US2116942A - Method and apparatus for the production of fibers - Google Patents

Method and apparatus for the production of fibers Download PDF

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US2116942A
US2116942A US88429A US8842936A US2116942A US 2116942 A US2116942 A US 2116942A US 88429 A US88429 A US 88429A US 8842936 A US8842936 A US 8842936A US 2116942 A US2116942 A US 2116942A
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fibers
sliver
spinning
nozzle
elements
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Formhals Anton
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RICHARD SCHREIBER GASTELL
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RICHARD SCHREIBER GASTELL
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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
    • D01D5/0076Electro-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
    • D01D7/00Collecting the newly-spun products

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  • This invention relates to the production of a continuous fiber band of artificial filaments by the electric splitting up or shattering of a stream of a solution or dispersion of filament forming material, and, will hereinafter, for convenience, be referred to as electrical spinning of fibers. More particularly the invention relates to an improved process and apparatus for the electric spinning of fibers between electrodes, one of which moves relative to the other and upon one of which the fibers are collected in the form of a continuous coherent fiber band, or sliver.
  • a spinning solution is introduced between a stationary electrode, in the form of a serrated Wheel immersed in the spinning solution, and an oppositely charged movable electrode which may bein the form of a revolving wheel, ring, belt, bobbin or drum.
  • the high electric tension between the electrodes causes dispersion or shattering of the spinning solution into a plurality of fine filaments or fibers which are attracted to the movable electrode and temporarily collected thereon.
  • the prior art collecting devices are open to the further objections that they have not served to collect the fibers at once into a compact coherent form with the fibers arranged substantially parallel to each other.
  • the moving ciectrodes have heretofore exhibited plane or curved continuous surfaces. The entire surface area of these electrodes was charged electrically and the charge became uniformly distributed thereover. Thus the fibers tended to collect and distribute themselves more or less at random all over ⁇ these surfaces, rather than to concentrate noticeably in any particular fashion.
  • a compact organization of the fibers in good parallelism on the collector has not been heretofore achieved. While special devices were suggested to assemble the spun fiber masses from the previous collectors in a compact organized form, these devices have damaged the filaments in the process of loosening them from the continuous surface of the collector and at the same time have tended to cause entanglement thereof.
  • Another object of this invention is to produce a fiber band in which a high degree of parallelism exists between the individual fibers.
  • a further object of the invention pertains to the production, by an electrical spinning process, of a large quantity of fibers, in a continuous, compact, coherent form, while permitting rapid drying of the fibers, eliminating substantial adherence of the fibers not only to each other but to the electrode collecting device as well, and permitting an easy removal of the fiber band from the collecting device without damage to the fibers or the parallel construction of the fiber band. It is a further object of the invention to produce a parallel, con herent fiber band which will be easy to draw,
  • the objects of invention may be accomplished ccording to one embodiment thereof by delivering a Spinnin.cr solution from a plurality of nozzles connected to a feed pipe, said nozzles delivering streams spinning solution into a high potential electrical neld created between the nozzles and a moving collecting device, thereby causing said streams to shatter or disperse into a plurality of fibers, collecting the thus formed fibers on a moving ⁇ eollectincr device which constitutes one pole cf vthe held, the collecting device being ovided with projecting elements or prongs substantially separated from each other and acting as successive individual electrodes which receive the fibers support them ⁇ substantially parallel and in the form of a continuous fiber band at or near the points of said electrodes, the space between the prongs permitting rapid evaporation of the solvent in the fibers and making possible the easy removal of the continuous fiber band from the electrodes by means of any suitable device, such for example, stripping device described below, after which it be wound onto reels and the like.
  • the fibers are furthermore arranged in generally the same direction permitting the building up of an organized bundle or sliver ci substantial dimensions which can be continuously removed from the collector.
  • the threads due to the large amount of air or other gaseous drying agent coming in contact therewith from all sides, out thoroughly and do not adhere to each other to any substantial extent, even though the quantity of ber spun is large, per unit of time, in comparison with previously known spinning methods.
  • the stripping device which permits a continuous removal of the formed sliver from the collector generally comprises a disc provided on its circumference with iinger-like or lobe-like projections which are adapted to mesh with the electrode prongs on the collector in such a way that the fingers or lobe-like projections of the disc are inserted in the spaces of the belt between the prongs and close to the belt and upon revolution of the disc the lobes move farther and farther away from the belt to the extremities of the prong-like electrodes thereby stripping the sliver from the collector, so that the electrodes of the collecting device upon being moved again under the nozzles, are ready to receive another mass or bundle of fibers.
  • Figure l is a diagrammatic perspective view of a continuous belt-electrode collector.
  • Figure 2 an end elevational view showing one form of stripping disc.
  • Figure 3 is an end vdew of the endless belt collector and stripping disc.
  • a plurality of metal nozzles l are connecten with a pipe il which may or not be metal, and are supplied with spinning solution from the storage tank i2.
  • the nozzles and pipe are electically connected in circuit with a device it for producing high potential electric current.
  • Device iii may be a transformer and rotary converter for changing ordinary line current such as 110 volt, 60 cycle alternating electric current into a high voltage pulsating direct current or i3 may be any suitable device for producing a high potential direct current.
  • I3 may be a suitable device for producing an alternating current of high potential o1' any desired or varying frequency.
  • a long endless belt iti preferably comprising rubber or other suitable non-conductive material, although an electrically conducting material such as a metal be used.
  • the belt is provided with spaced metal prongs or lugs l5 which are fastened to the belt so as to project from at least one side thereof.
  • lugs l5 are disposed substantially witlr'n the plane of the belt with the projecting ends extending perpendicularly from the side of the said belt.
  • the projecting portions or ends of the lugs are preferably pointed as shown.
  • the belt is driven by pulleys i0 and il which are preferably composed of wood or some other suitably electrically non-conducting material. Positioned parallel to the under surface of the belt is shown a long conductor wireA l0 attached by means of a conductor lil to the circuit which includes the high potential source i3. Conductor l0 is spaced from the belt, the electrodes l5 receiving a charge from the wire it through the air gap therebetween. The potential between the nozzles and the electrodes i5 is maintained between 10,000 up to l00,000 volts and preferably at least 30,000 volts.
  • the high potential electric charge on the electrodes l5 is of opposite polarity to that imparted to the spinning solution and is preferably lower in potential than that imparted to the said s0- lution so as to prevent undesirable flying about of bers due to a repelling action of said electrodes. It is furthermore possible to spin with the electrodes l5 grounded so that they are at zero potential, and it is to be understood that such type of apparatus is intended to be ineluded within the broad scope of the invention.
  • a potential stabilizing and directing means such as a concavely curved screen or other wire network is preferably positioned in back of the nozzles i0 and is connected to a charge of high potential electricity of the same polarity as the potential imparted to the spinning solution.
  • the directing means serves primarily to direct the bers toward the prongs and in addition ser es repel any fibers toward the belt from which occasional fibers sometimes tend to fly back to the spinning nozzles.
  • the fibers during the spinning operation, are attracted to and electrostatically adhere to the electrode prongs i5 and travel with the belt supported by the prongs.
  • the bers form a sliver which is preferably removed continuously at one end of the belt collector by means of a stripping device 20 mounted on a shaft 2i the axis of which is inclined towards the axis of the shaft of pulley il, so that the lobes of the disc move outwardly as the disc revolves thereby scraping off rprojecting ends thereof.
  • the fibers will usually collect in the form of a continuous band at the tips of the said projecting ends and thereby leave room between the ends of the prongs and the belt for insertion of the lobes of the stripping device 20.
  • Electrodes I5 it is not necessary for the electrodes I5 to be connected with each other in apparatus of the type shown in Figure l, since they individually act as electrodes and acquire a charge from the spaced elongated conductor I8 whether they are connected together or not.
  • the present invention is advantageously applied to the spinning of solutions of cellulose acetate in organic solvents, for example of cellulose acetate in acetone.
  • Spinning solutions containing ydifferent solvents behave differently when spun in accordance with the present invention. 'I'he use of certain solvents in the spinning solution will cause a. greater' or lesser shattering of the stream of liquid than others, and some solutions will require a higher potential than others for the satisfactory breaking up of the stream and formation of fibers.
  • Other cellulose derivative solutions may also be spun in the same way, for example solutions of cellulose ethers such as ethyl cellulose and benzyl cellulose.
  • solutions of resins and other materials which can be formed into fibers may be spun according to the present invention.
  • Example A solution consisting of 200 grams commercial cellulose acetate, 700 grams acetone and 400 grams mono methyl ether of ethylene glycol is forced through single hole nozzles the orifice di ameter of which is approximately .0180. A potential difference of approximately 57,000 volts is maintained between the nozzle and the conductor wire I8 as illustrated in the drawing. The voltage is obtained from a source supplying pulsating direct current. The streams of cellulose acetate solution are split under the iniiuence of the high potential field into numerous fine fila ments which are deposited and then carried away supported by the prongs attached to the moving belt at or near the points thereof.
  • the streams of solution and the fibers therefrom are properly directed to the prongs by means of the high potential between the nozzles and the prongs which electric field ⁇ is suitably modified and shaped by means of the screen positioned in back of the nozzles said screen possessing an electrical charge of the same polarity as that of the nozzles.
  • the solvent evaporai: i the fibers quickly drying as carried .y from the spinning zone.
  • the fibers are thus oriented in a position substantially parallel to the direction of travel of the belt and due to their rapid drying adhere neither to the collecting device nor to one another to any objectionable gree.
  • the continuous sliver or ber thus formed is removed by the s ripping device and deposited in a suitable container or wound on a reel.
  • the fibers in the fiber band at this point are sufficiently loose and free, of one another, and lie substantially parallel in a compact sliver as to permit said sliver to be directly drawn and twisted into threads or yarns of good quality and strength.
  • the sliver Prior to vdrafting and twisting, the sliver may-be preferably treated with a suitable textile finish in a manner similar to the treatment of wool rovings to facilitate ease and smoothness of drafting.
  • the sliver treated with a suitable textile finish is drawn and/or twisted to yield a yarn of any weight desired.
  • the sliver as formed by this process possesses outstanding properties as regards the relative freedom from sticking together of the individual fibers, due to the fact that the fiber band collects at, and is supported as such by the points or near the peints of the electrodes, thus permitting free access, from all sides, of the air to the freshly spun fibers, assisting in drying.
  • Previous devices have been continuous fiat or curved surfaces, to which the fibers could stick, and which would permit drying out of the fiber from one side only, thus decreasing the rate of solvent evaporation and causing sticking together of the mass.
  • the electrode-collector be a continuous belt with prongs, but it will be understood that it may also be a wheel or other device provided in a similar fashion with electrode prongs around its circumference, which prongs are adapted to mesh with a suitable means for removing the fiber band from the wheel-collector. If desired suitably positioned air jets may be used t0 remove the fiber band, or may be used in conjunction with various mechanical devices in removing the sliver from the collecting electrode.
  • the moving collecting device on which the fibers are collected in a continuous sliver, may be driven at any desired speed to obtain varying effects.
  • the linear speed of the collecting device is at least as high, and preferably slightly higher, than the speed of the freshly formed fibers in their travel toward the collecting device.
  • the size of the sliver delivered from the machine may be regulated by a number of factors either singly or in suitable combination with each other.
  • the chief factors include the number of spinning nozzles in operation at any one time, the volume of solution delivered by the nozzles per unit time, the concentration of solids in the spinning solution and the speed of the collecting device.
  • the number of nozzles, speed of collecting device, etc so as to yield a wide range of sizes of the sliver band to be removed by the stripping device, without damage or rupture.
  • a convenient size sliver weighs between 0.1 gram and 0.25 gram per meter length. Slivers either much larger or somewhat smaller may be produced as desired.
  • the sliver in addition to possessing good, coherent, uniform and parallel construction, contains filaments of good strength.
  • cellulose acetate is used as the lament forming material, I have obtained threads after drawing and twisting showing good strength comparable to that of wool yarns.
  • Another desirable property of my sliver is its long staple as compared to the staple of cotton and the shorter staple Wools. I may vary my average staple length from 2 or 3 inches up to 12 inches or even higher. The somewhat longer staple is advantageous for most purposes because of the added strength that results in the twisted yarn thereby. Natural fibers such as cotton and wool are limited in staple length by the nature of their source.
  • I may spin lustrous fibers, I am not limited thereby, but may introduce into the spinning solution suitable delustering agents, such as pigments, oils, organic solids, and other materials known and used in the art to achieve delustered, semi-lustrous, and other effects. Likewise, I may spin dyed filaments by introducing suitable dyes or other coloring matters into the spinning solution.
  • suitable delustering agents such as pigments, oils, organic solids, and other materials known and used in the art to achieve delustered, semi-lustrous, and other effects.
  • I may spin dyed filaments by introducing suitable dyes or other coloring matters into the spinning solution.
  • I may exercise control over the average lament diameter and produce fibers as small as one denier per iilament or even smaller, or I may produce relatively coarse laments of 3, 5, l0 or even greater average denier per lament. This is accomplished by varying the solids content and/ or viscosity of my spinning solution, and will also be influenced to a certain extent by the voltage potential employed, and size of the nozzle pedal. In general, a fine filament sliver will be produced with the lower solids and/ or viscosities, the higher voltages, and the smaller nozzle orifices. Heavier laments, in general, go with higher solids, and/or viscosities, lower voltages, and larger nozzle oriiices. These and other factors may influence the filament size as well as the lament length. I thus have considerable latitude in the choice of conditions to produce slivers of greatly varying properties according to the use to which I put the material.
  • Coarse, harsh fibers may be used for mixture with coarse animal fibers, such as mohair, or may be used alone as substitute materials.
  • the fine soft bers lend themselves to use in fabrics for dress goods, where a light soft feel is desired, or they may be mixed with the finer grades of wool, camels hair, etc. A wide range of uses is thus comprehended for this new Vtextile material.
  • My fibers are to be distinguished from other articially produced fibers such as rayon from regenerated cellulose, cellulose acetate, etc. as well as from rayon staple fiber, which is produced by chopping up continuous ropes of continuous viscose ber, cellulose acetate and other bers, in that the individual liber structure of my sliver is heterogeneous.
  • a sample of ber from any of the conventional articial silk (or staple) spinning processes is comparatively uniform both longitudinally and laterally and the denier of the individual filaments along their length is quite constant. Indeed, the nature of the processes by which they are produced is such as to yield substantially uniform filament materials and I call these materials relatively homogeneous. That is to say, an individual fiber is substantially uniform throughout its length and cross section, and different bers from the same mass correspond closely with one another.
  • This heterogeneity is particularly useful when I come to draw and/or twist thread or yarn from my sliver, in that the fibers possess a cling or a sort of woolliness which is very dcsirable in building up a good yarn, or ior mixing with natural. staples.
  • cellulose acetate staple fiber produced by chopping up a multilament rope made for example in accordance with conventional cellulose acetate spinning processes has certain decient properties as a staple, due partly to the fact that all the laments are straight, possess an insignificant crimp or crinkle and in addition are quite smooth, sleek and regular.
  • Cellulose acetate bers from my process due to their heterogeneous nature overcome this difficulty and serve admirably to twist together to form threads resembling wool in many respects. They are likewise admirably adapted to mixture with wool.
  • my fiber band or sliver is of new and novel construction.
  • the individual fibers of my product are heterogeneous as compared to the homogeneous character of previous artificially produced staple fibers.
  • the fibers of the instant invention arc already built, constructed, and organized into a coherent, compact, free drawing ber band showing a high degree of parallelism, which sliver may be processed at once into twisted yarns.
  • Arti* ficial staple masses heretofore produced cutting or chopping continuous filaments to required staple length are in a completely disorganized condition so as to require all the usual preparatory operations of opening, carding, combing, etc. for the formation of slivers or rovings.
  • My present electrically spun sliver is furthermore a distinct advance over previous electric spun fiber masses which were produced with insufficient compactness, parallelism, and free drawing properties to permit their direct successful spinning into yarns or threads.
  • a nozzle In an apparatus for the electrical spinning of fibers, a nozzle, a continuously movable supporting means spaced from said nozzle, a plu rality of elements spaced from each other projecting from said means, and means for maintaining a high electric potential between said elements and said nozzle.
  • a nozzle means for imparting an electrical charge of high potential to said nozzle, a continuously movable supporting means spaced from said nozzle, a plurality of elements fixed to said supporting means, said elements spaced from each other and provided with ends projecting from said supporting means, means for imparting to the ends of said elements an electrical charge g of high potential of opposite polarity to the charge on said nozzle.
  • a nozzle means for imparting an electrical charge of high potential to said nozzle, a continuously movable supporting means spaced from said nozzle, a plurality of elements fixed to said supporting means, said elements spaced from each other, means for imparting to said elements an electrical charge of high potential of opposite polarity to the charge on said nozzle.
  • a nozzle means for imparting an electrical charge of high potential to said nozzle, a continuously movable supporting means spaced from said nozzle, a plurality of elements fixed to said supporting means, said elements spaced from each other and provided with ends projecting from said supporting means, means for imparting to the ends of said elements an electrical charge of high potential of opposite polarity to the charge on said nozzle, and means for continuously removing fibers collected on said elements.
  • a nozzle means for imparting an electrical charge of high potential to said nozzle, a continuously movable supporting means spaced from said nozzle, a plurality of elements fixed to said supporting means, said elements spaced from each other, means for imparting to said elements an electrical charge of high potential of opposite polarity to the charge on said nozzle, and means for continuously removing fibers collected on said elements.
  • a nozzle means fc' imparting an electrical charge of high potel to said nozzle, a continuously movable supporting means spaced m said nozzle, a plurality of elements fixed to said supporting means, elements spaced from each other, means for imparting to said elements an electrical charge of high potential of opposite polarity to the charge on said nozzle, and means cooperatively connected to said elements for continuously removing fibers collected on said elements.
  • a nozzle means for imparting an elece trical charge of high potential to said nozzle, a continuously movable supporting means spaced from said nozzle, a plurality of elements fixed to said supporting means, said elements spaced from each other, means for imparting to said elements an electrical charge of high potential of opposite polarity to the charge on said nozzle, and means meshing with said elements for continuously removing fibers collected on said elements.
  • a method for the electrical spinning of fibers comprising electrically dispersing a stream of spinning solution into fibers, collecting said electrically dispersed fibers in the form of a sliver and moving said sliver through the surrounding atmosphere until substantially dry, said sliver, during said collecting and drying thereof, being at all times supported in such a manner as to be completely surrounded by the atmosphere substantially along the length there" of whereby to prevent objectionable adherence of the iibers to each other, continuously removing said sliver from the drying atmosphere and winding it in the form of a package.
  • a method for t.e electrical spinning of fibers comprising electrically dispersing a stream of spinning solution into fibers, collecting said electrically dispersed bers in the form of a sliver, drying said sliver during the forming and collecting thereof by suspending the saine at spaced portions thereof in such manner as to be completely surrounded by the atmosphere substantially along the length thereof during said collecting and drying thereof whereby to obtain a substantially dry, compact, coherent sliver in which the individual fibers are substantially free from each other and continuously removing said sliver from the drying atmosphere and winding it in the form of a package.
  • a method for the electrical spinning of fibers comprising electrically dispersing a stream of spinning solution into fibers, collecting said electrically dispersed fibers in the form of a sliver and drying said sliver during the forming and collecting thereof by moving the sliver, suspended at spaced portions thereof in such. a manner as to be completely surrounded by the atmosphere substantially along the length thereof during said collecting and drying thereof, con:- tinuously removing said sliver and treating the same with a finishing composition prior to any drawing or twisting thereof.
  • a nozzle In an apparatus for the electrical spinning of fibers, a nozzle, a continuously movable supporting means spaced from said nozzle, said sup- CII porting means being constructed in such a manner as to permit fibers collected thereon to be surrounded by the atmosphere substantially along length of the supporting means, and means or maintaining a high electrical potential be- 12.
  • an apparatus for the electrical spinning of ibers means for forming a stream of spinning soluticn, a continuously movable supporting means spaced from said means, a plurality of spaced elements on said supporting means, electrical means connected relative to said stream of solution and said spaced elements to maintain a high electrical potential therebetween whereby to electrically disperse said stream of spinning solution to bers and collect the bers on said elements in the form of a compact coherent sliver in which the individual fibers are substantially free from each other.
  • a nozzle for forming a stream of spinning solution, means for imparting to said stream of spinning solution an electrical charge of high potential, a continuously movable supporting means spaced from said nozzle, a plurality of elements fixed to said supporting means, said elements spaced from each other, means for imparting to said elements an electrical charge of high potential of opposite polarity to the charge on said stream of spinning solution.

Description

A. FORMHALS May' 1o, 193s.
METHOD AND APPARATUS FOR PRODUCTION OF FIBERS Filed July l, 1936 INVENTOR! By .mon iig ila/5 A TTORNEY Patented May l0, 1938 UNITED STATES PATENT OFFQE METHOD AND APPARATUS FOR THE PRO- DUCTIGN OF FISE-RS Application July 1, 1936, Serial No. 88,429 In Germany November 28, 1934 This invention relates to the production of a continuous fiber band of artificial filaments by the electric splitting up or shattering of a stream of a solution or dispersion of filament forming material, and, will hereinafter, for convenience, be referred to as electrical spinning of fibers. More particularly the invention relates to an improved process and apparatus for the electric spinning of fibers between electrodes, one of which moves relative to the other and upon one of which the fibers are collected in the form of a continuous coherent fiber band, or sliver.
Reference is made to the applicants copending Claims.
y application, Serial No. 88,428, filed July 1, 1936,
relating to a new article of manufacture.
In accordance with the electrical spinning of fibers as disclosed in the U. S. Letters Patent to Formhals No. 1,975,504 of October 2, 1934, a spinning solution is introduced between a stationary electrode, in the form of a serrated Wheel immersed in the spinning solution, and an oppositely charged movable electrode which may bein the form of a revolving wheel, ring, belt, bobbin or drum. The high electric tension between the electrodes causes dispersion or shattering of the spinning solution into a plurality of fine filaments or fibers which are attracted to the movable electrode and temporarily collected thereon.
'I'he method and apparatus disclosed by the above said patent has certain limitations and disadvantages as regards the usable form in which the fibers are collected, and also as re gards the quantity of fibers produced at any one time.
In the method described hereinabove one encounters trouble with the spun fibers adhering to the surfaces of the moving collecting belts, drums, wheels, and the like, thereby making it difiicult or impossible to remove them satisfactorily in the form of a continuous compact bundle without their damage. Likewise, and especially when it is desired to spin a large mass of fibers as to yield a commercial self-sustaining sliver for direct processing into threads or yarns of good quality, it is found that the fibers themselves tend to be so stuck to one another as to prevent their free separation and drawing out in the subsequent textile spinning operation. This stick ing together becomes increasingly bothersome with average ber diameters of several denier per filament and upwards. Furthermore, these` sticking phenomena have served to greatly limit the number of spinning jets or streams which may be used with a single given collecting electrode.
In addition to the above recited disadvantages the prior art collecting devices are open to the further objections that they have not served to collect the fibers at once into a compact coherent form with the fibers arranged substantially parallel to each other. The moving ciectrodes have heretofore exhibited plane or curved continuous surfaces. The entire surface area of these electrodes was charged electrically and the charge became uniformly distributed thereover. Thus the fibers tended to collect and distribute themselves more or less at random all over` these surfaces, rather than to concentrate noticeably in any particular fashion. A compact organization of the fibers in good parallelism on the collector has not been heretofore achieved. While special devices were suggested to assemble the spun fiber masses from the previous collectors in a compact organized form, these devices have damaged the filaments in the process of loosening them from the continuous surface of the collector and at the same time have tended to cause entanglement thereof.
The fiber masses heretofore produced have thus been relatively disorganized, weak, tangled, and badly stuck together, which faults have prevented them from being directly processed into spun threads or yarns of good strength and quality without intermediate textile operations such as opening, carding, combing and the like.
It is the object of the present invention to overcome the above and other limitations, and to yield an artificial fibrous band or sliver capable of being commercially processed to a strong twisted thread, yarn and the like, without intermediate textile operations intervening between the electrical spinning of the sliver and thread spinning operation.
Another object of this invention is to produce a fiber band in which a high degree of parallelism exists between the individual fibers. A further object of the invention pertains to the production, by an electrical spinning process, of a large quantity of fibers, in a continuous, compact, coherent form, while permitting rapid drying of the fibers, eliminating substantial adherence of the fibers not only to each other but to the electrode collecting device as well, and permitting an easy removal of the fiber band from the collecting device without damage to the fibers or the parallel construction of the fiber band. It is a further object of the invention to produce a parallel, con herent fiber band which will be easy to draw,
CAI
that is, one in which the individual filaments are relatively disentangled and are free to slide or move relative to other without substantial damage.
Other objects of the invention will appear hereinafter.
rThe objects of invention may be accomplished ccording to one embodiment thereof by delivering a Spinnin.cr solution from a plurality of nozzles connected to a feed pipe, said nozzles delivering streams spinning solution into a high potential electrical neld created between the nozzles and a moving collecting device, thereby causing said streams to shatter or disperse into a plurality of fibers, collecting the thus formed fibers on a moving` eollectincr device which constitutes one pole cf vthe held, the collecting device being ovided with projecting elements or prongs substantially separated from each other and acting as successive individual electrodes which receive the fibers support them` substantially parallel and in the form of a continuous fiber band at or near the points of said electrodes, the space between the prongs permitting rapid evaporation of the solvent in the fibers and making possible the easy removal of the continuous fiber band from the electrodes by means of any suitable device, such for example, stripping device described below, after which it be wound onto reels and the like. lThe fibers are furthermore arranged in generally the same direction permitting the building up of an organized bundle or sliver ci substantial dimensions which can be continuously removed from the collector. The threads, due to the large amount of air or other gaseous drying agent coming in contact therewith from all sides, out thoroughly and do not adhere to each other to any substantial extent, even though the quantity of ber spun is large, per unit of time, in comparison with previously known spinning methods.
The stripping device which permits a continuous removal of the formed sliver from the collector generally comprises a disc provided on its circumference with iinger-like or lobe-like projections which are adapted to mesh with the electrode prongs on the collector in such a way that the fingers or lobe-like projections of the disc are inserted in the spaces of the belt between the prongs and close to the belt and upon revolution of the disc the lobes move farther and farther away from the belt to the extremities of the prong-like electrodes thereby stripping the sliver from the collector, so that the electrodes of the collecting device upon being moved again under the nozzles, are ready to receive another mass or bundle of fibers.
For a further understanding of the invention, reference is made to the following detailed descrption taken in connection with the accompanying drawing of one specific embodiment of the invention in which:
Figure l. is a diagrammatic perspective view of a continuous belt-electrode collector.
Figure 2 an end elevational view showing one form of stripping disc.
Figure 3 is an end vdew of the endless belt collector and stripping disc.
Referring to the drawing, a plurality of metal nozzles l are connecten with a pipe il which may or not be metal, and are supplied with spinning solution from the storage tank i2. The nozzles and pipe are electically connected in circuit with a device it for producing high potential electric current. Device iii may be a transformer and rotary converter for changing ordinary line current such as 110 volt, 60 cycle alternating electric current into a high voltage pulsating direct current or i3 may be any suitable device for producing a high potential direct current. For obtaining special effects in the shattering of a stream of spinning solution, I3 may be a suitable device for producing an alternating current of high potential o1' any desired or varying frequency. Spaced from the nozzles is a long endless belt iti preferably comprising rubber or other suitable non-conductive material, although an electrically conducting material such as a metal be used. The belt is provided with spaced metal prongs or lugs l5 which are fastened to the belt so as to project from at least one side thereof. rEhe lugs l5 are disposed substantially witlr'n the plane of the belt with the projecting ends extending perpendicularly from the side of the said belt. The proiecting portions or ends of the lugs are preferably pointed as shown. These lugs constitute the individual electrodes to which the bers are attracted and which serve to support the fiber band at intervals. It is to be understood, however, that the individual prongs may be electrically connected with each other, in which case electric charge will nevertheless be accumulated on the individual prongs. The belt is driven by pulleys i0 and il which are preferably composed of wood or some other suitably electrically non-conducting material. Positioned parallel to the under surface of the belt is shown a long conductor wireA l0 attached by means of a conductor lil to the circuit which includes the high potential source i3. Conductor l0 is spaced from the belt, the electrodes l5 receiving a charge from the wire it through the air gap therebetween. The potential between the nozzles and the electrodes i5 is maintained between 10,000 up to l00,000 volts and preferably at least 30,000 volts.
The high potential electric charge on the electrodes l5 is of opposite polarity to that imparted to the spinning solution and is preferably lower in potential than that imparted to the said s0- lution so as to prevent undesirable flying about of bers due to a repelling action of said electrodes. It is furthermore possible to spin with the electrodes l5 grounded so that they are at zero potential, and it is to be understood that such type of apparatus is intended to be ineluded within the broad scope of the invention.
A potential stabilizing and directing means such as a concavely curved screen or other wire network is preferably positioned in back of the nozzles i0 and is connected to a charge of high potential electricity of the same polarity as the potential imparted to the spinning solution. The directing means serves primarily to direct the bers toward the prongs and in addition ser es repel any fibers toward the belt from which occasional fibers sometimes tend to fly back to the spinning nozzles.
The fibers, during the spinning operation, are attracted to and electrostatically adhere to the electrode prongs i5 and travel with the belt supported by the prongs. The bers form a sliver which is preferably removed continuously at one end of the belt collector by means of a stripping device 20 mounted on a shaft 2i the axis of which is inclined towards the axis of the shaft of pulley il, so that the lobes of the disc move outwardly as the disc revolves thereby scraping off rprojecting ends thereof. the fibers will usually collect in the form of a continuous band at the tips of the said projecting ends and thereby leave room between the ends of the prongs and the belt for insertion of the lobes of the stripping device 20.
It is not necessary for the electrodes I5 to be connected with each other in apparatus of the type shown in Figure l, since they individually act as electrodes and acquire a charge from the spaced elongated conductor I8 whether they are connected together or not.
The present invention is advantageously applied to the spinning of solutions of cellulose acetate in organic solvents, for example of cellulose acetate in acetone. Spinning solutions containing ydifferent solvents behave differently when spun in accordance with the present invention. 'I'he use of certain solvents in the spinning solution will cause a. greater' or lesser shattering of the stream of liquid than others, and some solutions will require a higher potential than others for the satisfactory breaking up of the stream and formation of fibers. Other cellulose derivative solutions may also be spun in the same way, for example solutions of cellulose ethers such as ethyl cellulose and benzyl cellulose. Generally, solutions of resins and other materials which can be formed into fibers may be spun according to the present invention.
Example A solution consisting of 200 grams commercial cellulose acetate, 700 grams acetone and 400 grams mono methyl ether of ethylene glycol is forced through single hole nozzles the orifice di ameter of which is approximately .0180. A potential difference of approximately 57,000 volts is maintained between the nozzle and the conductor wire I8 as illustrated in the drawing. The voltage is obtained from a source supplying pulsating direct current. The streams of cellulose acetate solution are split under the iniiuence of the high potential field into numerous fine fila ments which are deposited and then carried away supported by the prongs attached to the moving belt at or near the points thereof. The streams of solution and the fibers therefrom are properly directed to the prongs by means of the high potential between the nozzles and the prongs which electric field `is suitably modified and shaped by means of the screen positioned in back of the nozzles said screen possessing an electrical charge of the same polarity as that of the nozzles. During the splitting of the stream of solution and deposition of the fibers the solvent evaporai: i the fibers quickly drying as carried .y from the spinning zone. The fibers are thus oriented in a position substantially parallel to the direction of travel of the belt and due to their rapid drying adhere neither to the collecting device nor to one another to any objectionable gree. The continuous sliver or ber thus formed is removed by the s ripping device and deposited in a suitable container or wound on a reel. The fibers in the fiber band at this point are sufficiently loose and free, of one another, and lie substantially parallel in a compact sliver as to permit said sliver to be directly drawn and twisted into threads or yarns of good quality and strength. Prior to vdrafting and twisting, the sliver may-be preferably treated with a suitable textile finish in a manner similar to the treatment of wool rovings to facilitate ease and smoothness of drafting. The sliver treated with a suitable textile finish is drawn and/or twisted to yield a yarn of any weight desired.
The sliver as formed by this process possesses outstanding properties as regards the relative freedom from sticking together of the individual fibers, due to the fact that the fiber band collects at, and is supported as such by the points or near the peints of the electrodes, thus permitting free access, from all sides, of the air to the freshly spun fibers, assisting in drying. Previous devices have been continuous fiat or curved surfaces, to which the fibers could stick, and which would permit drying out of the fiber from one side only, thus decreasing the rate of solvent evaporation and causing sticking together of the mass. Compactness of sliver is achieved as it is formed due to the fact that the electrical charge on the DTODSS f the COHeCiDg device tends to be more concentrated at the tips or points and thus attracts the fibers to these points, thereby concentrating and organizing them at once into a narrow band suspended from the points, thus yield ing a coherent sliver easily removed and substantially free from entanglement both as -laid down and as removed from the electrodes. Fur thermore, the coinpactness of fiber band is accompanied by an improved and excellent parallelism of the individual fibers. This feature not only adds strength to the fiber band, but taken together with the freeness of the individual fibers, is particularly important when the sliver band is later processed into threads as by drawing or twisting equipment.
With the fiber band or sliver of the instant invention it is thus possible to dispense with the usual combing or carding operations, thereby greatly simplifying and cheapening manufacture of the final twisted threads or yarns. The desirable construction of my sliver also tends toward smoothness of operation in drawing and/ or twisting as well as toward good uniformity in the final yarn.
It is preferred that the electrode-collector be a continuous belt with prongs, but it will be understood that it may also be a wheel or other device provided in a similar fashion with electrode prongs around its circumference, which prongs are adapted to mesh with a suitable means for removing the fiber band from the wheel-collector. If desired suitably positioned air jets may be used t0 remove the fiber band, or may be used in conjunction with various mechanical devices in removing the sliver from the collecting electrode.
The moving collecting device, on which the fibers are collected in a continuous sliver, may be driven at any desired speed to obtain varying effects. However, when it is desired to collect the fibers in a compact, coherent fiber band in which the fibers are arranged substantially parallel to each other which fiber band may be directly drawn and twisted into a yarn or thread, it is essential that the linear speed of the collecting device is at least as high, and preferably slightly higher, than the speed of the freshly formed fibers in their travel toward the collecting device.
The size of the sliver delivered from the machine may be regulated by a number of factors either singly or in suitable combination with each other. The chief factors include the number of spinning nozzles in operation at any one time, the volume of solution delivered by the nozzles per unit time, the concentration of solids in the spinning solution and the speed of the collecting device. With the type of equipment here described, one may choose the number of nozzles, speed of collecting device, etc, so as to yield a wide range of sizes of the sliver band to be removed by the stripping device, without damage or rupture. I have found that a convenient size sliver weighs between 0.1 gram and 0.25 gram per meter length. Slivers either much larger or somewhat smaller may be produced as desired. While slivers of quite large size may be produced by using an even larger number of nozzles and a longer belt, there is a lower limit to the size of the sliver as determined by the fact that it must be sufciently coherent to permit winding, unwinding and handling. This means that the rate of deposition of fibers on the collecting device must be such that for each revolution of the belt (or 1/2 revolution when two stripping devices and two rows of nozzles are used) there is formed a sliver of sufficient weight to be coherent for the purposes of winding and handling without breaking. I thus use a plurality of nozzles with one collecting device. The number may vary from l or 20 to upwards of several hundred, or even more per collecting device.
The sliver, in addition to possessing good, coherent, uniform and parallel construction, contains filaments of good strength. When cellulose acetate is used as the lament forming material, I have obtained threads after drawing and twisting showing good strength comparable to that of wool yarns. Another desirable property of my sliver is its long staple as compared to the staple of cotton and the shorter staple Wools. I may vary my average staple length from 2 or 3 inches up to 12 inches or even higher. The somewhat longer staple is advantageous for most purposes because of the added strength that results in the twisted yarn thereby. Natural fibers such as cotton and wool are limited in staple length by the nature of their source.
While I may spin lustrous fibers, I am not limited thereby, but may introduce into the spinning solution suitable delustering agents, such as pigments, oils, organic solids, and other materials known and used in the art to achieve delustered, semi-lustrous, and other effects. Likewise, I may spin dyed filaments by introducing suitable dyes or other coloring matters into the spinning solution.
I may exercise control over the average lament diameter and produce fibers as small as one denier per iilament or even smaller, or I may produce relatively coarse laments of 3, 5, l0 or even greater average denier per lament. This is accomplished by varying the solids content and/ or viscosity of my spinning solution, and will also be influenced to a certain extent by the voltage potential employed, and size of the nozzle orice. In general, a fine filament sliver will be produced with the lower solids and/ or viscosities, the higher voltages, and the smaller nozzle orifices. Heavier laments, in general, go with higher solids, and/or viscosities, lower voltages, and larger nozzle oriiices. These and other factors may influence the filament size as well as the lament length. I thus have considerable latitude in the choice of conditions to produce slivers of greatly varying properties according to the use to which I put the material.
Coarse, harsh fibers, for instance, may be used for mixture with coarse animal fibers, such as mohair, or may be used alone as substitute materials. The fine soft bers lend themselves to use in fabrics for dress goods, where a light soft feel is desired, or they may be mixed with the finer grades of wool, camels hair, etc. A wide range of uses is thus comprehended for this new Vtextile material.
My fibers are to be distinguished from other articially produced fibers such as rayon from regenerated cellulose, cellulose acetate, etc. as well as from rayon staple fiber, which is produced by chopping up continuous ropes of continuous viscose ber, cellulose acetate and other bers, in that the individual liber structure of my sliver is heterogeneous. A sample of ber from any of the conventional articial silk (or staple) spinning processes is comparatively uniform both longitudinally and laterally and the denier of the individual filaments along their length is quite constant. Indeed, the nature of the processes by which they are produced is such as to yield substantially uniform filament materials and I call these materials relatively homogeneous. That is to say, an individual fiber is substantially uniform throughout its length and cross section, and different bers from the same mass correspond closely with one another.
In the case of my fibers, however, there a marked degree of heterogeneity as evidenced by a microscopic examination either along the fiber aires or in cross section. I may control the statistical average iilament diameter and length of the fibers constituting the sliver it being unnecessary to control closely the iilamcnt diameter and length of each and every ber. I will thus have in the sliver fibers of somewhat larger and smaller diameter than the statistical average diameter as well as fibers both somewhat longer and shorter than the average length. Furthermore, the individual fibers of my process are non-uniform in the direction of their ber axis and tend to show various degrees of natural crinkle and crimp. Many are twisted along this axis, some have small nodules, a few are even forked, and still other types of irregularities are present. Furthermore, the fiber diameter and cross sectional shape of single fiber will usually vary from one end of the fiber to the other. While many of these properties heretofore have never characterized articially produced iibers, and have even been regarded as detrimental were they to be accidentally encountered, they constitute new and useful properties with my product and give rise to new and novel fabric effects which can be achieved with my invention. This heterogeneity is particularly useful when I come to draw and/or twist thread or yarn from my sliver, in that the fibers possess a cling or a sort of woolliness which is very dcsirable in building up a good yarn, or ior mixing with natural. staples. For instance, cellulose acetate staple fiber produced by chopping up a multilament rope made for example in accordance with conventional cellulose acetate spinning processes has certain decient properties as a staple, due partly to the fact that all the laments are straight, possess an insignificant crimp or crinkle and in addition are quite smooth, sleek and regular. Cellulose acetate bers from my process, however, due to their heterogeneous nature overcome this difficulty and serve admirably to twist together to form threads resembling wool in many respects. They are likewise admirably adapted to mixture with wool.
It will be thus apparent that my fiber band or sliver is of new and novel construction. The individual fibers of my product are heterogeneous as compared to the homogeneous character of previous artificially produced staple fibers. Furthermore, the fibers of the instant invention arc already built, constructed, and organized into a coherent, compact, free drawing ber band showing a high degree of parallelism, which sliver may be processed at once into twisted yarns. Arti* ficial staple masses heretofore produced cutting or chopping continuous filaments to required staple length, are in a completely disorganized condition so as to require all the usual preparatory operations of opening, carding, combing, etc. for the formation of slivers or rovings.
My present electrically spun sliver is furthermore a distinct advance over previous electric spun fiber masses which were produced with insufficient compactness, parallelism, and free drawing properties to permit their direct successful spinning into yarns or threads.
In view of the fact that the invention is susceptible to considerable modification, any change to the description given above which conforms to the spirit of the invention is intended to be included within the scope of the claims.
What is claimed is:
1. In an apparatus for the electrical spinning of fibers, a nozzle, a continuously movable supporting means spaced from said nozzle, a plu rality of elements spaced from each other projecting from said means, and means for maintaining a high electric potential between said elements and said nozzle.
2. In an apparatus for the electrical spinning of fibers, a nozzle, means for imparting an electrical charge of high potential to said nozzle, a continuously movable supporting means spaced from said nozzle, a plurality of elements fixed to said supporting means, said elements spaced from each other and provided with ends projecting from said supporting means, means for imparting to the ends of said elements an electrical charge g of high potential of opposite polarity to the charge on said nozzle.
3. In an apparatus for the electrical spinning of fibers, a nozzle, means for imparting an electrical charge of high potential to said nozzle, a continuously movable supporting means spaced from said nozzle, a plurality of elements fixed to said supporting means, said elements spaced from each other, means for imparting to said elements an electrical charge of high potential of opposite polarity to the charge on said nozzle.
4. In an apparatus for the electrical spinning of fibers, a nozzle, means for imparting an electrical charge of high potential to said nozzle, a continuously movable supporting means spaced from said nozzle, a plurality of elements fixed to said supporting means, said elements spaced from each other and provided with ends projecting from said supporting means, means for imparting to the ends of said elements an electrical charge of high potential of opposite polarity to the charge on said nozzle, and means for continuously removing fibers collected on said elements.
5. In an apparatus for the electrical spinning of fibers, a nozzle, means for imparting an electrical charge of high potential to said nozzle, a continuously movable supporting means spaced from said nozzle, a plurality of elements fixed to said supporting means, said elements spaced from each other, means for imparting to said elements an electrical charge of high potential of opposite polarity to the charge on said nozzle, and means for continuously removing fibers collected on said elements.
5. In an apparatus for the electrical spinning fibers, a nozzle, means fc' imparting an electrical charge of high potel to said nozzle, a continuously movable supporting means spaced m said nozzle, a plurality of elements fixed to said supporting means, elements spaced from each other, means for imparting to said elements an electrical charge of high potential of opposite polarity to the charge on said nozzle, and means cooperatively connected to said elements for continuously removing fibers collected on said elements.
7. In an apparatus for the electrical spinning of fibers, a nozzle, means for imparting an elece trical charge of high potential to said nozzle, a continuously movable supporting means spaced from said nozzle, a plurality of elements fixed to said supporting means, said elements spaced from each other, means for imparting to said elements an electrical charge of high potential of opposite polarity to the charge on said nozzle, and means meshing with said elements for continuously removing fibers collected on said elements.
8. In a method for the electrical spinning of fibers, the steps comprising electrically dispersing a stream of spinning solution into fibers, collecting said electrically dispersed fibers in the form of a sliver and moving said sliver through the surrounding atmosphere until substantially dry, said sliver, during said collecting and drying thereof, being at all times supported in such a manner as to be completely surrounded by the atmosphere substantially along the length there" of whereby to prevent objectionable adherence of the iibers to each other, continuously removing said sliver from the drying atmosphere and winding it in the form of a package.
9. In a method for t.e electrical spinning of fibers, the steps comprising electrically dispersing a stream of spinning solution into fibers, collecting said electrically dispersed bers in the form of a sliver, drying said sliver during the forming and collecting thereof by suspending the saine at spaced portions thereof in such manner as to be completely surrounded by the atmosphere substantially along the length thereof during said collecting and drying thereof whereby to obtain a substantially dry, compact, coherent sliver in which the individual fibers are substantially free from each other and continuously removing said sliver from the drying atmosphere and winding it in the form of a package.
10. In a method for the electrical spinning of fibers, the steps comprising electrically dispersing a stream of spinning solution into fibers, collecting said electrically dispersed fibers in the form of a sliver and drying said sliver during the forming and collecting thereof by moving the sliver, suspended at spaced portions thereof in such. a manner as to be completely surrounded by the atmosphere substantially along the length thereof during said collecting and drying thereof, con:- tinuously removing said sliver and treating the same with a finishing composition prior to any drawing or twisting thereof.
l1. In an apparatus for the electrical spinning of fibers, a nozzle, a continuously movable supporting means spaced from said nozzle, said sup- CII porting means being constructed in such a manner as to permit fibers collected thereon to be surrounded by the atmosphere substantially along length of the supporting means, and means or maintaining a high electrical potential be- 12. In an apparatus for the electrical spinning of ibers, means for forming a stream of spinning soluticn, a continuously movable supporting means spaced from said means, a plurality of spaced elements on said supporting means, electrical means connected relative to said stream of solution and said spaced elements to maintain a high electrical potential therebetween whereby to electrically disperse said stream of spinning solution to bers and collect the bers on said elements in the form of a compact coherent sliver in which the individual fibers are substantially free from each other.
13. In an apparatus for the electrical spinning of bers, a nozzle for forming a stream of spinning solution, means for imparting to said stream of spinning solution an electrical charge of high potential, a continuously movable supporting means spaced from said nozzle, a plurality of elements fixed to said supporting means, said elements spaced from each other, means for imparting to said elements an electrical charge of high potential of opposite polarity to the charge on said stream of spinning solution.
ANTON FORMHALS.
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US2437264A (en) * 1944-09-18 1948-03-09 Fred W Manning Magazine spinning gun for the production of filaments and fabrics
US2483404A (en) * 1941-08-01 1949-10-04 American Viscose Corp Process of making a fibrous product
US4157236A (en) * 1977-02-28 1979-06-05 Beloit Corporation Electrostatic dry former
US4689186A (en) * 1978-10-10 1987-08-25 Imperial Chemical Industries Plc Production of electrostatically spun products
US5102738A (en) * 1990-11-01 1992-04-07 Kimberly-Clark Corporation High hydrohead fibrous porous web with improved retentive absorption and acquision rate
US5112690A (en) * 1990-11-01 1992-05-12 Kimberly-Clark Corporation Low hydrohead fibrous porous web with improved retentive wettability
US5227172A (en) * 1991-05-14 1993-07-13 Exxon Chemical Patents Inc. Charged collector apparatus for the production of meltblown electrets
US6616435B2 (en) * 2000-12-22 2003-09-09 Korea Institute Of Science And Technology Apparatus of polymer web by electrospinning process
US20050048274A1 (en) * 2003-08-26 2005-03-03 Rabolt John F. Production of nanowebs by an electrostatic spinning apparatus and method
EP1716274A1 (en) * 2004-02-02 2006-11-02 Kim, Hag-Yong A process of preparing continuous filament composed of nanofibers
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US20080241297A1 (en) * 2007-03-27 2008-10-02 Jong-Chul Park Electric spinning apparatus for mass-production of nano-fiber
US20090061225A1 (en) * 1999-03-08 2009-03-05 The Procter & Gamble Company Starch fiber
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US2483404A (en) * 1941-08-01 1949-10-04 American Viscose Corp Process of making a fibrous product
US2437264A (en) * 1944-09-18 1948-03-09 Fred W Manning Magazine spinning gun for the production of filaments and fabrics
US4157236A (en) * 1977-02-28 1979-06-05 Beloit Corporation Electrostatic dry former
US4689186A (en) * 1978-10-10 1987-08-25 Imperial Chemical Industries Plc Production of electrostatically spun products
US5102738A (en) * 1990-11-01 1992-04-07 Kimberly-Clark Corporation High hydrohead fibrous porous web with improved retentive absorption and acquision rate
US5112690A (en) * 1990-11-01 1992-05-12 Kimberly-Clark Corporation Low hydrohead fibrous porous web with improved retentive wettability
US5227172A (en) * 1991-05-14 1993-07-13 Exxon Chemical Patents Inc. Charged collector apparatus for the production of meltblown electrets
US20090061225A1 (en) * 1999-03-08 2009-03-05 The Procter & Gamble Company Starch fiber
US8168003B2 (en) 1999-03-08 2012-05-01 The Procter & Gamble Company Fiber comprising starch and a surfactant
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US20110177335A1 (en) * 1999-03-08 2011-07-21 The Procter & Gamble Company Fiber comprising starch and a surfactant
US9458556B2 (en) 1999-03-08 2016-10-04 The Procter & Gamble Company Fiber comprising polyvinylpyrrolidone
US7666261B2 (en) 1999-03-08 2010-02-23 The Procter & Gamble Company Melt processable starch compositions
US7938908B2 (en) 1999-03-08 2011-05-10 The Procter & Gamble Company Fiber comprising unmodified and/or modified starch and a crosslinking agent
US8764904B2 (en) 1999-03-08 2014-07-01 The Procter & Gamble Company Fiber comprising starch and a high polymer
US20090124729A1 (en) * 1999-03-08 2009-05-14 The Procter & Gamble Company Melt processable starch compositions
KR100406981B1 (en) * 2000-12-22 2003-11-28 한국과학기술연구원 Apparatus of Polymer Web by Electrospinning Process and Fabrication Method Therefor
US6616435B2 (en) * 2000-12-22 2003-09-09 Korea Institute Of Science And Technology Apparatus of polymer web by electrospinning process
US20050048274A1 (en) * 2003-08-26 2005-03-03 Rabolt John F. Production of nanowebs by an electrostatic spinning apparatus and method
EP1716274A4 (en) * 2004-02-02 2008-12-10 Kim Hag Yong A process of preparing continuous filament composed of nanofibers
EP1716274A1 (en) * 2004-02-02 2006-11-02 Kim, Hag-Yong A process of preparing continuous filament composed of nanofibers
EP1809794A4 (en) * 2004-11-12 2008-11-05 Hak-Yong Kim A process of preparing continuos filament composed of nano fibers
EP1809794A1 (en) * 2004-11-12 2007-07-25 Hak-Yong Kim A process of preparing continuos filament composed of nano fibers
US20090224437A1 (en) * 2005-12-12 2009-09-10 Mitsuhiro Fukuoka Electrostatic spray apparatus and method of electrostatic spray
US7980838B2 (en) * 2007-03-27 2011-07-19 Finetex Ene, Inc. Electric spinning apparatus for mass-production of nano-fiber
US20080241297A1 (en) * 2007-03-27 2008-10-02 Jong-Chul Park Electric spinning apparatus for mass-production of nano-fiber
WO2009049564A3 (en) * 2007-10-18 2010-02-25 Nanopeutics S.R.O. Collecting electrode of the device for production of nanofibres through electrostatic spinning of polymer matrices, and device comprising this collecting electrode
WO2009049564A2 (en) * 2007-10-18 2009-04-23 Nanopeutics S.R.O. Collecting electrode of the device for production of nanofibres through electrostatic spinning of polymer matrices, and device comprising this collecting electrode
US20100028674A1 (en) * 2008-07-31 2010-02-04 Fredrick O Ochanda Nanofibers And Methods For Making The Same
US20120322154A1 (en) * 2011-06-15 2012-12-20 Korea Institute Of Machinery & Materials Apparatus and method for manufacturing cell culture scaffold
US9126366B2 (en) * 2011-06-15 2015-09-08 Korea Institute Of Machinery & Materials Apparatus and method for manufacturing cell culture scaffold
US11090850B2 (en) * 2013-09-18 2021-08-17 Oxford University Innovation Limited Electrospun filaments
US20150345048A1 (en) * 2014-05-28 2015-12-03 University Of Georgia Research Foundation, Inc. Magnetospinning apparatus and methods of use
US11890384B2 (en) 2016-02-12 2024-02-06 Tricol Biomedical, Inc. Chitosan superfine fiber systems
US11105017B2 (en) * 2017-01-18 2021-08-31 Kabushiki Kaisha Toshiba Fiber manufacturing apparatus and fiber manufacturing method
US11427935B2 (en) * 2020-12-01 2022-08-30 Taipei Medical University Passive intermittent rotating assembly and electrospinning equipment
US20220372659A1 (en) * 2021-05-19 2022-11-24 Panasonic Intellectual Property Management Co., Ltd. Device and method for manufacturing fiber assembly
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