CN103088444A - Method and device for improving number of electrostatic spinning multiple jet flows - Google Patents
Method and device for improving number of electrostatic spinning multiple jet flows Download PDFInfo
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Abstract
The invention discloses a method and a device capable of improving the number of electrostatic spinning jet flows. The production method includes the following process steps: (1) preparation of polymer solution or molten liquid; (2) formation of multiple jet flows at the top end of a spinning jet: an appropriate flow rate of the polymer solution or the molten liquid is extruded from a liquid storage device, and forms liquid drops or molten drops at the position of the spinning jet connected with the positive pole of a high-voltage static generator; a metal needle is arranged at the position opposite to the spinning jet and on the same side with a receiving device; and appropriate voltage is supplied, under the action of electrostatic field force, the solution or the molten liquid forms a conical protrusion at the position of the spinning jet, namely a Taylor cone, and when electric field intensity reaches a certain value, multiple jet flows are jetted from the Taylor cone; and (3) forming and receiving of nanofibers. The production device is designed according to the production method, and mainly comprises a liquid supply system, a spinning system, a receiving system and a transmission and control system. According to the method and the device capable of improving the number of the electrostatic spinning jet flows, a single jet flow in a traditional electrostatic spinning process is changed into the multiple jet flows under the premise that other conditions such as voltage increase or conducting material addition are not needed, meanwhile, the shortcomings that nanofiber membranes are uneven in structure due to mutual interference of multi-jet static, and the like are overcome, production efficiency is high, and needs of large-scale production of the nanofibers can be met.
Description
Technical field
The invention belongs to weaving and new material technology field, relate to a kind of method and device that improves the many jets of electrostatic spinning process, be specially by introduce metal needle at spinning zone and impel taylor cone surface formation multiple jets to improve method and the device of micro nanometer fiber preparation efficiency.
Background technology
Electrostatic spinning technique is to utilize the high-voltage electrostatic field to make Polymer Solution or melt produce distortion and flow and a kind of technology of acquisition nanofiber.The cardinal principle of electrostatic spinning technique is to make on polymer solution or melt band several thousand to volt high-pressure electrostatics up to ten thousand, solution or melt swell at spinning head place's formation pyramid type under the electric field force effect, when electric field force was enough large, polymer solution or melt can overcome surface tension and form the injection thread.The refinement that is stretched under the effects such as electric field force, surface tension of charged jet, and in course of injection solvent evaporation or melt cooling and solidify, finally be deposited on receiving system, form micro nanometer fiber non-weaving cloth felt.Because the electrostatic spinning nano fiber fineness is thin, specific area is large, and porosity is high, and the advantages such as applied range are successfully applied at aspects such as filtering material, sensor, organizational project, medicament slow release, biomaterial, catalysis, textile garments.
Generally, in the electrostatic spinning process process, each taylor cone only sprays one jet, thereby nanofiber output is lower, and production cost is high.Therefore, domestic and international many researchers are in the method for making great efforts research raising Static Spinning production efficiency.
The method of enhancing productivity is generally the method that increases spinning head quantity, namely uses the multi-nozzle electrospinning technology.the bibliographical information of these class methods mainly contains: " Fabrication of blend biodegradable nanofibrous nonwoven mats via multi-jet electrospinning " (B.Ding, E.Kimura, et.al, Polymer[J], 45 (6) (2004) 1895-1902.), " Multiple jets in electrospinning:experiment and modeling (S.A.Theron, A.L.Yarin.et.al., Poly mer[J], 46 (9) (2005) 2889-2899.), " multiple spray head static spinning machine spinning state and fibre structure are arranged in parallel " (Pan Fangliang etc., silk [J], 2012 (1), 21-26.) etc., Chinese patent CN200999274, CN101929035, CN101225554D etc., US Patent No. 6616435 B2, US6713011B2, US6753454, US6656394 etc., world patent WO2012177220, WO2005/073441, WO 2006/018838, WO 2006/007287, WO 2004/016839, WO0209288 A1, WO 2005/090653A1 etc. belong to many spray nozzle types electrospinning process.These class methods are mainly to form a plurality of taylor cones by a plurality of shower nozzles are set, thereby each taylor cone forms the many jets of the whole formation of one jet.But also there are many problems in many showerhead approach when increasing output, such as shower nozzle stop up to clean between difficulty, many jets Coulomb repulsion mutually and some shower nozzle is difficult to form the problems such as jet, cause that the influenced even product structure of production efficiency is irregular, percent defective is crossed high defective.
the novel electrostatic spinning process that some spinneret-frees also occurred in recent years, bibliographical information mainly contains: " Upward needleless electrospinning of multiple nanofibers " (A.L.Yarin and E.Zussman, Polymer[J], 45 (9) (2004) 2977-2980.), " The Effect of Salt on the Roller Electrospinning of Polyurethane Nanofibers " (F.Cengiz and O.Jirsak, , Fibers and Polymers[J], 10 (2009) 177-184.), Chinese patent CN101775706B, CN101050550A, CN102864503A etc., US Patent No. 7, 959, 848, world patent WO2005/024101, European patent EP 2557206 etc.These class methods method production nanofibers that produce taylor cone at free surface that adopt more.Yet still there are the problems such as solvent evaporates is too fast, equipment is relatively complicated, production cost is higher, commercialization is difficult in this class novel electrostatic spining technology, and therefore, these novel electrostatic spining technologies are generally applied and also had certain difficulty.At present in most of laboratories or manufacturing enterprise's great majority still adopt the mode of single spraying head or a plurality of shower nozzle assembled arrangement to reach the purpose that improves nanofiber production efficiency.Therefore, the Static Spinning taylor cone sprays the target that many jets are many researchers' pursuits always.Simultaneously, many jets spray and also can improve to a certain extent one-jet skew that between many shower nozzles, electrostatic interference causes and finally cause the problems such as the tunica fibrosa structure is irregular.But make little progress at present, existing bibliographical information mainly contains " Mass production of nanofibre assemblies by electrostatic spinning " (F.-L.Zhou, et.al, Polymer International[J], 58 (2009) 331-342.) and " Controlled formation of multiple Taylor cones in electrospinning process (A.Vaseashta, Appl Phys Leu[J], 90 (2007) 093115.) etc. have related.Jet stream generating method more than the Static Spinning single spraying of these existing bibliographical informations is mainly by increasing voltage or adding conductive material or form jet more than single spraying with the special-shaped surfaces dash receiver in solution.Increase voltage not only high to matching requirements, increased energy consumption and cost, also increased insecurity simultaneously; Add conductive material not only to increase production cost but also introduce other materials performance and the application of final products had certain influence; Use the special-shaped surfaces dash receiver can cause the nanofiber membrane structure that receives irregular, so these methods all are being restricted aspect the nanofiber industrial applications.
Summary of the invention
According to the deficiencies in the prior art.The invention provides a kind of reasonable in design, simple in structure, cost of manufacture is low, can make the method and apparatus of single taylor cone emission multiple jets in Static Spinning technique.The method can combine the many jetting methods of single injector with many shower nozzles technology simultaneously, can improve the defectives such as the nanofiber membrane structure that causes due to the mutual interference of many shower nozzles static phase is irregular, significantly improve nanofiber output, solve the problems such as in prior art, the nanofiber preparation efficiency is low, fiber production is low.The method equipment therefor is simple, has reduced production cost, and has saved the energy, meets the requirement of low-carbon environment-friendly, and easy to operate, and industrializing implementation is easy.
The technical scheme that the present invention solves described production method is: design a kind of method that improves the many jets of Static Spinning, the method comprises following processing step:
(1) preparation polymer solution or melt: during the preparation polymer solution, first solid polymer and good solution thereof are mixed in agitator with suitable mass fraction specific concentration, after sufficient standing, then send into the polymer solution for preparing in sump assemblies standby; Described solid mixture refers to the solubility mixture, comprises polyvinyl alcohol, polyvinylpyrrolidone, polyacrylonitrile or polyester; Described good solvent comprises water, ethanol, dimethyl methylamine or chloroform.During the preparation polymer melt, first solid polymer is heated to molten condition, makes the spinning melt of modest viscosity; Described solid polymer polypropylene, polyethylene, polycaprolactone, PLA, polyethylene terephthalate, polymethyl methacrylate etc.
(2) the most advanced and sophisticated many jets of spinning head form: syringe pump is with suitable flow, polymer solution or melt are extruded from sump assemblies, the place forms drop or molten drop at spinning head, spinning head is connected with HV generator is anodal, with metal needle of spinning head relative position configuration, metal needle and receiving system all with earth electrode limit mutually, apply suitable voltage, under the effect of electrostatic field force, solution or melt form coniform protuberance at the spinning head place, be taylor cone, when electric-field intensity reaches certain value, have multiple jets to penetrate from taylor cone.
(3) nanofiber is shaped: many jets move in the space under described electric field force effect, and in motion process, solvent evaporates or melt cooling, jet stretch under the effect of electrostatic force and be refined into nano-scale fiber.
(4) nanofiber receives: at receiving system of the other increase of metal needle, this receiving system is placed on the suitable distance with the spinning head relative position, be advisable not block metal needle, receiving system receives nanofiber, forms nanofiber mats or nano-fibre yams.
The technical scheme that the present invention solves described production method technique device is: design a kind of device that improves the many jets of Static Spinning, this process units is applicable to the method for the many jets of raising Static Spinning of the present invention, mainly comprises liquid-supplying system, spinning system, receiving system, transmission and control system.Wherein said liquid-supplying system mainly comprises sump assemblies, feed pipe, syringe pump, sump assemblies is connected with syringe pump and controlled by it, sump assemblies is connected with the spinning head of spinning system by feed pipe simultaneously, distributes to the liquid inventory of spinning head and is accurately controlled by syringe pump; Described spinning system mainly comprises spinning head, HV generator, metal needle; Described receiving system mainly comprises swing roller, pedestal, dash receiver etc.; Described transmission and control system mainly comprise motor, control device etc., for receiving system provides driving powered by conventional energy.
Compared with prior art, the present invention is the introducing by metal needle, make polymer solution improve the method and apparatus of the many jets of Static Spinning at the many jets of the most advanced and sophisticated formation of spinning head, can realize at normal temperatures and pressures the many jets of Static Spinning, and many jets finally form nanofiber and are collected on receiving system, and method is simple and easy to operate, have greatly improved production efficiency, reduce production cost, saved the energy; The method just can form many jets under relatively low voltage, reduced equipment requirement, has avoided the equipment complexity problem under the condition of high voltage; This equipment need not to add the guidance quality material, has avoided the material that adds on the impact of the product produced; This process units manufacturing is simple, simple to operate, and implementation cost is low, and output is high, and industrialization promotion is easy.
Description of drawings
Fig. 1 is that the present invention utilizes a metal needle to improve method and the principle of device schematic diagram of single spinning head Static Spinning jet quantity.
Fig. 2 is that the present invention utilizes a metal needle to improve method and the principle of device schematic diagram of double-spinneret Static Spinning jet quantity.
Fig. 3 is that the present invention utilizes two metal needles to improve method and the principle of device schematic diagram of double-spinneret Static Spinning jet quantity.
Fig. 4 is that the present invention utilizes a metal needle to improve single spinning head Static Spinning jet quantity and the method take cylinder as receiving system and principle of device schematic diagram.
Fig. 5 is that the present invention utilizes a metal needle to improve double-spinneret Static Spinning jet quantity and the method take cylinder as receiving system and principle of device schematic diagram.
Fig. 6 is spinning head of the present invention top and taylor cone, jet schematic diagram.
Fig. 7 is metal needle of the present invention and spinning head relative position relation schematic diagram.
Fig. 8 is that the many jets of Static Spinning corresponding to the present invention are from the scene photograph (5 of jet quantity) of spinning head top emission.
Fig. 9 is that the many jets of Static Spinning corresponding to the present invention are from the scene photograph (7 of jet quantity) of shower nozzle top emission.
Figure 11 is that the bimetallic pin that utilizes corresponding to the present invention improves the scene photograph of two shower nozzle Static Spinning jet quantity.
Figure 10 is that the metal needle that utilizes corresponding to the present invention improves single spinning head Static Spinning jet quantity and the scene photograph take cylinder as receiving system.
In figure: 1. sump assemblies 2. spinning head 3. metal needle 4. HV generator 5. syringe pump 6. jet 7. swing roller 8. taylor cones
The specific embodiment
Further set forth the present invention below in conjunction with embodiment and accompanying drawing.
The method of the many jets of raising static that the present invention relates to referring to Fig. 1, mainly comprises following processing step:
(1) preparation polymer solution: solid polymer and good solution thereof are mixed in mixer with suitable mass fraction specific concentration, after standing 1-2 hour, then the polymer solution for preparing is put into liquid reservoir 1 or the polymer melt that melting makes is put into liquid reservoir 1; Described solid mixture refers to solvable/fusibleness polymer comprises polyvinyl alcohol, polyvinylpyrrolidone, polyacrylonitrile, polyester, PLA, polypropylene etc.; Described good solvent comprises water, ethanol, dimethyl formamide, chloroform etc.; Described suitable mass percent concentration refers to that described polymer solution can be at the most advanced and sophisticated mass percent concentration that forms the circular cone protuberance of spinning head under suitable electrostatic field.
(2) the most advanced and sophisticated many jets of spinning head form: syringe pump 5 extrudes polymer solution or melt with suitable flow from sump assemblies 1.Spinning head 2 is connected with HV generator 4 is anodal, and metal needle 3 is connected with earthing pole.Apply suitable voltage, form strong electrostatic field between spinning head 2 and receiving system 7, metal needle 3, under the effect of electrostatic field force, solution or melt are at the coniform protuberance of the most advanced and sophisticated formation of spinning head, and namely taylor cone 8, and a plurality of jets 6 spray from taylor cone subsequently.
(3) micro-nano many jets are injected into nanofiber: many jets 6 move in the space under described electric field force effect, in course of injection, good solvent volatilization in solution jet, many jets stretch under the effect of electrostatic force and are refined into nano-scale fiber, fly to receiving system 7.
(4) nanofiber receives: at an other reception cylinder 7 or other receiving system of increasing of metal needle 3, place suitable position with receiving cylinder 7, with suitable rotating speed rotation, the nanofiber that jet 6 forms is winding on cylinder 7 or other receiving system.
The technical scheme that the present invention solves described production method technique device is: design a kind of device that improves the many jets of Static Spinning, this process units is applicable to the method for the many jets of raising Static Spinning of the present invention, mainly comprises sump assemblies 1, spinning head 2, metal needle 3, HV generator 4, syringe pump 5, receiving system 7.
in method of the present invention, the suitable mass percent concentration of described spinning solution is main relevant with good solvent used with macromolecule polymer material and molecular weight thereof, when polymer is as described selected polyvinylpyrrolidone (PVP K-30), it dissolves in water and ethanol mass ratio are the mixing liquor of 1: 9 ratio, when mass percent concentration reaches 30% when above, just can satisfy described technological requirement: and be 86～89mol% for alcoholysis degree, during the polyvinyl alcohol of molecular weight 2700～3200, dissolve in the mixed solvent of mass ratio with 1: 1 ratio at water and ethanol, when mass percent concentration reaches 10% when above, just can satisfy described technological requirement.This minimum debita spissitudo that satisfies technological requirement can be described as critical concentration.Described different polymeric material uses and different good solvents, and different critical concentrations is also arranged simultaneously.For the same polymer, higher debita spissitudo has higher solution viscosity, and during spinning, the solution of spinning head affects technique and carries out owing to using volatile solvent to volatilize to cause syringe needle to stop up.Therefore, the technological design of debita spissitudo preferably is to select its critical concentration of polymer or a little more than the debita spissitudo of its critical concentration.In method of the present invention, described polymer melt is advisable with melt well.
Appropriate voltage of the present invention is 0～100KV, can adjust voltage according to technological requirement.
Method of the present invention is characterized in that having introduced metal needle 3, and this metal needle can make solution can form many jets.
Method of the present invention, polymer solution is in the most advanced and sophisticated number that forms many jets of spinning head 2 〉=2.
Method of the present invention, the diameter of metal needle 3 be at 0.1～5mm, the length 〉=0.1cm of metal needle 3.
Method of the present invention, metal needle 3 can be hollow can be also solid.
Method of the present invention, the most advanced and sophisticated distance with spinning head 2 tips of metal needle 3 is 0.5～50cm.
Arrangements that be in line of method of the present invention, metal needle 3 and spinning head 2 can make many jets formation.
Method of the present invention, metal needle 3 have a certain degree with spinning head 2 center lines on the face vertical with spinning head 2, and many jets also can form, and the angle of inclination angular range is-90～+ 90 °.
Method of the present invention, metal needle 3 maintains a certain distance with the spinning head center line on the face vertical with spinning head 2, and many jets also can form, and distance range is 0～50cm.
Method of the present invention for obtaining more spinning efficiency, can be used many spinning head 2 spinning simultaneously.More than or equal to 2 the time, introduce a metal needle 3 in the middle of every two shower nozzles when spinning head quantity, each spinning head all can form many jets.
Method of the present invention, more than or equal to 2 the time, each spinning head is corresponding introduces a metal needle 3 when spinning head 2 quantity, can form many jets at each shower nozzle tip.
Method of the present invention, the nanofiber that forms in order to collect many jets increases by one and receives cylinder or other receiving system metal needle is other, this cylinder or device can place metal needle above or below, receiving range is 5～20cm, to receive nanofiber.
The present invention is according to the method for the many jets of described raising Static Spinning, designed simultaneously the device that improves the many jets of Static Spinning, this process units is adapted to the method for the many jets of the described raising Static Spinning of claim, mainly comprises sump assemblies, spinning head, syringe pump, metal needle, reception cylinder, HV generator.Syringe pump, sump assemblies are connected with spinning head, the liquid reservoir effect is to store spinning solution or the continuous Static Spinning of melt assurance, the syringe pump effect is to provide continuous polymer solution or melt to spinning head, and the spinning head effect is as anode and can forms on the top stable taylor cone.Receive cylinder, metal needle ground connection respectively, as negative electrode.
Method and apparatus under the present invention, it is characterized in that having introduced metal needle 3, can metal needle 3 be form the crucial spinning head 2 of many jets, metal needle 3 and the distribution of receiving system 7 in the space rationally can produce many jets and collect nanofiber with the spatial distribution of spinning head 2.Metal needle 3 is just relevant to the voltage that this method applies to the distance of spinning head head.
The present invention improves the method for the many jets of Static Spinning and operation principle and the process of device is: during work, first put into polymer solution or the melt of the debita spissitudo for preparing on request in sump assemblies 1, syringe pump 5 is arranged suitable flow, guarantee that continuous polymer solution or melt are supplied to spinning head 2; Then open electrostatic generator 4, generator 4 positive poles are connected with spinning head 2, apply suitable voltage, form strong electrostatic field between spinning head 2 and metal needle 3, under the effect of electrostatic field force, solution is at the coniform protuberance of the most advanced and sophisticated formation of spinning head, it is taylor cone 8, solution sprays a plurality of jets from protuberance subsequently, and jet is in the solvent evaporates described in course of injection, and many jets stretch under the effect of electrostatic force and are refined into nano-scale fiber simultaneously.When increasing again a reception cylinder 7, receive between cylinder 7 and spinning head 2 and also have electric field, can collect preferably the nanofiber that many jets form.
The below provides specific embodiments of the invention.Specific embodiment only is used for further illustrating the present invention, does not consist of the restriction to the present patent application claim.
Embodiment 1
Design a kind of device that improves the many jets of Static Spinning, comprise sump assemblies 1, syringe pump 5, spinning head 2, metal needle 3, as shown in Figure 1.Wherein metal needle 3 length are that 10cm, diameter are 0.5mm, hollow-core construction.Syringe pump 5, sump assemblies 1, spinning head 2 are connected, and metal needle 3 is placed on and the straight position of spinning head 2, and the most advanced and sophisticated distance with the metal needle tip of spinning head is 3cm.
Before spinning, first weighing polyvinyl alcohol polymer powder 14 grams, and mix than concentration with 14% quality with mixed solvent (distilled water mixes with the mass ratio of absolute ethyl alcohol with 1: 1), heating water bath (80 ℃) is after 3-4 hour, standing two hours, make the polyvinyl alcohol spinning solution; Then the poly-vinyl alcohol solution that configures is packed in sump assemblies 1, sump assemblies 1 is connected with syringe pump 5, sump assemblies 1 is connected with spinning head 2.Guarantee syringe pump 5, sump assemblies 1, spinning head 2 good airproof performances.The positive pole of electrostatic generator 4 is connected with spinning head 2, minus earth; Metal needle 3 ground connection.Metal needle 3 on spinning head 2 center lines with the spinning head 2 relative distribution that is in line, between two tips apart from l
0Be 3cm.Open electrostatic generator 4, voltage rises to 10KV; The flow that syringe pump 5 is set is 1ml/h, guarantee sump assemblies continuous offer spinning head 2 solution, spinning head this moment 2 tips are due to the effect of electrostatic field force, form conical protuberance, be taylor cone 8 (as shown in Figure 6), under the continuous action of electric field force, solution forms many jet ejections from taylor cone, many jets 6 are in the solvent evaporates described in course of injection, and many jets 6 stretch under the effect of electrostatic force and are refined into nano-scale fiber simultaneously.
The present embodiment adopts the device identical with embodiment 1, as shown in Figure 2.
Before spinning, first take high molecular polymer---polyvinylpyrrolidone (model: k-30) powder 34 grams, and mix than concentration with 34% quality with mixed solvent (distilled water and absolute ethyl alcohol mix formation with the mass ratio of 1: 9), after stirring, standing 2 hours, make the polyvinylpyrrolidone spinning solution; Then the polyvinylpyrrolidonesolution solution that configures is packed in sump assemblies 1, sump assemblies 1 is connected by catheter with syringe pump 5, sump assemblies 1 is connected with spinning head 2.Guarantee syringe pump 5, sump assemblies 1, spinning head 2 good airproof performances.The positive pole of electrostatic generator 4 is connected with spinning head 2, minus earth; Cylinder 7 and metal needle 3 be ground connection all.Metal needle 3 and spinning head 2 tips apart from l
0Be 3.5cm, be respectively 60 ° and 110 ° with tilt certain angle [alpha] and β of this plane on metal needle 3 plane vertical with spinning head 2 center lines, metal needle 3 be offset left spinning head 2 center extended lines apart from l
1Be 1.5cm, metal needle 3 offset downward spinning head 2 center extended lines apart from l
2Be 1cm.Open electrostatic generator 4, voltage rises to 15KV; The flow that syringe pump 5 is set is 0.8ml/h, guarantee sump assemblies 1 continuous offer spinning head 2 solution, spinning head this moment 2 tips are due to the effect of electrostatic field force, form taper shape and fallen, i.e. taylor cone 8 (as shown in Figure 6) is under the continuous action of electric field force, solution forms many jet ejections from taylor cone, many jets 6 are in the solvent evaporates described in course of injection, and many jets 6 stretch under the effect of electrostatic force and are refined into nano-scale fiber, and fiber is received into nanofiber mats by cylinder.
The present embodiment adopts and implements 1 essentially identical device and technique, and its variation is to have increased a spinning head 2, sump assemblies 1, as shown in Figure 3.
Before spinning, first take high molecular polymer-polyacrylonitrile powder 20 grams, and mix than concentration with 12% quality with the solvent dimethyl formamide, heating water bath (50 ℃) standing two hours, made polyacryl-nitrile spinning fluid after 3-4 hour; Then the polyacrylonitrile solution that configures is packed in sump assemblies 1, each sump assemblies 1 is connected with syringe pump 5, sump assemblies 1 is connected with spinning head 2, and the vertical range of two spinning heads 2 is 4cm.Guarantee the junction good airproof performance between syringe pump 5, sump assemblies 1, spinning head 2.The positive pole of electrostatic generator 4 is connected with spinning head 2, minus earth; Receive all ground connection of cylinder 7 and metal needle 3.A metal needle 3 is placed on apart from two spinning heads approximately on the vertical plane of 3cm, with two relative configurations of spinning head, and apart from two spinning head vertical range l
0Be 2cm.Open electrostatic generator 4, voltage rises to 8KV; The flow that syringe pump is set is 0.6ml/h, guarantee sump assemblies 1 continuous offer spinning head 2 solution.Two spinning heads 2 and metal needles 3 and receive 7, cylinder and can form electric field, each spinning head this moment tip is due to the effect of electrostatic field force, form conical protuberance, it is taylor cone 8 (as shown in Figure 6), under the continuous action of electric field force, solution forms many jet ejections from taylor cone 8, and many jets 6 are in the solvent evaporates described in course of injection, and stretching is refined into nano-scale fiber under the effect of electrostatic force, and the received cylinder 7 of fiber receives.
Embodiment 4
The present embodiment adopts device and technique substantially the same manner as Example 3, and its variation is to have increased a metal needle 3, as shown in Figure 4.
Before spinning, first take high molecular polymer---polypropylene agglomerate 100 grams, melting makes melt polypropylene; Then the melt polypropylene that configures is packed in storage liquid 1, each sump assemblies 1 is connected with syringe pump 5, sump assemblies 1 is connected with spinning head 2, and the vertical range of two spinning heads is 5cm.Guarantee the good airproof performance of syringe pump 5, sump assemblies 1, spinning head 2, the positive pole of electrostatic generator 4 is connected with spinning head 2, minus earth; The corresponding metal needle 3 of each spinning head 2, this belongs to pin 3 and is placed on apart from two spinning heads approximately on the vertical plane of 5cm, with two relative configurations of spinning head, and apart from two spinning head vertical range l
0Be 3cm.The most advanced and sophisticated distance with metal needle 3 tips of each shower nozzle 2 is 2.5cm.Be respectively 45 ° and 10 ° with tilt certain angle [alpha] and β of this plane on metal needle 3 plane vertical with spinning head 2 center lines, metal needle 3 offset downward spinning head 2 center extended lines apart from l
2Be 0.8cm.Open electrostatic generator 4, voltage rises to 30KV; The flow that syringe pump 5 is set is 1.5ml/h, guarantee sump assemblies 1 continuous offer spinning head 2 melts, spinning head this moment 2 tips are due to the effect of electrostatic field, form conical protuberance, be taylor cone 8 (as shown in Figure 6), under the continuous action of electric field force, solution forms many jet ejections from taylor cone, many jets 6 are in the solvent evaporates described in course of injection, and many jets 6 stretch under the effect of electrostatic force and are refined into nano-scale fiber.
The present embodiment adopts device and technique substantially the same manner as Example 1.Its variation is to have increased by one and receives cylinder.
Before spinning, first take high molecular polymer-pva powder 30 grams, and mix than concentration with 15% quality with mixed solvent (distilled water mixes with the mass ratio of absolute ethyl alcohol with 1: 1), heating water bath (80 ℃) is after 3-4 hour, standing two hours, make the polyvinyl alcohol spinning solution; Then the poly-vinyl alcohol solution that configures is packed in sump assemblies 1, each sump assemblies 1 is connected by catheter with syringe pump 5, sump assemblies 1 is connected with spinning head 2, and two spinning heads 2 are on same level, and vertical range both is 3cm.Guarantee syringe pump 5, sump assemblies 1, spinning head 2 good airproof performances.The positive pole of electrostatic generator 4 is connected with spinning head 2, minus earth; Receive cylinder 7 and metal needle 3 ground connection.Metal needle 3 and spinning head 2 tips apart from l
0Be 4cm.Be respectively 90 ° and 10 ° with tilt certain angle [alpha] and β of this plane on metal needle 3 plane vertical with spinning head 2 center lines, metal needle 3 be offset left spinning head 2 center extended lines apart from l
1Be 1cm, metal needle 3 offset downward spinning head 2 center extended lines apart from l
2Be 0.7cm.Open electrostatic generator 4, voltage rises to 14KV; The flow that two syringe pumps 5 are set is 0.9ml/h, guarantee sump assemblies continuous offer spinning head 2 solution, spinning head this moment 2 tips are due to the effect of electrostatic field, form conical protuberance, it is taylor cone, under the effect of electric field force, solution forms many jet ejections from taylor cone, many jets 6 are in the solvent evaporates described in course of injection, many jets stretch under the effect of electrostatic force and are refined into nano-scale fiber because there are electric field in spinning head and reception cylinder 7 simultaneously, many jets mainly fly to and receive cylinder 7, and the nanofiber ripple of formation is wound up into and receives on cylinder 7.
Embodiment adopts device substantially the same manner as Example 3 and technique.Its variation is to have increased by one and receives cylinder.
Before spinning, first take high molecular polymer-pva powder 16 grams, and mix than concentration with 16% quality with mixed solvent (distilled water mixes with the mass ratio of absolute ethyl alcohol with 1: 1), heating water bath (80 ℃) is after 3-4 hour, standing two hours, make the polyvinyl alcohol spinning solution; Then the poly-vinyl alcohol solution that configures is packed in sump assemblies 1, each sump assemblies 1 is connected by catheter with syringe pump 5, sump assemblies 1 is connected with spinning head 2, and the vertical range of two spinning heads 2 is 6cm.Guarantee syringe pump 5, sump assemblies 1, spinning head 2 good airproof performances.The positive pole of electrostatic generator 4 is connected with spinning head 2, minus earth; Receive cylinder 7 and metal needle 3 ground connection.Metal needle 3 is placed between two spinning heads 2, to the vertical range l of two spinning heads
0Be 3cm.That metal needle 3 is offset left is parallel with two spinning heads, apart from two equidistant center lines of spinning head apart from l
1Be 0.3cm, metal needle 3 offset downward center line apart from l
2Be 1.2cm.Certain angle [alpha] and the β of metal needle 3 and the inclination of this center line is respectively 25 ° and 5 °.Open electrostatic generator 4, voltage rises to 17KV; The flow that syringe pump 5 is set is 1.2ml/h, guarantee sump assemblies continuous offer spinning head 2 solution.Two spinning heads 2 can form electric field with metal needle 3, and two spinning heads 2 have also formed electric field with reception cylinder 7.Each spinning head 2 tips are due to the effect of electrostatic field, form conical protuberance, it is taylor cone, under the effect that electric field force continues, solution forms many jet 6 ejections from taylor cone, many jets 6 are in the solvent evaporates described in course of injection, and many jets 6 stretch under the effect of electrostatic force and are refined into nano-scale fiber simultaneously.Due to spinning head 2 and receive 7, cylinder and have electric field, many jets 6 mainly fly to and receive cylinder 7, and the nanofiber of formation is winding to and receives on cylinder 7.
Claims (14)
1. method and device that improves the many jets of electrostatic spinning, this production method comprises following processing step:
(1) preparation polymer solution or melt: during the preparation polymer solution, first solid polymer and good solution thereof are mixed in mixer with suitable mass fraction specific concentration, after standing 1-2 hour, then send into the polymer solution for preparing in device for storing liquid standby; Described solid mixture refers to the solubility mixture, comprises polyvinyl alcohol, polyvinylpyrrolidone, polyacrylonitrile or polyester; Described good solvent comprises water, ethanol, dimethyl formamide or chloroform etc.; Described suitable mass percent concentration refers to described polymer solution at suitable electrostatic field work and can form on the spinning head top mass percent concentration of circular cone protuberance down.During the preparation polymer melt, first solid polymer is heated to molten condition, makes the spinning melt of modest viscosity; Described solid polymer polypropylene, polyethylene, polycaprolactone, PLA, polyethylene terephthalate, polymethyl methacrylate etc.; The spinning melt of described modest viscosity forms the viscosity of coniform protuberance on the spinning head top under the electric field force effect.
(2) electrostatic spinning process process: syringe pump extrudes polymer solution or melt with suitable flow from device for storing liquid.Spinning head and HV generator are anodal to be connected, and receiving system is placed in spinning head over against direction a distance, and receiving system is connected with the earth.Apply suitable voltage, solution forms conical protuberance on the spinning head top, and this protuberance is called as taylor cone, when electrostatic field force during more than or equal to solution or smelt surface tension, has jet to penetrate from the taylor cone top.
(2) multiple jets forms: place a grounded metal pin nearby at spinning head, this metal needle is relative with spinning head, and maintains a certain distance and angle.Introduce this metal needle in normal electrostatic spinning process after, originally the jet in electrostatic field can become multiple jets at once.
(3) nanofiber forms: many jets move under described electric field force effect, and in course of injection, solvent evaporates or melt jet are cooling, and many jets stretch under the effect of electrostatic force and are refined into nano-scale fiber.
(4) nanofiber receives: with spinning head relative position a distance, a receiving system being set, receive multiple jets and solidify the nanofiber that forms, form nanofiber mats or nano fibre yarn.
2. device that improves the many jets of Static Spinning, this process units is adapted to the method for the many jets of raising Static Spinning claimed in claim 1, comprise that mainly device for storing liquid, spinning head, syringe pump, metal needle, receiving system, HV generator, syringe pump, device for storing liquid, spinning head are connected, the reservoir effect is that storage solutions or melt guarantee continuous solution or melt supply, the syringe pump effect is to provide continuous polymer solution or melt to spinning head, and the spinning head effect is to form taylor cone and as anode as solution or melt canal, top.Metal needle and receiving system be ground connection all, as negative electrode.
3. as claim 1 and 2 described a kind of method and apparatus that improve the many jets of electrostatic spinning, it is characterized in that having introduced a metal needle, metal needle makes the Static Spinning taylor cone form many jets.
4. as claim 1 and 2 described a kind of method and apparatus that improve the many jets of electrostatic spinning, metal needle can be hollow needle, can be also solid needle.
5. as claim 1 and 2 described a kind of method and apparatus that improve the many jets of electrostatic spinning, the diameter of metal needle is at 0.1～5mm, the length 〉=0.1mm of metal needle.
6. as claim 1 and 2 described a kind of method and apparatus that improve the many jets of electrostatic spinning, metal needle and spinning head are at a distance of a segment distance l
0Be in space arrangement in alignment, many jets are formed.
7. as claim 1,2 and 6 described a kind of method and apparatus that improve the many jets of electrostatic spinning, the space length l on metal needle top and spinning head top
0Scope is 0.5～50cm.
8. as claim 1 and 2 described a kind of method and apparatus that improve the many jets of electrostatic spinning, metal needle on right 6 described basis on the plane vertical with the spinning head center line with this plane tilt certain angle [alpha] and β, many jets can form, and the scope of tilt angle alpha and β is-90～+ 90 °.
9. as claim 1 and 2 described a kind of method and apparatus that improve the many jets of electrostatic spinning, the metal needle top on right 6 described basis on the plane vertical with the spinning head center line with this center line left and right or depart from up and down certain for l
1And l
2, many jets can form, apart from l
1And l
2Scope be 0.5～50cm.
10. as claim 1 and 2 described a kind of method and apparatus that improve the many jets of electrostatic spinning, spinning head quantity can be more than or equal to 2, this moment in every two shower nozzle centre positions such as claim 7,8,9 described methods introduce a metal needle, each spinning head can form many jets on the top.
11. as claim 1 and 2 described a kind of method and apparatus that improve the many jets of electrostatic spinning, when shower nozzle quantity 〉=2, each shower nozzle is corresponding respectively introduces a metal needle as claim 7,8,9 described methods, can form many jets on the spinning head top.
12. as claim 1 and 2 described a kind of method and apparatus that improve the many jets of electrostatic spinning, at swing roller of the other increase of metal needle, the placement of this cylinder is advisable not block metal needle, receiving range is 1～50cm, can receive nanofiber.
13. as claim 1 and 2 described a kind of method and apparatus that improve the many jets of electrostatic spinning, at metal plate electrode of the other increase of metal needle, the placement of this plate electrode is advisable not block metal needle, receiving range is 1～50cm, can receive nanofiber.
14. as claim 1 and 2 described a kind of method and apparatus that improve the many jets of electrostatic spinning, polymer solution forms the number of many jets 〉=2 on the spinning head top.
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| CN111540848A (en) * | 2020-05-14 | 2020-08-14 | 华鼎国联四川动力电池有限公司 | Lithium ion battery aluminum plastic film and preparation method thereof |
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