CN101657571B - A process for the production of fibres - Google Patents
A process for the production of fibres Download PDFInfo
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- CN101657571B CN101657571B CN2008800123269A CN200880012326A CN101657571B CN 101657571 B CN101657571 B CN 101657571B CN 2008800123269 A CN2008800123269 A CN 2008800123269A CN 200880012326 A CN200880012326 A CN 200880012326A CN 101657571 B CN101657571 B CN 101657571B
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Abstract
A process is provided for producing fibres which includes forming a plurality of bubbles on the surface of a fibre spinning solution and applying a voltage between the solution and a counter- electrode spaced apart therefrom to cause jets to extend from the bubbles to the counter- electrode, characterised in that the solution is treated with a surfactant to stabilise the bubbles.
Description
Technical field
The present invention relates to produce the method for very fine fiber by various polymer, polymer blend, ceramic precursor mixture and metal precursor mixture.
Background technology
Very fine fiber available from polymer solution, often be called nanofiber, be applicable in the various uses, the electrode, catalyst carrier material, wiper (wiping cloths), absorption pad, postoperative antitack agent, the intelligence that comprise filter medium, tissue engineering bracket structure and device, fiber reinforced composite material, sensor, battery and fuel cell are spun product (smart-textiles), and are applicable in artificial cashmere and the dermatine.
The fiber electrostatic spinning is described in the United States Patent (USP) 692,631 first.On the principle, the droplet of polymer solution or melt is placed in the high electric field.Repulsive interaction and surface tension of liquid between the identical charges of inducing in the drop are at war with, (when typically being 0.5～4kV/cm), electrostatic force overcomes the jet of the surface tension of fluid and polymer solution or melt from droplet jet and when applying enough strong electric field.Electrostatic instability cause jet fast, chaotic vibration, cause rapid solvent evaporation thus, and the polymer fiber that stays elongates and attenuates.The fiber that forms is collected on counterelectrode subsequently, typically is collected with the nonwoven web form.Collected fiber usually very evenly and fibre diameter can be several microns, down to the low 5nm that reaches.
Technology barrier by a large amount of nanofibers of electrostatic spinning production comprises that productivity ratio is low, and most polymers needs the fact of carrying out spinning from solution.On an average, based on the electrostatic spinning of solution, adopt pin spinning device (or spraying silk pin, needle spinnerets), the through-rate of solution (throughput rate) is the order of magnitude of 1mL/h/ pin.Typically from having relatively low concentration, the solution of 0.5wt%～10wt% carries out spinning to diameter at the fiber of 50～100nm scope, and this depends on the type and the molecular weight of polymer.This means, suppose that density polymer is about 1g/mL, then the typical solid through-rate based on the electrospinning silk technology of pin is 0.005g～0.01g fiber/h/ pin.If deduce this calculating, then with 5m
2The speed production surface density (planar density) of/s is 80g/m
2Nanometer fiber net will need minimum 40000 pins.Except needing the so big pin of quantity, the electric field between the differing needles is interfered the minimum interval of also having limited between them, and needs frequent cleaning needle based on the continuous operation of the spinning device of pin, because polymer deposition can stop up spinning device.
Although electrospinning silk technology relative cost on laboratory scale is effective, lower fiber production speed on the singular needle apparatus, make with industrial capacity production too expensive, be difficult to use in most of commodity use as filter and the absorption textiles in.By improving throughput rate, can significantly reduce cost, thereby widen the range of application of electrospinning silk nanofiber and open the door of development of new techniques.
Formhals had attempted by adopting multi-gear source (multiplecogwheel sources) to improve electrospinning silk productivity ratio (United States Patent (USP) 1,975,504) in 1934.In design afterwards, the spininess device (United States Patent (USP) 2,109,333) that he adopts has just become first kind of remarkable method that improves electrospinning silk productivity ratio in the laboratory from that time.Spininess technology seems perhaps that simply still owing to the high probability of system complexity and pin obstruction, this often is inconvenient.
Recently a period of time, diverse ways has been proposed.In the technology that (PCT WO00/22207) such as Reneker describes, by charging in circular column become fiber solution, force gas by post to form annular membrane, then it to be broken into multiply and to become fibrous material, produce nanofiber.
Kim (PCT WO 2003/03004735) has designed complicated many nozzle components system (block system), and wherein spinning solution is controlled by air-flow.
By A.L.Yarin, the upwards needleless electrospinning silk of many nanometers fiber that E.Zussman, Polymer 45 (2004) 2977-2980 propose adopts two-layer system, and wherein lower floor is a ferromagnetic suspension and the upper strata is a polymer solution.When permanent-magnetic field put on this system, the stable top mounted rod of magnetic fluid (vertical spikes) upwards pushed away the ionized layers of interface layer and polymer solution.When highfield runs through this system with this state and when applying, (spike tips) causes multiple electrospinning silk jet from the plunger top, cause the fiber production of two-forty.When jet packed density (packing density) compared with the spininess device, the productivity ratio that calculates had improved 12 times.The potential problems that needleless technology has also avoided syringe needle to stop up.The latent defect of this system comprises the consistency problem of magnetic suspension liquid and polymer solution and the risk that fiber is subjected to fluid contamination.
Specific design for melt electrospinning silk spininess nozzle assembly (pack) is proposed by Chun and Park (PCT WO 2004/016839).Yet, except the additional polymer molten component, there is no significant difference with aforementioned spininess design in the design.
Karies etc. (PCT WO 2004/080681) have described spinning of more high production rate and the specifically various designs of counterelectrode that are used for formed fiber, but spininess and plunger hair brush type spinning source (spiked hairbrush-type) do not have marked change with pin and the gear source that nineteen thirties Formhals has described.
Kim improves on its design basis in 2003 together with Park, designs to have the upward spinning nozzle assembly (PCTWO 2005/090653) of removing flood nozzle assembly and additional air flow nozzle.In this design, spinning-nozzle is made of three concentric tubes.Interior pipe provides spinning solution, and intervalve is used for removing excessive not spinning solution when its overflow, and outer tube forms bubble around the spinning jet, has reduced jet to the formed Coulomb repulsion influence of contiguous jet.This design is incorporated in subsequently the patent (PCT WO2005/073442), and its description forms continuous yarn from electrospinning silk nanometer fiber net.
Andrady etc. design a kind of system that is made up of swivelling pipe (PCT WO2005/100654), are pumped to several jet exits of this tube-surface by this system's spinning solution.Be collected on another swivelling pipe of electricity spinning fibre spin duct outer periphery in placing then.Though exist gas to flow through the relevant this and additional complexity of system, the speed that the spinning solution pump is inhaled is about 1.5mL/h, these are high a lot of unlike the typical 1.0mL/h flow velocity that the one-jet device adopts.Although this system requirements is used for high production rate electrospinning silk, it more embodies the particular case of the laboratory scale rotary drum method of fiber collecting.
Andrady and Ensor have designed another kind of method subsequently, and wherein polymer solution is pumped in the single case type container, have 2～100 needle-like outlets (PCT WO2006/043968) on the one side.This design be very similar to NanoStatics (
Www.nanostatics.com) design used.In both cases, all obtained the fiber high production rate, but the fluid dead volume behind the pin causes more greatly the flow velocity control of every pin relatively poor.This might cause producing drop and spray polymer fragment in last fiber web.
Recent design (PCT WO 2006/047453) such as Beetz is by the high-pressure fog of fluid and electrojet or electrospinning silk constitute simultaneously.In fact, when when fluid applies high voltage, spin fluid under high pressure stressed and by path (＜1mm) pipe.
The lip-deep many jets of antipriming pipe that Dosunmu et al., Nanotechnology 17 (2006) 1123-1127 propose have been described the application of polymer solution, and polymer solution is energized and promotes tube wall by the porous polyethylene pipe by air pressure.On porous surface, form many jets and be electrospun to nanofiber.By fast about 250 times of the typical one-jet of the productivity ratio of this pipe.Further work also needs to implement, and is about every meter length antipriming pipe 4.2g/min but initial calculation shows potential productivity ratio.Although this method demonstrates many prospects, some restriction has been proposed for the spinnability of some polymer by solution parameter such as viscosity and electric conductivity.
The most significant at present high yield electrospinning silk system be known as NanoSpider (
Http:// www.nanospider.cz/).In this method, become fibre-forming polymer solution to be positioned in the dish, and conductive drum slowly rotate by spinning solution, on drum surface, form thin layer solution.When sufficiently high voltage puts on the spinning cylinder and be positioned between the counterelectrode of 10～20cm on the cylinder, will send hundreds of jet and electrospinning silk to target from drum surface.Polymer is depended in the laboratory scale design of NanoSpider, has the productivity ratio of about 1g/min.
Japan Patent JP 3918179 has described a kind of method, wherein by being blown into compressed air and producing bubble continuously on the polymer solution surface through perforated membrane or light wall pipe in solution.High voltage puts between polymer solution and the counterelectrode plate.When voltage was enough high, electrospinning silk jet just formed on the bubble in polymer solution, and the fiber that forms is collected on counterelectrode.This disclosed method requires the bubble in the polymer solution to form with high volume, and explosion very apace subsequently.Although it claims any suitable solvent that can use any soluble polymeric thing and comprise various organic solvents, well-known most of organic solvents also are not easy to form bubble.Therefore the bubble that forms in this organic solvent will be very of short duration.In addition, although this patent is claimed the general applicability to organic solvent, only adopt the polymer solution in water, 2-propyl alcohol and the acetone to carry out spinning to embodiment proof.This patent has also been described counterelectrode and bubble suitable distance and placing at interval, damages these fibers because the drop of the spinning solution that produces by constant explosion bubble can be splashed to the fiber that has formed on the counterelectrode.
Goal of the invention
An object of the present invention is to provide a kind of method of producd fibers, it alleviates some problem in above-mentioned at least in part.
Summary of the invention
According to the present invention, a kind of method that is used for producd fibers is provided, this method is included in to form a plurality of bubbles on the surface of fibre spinning solution and apply voltage between solution and the counterelectrode that is spaced from and extends to counterelectrode to impel jet from bubble, and this method feature is that solution is treated with stabilise bubbles.
Additional features of the present invention is that spinning solution is handled with surfactant; For surfactant, be selected from anion surfactant, cationic surfactant, non-ionic surface active agent and amphion (zitterionic) surfactant that is used for the aqueous solution; And, comprise the silicon surface active agent (siliconesurfactant) that is used for organic solvent for surfactant.
Other features of the present invention are thereby the speed that bubble in the solution forms to be controlled to make between bubble and the counterelectrode keep preset distance; Alternately bubble be formed on and have overfall (or overflow, in container overflow), the bubble that surpasses predetermined altitude is discharged from by overfall; And the level that the volume maintenance of solution is being scheduled in the container.
Other feature of the present invention is to adopt surfactant (or to have the phase, lifetime) and improve bubble-shaped and become efficient to prolong bubble lifetime; And adopt surfactant with further bubble structure and the uniformity improved.
Other feature of the present invention is that the fiber that will form by jet is used for further processing from counterelectrode discharge (or breaking away from draw off) continuously; And, comprise a plurality of isolated, mobile conductors for counterelectrode.
Provide according to an aspect of the present invention, formed bubble by under pressure, in solution, introducing gas.
The other feature of this aspect is that gas is introduced in the solution under being not more than the required pressure of generation bubble basically according to the present invention; And gas is introduced speed control so that bubble and counterelectrode are kept preset distance.
Description of drawings
The present invention will only reference will be made to the accompanying drawings by way of example, wherein:
Fig. 1 is the illustrating of device that is used for producd fibers;
Fig. 2 a and 2b are ESEM (SEM) figure that adopts the fiber that device forms among Fig. 1;
Fig. 3 is the image by the electrospinning silk jet of bubble eruption;
Fig. 4 a to 4c is by being 0.1,0.5 and the SEM image of the fiber produced as the 8wt% poly-vinyl alcohol solution of surfactant of the lauryl sodium sulfate of 1 * CMC with concentration;
Fig. 5 a to 5c is by being 0.1,0.5 and the SEM image of the fiber produced as the 10wt% poly-vinyl alcohol solution of surfactant of the lauryl sodium sulfate of 1 * CMC with concentration; And
Fig. 6 a to 6c is by being 0.1,0.5 and the SEM image of the fiber produced as the 12wt% poly-vinyl alcohol solution of surfactant of the lauryl sodium sulfate of 1 * CMC with concentration.
The specific embodiment
Method of the present invention is included in and forms bubble on the surface of fibre spinning solution and by at solution be spaced from and apply voltage impel jet to spray from bubble surface between the counterelectrode above the bubble surface.Jet forms fiber in a known way when it marches to counterelectrode.Importantly, this solution is handled with stabilise bubbles with suitable surfactant.
Surfactant is well-known in the effect aspect reduction surface tension and the raising bubble stability.Being chosen in the characteristic that depends on solution to a great extent and having various surfactants available of surfactant.The bubble that yet the principal element of option table surface-active agent is it to be passed through to form in the stabilizing solution prolongs the ability of bubble lifetime.Therefore, preferred bubble keeps stable as far as possible for a long time, and reduces the frequency of bubble wall rupture thus as far as possible.
Prolong bubble lifetime by adding the bubble stabilizes surfactant, compare when stablizing, can form more stable jet at each bubble surface, and become fiber with bubble.Bubble lifetime prolongs with relevant jet stability and improves, and also causes forming uniform fibers more.
And each bubble eruption will produce droplet by bubble wall rupture.Still disclosed in prior art, if these drops are fallen on the fiber that has formed, especially fallen on the fiber web that forms on the counterelectrode, their are understood dissolving once more and damage these fibers thus.Under the situation that does not adopt the surfactant stabilizing solution, walls is often broken and is caused forming this spattered droplets of high volume.
Add the frequency that the bubble stabilizes surfactant has improved bubble lifetime and reduced bubble wall rupture thus.This means that the spattered droplets volume reduction of polymer solution and the fiber quality that obtains improve.
Other factors of being considered when selecting suitable surfactant comprise that it improves bubble-shaped and becomes the inhomogeneity ability of efficient, bubble structure and bubble.Bubble structure is important, because have been found that under condition of similarity, the jet that forms on the jet ratio minute bubbles that form on the air pocket is many.In the solution that does not contain bubble surface of stability activating agent, the life-span of air pocket is also short than the life-span of minute bubbles.
Generally speaking, anion surfactant, cationic surfactant, non-ionic surface active agent and zwitterionic surfactant can be used in the aqueous solution and silicon surface active agent can be used in organic solvent.Adopting and can utilize specific nano particle and the polymer that also plays a role as surfactant recently, also is possible.In this manual, term " surfactant " should have its most wide in range meaning and comprise these products and any other reagent that is used for stabilise bubbles.Under the situation of needs, also can use any suitable mixture of surfactant.
Any suitable method that forms bubble in solution can both be used, and is included under the pressure blow gas by solution, agitating solution, expand in solution or the thermal decomposition in solution by particulate matter such as yeast powder by volatilised liq such as pentane.In most of the cases, the most realistic and method formation bubble that is easy to control is to blow to pass through solution.
The application surface activating agent is more favourable in these cases, and this has increased the amplitude of bubble wall rupture because form in stabilizing solution not that bubble needs high gas flow rate, the fiber that has formed has been increased splashed down risk.
Regulate the type and the gas pressure of used nozzle, also can form bigger bubble, it has advantage described above.
The pressure of gas being introduced solution will preferably be not more than the required pressure of generation bubble substantially further to guarantee bubble stability.Bigger pressure will cause bubble to form quickly and break.
When blow bubble in the polymer solution that does not contain bubble surface of stability activating agent, short and need continue the new bubble of generation when bubble is deposited by in solution, blowing at a high speed.In addition, when blowing when producing bubble to solution by tubule, bubble mainly concentrates on directly over the mouth of pipe, solution surface than in the zonule.When bubble is blown in this solution by perforated membrane, bubble will mainly be formed on the solution surface that is located immediately at film top, so membrane area needs to increase, and can effectively form bubble on whole solution surface.
These shortcomings can overcome by using stabilizing agent.When polymer solution contained suitable surfactant, bubble can be kept the longer time after formation.This means that the bubble that blows into solution forms gas and can more effectively utilize.And then this means that using gases reduces in proportion, this means the cost savings of input raw material, if use special gas then especially true.Similarly, if gas is compressed air, the employed volume that diminishes in proportion means the cost savings that produce compressed air institute energy requirement.In addition, long bubble will tend to sprawl into covering large-area solution surface automatically when depositing in this solution, and this causes being used for the more good utilisation of fibroplastic usable area.This has also simplified gas and has been incorporated into mode essential in the solution, because this has been avoided air pocket is produced the needs on surface.
When considering suitable surfactant and forming the mode of bubble, the generation of even bubble or bubble surface also should be considered on the solution.The surface is even more, and the fiber that is obtained is just consistent more.Bubble form the device adopted also should be provided for bubble (bubble) or foam (foam) surface to the distance of counterelectrode be controlled at setting in preset distance or the distance range (or means, means).Its plain mode provides and has overfall that (by overfall, excessive bubble is discharged from for or overflow, overflow) container that holds solution or groove, makes it to break and turns back in the solution subsequently.This can be by providing groove and realization easily around groove and with its top is spaced apart, the excessive bubble that overflows the top enters in this groove and is used for recirculation.
More complicated apparatus can comprise and is used for measuring the device that bubble height in the groove and control bubble form, and for example introduces the speed of gas and thus the height dimension of bubble is held in predeterminated level in solution by control.
Any suitable counterelectrode can both use.Counterelectrode will be preferably designed to allows fiber from wherein removing continuously, and can be the type of describing among the PCT/IB2007/003177, and it has a plurality of isolated, mobile conductive strip.Yet it is not essential directly collecting fiber on counterelectrode.
Following examples are used to illustrate various aspects of the present invention described above.
Concentration be the solution of 6wt% by polyacrylonitrile (PAN) (Mw=210000g/mol) at N, make in the dinethylformamide (DMF).The foaminess of solution is tested by solution by adopting thin plastic tube-shape nozzle to be blown into compressed air with the speed of 150～3000mL/min.The life-span of the single isolated bubbles that forms is far below 1 second, and fails to obtain stable bubble.To add in the solution with the concentration of 244g/L and repeat the foaminess test from the silicon surface active agent of industrial source (JSYK 580 (L580)) then.The stable foam that covers whole rooved face can produce and the life-span of single isolated bubbles is 10～80 seconds.
With reference to Fig. 1, the fibre spinning solution (1) that will comprise surfactant pours into that (the elongated slot surface area is 36cm in the elongated slot (2)
2And have along the hole pipe (4) of its length center extension), and by normal air compressor (not shown) injection air.Counterelectrode (6) is positioned at 13cm place on the groove.
Air (7) injects by pipe (4) then, and regulates flow velocity to obtain stable foam (8) on solution (1) surface.Between solution (1) and counterelectrode (6), apply 46kV DC high voltage then.
Bubble (8) jet surface and quick the form fiber of many electrospinning silk jets from forming foam.
Sem analysis shows, the solution of 6wt% produce have some pearl bodies and average diameter 1.18 μ m fiber (a) referring to Fig. 2.This method adopts the 8wt%PAN solution with the identical silicon surface active agent of 244g/L to repeat to implement.Sem analysis shows that formed fiber is more even, no pearl body, and fiber diameter is 1.29 μ m (referring to Fig. 2 b).Fig. 3 illustrates having from the single isolated bubbles of many jets of its jet surface of forming under these conditions.
Do not use surfactant only can form small amount of fibers under the same conditions.The electrospinning silk that the spattered droplets that these fibers mainly form by by bubble eruption the time is induced by electric field forms.Because the unpredictable characteristic that walls burst duration drop forms, and corresponding variation on the drop size, the diameter or the morphology of the fiber that is formed by these drops do not have repeatability.
Solution is made with variable concentrations in distilled water by polyvinyl alcohol (PVOH) (Mw=72000g/mol,＞98% hydrolysis), and it has the surfactant lauryl sodium sulfate (SLS) of variable concentrations as follows:
| Polymer concentration (wt%) | Surfactant concentration (* CMC SLS) * |
| 8 | 0.1 |
| 8 | 0.5 |
| 8 | 1 |
| 10 | 0.1 |
| 10 | 0.5 |
| 10 | 1.0 |
| 12 | 0.1 |
| 12 | 0.5 |
| 12 | 1.0 |
*1×CMC?SLS＝0.0082mol/l
Use the distance between time slot (2) and the counterelectrode (6) to be arranged to 10cm at the device shown in Fig. 1.To contain in the solution pan tank of polymer and surfactant, and open and regulate air-flow and obtain stable foam.Apply high voltage and regulation voltage between solution in groove and the counterelectrode extremely just above in concrete solution, causing the required voltage of jet.This scope is 25～35kV.Spray many electrospinning silk jets and form fiber apace from bubble surface.
The fibroreticulate sem analysis that is obtained clearly illustrates that, along with surfactant concentration increase and bubble more stable, the fiber quality raising that is obtained.In order to implement this analysis, counterelectrode covers with the aluminium foil plate and fiber is formed thereon.Obtain the plate sample subsequently and it is carried out sem analysis.
Fig. 4 a～4c shows the result of 8wt% solution.In Fig. 4 a (0.1 * CMC surfactant), the some fibre of observing initial formation is damaged by big polymer spattered droplets (spatters) and the fiber that formed afterwards is partly dissolved by solvent vapour.In Fig. 4 b (0.5 * CMC surfactant), see that fiber is drier, but big spattered droplets many fibers have still been damaged.In Fig. 4 c (1.0 * CMC surfactant), observe significant improvement, wherein most of fiber drying and spattered droplets significantly reduce.
Fig. 5 a～5c shows the similar results of 10wt% solution.In Fig. 5 a (0.1 * CMC surfactant), observe most of fiber and damaged by big polymer spattered droplets.In Fig. 5 b (0.5 * CMC surfactant), fiber is drier, but many fibers show pearl body flaw (or defective, defects) and the volume ratio between flaw and the fiber higher.In Fig. 5 c (1.0 * CMC surfactant), observe the improvement that is better than result among Fig. 5 b, wherein most of fiber drying, and the volume ratio between pearl body flaw and the normal fiber is improved.
Fig. 6 a～6c shows the result of 12wt% solution.In Fig. 6 a (0.1 * CMC surfactant), observe concealed wire (dark lines), wet herein jet is deposited on the counterelectrode, the fiber below having damaged.In Fig. 6 b (0.5 * CMC surfactant), the ratio of dried fiber improves, but some irregular fibre morphologies still can be observed.In Fig. 6 c (1.0 * CMC surfactant), observe further improvement, wherein most of fiber drying and fiber uniformity improve.
By these experiments obviously as seen, the bubble in the stabilizing solution has appreciable impact to fiber quality.Not only the sputter minimizing follows fibre damage to reduce, and fiber quality also is improved.
Should be appreciated that, many other embodiments that have the method that is used for producd fibers, these embodiments, especially about the type of fibre spinning solution and used surfactant, form the method for bubble and realize fibroplastic condition, fall within the scope of the present invention.
Claims (16)
1. method that is used for producd fibers, it is included in to form a plurality of bubbles on the surface of fibre spinning solution and apply voltage between described solution and the counterelectrode that is spaced from and extends to described counterelectrode to impel jet from described bubble, and described method is characterised in that described solution is treated to stablize described bubble.
2. method according to claim 1, wherein said solution is handled with surfactant.
3. method according to claim 2, wherein said surfactant are selected from anion surfactant, cationic surfactant, non-ionic surface active agent and the zwitterionic surfactant that is used for the aqueous solution.
4. method according to claim 2, wherein said surfactant comprises the silicon surface active agent that is used for organic solution.
5. according to each described method in the claim 2 to 4, wherein said surfactant prolongs bubble lifetime.
6. method according to claim 2, wherein said surfactant improve bubble-shaped and become efficient.
7. method according to claim 2, wherein said surfactant improves bubble structure and uniformity.
8. method according to claim 1, wherein said bubble and described counterelectrode are kept predetermined distance.
9. method according to claim 8, wherein, the bubble of controlling in the described solution forms speed so that described bubble and described counterelectrode are kept predetermined distance.
10. method according to claim 8, wherein, described bubble is formed in the container with overfall, and the bubble that surpasses predetermined altitude is discharged from by described overfall.
11. method according to claim 10, wherein, the volume maintenance of solution described in the described container is in predetermined level.
12. method according to claim 1, wherein, the fiber that forms by described jet is discharged continuously from the described counterelectrode and is used for further processing.
13. method according to claim 12, wherein said counterelectrode comprise a plurality of isolated, mobile conductors.
14. method according to claim 1 wherein, forms described bubble by introduce gas to described solution under pressure.
15. method according to claim 14 wherein, is introduced described gas in the described solution under being not more than the required pressure of generation bubble substantially.
16. method according to claim 15, wherein, thereby the speed that control is introduced described gas in the described solution makes described bubble and described counterelectrode keep predetermined distance.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ZA200703137 | 2007-04-17 | ||
| ZA2007/03137 | 2007-04-17 | ||
| ZA2007/09111 | 2007-10-23 | ||
| ZA200709111 | 2007-10-23 | ||
| PCT/IB2008/000935 WO2008125971A1 (en) | 2007-04-17 | 2008-04-17 | A process for the production of fibres |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101657571A CN101657571A (en) | 2010-02-24 |
| CN101657571B true CN101657571B (en) | 2011-03-30 |
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| CN2008800123269A Expired - Fee Related CN101657571B (en) | 2007-04-17 | 2008-04-17 | A process for the production of fibres |
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| ZA (1) | ZA200907987B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103361747A (en) * | 2013-08-05 | 2013-10-23 | 苏州大学 | Rotary film babble electrostatic spinning device |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798710B (en) * | 2010-03-11 | 2011-08-31 | 东华大学 | Mechanical air bubble spinning device for preparing micron or nanometer fibers |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE689870C (en) * | 1937-08-19 | 1940-04-08 | Anton Formhals Dipl Ing | Process for the production of artificial fibers from fiber-forming fluids, in particular acetyl cellulose |
| CN1861268A (en) * | 2006-05-29 | 2006-11-15 | 张爱华 | Interfacial boost type spinning-nozzle free electrofluid dynamic method, and its application |
-
2008
- 2008-04-17 CN CN2008800123269A patent/CN101657571B/en not_active Expired - Fee Related
-
2009
- 2009-11-13 ZA ZA200907987A patent/ZA200907987B/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE689870C (en) * | 1937-08-19 | 1940-04-08 | Anton Formhals Dipl Ing | Process for the production of artificial fibers from fiber-forming fluids, in particular acetyl cellulose |
| CN1861268A (en) * | 2006-05-29 | 2006-11-15 | 张爱华 | Interfacial boost type spinning-nozzle free electrofluid dynamic method, and its application |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103361747A (en) * | 2013-08-05 | 2013-10-23 | 苏州大学 | Rotary film babble electrostatic spinning device |
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| Publication number | Publication date |
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| CN101657571A (en) | 2010-02-24 |
| ZA200907987B (en) | 2010-07-28 |
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