CN113684548A - Variable electric field nanofiber spinning device - Google Patents

Variable electric field nanofiber spinning device Download PDF

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CN113684548A
CN113684548A CN202111057283.XA CN202111057283A CN113684548A CN 113684548 A CN113684548 A CN 113684548A CN 202111057283 A CN202111057283 A CN 202111057283A CN 113684548 A CN113684548 A CN 113684548A
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spinning
electric field
nanofiber
metal ring
spinning nozzle
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CN113684548B (en
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覃小红
熊健
王黎明
俞建勇
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Donghua University
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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
    • 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
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
    • 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
    • D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Nonwoven Fabrics (AREA)

Abstract

The invention relates to a variable electric field nanofiber spinning device which comprises an electric field gradient regulating and controlling device, a high-voltage generator, a high polymer spinning solution supply device and a nanofiber collecting device. The electric field gradient regulating and controlling device adopted by the invention changes the spatial distribution of the electric field force of the traditional electrostatic spinning technology, and can provide monotonically increasing electric field stretching force for the initial jet flow stretching section, so that the superfine nano fiber with the diameter obviously smaller than 100 nanometers can be obtained, and meanwhile, the orientation degree of macromolecular chains in the fiber is effectively improved, which has important significance for improving the size effect and the application capability of the nano fiber.

Description

Variable electric field nanofiber spinning device
Technical Field
The invention belongs to the field of spinning devices, and particularly relates to a variable electric field nanofiber spinning device.
Background
In the development of fiber aggregate materials and engineering, the realization of the ultra-fining of fibers is always an important research direction. The diameter of human hair is about 70 mu m, the diameter of cotton fibers commonly used in textile materials is about 12 mu m, silk is typically thin in natural fibers of traditional textiles, the diameter is about 4 mu m, and the diameter of the fibers produced by an ultrafine chemical fiber technology can reach 0.4-4 mu m. The preparation of 0.1-1 μm submicron fiber and finer 1-100 nm nanofiber by technical innovation is an important subject focused by textile industry and related industries.
With the intensive research of nanotechnology, the electrospinning technology for rapidly obtaining fibers with diameter distribution ranging from hundreds of nanometers to several micrometers has been rapidly developed in recent 20 years. The prepared nano-scale fiber has larger specific surface area, abundant pore channel structures, flexible surface functionalization characteristics and superior interface and surface effects. The electrostatic spinning technology is widely applied to the fields of energy, environment, bioscience, medical engineering, military, national security and the like.
The existing electrostatic spinning device mainly comprises a traditional single-needle electrostatic spinning device and a novel needle-free electrostatic spinning device. The traditional single-needle electrostatic spinning device mainly comprises a high-voltage power supply system, a capillary liquid supply system and a fiber collecting polar plate. The positive electrode and the negative electrode of the high-voltage power supply are respectively applied to the capillary nozzle and the collecting device end to form a high-voltage electric field. The capillary liquid supply system is generally a metal hollow needle, and the spinning solution is pushed and extruded at the tip of the needle through a syringe pump. And drawing the spinning solution into a Taylor cone by a high-voltage electric field. With the further accumulation of charges, jet flow is ejected from the top of the Taylor cone, and the nanofiber is finally generated through electric field force drafting and thinning and solvent volatilization. This process allows the production of submicron fibers with diameters ranging from 100nm to 3 μm.
Fiber refinement, especially when fiber fineness is reduced from submicron (100-1000 nm) to true nanoscale (<100nm), fiber characteristics such as specific surface area, pore structure, bending stiffness, strength, shear modulus, surface adhesion, wetting behavior will change significantly. With the continuous and deep research and application of one-dimensional nano materials, the traditional single-needle electrostatic spinning can not meet the preparation requirement of superfine nano fiber materials (<100 nm).
The development of a nanofiber production device which breaks through the refining limit of the existing electrostatic spinning fibers is very important in both the academic research field and the production application field.
Disclosure of Invention
The invention aims to provide a variable electric field nanofiber spinning device to solve the problem that superfine nanofibers with true nanometer sizes (<100nm) cannot be produced by the existing electrostatic spinning technology.
The electric field gradient regulating and controlling device adopted by the invention changes the spatial distribution of the electric field force of the traditional electrostatic spinning technology, and can provide monotonically increasing electric field stretching force for the initial jet flow stretching section, so that the superfine nano fiber with the diameter obviously smaller than 100 nanometers can be obtained, and meanwhile, the orientation degree of macromolecular chains in the fiber is effectively improved, which has important significance for improving the size effect and the application capability of the nano fiber.
The spinning device comprises a spinning solution supply device, a nanofiber collecting device, a high-pressure generator, a spinning spray head and a metal ring, wherein the nanofiber collecting device is arranged on the spinning solution supply device; the spinning solution supply device is connected with the spinning nozzle, and the nanofiber collecting device is arranged right above the spinning nozzle; wherein a metal ring is arranged outside the spinning nozzle, and the center of the metal ring is concentric with the spinning nozzle.
The spinning nozzle and the metal ring form an electric field gradient regulating device.
The spinning solution supply device comprises a propulsion pump, an injector and a liquid guide pipe, wherein one end of the liquid guide pipe is connected with the injector, and the other end of the liquid guide pipe is connected with the bottom of the spinning nozzle.
The liquid supply speed of the high polymer spinning solution supply device is 0-15 mL/h.
The top of the spinning nozzle is positioned between the metal ring and the nanofiber collecting device.
The nanofiber collecting device is a metal flat plate, a metal roller or a conductive conveying belt, wherein the metal roller is driven to rotate by a motor.
The nanofiber collecting device is grounded.
The distance between the nanofiber collecting device and the spinning nozzle is 5-30 cm.
The spinning nozzle is a metal hollow needle head; furthermore, the spinning nozzle is a metal hollow needle head with the specification of 15-25G.
The radius R of the metal ring ranges from 1cm to 30 cm.
The distance between the top of the spinning nozzle and the metal ring is L, L is determined by the physical relationship of variable electric field gradient, and the physical relationship is
Figure BDA0003255077030000021
Wherein R is the radius of the metal ring.
The metal ring is connected with the anode of the high-voltage generator through a lead; the voltage regulating range of the high-voltage generator is 0-60 KV.
Furthermore, the metal ring is connected with the positive electrode of the high-voltage spinning power supply through a lead wire which is reliably insulated from the outside.
The spinning nozzle is supported by the insulating support, and the distance L between the top of the spinning nozzle and the metal ring can be adjusted by the support.
The superfine nanofiber is obtained by spinning through the device.
The superfine nano fiber is not more than 100 nm.
Further, the spinning carried out by the device is as follows:
(1) adjusting the distance between the nanofiber collecting device and the spinning nozzle;
(2) selecting a metal ring with a radius R;
(3) adjusting the distance L between the top of the spinning nozzle and the metal ring;
(4) opening the high polymer spinning solution supply device and setting the liquid supply speed;
(5) turning on a power supply of the high-voltage generator, and adjusting spinning voltage;
(6) an ultrafine jet is excited from the top of a spinning nozzle and is subjected to stretching refinement and solvent volatilization solidification to form ultrafine nano fibers;
(7) the nanofiber collecting device receives the formed ultrafine nanofibers.
Advantageous effects
The invention provides a new gradient electric field distribution, which changes the monotonous decreasing electric field intensity distribution along the direction of a collecting device inherent in the electrostatic spinning technology. The new gradient electric field distribution has the characteristic that the electric field intensity is increased monotonously and then decreased monotonously. This facilitates the sufficient drawing and thinning of the jet flow at the starting point of the jet flow movement, thereby realizing the preparation of the superfine nano fiber with the fiber diameter being significantly lower than 100nm and further lower than 50 nm. Meanwhile, the orientation degree of macromolecular chains in the fibers is effectively improved, and the strength and the electrical property of the nano fibers are obviously enhanced.
Drawings
FIG. 1 is a schematic view of a variable electric field gradient superfine nanofiber manufacturing apparatus for spinning;
FIG. 2 is a schematic perspective view of an electric field gradient control device;
FIG. 3 is a front view of the electric field gradient adjustment device;
FIG. 4 is a top view of the electric field gradient controlling device.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
The variable electric field gradient nanofiber spinning device comprises a spinning solution supply device, a nanofiber collecting device, a high-voltage generator 4, a spinning spray head 6 and a metal ring 12; the spinning solution supply device is connected with the spinning nozzle 6, and the nanofiber collecting device is arranged above the spinning nozzle 6; wherein a metal circular ring 12 is arranged outside the spinning nozzle 6, and the center of the metal circular ring 12 is concentric with the spinning nozzle 6. The spinning nozzle 6 and the metal ring 12 form an electric field gradient regulation and control device, wherein the spinning nozzle is a metal hollow needle, and the metal ring is connected with the anode of the high-voltage generator through a conducting wire which is reliably insulated from the outside.
The spinning solution supply device comprises a propulsion pump 1, an injector 2 and a liquid guide pipe 3, wherein one end of the liquid guide pipe 3 is connected with the injector 2, and the other end of the liquid guide pipe is connected with the bottom of a spinning spray head 6. The top of the spinning nozzle 6 is positioned between the metal ring 12 and the nanofiber collecting device.
The top of the spinning nozzle and the metalThe distance of the circular ring is L, L is determined by the physical relation of the variable electric field gradient, and the physical relation is
Figure BDA0003255077030000031
Wherein R is the radius of the metal ring. The spinning nozzle is supported by the insulating support, and the distance L between the top of the spinning nozzle and the metal ring can be adjusted by the support.
Example 2
The polyacrylonitrile superfine nanofiber is produced by using a variable electric field gradient superfine nanofiber preparation device, and polyacrylonitrile powder with the molecular weight of 86000 is dissolved in N, N-dimethylformamide to prepare spinning solution with the mass fraction of 8%. Adjusting the distance between the nanofiber collecting device and the spinning nozzle 6 to be 15 cm; selecting a metal ring 12 with the radius of 5 cm; the distance between the top of the spinning nozzle 6 and the metal ring 12 is adjusted to be 0.5 cm; opening the high polymer spinning solution supply device and setting the liquid supply speed to be 1 mL/min; turning on a power supply of the high-voltage generator 4, and adjusting the spinning voltage to 12 kV; an ultrafine jet 7 is excited from the top of a spinning nozzle 6 and is subjected to drawing refinement and solvent volatilization solidification to form an ultrafine nanofiber 10; the nanofiber collecting device receives the formed ultrafine nanofibers 10. Thus, uniform superfine nano-fibers with the average fiber diameter of 58nm are prepared. The average diameter of the nanofiber obtained by electrospinning the same spinning solution under the same spinning distance and spinning voltage conditions by using a traditional single-needle electrostatic spinning device is 135 nm.
Example 3
The polyvinyl alcohol superfine nanofiber is produced by using a variable electric field gradient superfine nanofiber preparation device, and polyvinyl alcohol powder with the model of 1799 is dissolved in water at 80 ℃ to prepare a spinning solution with the mass fraction of 7%. Adjusting the distance between the nanofiber collecting device and the spinning nozzle 6 to be 18 cm; selecting a metal ring 12 with the radius of 6 cm; the distance between the top of the spinning nozzle 6 and the metal ring 12 is adjusted to be 1 cm; opening the high polymer spinning solution supply device and setting the liquid supply speed to be 0.8 mL/min; turning on a power supply of the high-voltage generator 4, and adjusting the spinning voltage to 10 kV; an ultrafine jet 7 is excited from the top of a spinning nozzle 6 and is subjected to drawing refinement and solvent volatilization solidification to form an ultrafine nanofiber 10; the nanofiber collecting device receives the formed ultrafine nanofibers 10. Thus, uniform ultrafine nanofibers having an average fiber diameter of 46nm were obtained. The average diameter of the nanofiber obtained by electrospinning the same spinning solution under the conditions of the same spinning distance and the same spinning voltage by using a traditional single-needle electrostatic spinning device is 111 nm.

Claims (10)

1.一种纺丝装置，其特征在于，所述装置包括纺丝液供液装置、纳米纤维收集装置、高压发生器、纺丝喷头、金属圆环；所述纺丝液供液装置与纺丝喷头连接，纳米纤维收集装置设于纺丝喷头上方；其中所述纺丝喷头外设有金属圆环，并且所述金属圆环的圆心与所述纺丝喷头同心。1. a spinning device, it is characterized in that, described device comprises spinning solution liquid supply device, nanofiber collecting device, high pressure generator, spinning nozzle, metal ring; Described spinning solution liquid supply device and spinning solution The spinning nozzles are connected, and the nanofiber collecting device is arranged above the spinning nozzle; wherein the spinning nozzle is provided with a metal ring, and the center of the metal ring is concentric with the spinning nozzle. 2.根据权利要求1所述装置，其特征在于，所述纺丝液供液装置包括推进泵、注射器和导液管，其中导液管一端同注射器连接，另一端同纺丝喷头的底部连接。2. device according to claim 1, is characterized in that, described spinning solution liquid supply device comprises propulsion pump, syringe and catheter, wherein one end of catheter is connected with syringe, and the other end is connected with the bottom of spinning nozzle . 3.根据权利要求1所述装置，其特征在于，所述纳米纤维收集装置为金属平板、金属滚筒或导电传送带。3 . The device according to claim 1 , wherein the nanofiber collecting device is a metal flat plate, a metal drum or a conductive conveyor belt. 4 . 4.根据权利要求1所述装置，其特征在于，所述纳米纤维收集装置接地。4. The device of claim 1, wherein the nanofiber collection device is grounded. 5.根据权利要求1所述装置，其特征在于，所述纳米纤维收集装置与纺丝喷头的距离为5～30cm。5 . The device according to claim 1 , wherein the distance between the nanofiber collecting device and the spinning nozzle is 5-30 cm. 6 . 6.根据权利要求1所述装置，其特征在于，所述纺丝喷头为金属中空针头；所述金属圆环的半径R的范围为1～30cm。6 . The device according to claim 1 , wherein the spinning nozzle is a metal hollow needle; and the radius R of the metal ring ranges from 1 to 30 cm. 7 . 7.根据权利要求1所述装置，其特征在于，所述纺丝喷头顶部与金属圆环的距离为L，L由变电场梯度的物理关系确定，物理关系为
Figure FDA0003255077020000011
其中R为金属圆环的半径。7. The device according to claim 1, wherein the distance between the top of the spinneret and the metal ring is L, and L is determined by the physical relationship of the variable electric field gradient, and the physical relationship is
Figure FDA0003255077020000011
where R is the radius of the metal ring. 8.根据权利要求1所述装置，其特征在于，所述金属圆环通过导线与高压发生器的正极相连；所述高压发生器电压调节范围为0～60KV。8 . The device according to claim 1 , wherein the metal ring is connected to the positive electrode of the high-voltage generator through a wire; the voltage adjustment range of the high-voltage generator is 0-60KV. 9 . 9.根据权利要求1所述装置，其特征在于，所述纺丝喷头通过绝缘支架支撑，并通过支架可调节纺丝喷头顶部和金属圆环的距离L。9 . The device according to claim 1 , wherein the spinning nozzle is supported by an insulating bracket, and the distance L between the top of the spinning nozzle and the metal ring can be adjusted by the bracket. 10 . 10.一种超细纳米纤维，其特征在于，所述超细纳米纤维通过采用权利要求1所述装置进行纺丝获得。10 . An ultrafine nanofiber, characterized in that, the ultrafine nanofiber is obtained by spinning using the device of claim 1 .
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116856111A (en) * 2023-06-06 2023-10-10 盐城工学院 Flexible TiO 2 Base nano-fiber net film and preparation method and application thereof

Citations (5)

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Publication number Priority date Publication date Assignee Title
US20090091065A1 (en) * 2007-10-09 2009-04-09 Indian Institute Of Technology Kanpur Electrospinning Apparatus For Producing Nanofibers and Process Thereof
CN107475785A (en) * 2017-08-11 2017-12-15 东华大学 A kind of electrostatic spinning apparatus and its application method of spinning solution curvature dynamic control
CN107955980A (en) * 2017-12-26 2018-04-24 东华大学 The spherical multiple injector electrostatic spinning device of bar transmission tandem and its application method
CN109629015A (en) * 2018-12-28 2019-04-16 李瑞锋 A kind of separation control electric field Round Porous cylindricality electrostatic spinning apparatus and its spinning process
CN110241467A (en) * 2019-05-23 2019-09-17 东华大学 Inner cone angie type electrostatic spinning apparatus and its application method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090091065A1 (en) * 2007-10-09 2009-04-09 Indian Institute Of Technology Kanpur Electrospinning Apparatus For Producing Nanofibers and Process Thereof
CN107475785A (en) * 2017-08-11 2017-12-15 东华大学 A kind of electrostatic spinning apparatus and its application method of spinning solution curvature dynamic control
CN107955980A (en) * 2017-12-26 2018-04-24 东华大学 The spherical multiple injector electrostatic spinning device of bar transmission tandem and its application method
CN109629015A (en) * 2018-12-28 2019-04-16 李瑞锋 A kind of separation control electric field Round Porous cylindricality electrostatic spinning apparatus and its spinning process
CN110241467A (en) * 2019-05-23 2019-09-17 东华大学 Inner cone angie type electrostatic spinning apparatus and its application method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116856111A (en) * 2023-06-06 2023-10-10 盐城工学院 Flexible TiO 2 Base nano-fiber net film and preparation method and application thereof

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