US2917806A - Method for crimping acrylonitrile polymer fibers - Google Patents

Method for crimping acrylonitrile polymer fibers Download PDF

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US2917806A
US2917806A US663693A US66369357A US2917806A US 2917806 A US2917806 A US 2917806A US 663693 A US663693 A US 663693A US 66369357 A US66369357 A US 66369357A US 2917806 A US2917806 A US 2917806A
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aquagel
crimped
fibers
crimp
crimping
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US663693A
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Thomas C Spence
Robert B Funk
Harry N Woessner
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Dow Chemical Co
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Dow Chemical Co
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Priority to BE568354D priority Critical patent/BE568354A/xx
Priority to NL228434D priority patent/NL228434A/xx
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Priority to FR1208314D priority patent/FR1208314A/fr
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    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G1/00—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
    • D02G1/12—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics using stuffer boxes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent

Definitions

  • This invention has reference to an improved method for crimping fibers, filaments and the like or related shaped articles that consist of and are fabricated from acrylonitrile polymers including, in particular, those that consist entirely of or are based essentially upon polymers that contain at least about 85 percent by weight of acrylonitrile polymerized in their molecules.
  • the invention is especially concerned with an effective method for imparting permanent crimp to acrylonitrile polymer fibers while they are in an aquagel condition. It is primarily intended for practice with fibers and filaments of acrylonitrile polymers that are capable of assuming such a water-swollen or hydrated structure during their prepa ration and which are processed and handled in such form during their manufacture.
  • acrylonitrile polymer fibers are crimped after they have been dried and, usually, while they are already in a permanently heat-set form. While it is known to attempt to directly impart crimp to fibers while they are in such a relatively stable condition, it is a widespread and generally more beneficial practice to crimp the dried fibers while they are in a temporarily swollen or plastified condition. In this way, the fibers are more amenable to assuming the desired alteration of their physical contour.
  • a suitable and appropriate deforming or crimp-effecting force or means (that usually causes the individual strands of filamentary material to adopt a relatively zig-zag or sinusoidal pattern) is applied while the fibers are under some plastifying influence that tends to diminish their natural resilience and render them more pliable to physical distortion. Dry heat, steam and various solvents and swelling agents have been utilized to exert and achieve the transient plastifying influence and effect.
  • the deforming means is held or maintained on the fibers that are being crimped until they are atent 0 ice 2,911,806 Patented freed or removed from the plas'tifying influence to which they have been temporarily subjected during theoperation.
  • the fibers are not permitted to be released from the distorted condition to which they have been converted until the plastifying influence has been removed.
  • acrylonitrile polymer fibers may advantageously be crimped during their manufacture in which and while they are in an aquagel form and contain an amount of water in the aquagel structure that is at least about equal in weight to the quantity of water-swollen polymer that is in the hydrated structure by a method which comprises applying a closely controlled deforming or crimp-effecting force to the strandular aquagel structure for a very short (almost instantaneous) period of time to impose a zig-zag or serrate crimp pattern in the aquagel fibers; then transferring the so-distorted aquagel fibers in the therebyimposed crimp pattern that they have assumed while they are in a completely unrestrained condition and substantially free from physical extending influences to a drying means; and, finally, drying and dehydrating the crimped aquagel fibers while they are maintained in a completely unrestrained and free-to-shrink condition so as to destroy the aquagel structure and convert it to a utile, crimped and heat
  • Aquagel structures in which the Water to polymer ratio is as high as2.5 :1 may be satisfactorily processed and crimped in the process of the invention.
  • the aquagel structure may be derived by the extrusion into and coagulation in an aqueous spin bath of a solution of the acrylonitrile polymer that is dissolved in an aqueous saline solvent therefor, such as an aqueous 60 percent by weight zinc chloride solution.
  • the acrylonitrile polymer fibers that are crimped in the practice of the invention may be the usual homopolymer or copolymer compositions that are adapted to provide the variety of filamentary products that are conventionally referred to as being acrylic fibers.
  • the basic acrylonitrile polymer composition may contain or have other beneficial additament ingredients incorporated therein. These may be the typical pigments, delusterants, textile assistants and the like or they may be dye-assisting adjuvant materials.
  • minor proportions of certain dye-receptive vinyl lactam polymers, such as polyvinylpyrrolidone may be incorporated in a polyacrylonitrile or other acrylonitrile polymer aquagel fiber that is to be crimped in accordance with the method of the present invention. It is generally preferred for purposes of terminological classification to characterize the latter, highly advantageous variety of dye-receptive fibers as being nitrile alloy fibers in order to clearly distinguish them from the conventional prototype acrylic fibers that were first known to the art.
  • any of the known crimp-effecting means and contrivances that are commonly employed for the purpose may be utilized to provide the deforming force upon the fibers in the practice of the invention.
  • the conventional stufiing box variety of crimping apparatus may be utilized as may gear crimpers, serrated belt crimpers and the like or equivalent devices. Regardless of the mechanism that is used, however, it is essential that the deforming force that is applied to effect the crimp pattern in the aquagel fiber be between about 50 and 1,000 pounds per square inch of fiber cross-section and that its application during the physical crimp-inducing distortion of the fibers persist for a period of time that is no longer than about five seconds.
  • the deforming force It is generally of greatest advantage for the deforming force to be maintained in a range that does not exceed about 250 pounds per square inch. If the minimum crimp-inducing force is not employed, there is great likelihood that an inadequately crimped product will be obtained. If the maximum force indi cated is exceeded, it is quite probable that the crimped product will exhibit undesirable irregularity in the crimp cycle and contain a large proportion of extremely sharp and distorted bends. The fiber structure in the area of such severe bends may be physically disrupted and the overcrimped product may exhibit such a reduction in: tensile strength and like diminution of other properties as to become relatively undesirable. Likewise, excessive residence times under the influence of the aquagel deform force may damage the fiber even when the crimp pattern is induced in the fiber within the mentioned range of pressures.
  • the crimping device must not be operated in such a manner as would permit it to exert the much greater crimping forces that are usual in the conventional techniques relied upon for crimping dried or merely plastified but already heat-set fibers.
  • crimping forces as great as 10,000 to 30,000 pounds or more per square inch of fiber cross-section are encountered.
  • These ponderous forces must be assidously avoided in the practice of the present crimping method on aquagel fibers.
  • Flat tows generally facilitate the most efiicient and uniform application of the crimp-inducing deforming force by any of the varieties of crimping ap paratus that may be employed.
  • fiat tow bundles which are comprised of individual aquagel filaments that will have ultimate dried sizes up to about 15 denier
  • the average thickness of the tow is preferable for the average thickness of the tow to be from about ten to forty thousandths of an inch. While its width may vary with the plurality of filaments in the tow, it is usually better for it to be at least about half an inch or so wide. Tows in widths up to four or more inches may be handled with ease.
  • the crimping apparatus that is employed in the practice of the invention is an improved. and especially adapted modification of a stutfing box type of crimper which is in general accordance with that which has been disclosed by Thomas C. Spence and Robert B. Funk in their copending application for United States Letters Patent covering Crimping Fibers and having Serial Number 663,764, which was concurrently filed on June 5, 1957.
  • a stutfing box type of crimper which is in general accordance with that which has been disclosed by Thomas C. Spence and Robert B. Funk in their copending application for United States Letters Patent covering Crimping Fibers and having Serial Number 663,764, which was concurrently filed on June 5, 1957.
  • preferably flat tow bundle of filaments is passed between the bight of an opposed pair of driven nip or feed rollers which discharge and force them into a crimping zone which is defined by and confined within a stufling box of peculiar and highly effective arrangement.
  • the feed rolls of the apparatus are devised and operated to exert only a minimum conveying force on the aquagel filament bundle so as to continuously advance the tow into the stufiing box without tending to crush or deleteriously compress the tender aquagel filaments being handled.
  • the spacing between the opposed filament conveying roll surfaces to exert such a controlled bight should be in the neighborhood of about -90 percent of the average thickness of the fiat aquagel tow.
  • the feed rolls are set with a bight clearance or spacing, proportional to the thickness of the tow, of from about eight to thirty six thousands of an inch.
  • a bight effected in this manner is generally found to be on the order of only about one-tenth or, more frequently, as little as only onehundredth, or so of the compressive force that is exerted by feed rolls in conventional stufiing box crimpers when they are operated in the usual manner on dried fibers.
  • the aquagel tow being forced into the crimping zone within the stuffing box folds over upon itself in a generally accordion pleat or zig zag pattern while forming a packed column of filaments.
  • This is due aerasoe to the resistance to the passage of the packed column that is developed in the stuffing box of the crimper.
  • such resistance is primarily and substantially completely in the form of an end thrusting or stopping physi- .cal restraint on the packed column that is created at and by the outlet gate or exit valve of the stuffing box against the exodus of the packed column from the crimper.
  • the pitch or linear frequency of the crimp in the individual filaments depends to a great extent upon the deforming or withholding force that is exerted on the packed column of filaments in the crimping zone within the stuffing box.
  • the amplitude and pitch of the crimp that is induced in the individual fibers is generally much reduced from and relatively unrelated to the accordion fold pattern that is assumed by the packed column of tow in the stuffing box.
  • the stufling box design of the crimper that is disclosed in the referred-to copending application is such as to readily achieve the desired deforming force on the filaments being crimped and to retain them under such critical force deforming conditions for only the requisite crimp-inducing period of time.
  • the stuffing box of such a crimper is expediently capable of the desired accomplishment with minimized and practically negligible frictional resistance on the packed column of crimped tow during its passage through and residence within the crimper.
  • the tow of aquagel filaments has relatively little crimp permanence. It must be carefully transported or conveyed to and through the drying means with negligible physical restraint or extending influence being permitted to prevail thereon.
  • the crimped aquagel must be dried in a completely unrestrained and free-to-shrink condition to avoid loss in crimp or other damage to the fiber during the drying operation in which the aquagel is transformed to a strong and useful heat set filamentary product.
  • the aquagel may be dried most satisfactorily at temperatures between about 100 and 150 C. for periods of time between about thirty and five minutes.
  • the drying means that is employed may be a heated zone or drying oven through which the crimped aquagel is conducted on an endless traveling belt or the like.
  • the crimped aquagel after it has been obtained from the crimper, can be gently deposited by suitable means on the belt in such a manner as will avoid disruption of the crimp pattern that has been induced in the aquagel or physical damage of the soft and delicate filaments themselves.
  • the crimped aquagel filaments in repose on the belt are completely unrestrained and free to shrink while passing through the drying oven wherein they are dried and simultaneously heat set to the desired filamentary product.
  • the crimped aquagel tow can be cut into staple lengths before being dried using suitable cutting means for the purpose.
  • FIG. 1 is a diagrammatic portrayal of one embodimen-t in which the method of the invention may be practiced.
  • Figures 2 through 9, inclusive, are greatly enlarged depictions of crimp in individual filamentary products, some of which are indicative of results obtained by and in practices other than that which would be in accordance with the invention. 1
  • Example 1 Using apparatus similar to that schematically delineated in Figure l of the accompanying drawing, and with initial reference thereto, a polyacrylonitrile spinning solution, contained in a suitable supply tank 1, was prepared by dissolving about one part of the polymer having an average molecular weight between about thirty and thirtyfive thousand in about ten parts of a 60 percent aqueous solution of zinc chloride.
  • the spinning solution had a viscosity of about 2,200 poises at a temperature of about 25 C. It was passed from the supply tank 1 through a conduit 2 and forwarded by a metering pump 3, connected therewith, through amass tube 4 having a spinnerette system 5 attached at its termination.
  • the extruded spinning solution was coagulated into a plurality of individual aquagel filaments in a coagulating liquid 6, contained in atrough 7, which was comprised of about a 43 percent aqueous solution of zinc chloride.
  • the spinning solution was extruded at a temperature of about 30 C. and the coagulating bath 6 was maintained at a temperature of about 15 C. during the spinning.
  • the aquagel filaments were passed around the submerged guide 8 in the coagulating liquid and were then withdrawn from the trough 7 through the guide means 9 in the form of a multiple filament tow bundle T.
  • the wet spun tow was then passed about the submerged guides 10 into a distilled water wash bath 11, contained in trough 12, wherein it was washed to the point at which the zinc chloride content of the aquagel filaments was not in excess of about 0.05 percent.
  • the washed tow was then oriented by being stretched to a total length of about twelve times its original length. This was accomplished after the tow was withdrawn from the wash bath on a series of stretch drawing rollers 13 which were operated at sequentially increased peripheral speeds. By these operations there was obtained a washedand oriented filamentary tow bundle of the fifteen thousand individual aquagel strands.
  • the total aquagel denier of the washed and oriented tow bundle was about one-hundred-thousand.
  • the individual aquagel strands in the washed and oriented tow bundle were arranged in aflat, ribbon-like array having a width of about one inch and an average thickness of about twenty thousandths of an inch.
  • the oriented aquagel structures contained about 2.0 parts of water for each part of fiber-forming polyacrylonitrile that was present therein.
  • the flat tow was then passed over a guide (or guides) 14 and f ed at a rate of about.200 linear feet per minute into the feed rolls 16 and 17 of a stufing box type of crimper, indicated generally by the reference numeral 15, that was similar in design, operation and function to that which is illustrated in and described in connection with the fifth figure in the drawing of the referred to copending application.
  • the feed rolls 16, 17, which were positively driven and rotated in opposite directions so as to-convey and force the tow into the stuffing box 18 of thecrimper, which were about four inches in diameter and which had tow engaging faces of about one inch thick,
  • the compressive force that was actually exerted on the tow was about 20 pounds.
  • the dimensions of the stufiing box 18, which was of the straight through variety, were such that the residence time of the fibers in the crimper was about 3 seconds with about a four pound restraining weight on the outlet gate of the stufiing box holding the packed column of crimped aquagel fibers in the crimper. The crimping operation was performed with the aquagel filaments atabout room temperature.
  • the individual crimped filaments in the crimped aquagel tow K (which had been transformed in the operation from the'tow T) had an average pitch of about 5.8 crimps per linear inch of unextended aquagel fiber.
  • the crimped aquagel tow K was passed through gentlehandling guide means 19 to be deposited on a moving belt 20 which passed through a drying oven 21 which was maintained at a temperature of about 140 C.
  • the crimped aquagel tow K was completely unrestrained and free to shrink on the surface of the belt 20 during its passage through the oven 21 which required about ten minutes.
  • the quagel structure of the crimped filaments in the tow was destroyed to produce dry, 3 denier crimped fibers that had an average pitch of about 8.5 crimps per linear, unextended inch and an average crimp amplitude (measured as the average fiber) of about 0.04 inch.
  • the dried crimped tow K was passed through a guide 22 to be fed to suitable cutting apparatus 23 wherein it was severed into staple length fibers S which were collected in a storage bin 24.
  • the product crimped staple fibers S exhibited excellent properties for crimped products. For example, their average tensile strength was about 3.7 grams per denier as compared to a strength of a similar uncrimped polyacrylonitrile fiber, prepared in the same manner, or" about 4.0 grams per denier.
  • the crimped staple fibers were transformed into webs and slivers during the manufacture of various textile products, their cohesiveness was entirely satisfactory.
  • the crimp in the fibers was permanently retained, even when subject to boiling water.
  • the desirable crimp pattern that had been permanently imparted to the fibers is illustrated in Figures 2 through of the accompanying drawing.
  • the crimp pattern of a single fiber F as may be obtained in the practice of the invention is shown in Figure 2 as it would appear under greatly enlarged microscopic examination.
  • the uniform angular pattern of the crimp is evident in the fiber which is physically undamaged in its structure.
  • Such a crimp pattern possibilitates the optimum desirable cohesive properties that are obtained in a mass of fibers crimped in accordance with the invention and is indicative of some of the reasons which are believed to be responsible for the crimped fiber retaining substantially all of the desirable physical properties that might be obtained in a similar, but not crimped, acrylonitrile polymer fiber.
  • the bends A of the magnified crimped filaments-in Figures 3, 4 and 5 further illustrate the nice, sharp, undamaged pattern of bending that is achieved in crimped fiber products manufactured by the present method.
  • Example 11 The procedure of Example I was essentially repeated with the exception that the restraining force employed on the outlet gate of the crimper stufiing box was only ab'outon'e pound.
  • the finally dried crimped fiber product had an average crimppitch of about 5 crimps per linear inch and an amplitude'of about 0.06 inch.
  • the crimped fibers had a crimp pattern imparted to them that had pronounced angularity and desirable uniformity.
  • the crimped fiber product had very desirable properties and was found to process quite well during its conversion from staple form into various textile articles.
  • Example I a polyacrylonitrile fiber tow was prepared as in Example I excepting that it was dried without. being crimped. Instead, it was crimped in tow form as a dried fiber in an embodiment of the conventional manner by being slightly plasticized by heat and then passed through a stufling box crimper which was operated in the usual fashion. The feed rolls of the crimper were thus compressed upon the tow being con veyed to the stuffing box with a bight-providing force of about thirty thousand pounds per square inch of tow cross-section in the rolls. The restraining gate on the stuffing box exerted a deforming force of about six thousand pounds per square inch of tow being crimped.
  • the crimped fibers obtained in this manner were not completely satisfactory, even though about 8 linear crimps per inch had been obtained in the dry crimped product.
  • Their overall crimp pattern in each individual crimped filament exhibited a typical, smoothly-undulating and sinusoidal configuration as is shown by the crimped filament S in Figure 9.
  • This sort of crimp pattern does not secure optimum cohesiveness for a mass of sic-crimped fibers since the individual filaments, due to their noninterlocking configurations, can easily slip past one another when such a crimped fiber mass is being physically processed in a textile operation.
  • the fibers that had beencrirnped dry and not in accordance with the present invention were immersed in hot water they lost a good part (about percent) of their crimp. Exposure of the so-crirnped fibers to boiling watercaused them to lose allof their crimp pattern for all practical intents and purposes.
  • Methodfor crimping synthetic textile fibers based upon acrylonitrile polymers which comprises formingan aquagel filamentary structure of said polymer that con tains an amount by weight of water that is at least about equal to the quantity of polymer in the hydrated structure; crimping the aquagel filamentary structure by de forming it into a crimp pattern under the influence of a force that is between about 50 and 1,000 pounds per square inch of aquagel cross section, said forcebeing applied for a period of time not longer than about five seconds to induce said crimp pattern in the individual filaments in said aquagel structure; transferring the crimped aquagel filamentary structure in an unrestrained condition to a drying means; and drying the crimped aquagel filamentary structure by said drying means while it is in an unrestrained and free-to-shrink condition to destroy the aquagel and convert it to a crimped and heatset fiber product.
  • the aquagel filamentary structure is formed as a relatively fiat, ribbonlike multiple filament tow bundle prior to being crimped and is crimped while in the form of said tow by being forced through the crimping zone of a stufiing box type of crimper wherein said deforming force is applied to said aquagel filamentary structure.
  • the aquagel filamentary structure is formed as a relatively flat ribhon-like multiple filament tow bundle prior to being crimped that has an average thickness of from about ten to forty thousandths of an inch and is crimped while in the form of said tow by being passed into and forced from between the bight of a pair of conveying feed rolls, having a clearance that is at least about 80-90 percent of the average thickness of the tow, through the crimping 10 zone of a smiling box type of crimper wherein said deforming force is applied to said aquagel filamentary structure.
  • drying means for the crimped aquagel filamentary structure is a heated zone through which the crimped aquagel structure is conveyed and dried in an unrestrained and free-to-shrink condition.

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  • Chemical & Material Sciences (AREA)
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  • Mechanical Engineering (AREA)
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  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
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US663693A 1957-06-05 1957-06-05 Method for crimping acrylonitrile polymer fibers Expired - Lifetime US2917806A (en)

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BE568354D BE568354A (nl) 1957-06-05
NL228434D NL228434A (nl) 1957-06-05
US663693A US2917806A (en) 1957-06-05 1957-06-05 Method for crimping acrylonitrile polymer fibers
FR1208314D FR1208314A (fr) 1957-06-05 1958-06-04 Procédé de plissage de fibres de polymère d'acrylonitrile

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Cited By (25)

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Publication number Priority date Publication date Assignee Title
US3072963A (en) * 1959-07-13 1963-01-15 Margon Corp Method of, and apparatus for, curling the lashes of a doll's eye
US3099064A (en) * 1961-04-13 1963-07-30 Eastman Kodak Co Method and apparatus for making rug yarn
US3101521A (en) * 1959-06-25 1963-08-27 Spunize Co Of America Inc Method of producing crimped continuous filament yarn
US3106763A (en) * 1960-07-27 1963-10-15 Courtaulds Ltd Production of crimped filaments
US3128527A (en) * 1960-11-23 1964-04-14 Ici Ltd Process for making fabric from bulked yarn
US3152380A (en) * 1961-05-05 1964-10-13 Du Pont Process for treating polypropylene fibers
US3176374A (en) * 1962-05-07 1965-04-06 Ici Ltd Method of treating filamentary tows
US3212157A (en) * 1961-11-29 1965-10-19 Klinger Mfg Co Ltd Yarn crimping apparatus
US3255064A (en) * 1961-07-17 1966-06-07 Du Pont Process for mechanical crimping of fibers in sheet form
US3258825A (en) * 1962-03-26 1966-07-05 Eastman Kodak Co Methods for the production of highshrink modacrylic yarn
US3298079A (en) * 1965-05-24 1967-01-17 Eastman Kodak Co Method for producing a novel crimped yarn and fabric
US3316612A (en) * 1962-07-30 1967-05-02 Du Pont Process of drawing and crimping asymmetrically quenched polyester filaments to provide a compact ribbon-like tow for shipping and enhanced bulk in end-products
US3373470A (en) * 1961-02-08 1968-03-19 Rhodiaceta Process for crimping yarn
US3376622A (en) * 1962-08-13 1968-04-09 Techniservice Corp Strand treatment
US3402236A (en) * 1964-01-29 1968-09-17 Chemstrand Ltd Manufacture and treatment of synthetic fibres and fabrics containing the same
US3435103A (en) * 1965-03-01 1969-03-25 Standard Oil Co Process for forming solid articles from expandable polymer
US3461521A (en) * 1967-11-24 1969-08-19 American Enka Corp Process for manufacture of yarns
US3462814A (en) * 1967-10-26 1969-08-26 Techniservice Corp Strand treatment
US3462815A (en) * 1967-11-20 1969-08-26 Techniservice Corp Strand treatment
US3492144A (en) * 1966-02-01 1970-01-27 Dow Chemical Co Method of making flocked fabrics
US3499953A (en) * 1966-04-05 1970-03-10 Techniservice Corp Strand treatment
US4233388A (en) * 1979-05-18 1980-11-11 Xerox Corporation Method for making toner particles
US4622195A (en) * 1983-03-11 1986-11-11 Bayer Aktiengesellschaft Continuous process for the production of polyacrylonitrile filaments and fibers
US4632321A (en) * 1984-02-06 1986-12-30 Oerlikon Motch Corporation Div. Jetstream Systems Co. Air conveyor for plastic film
US4925604A (en) * 1984-10-16 1990-05-15 Nikkiso Co., Ltd. Process for preparing a carbon fiber of high strength

Citations (5)

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US2311174A (en) * 1940-12-06 1943-02-16 Du Pont Textile crinkler
US2558733A (en) * 1949-06-08 1951-07-03 American Cyanamid Co Method of producing synthetic fibers from polymers and copolymers of acrylonitrile
US2686339A (en) * 1950-10-04 1954-08-17 Chemstrand Corp Treatiment of acrylonitrile polymer fibers
US2811770A (en) * 1953-12-08 1957-11-05 Du Pont Preparation of tow from filaments of acrylonitrile polymers
US2814837A (en) * 1954-06-04 1957-12-03 Ici Ltd Method and apparatus for crimping the filaments of a tow of extendable artificial filaments

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2311174A (en) * 1940-12-06 1943-02-16 Du Pont Textile crinkler
US2558733A (en) * 1949-06-08 1951-07-03 American Cyanamid Co Method of producing synthetic fibers from polymers and copolymers of acrylonitrile
US2686339A (en) * 1950-10-04 1954-08-17 Chemstrand Corp Treatiment of acrylonitrile polymer fibers
US2811770A (en) * 1953-12-08 1957-11-05 Du Pont Preparation of tow from filaments of acrylonitrile polymers
US2814837A (en) * 1954-06-04 1957-12-03 Ici Ltd Method and apparatus for crimping the filaments of a tow of extendable artificial filaments

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3101521A (en) * 1959-06-25 1963-08-27 Spunize Co Of America Inc Method of producing crimped continuous filament yarn
US3072963A (en) * 1959-07-13 1963-01-15 Margon Corp Method of, and apparatus for, curling the lashes of a doll's eye
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NL228434A (nl)
FR1208314A (fr) 1960-02-23
BE568354A (nl)

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