.

Next, as shown in Fig. 1, (i) a cylindrical radiation tube body (Ta) having an outer diameter of 45 mm and a length of 8 mm, a radiation tube body (9) formed along the longitudinal direction of the radiation tube body The rectangular tubular hollow portion Tb and the radial tube main body Ta are separated from each other by a distance of 3 mm (h) downward from the upper surface of the radiant tube main body Ta, And a nozzle (Tc) having a diameter of 0.9 mm and provided at a position facing each of the corner portions of the hollow portion (Tb) on the polygonal tube along the circumference of the hollow portion (Tb) A radial tube T having a structure in contact with the outer circumferential surface of the tube main body Ta and (ii) a radiating liquid distribution tube (not shown) connected to the radial tube T and having a cylindrical shape and a double- 1) is rotated at 350 rpm while the radiation tube (T) and the room A voltage of 35 kV was applied to the liquid distribution tube 1 and the radiation tube T was supplied with a polymethylmethacrylate solution (first spinning solution) into a nozzle Tc having a diameter of 0.9 mm, A polyacrylonitrile solution (a second spinning solution) is supplied into a hollow tube portion Tb of a triangular tube constituting a tube T and then a polyglycerol solution The supplied spinning solutions were spun through a corner of the hollow portion Tb in the direction of the collector 2 having a voltage of 35 kV to prepare a core-sheath type bicomponent composite nanofiber. The polyacrylonitrile solution (the second spinning solution), which is a polymer solution, was supplied at 0.25 cc / min and the polymethylmethacrylate solution (the first spinning solution) was supplied at 0.20 cc / min. The distance between the collector 2 and the radiation tube 1 was 35 cm.

SEM images of the core-sheath type two-component composite nanofiber prepared as described above were as shown in FIG.

In Fig. 6, it is shown that the two-component composite nanofiber composed of the polymethylmethacrylate component as the core component and the polyacrylonitrile as the sheath component is uniformly formed.

Example  2

The core-sheath type bicomponent composite nanofiber prepared in Example 1 was stabilized at 220 DEG C for 1 hour and 30 minutes and then carbonized at 1,500 DEG C under a nitrogen atmosphere to obtain a hollow carbon having a polymethylmethacrylate- Nanofibers were prepared. The SEM image of the prepared hollow carbon nanofibers was as shown in FIG. 7 shows that the hollow portion is well formed.

Example  3

Except that the nozzle Tc was provided so that the upper surface of the nozzle Tc was located at a position spaced 6 mm (h) from the upper surface of the radiation tube main body Ta in the lower direction by 6 mm (h) - cis - type bicomponent composite nanofiber. SEM images of the prepared core-sheath type two-component composite nanofiber were shown in FIG.

Example  4

The core-sheath type bicomponent composite nanofiber prepared in Example 3 was stabilized at 220 DEG C for 1 hour and 30 minutes, and then carbonized at 1,500 DEG C under a nitrogen atmosphere to obtain a hollow carbon having a polymethylmethacrylate- Nanofibers were prepared. A scanning electron microscope photograph of the prepared hollow carbon nanofibers was shown in FIG. 9 shows that the hollow portion is well formed.

Example  5

Except that the nozzle Tc was provided so that the upper surface of the nozzle Tc was located at a position away from the upper surface of the radiation tube main body Ta by 9 mm (h) - cis - type bicomponent composite nanofiber. SEM images of the prepared core-sheath type two-component composite nanofibers were shown in FIG.

Example  6

The core-sheath type bicomponent composite nanofiber prepared in Example 5 was stabilized at 220 DEG C for 1 hour and 30 minutes, and then carbonized at 1,500 DEG C under a nitrogen atmosphere to obtain a hollow carbon having a polymethylmethacrylate- Nanofibers were prepared. SEM images of the prepared hollow carbon nanofibers were shown in FIG. 11 shows that the hollow portion is well formed.

Comparative Example  One

The distance h of the upper surface of the nozzle Tc from the upper surface of the radiation tube main body Ta is set so that the upper surface of the nozzle Tc is positioned at the same position as the upper surface of the radiation tube main body Ta Core-sheath type bicomponent composite nanofiber was prepared in the same manner as in Example 1, except that the nozzle (Tc) was provided so as to be 0 mm. The prepared core-sheath type bicomponent composite nanofibers were stabilized at 220 ° C for 1 hour and 30 minutes, and then carbonized at 1,500 ° C under a nitrogen atmosphere to prepare hollow carbon nanofibers. The prepared hollow carbon nanofiber scanning electron micrograph was as shown in Fig.

In Fig. 12, it can be seen that fibers are formed separately from each other, not in the form of conjugate fibers in which polymethylmethacrylate core and polyacrylonite, sheath, are bonded. The reason for this is that each polymer is made in nanofiber form because there is no time to bond the two polymers together. 12, hollow carbon nanofibers having one side are seen, but carbon nanofibers other than hollow formed by polyacrylonitrile alone are formed as a whole.

T: Radiation tube Ta: Body of radiation tube
Tb: Hollow portion on the polygonal tube of the radiation tube
Tc: Nozzle
1: spinning liquid distribution tube
1a: body of spinning liquid dispensing tube
1b: Inner tube of spinning liquid distribution tube
1c: outer tube of the spinning liquid distribution tube
2: collector 3: spinning solution supply pipe
3a: First spinning solution (spinning liquid for forming a core) supply pipe
3b: Second spinning solution (spinning solution for forming sis)
4: Pump for supplying the first spinning solution (spinning liquid for forming a core)
5: Pump for supply of second spinning solution (spinning liquid for forming a sheath)
6: Voltage generator
F: two-component composite nanofiber Fc: core component of two-component composite nanofiber
Fs: sheath portion of two-component composite nanofiber
d is the distance between the nozzle Tc and the corner vertex of the hollow portion Tb on the polygonal tube closest to the nozzle.
A: First spinning solution (spinning solution for core formation)
B: Second spinning solution (spinning solution for forming a sheath)
Tb ': the corner portion of the hollow portion on the polygonal tube of the radiation tube
h: distance from the upper surface of the radiation tube main body Ta to the upper surface of the nozzle Tc

Claims (13)

(I) a radiation tube main body (Ta) having one shape selected from a cylindrical shape and a conical shape, a hollow tube-like body (Ta) formed on the inside of the radiation tube body Along a longitudinal direction of the radiation tube main body Ta from a position spaced a predetermined distance h downward from the upper surface of the radiation tube main body Ta to a lower surface of the radiation tube main body Ta, The hollow portion Tb on the polygonal tube Tb is connected to the outer circumferential surface of the radiation tube main body Ta by the nozzle Tc, A radiation tube (T) having a structure in contact with the radiation tube (T); And
(Ii) a spinning liquid distribution tube (1) connected to the spinning tube (T) and having a shape selected from a cylindrical shape and a cone shape of a double pipe structure; and Radiating device. The method as claimed in claim 1, further comprising: moving the tube at a position spaced apart from the upper surface of the tube body by a predetermined distance h from the upper surface of the tube body to a lower surface of the tube body; Characterized in that two or more nozzles (Tc) are provided at positions facing the respective corner portions of the hollow portion (Tb) on the polygonal tube constituting the radiation tube (T). The spinning device according to claim 1, wherein the spinning tube (T) and the spinning solution distribution tube (1) are integrally formed. 2. The spinning device for producing bicomponent nanofibers according to claim 1, wherein the spinning tube (T) and the spinning solution distribution tube (1) are manufactured and then connected to each other by assembly. (I) a radiation tube main body (Ta) having one shape selected from a cylindrical shape and a conical shape, a hollow tube-like body (Ta) formed on the inside of the radiation tube body Along a longitudinal direction of the radiation tube main body Ta from a position spaced a predetermined distance h downward from the upper surface of the radiation tube main body Ta to a lower surface of the radiation tube main body Ta, The hollow portion Tb on the polygonal tube Tb is connected to the outer circumferential surface of the radiation tube main body Ta by the nozzle Tc, A radiating tube (T) having a structure in contact with the radiating tube (1) and a radiating liquid distribution tube (1) connected to the radiating tube (1) and having a shape selected from cylindrical and conical shapes of a double- Turning and turning A high voltage is applied to the radiating liquid distribution tube 1 and the radiation tube T by the generating device 6 and then into the outer tube 1c constituting the radiating liquid distribution tube 1 of the double- Supplying a first spinning solution and supplying a second spinning solution different from the first spinning solution into an inner tube (1b) constituting the spinning solution distribution tube (1) of the double pipe structure, and (iii) The first spinning solution supplied into the outer tube 1c of the tube is supplied to the nozzle Tc constituting the spinning tube T and the second spinning solution supplied into the inner tube 1b of the spinning solution distribution tube is supplied to the spinning tube (Tb) on the polygonal tubular tube Tb constituting the radiation tube T and the first spinning liquid supplied to the nozzle Tc are supplied to the polygonal tube- The second spinning solution is supplied to the voltage generating device 6 through the corner portion of the polygonal tube-shaped hollow portion Tb constituting the radiation tube T by centrifugal force and electric force ) In the direction of the collector (2) in which a high voltage is applied. The method as claimed in claim 5, further comprising the step of: moving the radiation tube body (Ta) along a longitudinal direction of the radiation tube body (Ta) from a position spaced apart from the upper surface of the radiation tube body Characterized in that two or more nozzles (Tc) are provided at positions facing the respective corner portions of the hollow portion (Tb) on the polygonal tube constituting the radiation tube (T). The method of manufacturing a core-sheath type composite nanofiber according to claim 5, wherein the first spinning solution supplied into the nozzle (Tc) constituting the spinning tube (T) is a spinning solution for forming a core, Wherein the second spinning solution supplied into the polygonal tube-shaped hollow portion (Tb) constituting the spinning solution is a spinning solution for forming a sheath. The two-component composite nanofiber according to claim 5, wherein the two-component composite nanofiber is one of a core-sheath type composite nanofiber and a side by side type composite nanofiber. Way. The method for producing a two-component composite nanofiber according to claim 5, wherein the core-sheath type composite nanofiber has two or more core portions. The method according to claim 5, wherein the first spinning solution supplied into the nozzle (Tc) constituting the radiation tube (T) and the second spinning solution supplied into the hollow portion (Tb) on the polygonal tube constituting the radiation tube Wherein the polymer nanofibers are different polymer solutions. The method according to claim 5, wherein the first spinning solution supplied into the nozzle (Tc) constituting the radiation tube (T) and the second spinning solution supplied into the hollow portion (Tb) on the polygonal tube constituting the radiation tube Wherein the nanocomposite is a precursor solution containing different minerals. The method according to claim 5, wherein the first spinning solution supplied into the nozzle (Tc) constituting the spinning tube (T) is a polymer solution, Wherein the second spinning solution is a precursor solution containing an inorganic material. The method according to claim 5, wherein the first spinning solution supplied into the nozzle (Tc) constituting the spinning tube (T) is a precursor solution containing an inorganic substance, and the hollow portion on the polygonal tube (Tb Wherein the second spinning solution supplied into the second spinning solution is a polymer solution.
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