CN206308452U - A kind of electrostatic spinning nano fiber generating means - Google Patents

A kind of electrostatic spinning nano fiber generating means Download PDF

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Publication number
CN206308452U
CN206308452U CN201621384752.3U CN201621384752U CN206308452U CN 206308452 U CN206308452 U CN 206308452U CN 201621384752 U CN201621384752 U CN 201621384752U CN 206308452 U CN206308452 U CN 206308452U
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CN
China
Prior art keywords
wire casing
slit
fiber
spinneret
spinning
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Expired - Fee Related
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CN201621384752.3U
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Chinese (zh)
Inventor
林童
牛海涛
颜贵龙
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Nantong Newour New Mstar Technology Ltd
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Nantong Newour New Mstar Technology Ltd
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/0007Electro-spinning
    • D01D5/0061Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0069Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/0007Electro-spinning
    • D01D5/0061Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0076Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/0007Electro-spinning
    • D01D5/0061Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0092Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields

Abstract

The utility model discloses a kind of electrostatic spinning nano fiber generating means, including fiber generator, fiber collecting device and high-voltage generator, fiber generator includes spinning cavity, spinneret wire casing and fluid reservoir, it is slit in the middle of spinneret wire casing, the slit connects spinning inside cavity, fluid reservoir connects spinning cavity, and spinneret wire casing is full of twists and turns structure;Fiber collecting device is placed in the position directly above of spinneret wire casing;High-voltage generator has high-pressure side and earth terminal.A kind of electrostatic spinning nano fiber generating means of the present utility model, is the device for producing nanofiber using electrostatic spinning principle with viscous liquid as raw material;Prior art is compared; its core of the present utility model is the fiber generator with curved slit; the fiber generator not only with restrained effectively the solvent concentration of dope that causes of volatilization and change; so as to substantially increase the stability of nanofiber production; and the uniformity and production efficiency of produced nano-fiber film are improve, it is suitable to the continuous large-scale production of nanofiber.

Description

A kind of electrostatic spinning nano fiber generating means
Technical field
The present invention relates to a kind of fiber generating means, particularly a kind of electrostatic spinning nano fiber generating means belongs to electrostatic Spining technology field.
Background technology
Below in connection with background of invention description be in order to explain present disclosure, rather than recognize to refer to it is all Material is priority date of the present application is disclosed, known or a part of general knowledge.
Nanofiber typically refers to superfine fibre of the diameter less than 1000nm.Relative to common fiber, nanofiber tool There is the advantages of specific surface area is big, and porosity is high, had broad application prospects in numerous areas.Electrostatic spinning technique is a kind of system The technology that standby nanofiber is commonly used, applied widely, simple to operate, technique is controllable.The general principle of electrostatic spinning technique is, The polymer drop being placed in high-voltage electrostatic field can form taylor cone, when electric field force is sufficiently large, drop can overcome surface tension from Taylor cone cone is sprayed and forms jet, and jet is constantly refined under the effect such as electrostatic field force, viscosity resistance, surface tension, most Fall eventually and nanofiber is formed on collection device.Traditional electrostatic spinning technique is mainly using hollow needle as spinneret, its Spinning production capacity is limited, and each spinneret syringe needle is typically only capable to produce a polymer spinneret, and each pin produces fiber per hour Amount is less than 300 milligrams.Low nanofiber production efficiency significantly limit the process of industrialization of electrostatic spinning technique.
A kind of method of conventional raising Electrospun nano-fibers yield is with multiple syringe needles.Due to single syringe needle Fiber production is extremely low, causes to produce the nanofiber for reaching market demand grammes per square metre, must the substantial amounts of syringe needle of arrangement.But it is different Electric jamming is there is between syringe needle, their minimum spacing is limited, device space cost is increased.Meanwhile, polymer Deposit or impurity easily block syringe needle, therefore the continued operation of spinning process needs continually to clear up syringe needle, makes Nanowire The quality and yield for tieing up product are all affected.
In order to increase the production efficiency of electrostatic spinning, various needle-free spinnerets are introduced into.Formhals (United States Patent (USP)s US1975504 jagged runner) is used as the generator of nanofiber, has prepared cellulose fibre and acetic acid is fine Cellulose fiber, and devise the collection device of dry and wet spinning.(international monopoly WO2000022207) such as Reneker is used A kind of special circular cylindrical body as fiber generator, in the apparatus, polymer viscous liquid is extruded to ring first Shape column end, then makes spinning solution form film centrally through air-flow, and film is further stretched to form spinning into electric field Silk jet.(international monopoly WO2005024101) such as Lucas uses a powered cylinder as the generator of fiber, herein In device, a part for powered cylinder is immersed in polymer viscous liquid, and spinning liquid is entered by rotating the cylinder Enter in electric field, substantial amounts of jet is formed in periphery, finally can on the collector obtain nanofiber.It is basic herein On, powered cylinder is replaced with PETRAS etc. (international monopoly WO2006131081) the powered rotary body of a series of complex, with The patent of Lucas et al. is similar, and spinning liquid also forms jet on its surface.(international monopoly WO2010043002) such as Tong is public Opened a kind of needleless electrostatic spinning device, including it is local be immersed in polymer solution reservoir spiral yarn shaped spinning electrode (or Spinneret).Electrode is on the collector with a certain distance from screw electrode.Polymer solution in container is in spiral winding table Face forms thin film, into electric field between spinning electrode and receiving electrode.When the electrostatic field intensity between electrode is sufficiently large When can stretch to form taylor cone by solution, nanofiber is formed at coil surface some points.Nanofiber is deposited in collection Device surface, formation is non-to knit nanofiber mats.
Above-mentioned various electrostatic spinning apparatus use the surface of open system, polymer viscous liquid to be exposed to air In, cause a large amount of solvents to volatilize.As spinning process is carried out, solution concentration can be increasing, and fiber is also with the increasing of solution concentration Plus it is more and more thicker.The stability that thus influence nanofiber is produced.
Patent CN104790048 discloses a kind of needleless electrostatic spinning apparatus, and the device is with linear pattern slit as spinning Head, and spinneret can be heated, spinning can be carried out to the molten mass of polymer.World patent WO2014062627 is public A kind of electrostatic spinning apparatus for preparing skin-core structure nanofiber are opened.The main linear pattern slit with bilayer of the device is nanometer The generator of fiber.One of which spinning liquid enters slit surface by inner-layer channel, and another liquid passes through outer layer channel Also into slit surface, two kinds of solution contacts, and be stretched simultaneously in the presence of electric field force, form the Nanowire of skin-core structure Dimension.Further, world patent WO2015017793 discloses a kind of electrostatic spinning apparatus, and the device is with linear pattern slit as base Plinth, is improved to the slit of the varying cross-section shape such as pearls knot type, sawtooth pattern, and spinning liquid forms spinning jet on slit top.
Above-mentioned slit electrostatic spinning apparatus, the non-uniform electric on along slit direction, two ends electric-field intensity is much Higher than centre, therefore spinning process can be caused, spinning jet skewness, and then make the nanofiber product being collected into uneven It is even.And carry out the phenomenon that electrostatic spinning is easy to two ends electric discharge or centre not wire vent using too long of straight slit.
Therefore, necessary to provide a kind of new device for preparing nanofiber, described device has the above advantage.
The content of the invention
The technical problem to be solved in the invention is directed to above-mentioned the deficiencies in the prior art, and provides a kind of generation undulation degree Material uniformity electrostatic spinning nano fiber generating means higher.
In order to solve the above technical problems, the technical solution adopted by the present invention is:
A kind of electrostatic spinning nano fiber generating means, including fiber generator, fiber collecting device and high-voltage generator, The fiber generator includes spinning cavity, spinneret wire casing and fluid reservoir, and the spinneret wire casing is located on spinning cavity, spinneret line It is slit in the middle of groove, slit connection spinning inside cavity, the fluid reservoir connects spinning cavity, the spinneret wire casing is for can be with Produce the full of twists and turns structure of uniform electric field;The fiber collecting device is placed in the position directly above of spinneret wire casing;The electricity high Pressure life utensil has high-pressure side and earth terminal, and high-pressure side is inserted in spinning inside cavity, earth terminal connection fiber collecting device.
Used as further preferred scheme, the full of twists and turns structure of the spinneret wire casing is annular, arc line shaped, broken line Shape, zigzag, rectangle, rhombus, irregular curved line or more variously-shaped combination.
Used as further preferred scheme, the slit in the middle of the spinneret wire casing is continuous gap structure, interruption gap The structure of structure or continuous through hole arrangement.
Used as further preferred scheme, the gap spacing of the slit of the interruption gap structure is 1mm to 100mm.
Used as further preferred scheme, the gap width of the slit in the middle of the spinneret wire casing is 0.5mm to 10mm, Its length is not less than 10mm, and it is highly not less than 0.1mm.
As further preferred scheme, there are several spinneret wire casings, the spray described in multiple on the spinning cavity Silk thread groove moves towards opposing parallel setting, and spacing between two neighboring spinneret wire casing is 2mm to 1000mm.
Used as further preferred scheme, slit in the middle of the spinneret wire casing goes out liquid speed rate in 0.01mL/h/cm To 100mL/h/cm.
Used as further preferred scheme, the high-voltage generator is that the potential difference between high-pressure side and earth terminal is big In 30kV.
As further preferred scheme, the distance between the fiber collecting device and spinneret wire casing be 10mm extremely 2000mm。
Beneficial effect
Compared with prior art, a kind of electrostatic spinning nano fiber generating means of the invention, is given birth to using electrostatic spinning principle Produce the device of nanofiber;Its core utilizes the spinneret wire casing in fiber generator, in the presence of high potential difference, from slit Injection nanofibers, and the spinneret wire casing structure of full of twists and turns structure, not only restrained effectively the spinning that solvent volatilization causes Silk liquid change in concentration, so as to substantially increase the stability of nanofiber production, improves the equal of produced nano-fiber film Even property and production efficiency, are suitable to the continuous large-scale production of nanofiber.Full of twists and turns structure can effectively overcome straight slit Electric field two ends are high and the drawbacks of middle low uneven distribution, and the nano-fiber film caused by electric field uneven distribution Production defect.Specifically include inhomogeneities of the nano-fiber film along warp-wise;Spinning speed in nano fibrous membrane two ends is much higher than Center section;Fiber membrane both sides nanofiber is thinner than centre.Full of twists and turns result can improve electric field in slit length direction Uniformity, so as to obtain uniform nano fibrous membrane.
Brief description of the drawings
Fig. 1 is schematic structural view of the invention;
Fig. 2 is spinneret wire casing structure schematic diagram;
The schematic diagram that Fig. 3 is arranged opposite to each other for the cambered surface of multiple arcs spinneret wire casing;
The schematic diagram that Fig. 4 is arranged in opposite directions for the cambered surface of multiple arcs spinneret wire casing;
Fig. 5 is the electric-field intensity distribution view of arc spinneret wire casing;
Fig. 6 is the electric-field intensity distribution view of linear pattern spinneret wire casing;
Fig. 7 is the electric-field intensity schematic diagram that equal length curved slit is produced with straight slit;
The yield diameter of the PVA nanofibers that Fig. 8 is obtained for apparatus of the present invention and single syringe needle, spiral winding spinneret Compare;
Fig. 9 is the scanning electron microscope image of the PVA nanofibers that the present invention is prepared;
Figure 10 is the zoomed-in view of the PVA nanofibers that the present invention is prepared;
Figure 11 is fold-line-shaped spinneret wire casing schematic diagram;
Figure 12 is zigzag spinneret wire casing schematic diagram;
Figure 13 is annular spinneret wire casing schematic diagram;
Figure 14 is rectangle spinneret wire casing schematic diagram;
Figure 15 is rhombus spinneret wire casing schematic diagram;
Figure 16 is discontinuous arc spinneret wire casing schematic diagram;
Figure 17 is the stereogram of big fiber type generator;
Specific embodiment
The optimal technical scheme that the invention will now be described in detail with reference to the accompanying drawings.
As shown in figure 1, a kind of electrostatic spinning nano fiber generating means of the invention, including fiber generator, fiber are collected Device 5 and high-voltage generator 3, the fiber generator include spinning cavity 1, spinneret wire casing 2 and fluid reservoir 4, the spinneret Wire casing 2 is located on spinning cavity 1, is slit in the middle of spinneret wire casing 2, inside slit connection spinning cavity 1, the fluid reservoir 4 Connection spinning cavity 1, the spinneret wire casing 2 is full of twists and turns structure;The fiber collecting device 5 is being placed in spinneret wire casing 2 just Top position;The high-voltage generator 3 has high-pressure side and earth terminal, and high-pressure side is inserted in inside spinning cavity 1, earth terminal Connection fiber collecting device 5;Storage viscous materials liquid in fluid reservoir 4, viscous materials liquid enters narrow in spinneret wire casing 2 Seam, produces nanofiber under electric field action, and the surface that the nanofiber of generation is uniformly deposited on fiber collecting device 4 is entered again Row is collected, and narrow slit structure can produce the electric field of higher-strength in the presence of extra electric field on surface.
Electric-field intensity distribution depends on shape of slit and curvature on slit, and the big local electric-field intensity of curvature is big.Straight line is narrow Stitch the Electric Field Distribution for producing uneven, high field is distributed in the two ends of slit, electric-field intensity is in from both ends to the middle gradually to pass Subtract trend.Such distribution can result in zone line due to the too low spinning not wire vent of electric-field intensity, and slit two ends are due to electric field Intensity is too high and corona discharge occurs.Even if in the middle of under certain condition and two ends can spinning, produced by straight slit two ends Fiber it is thinner and yield is also higher.The nano fiber non-woven fabric for preparing can be so caused the uneven of both sides thickness intermediate thin occur Problem, and fiber is in the thick inhomogeneities in the thin center section in non-woven fabrics both sides.
When slit introduces full of twists and turns structure, these meander lines have larger curvature, it is possible to increase respective regions Electric-field intensity, reduce slit in the middle of and two ends electric-field intensity difference, fundamentally solve straight slit along its length The uneven problem of upper Electric Field Distribution.Speed that equally distributed electric field makes not only to be produced along slit length direction fiber is consistent, And fibre fineness is also consistent, it is ensured that the uniformity of prepared fiber film thickness and fiber quality.Full of twists and turns structure is improved Slit entirety electric-field intensity can improve the yield reduction fibre fineness of nanofiber.And this full of twists and turns structure also increases Add effective spun length of slit, increase the yield of nanofiber fiber
Fiber collector 5 can be various multi-forms, and rotating collecting pipe is one of which.Can be flat Plate, the flat board of V belt translation, rotatable drum or base fabric include woven cloth, woven fabric, non-woven fabrics, paper and plastic sheeting.
The structure of the spinneret wire casing 2 is annular, arc line shaped, fold-line-shaped, zigzag, rectangle, rhombus, irregular curved The variously-shaped combination of line or more, this can form the combination of multiple units with curved slit as elementary cell, be conducive to big Amount spinning production, compared to straight slit, the two ends of the curved slit are smaller with center electric-field intensity difference, and Electric Field Distribution is more Plus it is uniform, it can be made equably to produce nanofiber along slit direction.
Spinneret wire casing 2 with curved slit can be made up of conductive or electrically non-conductive material.As therein a kind of preferred Pattern, curved slit part is made of metal, and liquid bath part is prepared by electrically non-conductive material.Non electrically conductive material can select propylene Nitrile-butadiene-styrene, makrolon, polyamide, polybutylene terephthalate (PBT), poly terephthalic acid Glycol ester, polyphenylene oxide, polysulfones, polyethers, polyether-ether-ketone, polyimides, ceramics or timber etc..No matter which kind of material is used, it is narrow Slit body is inert (such as being not dissolved in polymer solution) preferably for the liquid of electrostatic spinning.
Typically spinneret wire casing 2 can be referred to as spinneret in the art, the Nanowire produced using apparatus of the present invention Dimension is that the high electric field full of viscous liquid, and using the power supply in spinning zone stretches solution to form a large amount of in spinneret slit Taylor cone, be consequently formed a large amount of nanofibers.
Slit in the middle of the spinneret wire casing 2 is the knot of continuous gap structure or interruption gap structure or continuous through hole arrangement Structure.
The gap width of the slit of the interruption gap structure is 1mm to 100mm.
The gap width of the slit in the middle of the spinneret wire casing 2 is 0.5mm to 10mm, and its length is more than 10mm, and it is highly More than 0.1mm.
There are several spinneret wire casings 2, the spinneret wire casing 2 described in multiple moves towards opposing parallel on the spinning cavity 1 Set, the spacing between two neighboring spinneret wire casing 2 is 2mm to 1000mm;Each spinneret wire casing 2 has a central shaft, The central shaft of generally relative other the spinneret wire casings 2 of the central shaft of each spinneret wire casing 2 is parallel to each other.Between adjacent spinneret wire casing 2 Away from least 2mm.
Slit in the middle of the spinneret wire casing 2 goes out liquid speed rate in 0.01mL/h/cm to 100mL/h/cm.
The high-voltage generator 3 is that the potential difference between high-pressure side and earth terminal is more than 30kV;Critical electric field can be produced Intensity depends on many factors higher than the potential difference of critical electric field strength, including spinneret and to the spacing of electrode (receive away from From) and viscous liquid physical property.Under normal circumstances, power supply for being higher than in charged electrode and to being produced between electrode The potential difference of 30kV, preferably above 40kV, more preferably higher than 60kV;Receive distance or belt electrode and can to the spacing between electrode Influence the electric field for producing therebetween, the thus size of the nanofiber of device production and produce the voltage of critical electric field strength.This Outward, the spacing is also influenceed by many aspects factor, including spinneret and the size to electrode, potential difference and viscous liquid Composition.In certain embodiments, the spacing between charged electrode and counterelectrode is between 10mm to 1500mm.
Viscous liquid can be any liquid that can in the electric field carry out electrostatic spinning.Suitable viscous liquid includes poly- Polymer solution, sol-gel, particle suspension and/or melt.In certain embodiments, the viscosity of viscous liquid be 1mPa s extremely 100Pa s.The preferred form of viscous liquid is polymer solution, generally includes at least one polymer and at least one volatilization is molten Agent.Can be synthetic polymer, natural polymer and boiomacromolecule, heat for the polymer in the viscous liquid of electrostatic spinning Thermoplastic polymer and/or living polymer.The solvent for using determines preferably based on the dissolubility of polymer.In some embodiments In, solvent may include water, ethanol, chloroform, dimethylformamide or other volatile liquids.Solvent during electrostatic spinning Volatilization contribute to liquid curing and form solid nano fiber.
The distance between the fiber collecting device 5 and spinneret wire casing 2 are 10mm to 2000mm.
Fluid reservoir of the invention 4 is closed tank body.The one end of fluid reservoir 4 can be connected with a kind of propeller, and the propeller can be by Viscous liquid in fluid reservoir 4 is advanced into the spinning cavity 1 that the reservoir other end is connected with spinneret wire casing 2.Now, spinneret wire casing 2 are located at the top of spinning cavity 1, and viscous liquid enters back into electrostatic spinning region by spinning cavity 1 into spinneret wire casing 2.Counterelectrode It is almost parallel with the central shaft of spinneret wire casing 2 and along the length direction of spinneret wire casing 2 extend.
Embodiment 1
As shown in figure 1, fiber collecting device by the invention 5 is rotated under drive device driving, such as electricity Machine drives fiber collecting device 5 to rotate with 40 revs/min of speed.Fiber collecting device 5 connects with the earthing pole of high-voltage generator 3 Connect, for receiving the nanofiber for producing.The curved slit of spinneret wire casing 2 is 200mm with the distance of fiber collecting device 5.
Fig. 2 show the more detailed view of spinneret in Fig. 1.The concrete shape of curved slit is circular arc, slit Width d1 is 2mm, and the diameter phi 2 of the inner circle where each spinneret wire casing 2 is 8mm, and cylindrical diameter phi 1 is 12mm, spinneret line The slit of groove 2 is 100mm along the effective length d2 of X axis, and slit top is 10mm apart from h apart from spinning cavity 1.Spinning chamber The length L of body 1 is 120mm, and width W is 50mm, and height H is 20mm.The one end of spinning cavity 1 is connected with high-voltage generator 3, Wherein polymer solution is injected pump and is pushed into spinning cavity 1 by fluid reservoir 4, and this is not shown in the diagram.Spinning cavity 1 with it is curved The material of bent slit is polypropylene plastics.
During electrostatic spinning, electric field force is the main drive for promoting polymer solution to start spinning.Fig. 5 is illustrated Use the electric-field intensity distribution of the slit of the curve that business software COMSOL4.3 versions calculate top view (voltage for 70kV), in the middle of its arc spinneret wire casing 2 circular arc and the circular arc at two ends has similar electric-field intensity.Analysis shows, electric-field strength Degree is along the distribution in curved slit direction than more uniform.Fig. 6 is compared when voltage is 70kV, curvilinear slits of equal length and straight , along the electric-field intensity distribution in slit direction, the electric-field intensity of circular arc will be far smaller than in the middle of display straight line spinneret wire casing for line slit The electric-field intensity of two ends circular arc.As shown in fig. 7, the electric-field intensity numerical value that one meter long curvilinear slits are produced be substantially higher it is narrow in straight line Seam, and electric field is more uniform in the distribution of curvilinear slits length direction, and under the same experiment condition of this meaning, curvilinear slits are than straight Line slit is easier spinneret, and the nanofiber productivity ratio of curvilinear slits is higher, distribution of fiber diameters is narrower, shown straight in Fig. 7 The electric-field intensity at line slit two ends is 10kV along the drop of slit, and electric-field intensity drop of the curved slit in relevant position is less than 2kV.Electric-field intensity drop big in straight slit can cause problems with spinning process:Be not easy in the middle of slit wire vent or Two ends Discharge Phenomena;Spun fiber fiber more spun than two ends is thick in the middle of slit;Middle and two ends fiber production differs Cause, it is different with both sides thickness in the middle of the tunica fibrosa being collected into.
For experiment purpose, the aqueous solutions of polymers that nanofiber uses Sigma-Aldrich to produce is formed, glued It is 1200mPa s to spend, and is contained PVA (polyvinyl alcohol, mean molecule quantity is 146,000 to 186,000,96% degree of hydrolysis).In figure Shown device can also produce nanofiber using other polymers solution.Polymer solution in spinning cavity 1 can be by height Piezoelectricity pole and the connection of high-voltage generator 3.When spinning is carried out, high-voltage generator 3 charges to polymer solution, makes bending The potential difference produced between slit and fiber collecting device 5 is 70kV.The feed liquor speed of the PVA aqueous solution is 20mL/h.
The PVA nanofibers that the present embodiment is prepared are scanned through electronic microscope photos, as shown in Figure 9, Figure 10.Fiber thickness Uniformly, surface does not have drop, and nanofiber average diameter is 281nm.
For comparative purposes, using traditional needle-like electrostatic spinning apparatus and spiral line type electrostatic spinning apparatus, and use Identical polymer solution produces nanofiber.In traditional needle-like electrostatic spinning apparatus, the material of pin is stainless steel, and external diameter is 0.82mm, internal diameter is 0.51mm, and applied voltage is 22kV, and it is 200mm to receive distance.In spiral line type electrostatic spinning apparatus, The material of helix is stainless steel, and a diameter of 80mm of helix, spacing between coil is 20mm, and coil turn is 50, spiral shell The slewing rate of spin line circle is 40 revs/min, and applied voltage is 70kV, and it is 200mm to receive distance.Fig. 8 is shown by above-mentioned Three kinds of comparings of the yield and fibre diameter of the nanofiber of different device preparations.The fiber production of wherein spiral winding is higher than Curved slit, significantly larger than traditional stainless pin.The fibre diameter of curved slit is suitable with the fibre diameter of spiral winding, but two Person is all higher than traditional needle-like Electrospun nano-fibers.
Embodiment 2
The spinneret wire casing 2 that the present embodiment is used refers to Fig. 3, specially three curved slits of spinneret wire casing shown in figure 2 A kind of arranged in parallel, the spacing distance d3 between the slit of two neighboring spinneret wire casing 2 is 10mm.This rule arranged in parallel Be adjacent flex slit crest it is relative with crest, trough is relative with trough.Wherein the parameter of each curved slit with implementation Parameter in example 1 is identical, and the parameter of spinning cavity 1 is also identical with the parameter in embodiment 1.The material of spinning cavity 1 is poly- four PVF plastics, the material of curved slit is aluminium.
For experiment purpose, the polymer solution that nanofiber uses Sigma-Aldrich to produce, viscosity are formed Be 1800mPa s, contain PVDF (Kynoar, mean molecule quantity is 10,000).When carrying out spinning, applied voltage is 70kV.The feed liquor speed of the PVA aqueous solution is to be 300mL/h.
The average diameter of the PVDF nanofibers that the present embodiment is prepared is 335nm, and average product is 62g/h.
For comparative purposes, with reference to Fig. 4, the present embodiment has used another arranged in parallel containing 3 curved slits 2 Spinneret.Spacing distance between slit is mutually all 10mm.This rule arranged in parallel be adjacent flex slit 2 crest with Trough is relative, and trough is relative with crest.Other specification all same.The average diameter of the nanofiber for preparing is 356nm, is put down Equal yield is 60g/h.
Embodiment 3
The spinneret wire casing 2 that the present embodiment is used refers to Figure 11, and spinneret wire casing shown in figure 2 is specially broken line type structure, and The half-breadth d4 of broken line slit is 10mm, and the inner width d5 of the single repeat unit of broken line slit is 6mm, and outer d6 wide is 10mm.Spinning The parameter of cavity 1 is same as Example 1.The material of spinning cavity 1 and curved slit is polypropylene plastics.
For experiment purpose, the aqueous solutions of polymers that nanofiber uses Sigma-Aldrich to produce is formed, glued It is 1200mPa s to spend, and is contained PVA (polyvinyl alcohol, mean molecule quantity is 146,000 to 186,000, and 96% is hydrolyzed).In figure Shown device can also produce nanofiber using other polymers solution.When spinning is carried out, 3 pairs of polymerizations of high-voltage generator Thing solution charges, and makes the potential difference produced between curved slit and fiber collecting device 5 be 70kV.The PVA aqueous solution enters liquid speed Rate is 200mL/h.
The average diameter of the PVA nanofibers that the present embodiment is prepared is 334nm, and average product is 21g/h.
Embodiment 4
The spinneret wire casing 2 that the present embodiment is used refers to Figure 12, and spinneret wire casing shown in figure 2 is specially saw-tooth-type structures, and The half-breadth d7 of broken line slit is 10mm, and the length d8 of the single repeat unit of broken line slit is 20mm.The parameter of spinning cavity 1 with Embodiment 1 is identical.The material of spinning cavity 1 and curved slit is polypropylene plastics.
For experiment purpose, the aqueous solutions of polymers that nanofiber uses Sigma-Aldrich to produce is formed, glued It is 1200mPa s to spend, and is contained PVA (polyvinyl alcohol, mean molecule quantity is 146,000 to 186,000, and 96% is hydrolyzed).In figure Shown device can also produce nanofiber using other polymers solution.Polymer solution in spinning cavity 1 can be by one The electrode (not shown) of individual submergence is connected with high-voltage generator 3.When spinning is carried out, high-voltage generator 3 is molten to polymer Liquid charges, and makes the potential difference produced between curved slit and fiber collecting device 4 be 70kV.The feed liquor speed of the PVA aqueous solution is 200mL/h。
The average diameter of the PVA nanofibers that the present embodiment is prepared is 368nm, and average product is 18g/h.
Embodiment 5
The spinneret that the present embodiment is used refers to Figure 13, and spinneret wire casing shown in figure 2 is specially circular ring type narrow slit structure, and Spacing d9 between each annulus slit unit is 10mm, and the internal diameter φ 3 of the single repeat unit of circular ring type slit is 6mm, outward Footpath φ 4 is 10mm.The parameter of spinning cavity 1 is same as Example 1.The material of spinning cavity 1 and curved slit is polypropylene Plastics.
For experiment purpose, the aqueous solutions of polymers that nanofiber uses Sigma-Aldrich to produce is formed, glued It is 1200mPa s to spend, and is contained PVA (polyvinyl alcohol, mean molecule quantity is 146,000 to 186,000, and 96% is hydrolyzed).In figure Shown device can also produce nanofiber using other polymers solution.Polymer solution in spinning cavity 1 can be by one The electrode (not shown) of individual submergence is connected with high-voltage generator 3.When spinning is carried out, high-voltage generator 3 is molten to polymer Liquid charges, and makes the potential difference produced between curved slit and fiber collecting device 4 be 70kV.The feed liquor speed of the PVA aqueous solution is 200mL/h。
The average diameter of the PVA nanofibers that the present embodiment is prepared is 286nm, and average product is 26g/h.
Embodiment 6
The spinneret wire casing 2 that the present embodiment is used refers to Figure 14, and spinneret wire casing shown in figure 2 is specially rectangular slot composition, And the distance between each unit of rectangular slot d12 is 10mm, the inner width d11 of the single repeat unit of rectangular slot is 8mm, Interior d10 long is 8mm, and outer d13 wide is 10mm.The parameter of spinning cavity 1 is same as Example 1.Spinning cavity 1 and curved slit Material is polypropylene plastics.
For experiment purpose, the aqueous solutions of polymers that nanofiber uses Sigma-Aldrich to produce is formed, glued It is 1200mPa s to spend, and is contained PVA (polyvinyl alcohol, mean molecule quantity is 146,000 to 186,000, and 96% is hydrolyzed).In figure Shown device can also produce nanofiber using other polymers solution.Polymer solution in spinning cavity 1 can be by one The electrode (not shown) of individual submergence is connected with high-voltage generator 3.When spinning is carried out, high-voltage generator 5 is molten to polymer Liquid charges, and makes the potential difference produced between curved slit and fiber collecting device 5 be 70kV.The feed liquor speed of the PVA aqueous solution is 200mL/h。
The average diameter of the PVA nanofibers that the present embodiment is prepared is 312nm, and average product is 28g/h.
Embodiment 7
The spinneret wire casing 2 that the present embodiment is used refers to Figure 15, the specially diamond structure of spinneret wire casing shown in figure 2, and water chestnut The d14 long of each unit of shape slit is 10mm, and d16 high is 10mm, the spacing between the single repeat unit of rhombus slit D15 is 10mm.The parameter of spinning cavity 1 is same as Example 1.The material of spinning cavity 1 and curved slit is polypropylene plastics Material.
For experiment purpose, the aqueous solutions of polymers that nanofiber uses Sigma-Aldrich to produce is formed, glued It is 1200mPa s to spend, and is contained PVA (polyvinyl alcohol, mean molecule quantity is 146,000 to 186,000, and 96% is hydrolyzed).In figure Shown device can also produce nanofiber using other polymers solution.Polymer solution in spinning cavity 1 can be by one The electrode (not shown) of individual submergence is connected with high-voltage generator 3.When spinning is carried out, high-voltage generator 3 is molten to polymer Liquid charges, and makes the potential difference produced between curved slit and fiber collecting device 5 be 70kV.The feed liquor speed of the PVA aqueous solution is 200mL/h。
The average diameter of the PVA nanofibers that the present embodiment is prepared is 390nm, and average product is 19g/h.
Embodiment 8
The spinneret wire casing 2 that the present embodiment is used refers to Figure 16.The concrete shape of curved slit is arc-shaped structure, slit Width d1 is 2mm, and the diameter phi 2 of the inner circle where each circular arc is 8mm, and cylindrical diameter phi 1 is 12mm, and slit is along X axis Effective length d2 be 1000mm, slit top apart from spinning cavity 1 apart from h be 10mm.The length L of spinning cavity 1 is 1200mm, width W are 50mm, and height H is 30mm.The material of curved slit is aluminium.
For experiment purpose, the polymer solution that nanofiber uses Sigma-Aldrich to produce, viscosity are formed It is 1400mPa s, containing PAN, (100000) polyacrylonitrile, mean molecule quantity is.Device shown in figure can also be poly- using other Polymer solution produces nanofiber.When spinning is carried out, high-voltage generator 3 to polymer solution charge, make curved slit with The potential difference produced between fiber collecting device 5 is 70kV.The feed liquor speed of the PVA aqueous solution is 200mL/h.
The average diameter of the PVA nanofibers that the present embodiment is prepared is 390nm, and average product is 48g/h.
Figure 17 is the stereogram of the big fiber type generator that length is a meter, and the concrete shape of its curved slit is circular arc Structure.

Claims (9)

1. a kind of electrostatic spinning nano fiber generating means, it is characterised in that:Including fiber generator, fiber collecting device (5) and High-voltage generator (3), the fiber generator includes spinning cavity (1), spinneret wire casing (2) and fluid reservoir (4), the spinneret Wire casing (2) is slit on spinning cavity (1), in the middle of spinneret wire casing (2), and the slit connects spinning cavity (1) inside, described Fluid reservoir (4) connects spinning cavity (1), and the spinneret wire casing (2) is full of twists and turns structure;The fiber collecting device (5) is put In the position directly above of spinneret wire casing (2);With high-pressure side and earth terminal, high-pressure side is inserted in the high-voltage generator (3) Spinning cavity (1) is internal, and earth terminal connects fiber collecting device (5).
2. a kind of electrostatic spinning nano fiber generating means according to claim 1, it is characterised in that:The spinneret wire casing (2) full of twists and turns structure is each annular, arc line shaped, fold-line-shaped, zigzag, rectangle, rhombus, irregular curved line or more Plant the combination of shape.
3. a kind of electrostatic spinning nano fiber generating means according to claim 1, it is characterised in that:The spinneret wire casing (2) slit in the middle of is the structure of continuous gap structure, interruption gap structure or continuous through hole arrangement.
4. a kind of electrostatic spinning nano fiber generating means according to claim 3, it is characterised in that:The interruption gap knot The gap spacing of the slit of structure is 1mm to 100mm.
5. a kind of electrostatic spinning nano fiber generating means according to claim 1, it is characterised in that:The spinneret wire casing (2) gap width of the slit in the middle of is 0.5mm to 10mm, and its length is not less than 10mm, and it is highly not less than 0.1mm.
6. a kind of electrostatic spinning nano fiber generating means according to claim 1, it is characterised in that:The spinning cavity (1) there is at least one spinneret wire casing (2), spinneret wire casing (2) described in multiple moves towards opposing parallel setting, two neighboring on Spacing between spinneret wire casing (2) is 2mm to 1000mm.
7. a kind of electrostatic spinning nano fiber generating means according to claim 1, it is characterised in that:The spinneret wire casing (2) slit in the middle of goes out liquid speed rate in 0.01mL/h/cm to 100mL/h/cm.
8. a kind of electrostatic spinning nano fiber generating means according to claim 1, it is characterised in that:The high voltage occurs Device (3) is that the potential difference between high-pressure side and earth terminal is more than 30kV.
9. a kind of electrostatic spinning nano fiber generating means according to claim 1, it is characterised in that:The fiber collects dress The distance between (5) and spinneret wire casing (2) are put for 10mm to 2000mm.
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