CN109097849A - Nanofiber generating device - Google Patents
Nanofiber generating device Download PDFInfo
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- CN109097849A CN109097849A CN201811143049.7A CN201811143049A CN109097849A CN 109097849 A CN109097849 A CN 109097849A CN 201811143049 A CN201811143049 A CN 201811143049A CN 109097849 A CN109097849 A CN 109097849A
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- generating device
- spinning solution
- spinning
- nanofiber generating
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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
- D01D13/00—Complete machines for producing artificial threads
-
- 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
-
- 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
- D01D5/12—Stretch-spinning methods
- D01D5/14—Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing
-
- 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
- D01D5/18—Formation of filaments, threads, or the like by means of rotating spinnerets
-
- 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
- D01D7/00—Collecting the newly-spun products
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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 discloses a kind of nanofiber generating devices, comprising: stored spinning solution in internal liquid storage chamber is guided into external spinneret channel equipped at least one by a rotatable spinning solution storage device；One fiber collecting device；One guides high-speed flow into the spinneret channel outlet and migrates the spinning solution jet stream flowed out in outlet or its formed spinning auxiliary to the air-stream generating device of fiber collecting device；And one be placed in liquid storage chamber and the built-in electrode being in contact with spinning solution and one is placed in external electrode outside spinning solution storage device, has potential difference between the built-in electrode and external electrode；The built-in electrode and external electrode and the spinning solution storage device synchronous rotary.
Description
Technical field
The present invention relates to a kind of novel nano fiber generating devices.
Background technique
Electrostatic spinning nano fiber diameter mainly between 50-1000nm, has continuous length and very big specific surface area/body
Product ratio.There is large specific surface area by the non-woven cloth that electrostatic spinning nano fiber is formed, porosity is high, and aperture is small, and permeability is good etc.
Advantage has broad application prospects in numerous areas such as biologic medical, environment, the energy, chemical industry, clothes, materials.
And traditional electrostatic spinning technique is mainly using hollow needle as spinning head, spinning capability is very limited, often
A spinneret syringe needle can only generate a polymer spinneret, and each needle produces fibre weight less than 0.3 gram per hour.So low nanometer
Fibre production efficiency significantly limits the application of conventional electrostatic spining technology industrially.In order to improve electrostatic spinning yield,
High efficiency electrostatic spining technology mostly uses needleless spinneret to design.Formhals (US1975504) use jagged runner as
Cellulose fibre and cellulose acetate fibre has been prepared in the generator of nanofiber, and devises dry and wet spinning
The collection device of silk.Lucas etc. (WO2005024101) uses generator of the conductive cylinder as fiber, in this device
In, a part of conductive drum is immersed in polymer viscous liquid, so that cylinder is covered viscous liquid by rotation and is entered
In electric field, when electric field strength is sufficiently strong, the liquid of drum surface forms taylor cone and generates a large amount of solution jet, finally may be used
Nanofiber is obtained on the collector.Lin etc. (WO2010043002) discloses a kind of needleless electrostatic spinning device, including part
The spiral yarn shaped spinning electrode (or spinning head) being immersed in polymer solution reservoir is in from one spacing of screw electrode electrode
From collector on.Polymer solution in container forms thin film on helical structure surface, into spinning electrode and reception
Between electrode in electric field.When the electrostatic field intensity between electrode is sufficiently large solution can be drawn in taylor cone, in helical structure
Surface forms nanofiber.Other needleless spinnerets include that the circle of deformation leads to (WO2006131081), wire
(WO2011015161), thin plate (WO2006131081), screw rod (CN103774250), ladder (CN 103572388) etc. have
The spinning head of small radius of curvature can obviously increase electric field strength raising fiber production to carry out spinning.
On the other hand, centrifugal spinning be by rotary spinning head generate centrifugal force come shear polymer solution solution/melt from
And a kind of spinning technique of fiber is formed, United States Patent (USP) (US3358323) is appeared in earliest.Centrifugal spinning is for nanofiber
Preparation provides a kind of new way, a variety of different centrifugal spinning technologies is had already appeared by development, such as using centrifugation electrostatic spinning work
Skill prepares the compound nano micron fibre of core-shell structure (CN104928774B)；Centrifugal spinning process production nanofiber is simultaneously directly collected
At twist yarn (CN105386167B)；Using air-flow complementary melt centrifugal spinning device, melt jet stream is in inertia force and high speed
Succeeding stretch (CN104674360B) under airflow function.
It further, is the important channel for improving nanofiber production capacity by electrostatic spinning in conjunction with centrifugal spinning.Centrifugation
Collective effect when Static Spinning refers to fiber formation by centrifugal force and high-pressure electrostatic power.Centrifugal force strengthens right in spinning process
The drawing-off of jet stream and fiber, high-speed mobile circumferentially accelerate the volatilization of solvent in fiber simultaneously.It is centrifuged electrostatic spinning technique
Centrifugal spinning process and electrostatic spinning process respectively advantage are combined, has many advantages, such as that fiber is uniform, diameter is small, yield is high.
Chinese patent CN104328514B discloses jet stream under a kind of traditional vacuum electrostatic spinning apparatus vacuum environment, and there is no disturbances, real
Now more stably prepare higher performance, higher-quality nanofiber technology.CN105755557B then discloses a kind of magnetcisuspension
Flotation electrostatic spinning apparatus can overcome dependence of the centrifugal spinning to motor, and simplifying device for spinning keeps operation simpler.
The top that CN105568403B devises a kind of centrifugation electrostatic spinning apparatus centrifugal energy nozzle of tool rotating air suction is equipped with fan, fan
It can be rotated synchronously with centrifugal energy nozzle, and extraneous gas is blasted in liquid storage chamber to generate the gas for blowing to reception device by wire vent pore
Stream.It assists the formation of spinning jet and further stretches, form nanofiber and be collected device collection.
The speed of production of nanofiber and lower to the regulating power of fibre fineness in the prior art, and in production process
Fiber produced is more demanding to the substrate of deposition.
Summary of the invention
Technical problem to be solved by the present invention lies in providing, a kind of spinning fibre yield is big, thin and uniform, and to fibre
The adjustable range of dimension diameter greatly improves；In continuous spinning, specific collection device is not needed, fiber can be arrived with orientated deposition
The nanofiber generating device on arbitrary surface.
Its technical problem to be solved can be implemented by the following technical programs.
A kind of nanofiber generating device, comprising:
One rotatable spinning solution storage device guides stored spinning solution in internal liquid storage chamber outside into equipped at least one
The spinneret channel in portion；
One fiber collecting device；
One by high-speed flow guide into the spinneret channel outlet and by the spinning solution jet stream flowed out in outlet or its formed
Spinning auxiliary is migrated to the air-stream generating device of fiber collecting device；And
One is placed in liquid storage chamber and the built-in electrode being in contact with spinning solution and one is placed in outside spinning solution storage device
External electrode has potential difference between the built-in electrode and external electrode；The built-in electrode and external electrode and the spinning
Silk liquid storage device synchronous rotary.
As the further improvement of the technical program, the built-in electrode is high-voltage positive electrode, and the external electrode is cathode；
Or, the built-in electrode is high pressure termination electrode, the external electrode is to electrode.
Also as the further improvement of the technical program, the built-in electrode is through spinneret channel and external high pressure generator
Output end is connected, and the external electrode is a grounding electrode, and the external electrode is fixed on the spinning through insulator
Liquid storage device outer surface.
Also as the further improvement of the technical program, the revolving speed of the spinning solution storage device be 1000-6000 turn/
Point.
As the further improvement of the technical program, the electricity of the high voltage electric field formed between spinning solution and the external electrode
Pressure range is 5-40KV.
Further, the high pressure generator is high-pressure electrostatic DC generator or high-voltage alternating electrostatic generator.
As the preferred embodiment of the present invention, along the direction of rotation of spinning solution storage device, the external electrode is located at it
The front position in corresponding spinneret channel.
Preferably, the number in the spinneret channel is even number.
As the further improvement of the technical program, the spinning solution storage device includes a reservoir, the liquid storage
The occlusion part that there is slot the other channels for preventing spinning solution outside spinneret channel or outlet to throw away；The outlet in the spinneret channel is in
Poroid or slit-shaped.
Preferably, the groove body of the reservoir axisymmetricly structure or centrosymmetric structure.
Wherein, the reservoir is cylindrical shape；The outer dia for not including filament mouth needle like section is 20-1000mm；Institute
The axial width for stating reservoir is 10-500mm.
As another preferred embodiment of the invention, the outlet in the spinneret channel is in slit-shaped, slit length direction with
Rotary shaft is in 0-70 ° of angle, and slit is less than the outside thickness of reservoir, slit width 0.1- along the length of rotary axis direction
5mm。
Equally as preferred form of the invention, when the outlet in the spinneret channel is in poroid, the top of the external electrode
End is tip；When the outlet in the spinneret channel is in slit-shaped, the external electrode is slim-lined construction.
As another preferred embodiment of the invention, the external electrode is in same flat with corresponding spinneret channel
Face.
As another preferred embodiment of the invention, the external electrode is in different planes from corresponding spinneret channel,
It is 0-90 degree that the external electrode, which is formed by angle in the projection of rotary shaft vertical plane with corresponding slinning cabinet,.
Wherein, when the outlet in the spinneret channel is in slit-shaped, slit spinneret orifice is 5mm- at a distance to electrode
100mm。
Also as the further improvement of the technical program, which includes more than one described spinneret channel, described interior
It sets electrode and is connected through one above spinneret channel with the output end of external high pressure generator, each described spinneret channel
All correspond to an external electrode.
Further improvement equally as the technical program, the device can provide the air-flow for intervening fiber deposition direction
Air-stream generating device, airflow direction be from the spinning solution storage device to the fiber collecting device, air-flow velocity is
0.1-5 meter per second.
Wherein, the gas of the air-flow is air, nitrogen, carbon dioxide or argon gas.
In addition, the spinning solution is the viscous liquid that viscosity is 1-100000mPa s.
Further, the viscous liquid is selected from the solution of polymer solution, sol-gel solution or particle suspension.
Further, the spinning solution is the molten mass polymerization for including at least one polymer and at least one solvent flashing
Object solution.
This nanometer of generating device by adopting the above technical scheme has the characteristics that as follows:
1, the spinning process is completed under three kinds of field of force collective effects of centrifugal force and air-flow, any of them by electrostatic force
The exclusive use in one field of force；
For example, during the spinning process if only rotation liquid bath is without electrostatic field and the air-flow of adding high pressure, due to it is generated from
Mental and physical efforts are smaller, spinning solution or can only be drafted into thicker micrometer fibers or can not form uniform nanofiber product；
If only using high-voltage electrostatic field, solution would not flow to the outside of pore or slit, so that spinning cannot be formed.It is used alone
Fluid can not be also processed into fiber by airflow function.Similarly, it also cannot achieve nanofiber in conjunction with two kinds of field of forces therein
Mass production and orientated deposition.When three kinds of field of force collective effects, nanofibers can not only be effectivelyed prepared, yield is big, carefully
And it is uniform, and the adjustable range of fibre diameter is greatly improved；In continuous spinning, specific collection device is not needed, it is fine
Dimension can be with orientated deposition to arbitrary surface.
2, generating device is not necessarily to external collecting electrodes, and the fiber of generation can be deposited to any material surface immediately, and
And it is not influenced by material electric conductivity.
Compared with nanofiber generator before, the generating device is in design principle, filamentation process and fiber collection side
There are apparent difference, specific manifestation in formula are as follows:
1, electric field force is generated by two electrodes of synchronous rotary, since the distance between two high-field electrodes are much small
In conventional electrostatic spinning distance, they can generate higher intensity electric field under the conditions of lower voltage, carry out to solution jet
Drawing-off；
2, centrifugal force increases solution jet in the drawing-off of normal direction, make the fiber to be formed more it is thin more evenly；
3, from the high speed rotation of liquid bath, generated airflow field not only increases leading for normal direction for the generation of air-flow
It stretches, and effectively prevents fiber to the deposition on electrode, while guidance forms fiber and migrates to collector；
4, collection device, which is not necessarily to form electric field with fiber generating device, be associated with, can be insulator or conductor, and shape
Fiber is not influenced with distance to be formed and collected.
Detailed description of the invention
Fig. 1 is the structure and operation schematic diagram of nanofiber generating device of the present invention.
Fig. 2 is the structural schematic diagram of pin-hole type disk fiber generator；
The sectional view of Fig. 3 pin-hole type disk fiber generator.
Fig. 4 is the structural schematic diagram of slit-type disk fiber generator.
Fig. 5 is rod-like fibre generator simplified schematic diagram.
Fig. 6 is the structural schematic diagram of symmetrical structure nanofiber generator.
Fig. 7 is the scanning electron microscope image of nanofiber.
Fig. 8 is the schematic illustration of nanofiber generating device of the present invention；Wherein Fig. 8 a illustrates receiver and liquid bath
Positive angle, Fig. 8 b illustrate the depression angle of liquid bath.
Fig. 9 is traditional centrifugation Static Spinning schematic illustration；Wherein Fig. 9 a illustrates the positive angle of receiver and liquid bath,
Fig. 9 b illustrates the depression angle of liquid bath.
--- --- air-flow 3 --- spinneret 4 --- grounding electrode of high-speed motor 2 in figure: 1
5 --- --- --- the steps 8 on liquid bath top --- liquid bath 81 --- of DC high-voltage power supply 7 of fiber 6
--- --- spinneret 11 --- the grounding electrode 13,14 --- liquid bath of step 10,12 of liner 82
Specific embodiment
A specific embodiment of the invention is described in further detail with reference to the accompanying drawing.
The present invention provides a kind of novel nanofiber generating devices, in conjunction with electrostatic force, three kinds of power of centrifugal force and air-flow
The synergistic effect of field, is processed into nanofiber for viscous fluid.The centrifugal force that liquid bath generates when rotating makes the solution inside liquid bath
It is squeezed out from spinneret orifice；The solution of extrusion is drafted into nanofiber under the collective effect of extra electric field and centrifugal force；Nanowire
Dimension is moved downward in the effect of air-flow and is collected on collection device.
Specifically, as shown in Figure 1, nanofiber generator of the present invention includes a rotatable liquid bath 8, one
(electricity is grounded with to electrode to by high-field electrode (output end of external high pressure generator enters inside liquid bath through the connection of spinneret 3)
Pole 4) composition electrode, a set of rotary power driving device (including high-speed motor 1, controller and connection attachment etc.) and a height
Fast air flow source (air-flow 2).
It is hollow structure inside liquid bath 8, for storing spinning solution.Liquid bath liner is connected with outer surface by pore or slit
Logical (can referring also to Fig. 2 to Fig. 4 provided in different forms of implementation), conveys spinning solution by pore (slit)
To outer surface.High-field electrode is all set on rotation liquid bath with to electrode, one of those is placed in inside liquid bath and spinning liquid phase
The spinning solution that polarizes is played the role of in connection, another electrode is set to outside liquid bath, in spinning process and liquid bath synchronous rotary.
When spinning, spinning solution in liquid bath reaches spinning by pore (or slit) due to the effect for the centrifugal force that liquid bath rotates
The outlet of silk head 3, and form jet stream (fiber 5).The jet stream is charged since internal high-voltage polarization of electrode acts on, thus by
The attraction of external electrode (i.e. grounding electrode 4)；Under the action of electric field force, jet stream is to external electrode transfer；However, due to air-flow
2 effect, jet stream are changed path again before not up to external electrode, the spinning generator of rotation are left, in air-flow 2
It under guidance, deposits in external collector, forms solid nano fiber.It high-speed flow source, can as a kind of external auxiliary device
The auxiliary of fiber 5 that jet stream produces is migrated to fiber collecting device with the high-speed flow needed using acquisitions such as pipeline, blowers.
The shape of liquid bath 8 can be axially symmetric structures or the centrosymmetric structures such as disc, spherical shape or cylinder.Liquid bath has
Liner, liner are connected with outer surface by pore or slit, and spinning solution is allow to be transported to appearance by pore (slit)
Face.It is controlled by the shape of liquid bath, two can be played the role of: 1), flow direction, speed and the distribution of change spontaneous air-flow, thus
Change nanofiber involves path, migratory direction；2) it, adjusts yield: by change shape, adjusting effective spinning zone area,
To adjust fiber throughput rate.The rotating diameter of liquid bath is 20mm to 1000mm；Axial width be 10mm to 500mm (here
Diameter and thickness refer to the diameter and height of liquid bath cylindrical outer shape).Wherein axial width is preferably the 1/2 of rotating diameter.Axis
Also bigger to the more big corresponding rotating diameter of thickness, the spinning solution of the bigger splendid attire of axial width is more.Liquid bath is to rotate integrally.Rotation
Turn the size that diameter directly determines centrifugal force, the big centrifugal force of diameter is big, and the bigger solution of centrifugal force is easier to be squeezed out out from spinneret
Form solution jet.Same rotational speed, rotating diameter is bigger, and the fiber of generation is thinner.
Liquid bath 8 is made of high-insulativity material, and polytetrafluoroethylene (PTFE), polyolefin, polyimides, polyamide, poly- carbon can be selected
Acid esters, polyethers, polysulfones, polyether-ether-ketone, ceramics etc., liquid bath material therefor have high stability, physicochemical property in spinning solution
It is not influenced by spinning solution with shape.
The spinning generator liquid bath has rotation function.In spinning, by the driving single direction rotation of external motor.Rotation
Speed is at 1000-6000 revs/min.
As shown in figure 3, the spinneret orifice (slit) of 81 two sides of liner of liquid bath has the step 82 of 0-5mm in outer, to avoid
Spinning solution spreads into liquid bath outer wall before forming jet stream.The number of spinneret orifice (i.e. spinneret 4) is even number, they are along center pair
Claim arrangement, can prevent eccentric force.
Internal high-voltage electrode is made of corrosion resistant stainless steel or alloy material, and built-in electrode can use line style, plate
Or reticular structure, it is homogeneously disposed in inside liquid bath, to ensure effectively to contact with spinning solution.The internal high-voltage electrode is in spinneret
It inside 4, is connect with external high pressure generator by line, high voltage thus is applied to spinning solution.
External electrode (grounding electrode 4) is fixed on except rotation liquid bath by insulating materials simultaneously, and is occurred with external high pressure
Device is connected.The electrode is made of corrosion resistant stainless steel or alloy material, and top has lesser radius of curvature (usually electricity
The diameter on pole top is less than 1mm, to guarantee that lesser radius of curvature can form stronger internal field in spinneret).It is grasping
When making, the electrode and liquid bath synchronous rotary.
Due to applying high voltage to solution inside high-field electrode access liquid bath, grounding electrode is outside liquid bath.Liquid bath itself
It is insulating materials, in this way, spinning nozzle spinning solution and liquid bath external electrode form partial high pressure field, plays effective drawing-off to spinning solution
Effect.It is all set on rotation liquid bath that is, being equivalent to two electrodes, one of those is placed in inside liquid bath is connected with spinning solution
It connects, plays the role of the spinning solution that polarizes, another electrode is set to outside liquid bath；During the spinning process, two electrodes and liquid bath are same
Step rotation.
As shown in figure 4, spinneret slit length direction has 0-70 ° of angle (to refer to slit length trend and rotation along rotary shaft
Axis is formed by angle), in favor of fiber row at.Axial length is less than the height of liquid bath tank liquor, slit width 0.1-
5mm.Slit is that even number arranges in pairs, axisymmetricly with liquid bath rotary shaft.Fig. 4 includes two slit spinneret orifices, and two elongated
Grounding electrode, spinneret orifice and grounding electrode mutually insulated, to form high voltage.
Each external grounding electrode is in the front end of direction of rotation relative to its corresponding spinneret 3 (wire hole out).Its
In, external electrode can be parallel or in the same plane with spinneret orifice (it can be appreciated that spinneret channel)；It can also locate
In different planes.When the two is in different planes, projection of the two in shaft vertical plane is formed by clamping and is not more than
90 degree.
Also, refering to what is shown in Fig. 2, electrode tip is maintained a certain distance with spinneret orifice (slit), which (refers to spinning nozzle
At a distance from grounding electrode) preferred 5mm-100mm.
When liquid bath spinning using it is as shown in Figure 2 and Figure 5 poroid when, external electrode apex structure shape is preferably sharp
Dots structure；And when using Fig. 4 and slit-shaped shown in fig. 6, external electrode is preferably slim-lined construction.It is this corresponding external
Electrode structural designs are to act on to generate stronger drawing-off to spinning solution for the ease of generating stronger electric field, be conducive to shape
At thinner fiber.
Also, the quantity of external electrode (herein referring to grounding electrode) and the quantity of spinneret orifice (slit) want identical.To guarantee
Each filament mouth has a corresponding grounding electrode.
And high voltage is added between external electrode and built-in electrode when external high pressure generator, make spinning solution surface and outer
It sets after forming high voltage electric field between electrode.The range of ideal high voltage is in 5kV between 40kV.
Also, external high pressure generator can be high-pressure electrostatic DC generator, be also possible to high-voltage alternating electrostatic hair
Raw device.When using DC generator, high-voltage end may be coupled to internal or external electrode.
In addition, external grounding electrode 4 can be designed to, master similar with spinneret orifice/spinneret channel (spinneret 3) in shape
If in order to realize control field distribution, point electrode corresponds to point electrode, gap electrode respective elongated electrode.Two electrode interiors are
It is disconnected, there is respective path.
The spinning generator can add simultaneously and (refer to relative to spontaneous air-flow) an outer gas stream field, for controlling fibre
Tie up deposition direction.Airflow direction is the direction from liquid bath to fiber collector, prevents jet stream from throwing away by spinning nozzle to assist
Deposition on external electrode afterwards reinforces the drawing-off to jet stream, and controls the direction of motion of fiber.It is mainly used for adjusting fiber
Migratory direction, be conducive to the collection of fiber.
And in fact, although the rotation of generator itself can generate a gas field, the fiber of this airflow field and fiber
Drawing-off direction it is often inconsistent, method mutually part can counter extensioin apply shearing force, be conducive to drawing of fiber and attenuate.Due to rotation
The direction of airflow field can be adjusted by the shape of generator, and the drawing-off direction of fiber can pass through the opposite of two electrodes
Position is adjusted, by optimization liquid bath shape and electrode position adjustable shearing force, to adjust fibre diameter.The rotation of liquid bath
Turn to have an impact to the flow direction of swirling eddy with rough air, outer shape.It can be by adjusting the outer shape of liquid bath and turning
The flow velocity of air-flow around speed control and flow direction adjust fibre diameter to cooperate spinning.
Air-flow can be air, nitrogen, carbon dioxide or argon gas.They are directly guided by pipeline or/and fan, gas
Flow control is in 0.1 meter per second to 5 meter per seconds.
The spinning generator is mainly used for processing viscous liquid, including solution or molten mass.When spinning solution is solution, it
Include polymer solution, sol-gel, particle suspension etc..The viscosity of viscous liquid is 1mPa s to 100000mPa s.It is glutinous
Property the preferred form of liquid be polymer solution, generally include at least one polymer and at least one solvent flashing.When being molten
When melt body, they include a variety of materials that can melt in certain temperature, including polymer, small molecule, inorganic material and metal
Deng.
Fiber collecting device can be various different forms, for example, roller, plate, plate V belt translation, rotatable drum；
It or is base fabric, including woven cloth, woven fabric, non-woven fabrics, paper and plastic film.
Below with reference to embodiment, the present invention is described in further detail.
Embodiment 1:
The electrostatic spinning apparatus used is as shown in Figure 1.The electrostatic spinning apparatus includes a pin-hole type disk fiber hair
Raw device, a DC high-voltage power supply, a flat panel collector and a fan.3000 revs/min of liquid bath revolving speed, 20,000 volts of voltage
(built-in electrode connects high-voltage output end, external electrode ground connection), 1 m/min of wind speed.Preparing used in nanofiber is Austria of Sigma
The 8%PVA aqueous solution that Delhi surprise polyvinyl alcohol (PVA, average molecular weight 146,000-186,000, degree of hydrolysis 96%) is prepared.
During the spinning process, rotation liquid bath is added in spinning solution, and liquid bath high speed rotation is driven by motor.When solution reaches spinneret
Mouthful, DC high-voltage power supply is opened, applies the voltage of 20kV, and start air-flow, nanofiber is made equably to deposit to collected outside
On device.Nanofiber yield is up to 200 Grams Per Hours, and 150 nanometers of average fibre diameter.If Fig. 6 is the present embodiment is prepared
The electron scanning micrograph of PVA nanofiber.
Embodiment 2:
The electrostatic spinning apparatus used is as shown in Figure 1.The electrostatic spinning apparatus includes a pin-hole type disk fiber hair
Raw device, a DC high-voltage power supply, a flat panel collector and a fan.3000 revs/min of liquid bath revolving speed, 20,000 volts of voltage
(external electrode connects high-voltage output end, built-in electrode ground connection), 1 m/min of wind speed.Preparing used in nanofiber is Austria of Sigma
The 10%PAN-DMF solution that Delhi surprise polyacrylonitrile (PAN, average molecular weight 150,000) is prepared.During the spinning process, will
Rotation liquid bath is added in spinning solution, and drives liquid bath high speed rotation by motor.Apply the DC voltage of 22kV to solution, and starts
Air-flow deposits to nanofiber equably in external collector.Nanofiber yield can big 175 Grams Per Hour, fiber is average straight
180 nanometers of diameter.
Embodiment 3:
The electrostatic spinning apparatus used is as shown in Figure 1.The electrostatic spinning apparatus includes a pin-hole type disk fiber hair
Raw device, an ac high voltage source, a flat panel collector and a fan.3000 revs/min of liquid bath revolving speed, 20,000 volts of voltage,
1 m/min of wind speed.Prepare used in nanofiber is that (PVDF, average molecular weight are Sigma-Aldrich Kynoar
275,000) the DMF- acetone soln of the 15%PVDF prepared.During the spinning process, rotation liquid bath is added in spinning solution, and passed through
Motor drives liquid bath high speed rotation.Apply the voltage of 16kV to solution, and start air-flow, deposits to nanofiber equably outer
On portion's collector.Nanofiber yield can big 230 Grams Per Hour, 210 nanometers of average fibre diameter.
Electric field before nanofiber generating device provided by the invention and the maximum difference of the prior art are is formed in hair
Between raw device and collector, if ground connection is connected on collection device in CN105568403B, since spinning is apart from larger, even if
In addition higher voltage, the effect of electric field force is also very weak when spinning, inadequate to the drawing-off of fiber, causes fiber thick and uneven.
And in the technical program, spinning electric field is two electrodes by being added on rotation liquid bath to realize, due to high pressure
The distance between electrode and grounding electrode are smaller (the distance between two electrodes are inversely proportional with the intensity for forming electric field), although applying
The voltage added is lower, but the intensity for being actually formed by electric field is very big, and big electric field force is easy to shape to the drawing-off of solution jet
At thin and uniform fiber.
Such as Fig. 8 and Fig. 9, the principle comparison of conventional centrifugal electrostatic spinning technique and technical scheme is illustrated；In order to
Convenient for explanation, one or a pair of of spinneret are only illustrated in figure.Spinneret 12 is high-field electrode in Fig. 8, with grounding electrode 11
Centre forms electric field E, and liquid bath 13 generates centrifugal force by the rotation direction that arrow is indicated, and fiber is in electric field force FE, centrifugal force FC
With wind-force FWCollective effect under towards receiver.Illustrated in Figure 9 spinneret 10 is high-field electrode in the prior art, is received
Device ground connection generates electric field E between the two, and liquid bath 14 generates centrifugal force by the rotation direction that its arrow is indicated, and fiber is in electric field force
FEWith centrifugal force FCCollective effect under towards receiver.
The following table 1 is the depth correlation of the prior art and each technology of technical solution of the present invention and performance parameter, can side by following table
Verify the excellent performance of the application nanofiber generating device in face.
Table 1:
It is provided by the invention by electrostatic, the nanofiber generating device of three kinds of external force field coordinated drives of centrifugation and air-flow, use
In viscous fluid is processed into nanofiber.The technology can not only increase substantially the speed of production of nanofiber and to fiber
The regulating power of fineness, and the fiber produced can deposit on any substrate, form uniform nanometer non-woven cloth.The dress
It sets and is suitable for large-scale production nanofiber, and the fiber produced is more carefully, more evenly.
Claims (22)
1. a kind of nanofiber generating device characterized by comprising
One rotatable spinning solution storage device guides stored spinning solution in internal liquid storage chamber into outside equipped at least one
Spinneret channel；
One fiber collecting device；
One guides high-speed flow into the spinneret channel outlet and by the spinning solution jet stream flowed out in outlet or its formed spinning
Auxiliary is migrated to the air-stream generating device of fiber collecting device；And
One be placed in liquid storage chamber and the built-in electrode being in contact with spinning solution and one be placed in it is external outside spinning solution storage device
Electrode has potential difference between the built-in electrode and external electrode；The built-in electrode and external electrode and the spinning solution
Storage device synchronous rotary.
2. nanofiber generating device according to claim 1, which is characterized in that the built-in electrode is high-voltage positive electrode,
The external electrode is cathode；Or, the built-in electrode is high pressure termination electrode, the external electrode is to electrode.
3. nanofiber generating device according to claim 1, which is characterized in that the built-in electrode through spinneret channel with
The output end of external high pressure generator is connected, and the external electrode is a grounding electrode, and the external electrode is solid through insulator
Due to the spinning solution storage device outer surface.
4. nanofiber generating device according to claim 1, which is characterized in that the revolving speed of the spinning solution storage device
It is 1000-6000 revs/min.
5. nanofiber generating device according to claim 1,2,3 or 4, which is characterized in that spinning solution with it is described external
The voltage range of the high voltage electric field formed between electrode is 5-40KV.
6. nanofiber generating device according to claim 3, which is characterized in that the high pressure generator is high-pressure electrostatic
DC generator or high-voltage alternating electrostatic generator.
7. nanofiber generating device according to claim 3, which is characterized in that along the rotation side of spinning solution storage device
To the external electrode is located at the front position in its corresponding spinneret channel.
8. nanofiber generating device according to claim 1 or 3, which is characterized in that the number in the spinneret channel is
Even number.
9. nanofiber generating device according to claim 1 or 3, which is characterized in that the spinning solution storage device packet
Include a reservoir, the occlusion part that there is the reservoir the other channels for preventing spinning solution outside spinneret channel or outlet to throw away；
The outlet in the spinneret channel is in poroid or slit-shaped.
10. nanofiber generating device according to claim 9, which is characterized in that the groove body of the reservoir is in axis pair
Claim structure or centrosymmetric structure.
11. nanofiber generating device according to claim 10, which is characterized in that the reservoir is cylindrical shape；No
Outer dia including filament mouth needle like section is 20-1000mm；The axial width of the reservoir is 10-500mm.
12. nanofiber generating device according to claim 9, which is characterized in that the outlet in the spinneret channel is in narrow
When gap-like, slit length direction and rotary shaft are in 0-70 ° of angle, and slit is less than the outside of reservoir along the length of rotary axis direction
Thickness, slit width 0.1-5mm.
13. according to claim 1, nanofiber generating device described in 3 or 7, which is characterized in that the outlet in the spinneret channel
In poroid or slit-shaped；When the outlet in the spinneret channel is in poroid, the top of the external electrode is tip；The spinneret is logical
When the outlet in road is in slit-shaped, the external electrode is slim-lined construction.
14. nanofiber generating device according to claim 7, which is characterized in that the external electrode with it is corresponding
Spinneret channel is in same plane.
15. nanofiber generating device according to claim 7, which is characterized in that the external electrode and corresponding spinneret
Channel is in different planes, and it is 0- that the external electrode, which is formed by angle in the projection of rotary shaft vertical plane with corresponding slinning cabinet,
90 degree.
16. nanofiber generating device according to claim 9, which is characterized in that the outlet in the spinneret channel is in narrow
When gap-like, slit spinneret orifice is 5mm-100mm at a distance to electrode.
17. nanofiber generating device according to claim 3, which is characterized in that the device includes described in more than one
Spinneret channel, the built-in electrode are connected through one above spinneret channel with the output end of external high pressure generator, often
One spinneret channel all corresponds to an external electrode.
18. nanofiber generating device according to claim 1, which is characterized in that the air-flow of the air-stream generating device
Direction is from the spinning solution storage device to the fiber collecting device, and air-flow velocity is 0.1-5 meter per second.
19. nanofiber generating device according to claim 18, which is characterized in that the gas of the air-flow be air,
Nitrogen, carbon dioxide or argon gas.
20. nanofiber generating device according to claim 1, which is characterized in that the spinning solution is that viscosity is 1-
The viscous liquid of 100000mPa s.
21. nanofiber generating device according to claim 20, which is characterized in that the viscous liquid is selected from polymer
The solution of solution, sol-gel solution or particle suspension.
22. nanofiber generating device described in 8 or 19 according to claim 1, which is characterized in that the spinning solution be include to
The molten mass polymer solution of few a kind of polymer and at least one solvent flashing.
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| CN110735192A (en) * | 2019-10-31 | 2020-01-31 | 东华大学 | -electrode-assisted disc type porous electrostatic spinning spray head assembly |
| CN111945237A (en) * | 2020-08-03 | 2020-11-17 | 武汉大学 | Spinning and collecting equipment capable of being directly woven and fiber weaving method |
| CN113423878A (en) * | 2019-02-14 | 2021-09-21 | Uab研究基金会 | Alternating field electrode system and method for generating fibers |
| CN113502552A (en) * | 2021-06-10 | 2021-10-15 | 武汉纺织大学 | Spinning equipment for preparing nano fibers |
| CN115110160A (en) * | 2022-08-30 | 2022-09-27 | 江苏新视界先进功能纤维创新中心有限公司 | Electrostatic spinning device and preparation method of nano-fibers |
| CN115537947A (en) * | 2022-09-29 | 2022-12-30 | 浙江理工大学桐乡研究院有限公司 | Superfine fiber-based fiber membrane airflow centrifugal spinning device and preparation method |
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| CN113423878B (en) * | 2019-02-14 | 2024-06-07 | Uab研究基金会 | Alternating field electrode system and method for generating fibers |
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| CN115537947A (en) * | 2022-09-29 | 2022-12-30 | 浙江理工大学桐乡研究院有限公司 | Superfine fiber-based fiber membrane airflow centrifugal spinning device and preparation method |
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