EP0199567B1 - Fibres du genre carbone ayant des propriétés de déflexion réversible comme un ressort et méthode de préparation - Google Patents

Fibres du genre carbone ayant des propriétés de déflexion réversible comme un ressort et méthode de préparation Download PDF

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Publication number
EP0199567B1
EP0199567B1 EP86302959A EP86302959A EP0199567B1 EP 0199567 B1 EP0199567 B1 EP 0199567B1 EP 86302959 A EP86302959 A EP 86302959A EP 86302959 A EP86302959 A EP 86302959A EP 0199567 B1 EP0199567 B1 EP 0199567B1
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EP
European Patent Office
Prior art keywords
fiber
fibers
tow
temperature
cloth
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EP86302959A
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German (de)
English (en)
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EP0199567A2 (fr
EP0199567A3 (en
Inventor
Francis Patrick Mccullough, Jr.
David Michael Hall
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Dow Chemical Co
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Dow Chemical Co
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Classifications

    • 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
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • 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
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • 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
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
    • 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
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
    • D01F9/15—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from coal pitch
    • 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
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
    • D01F9/155—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from petroleum pitch
    • 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
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/24—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the invention resides in a carbonaceous resilient fiber or fiber assembly derived from a stabilized carbonaceous precursor material having imparted thereto a spring-like structural configuration capable of reversible deflection of greater than 1.2 times the length of the fiber when in a relaxed condition.
  • the carbonaceous fiber of the present invention is provided with a substantially permanent, non-linear, resilient, elongatable, spring-like structural configuration, e.g. of a substantial coil-like, sinusoidal or other multi-curvilinear configuration having no sharp or acute angular bends in the fiber.
  • the spring-like structural configuration and the resilient, elongatable, characteristics of the fiber allows for a dimensional change of the fiber from a relaxed condition (ie. spring-like configuration) to an elongated, stretched, and substantially linear state, or any degree there-in-between, in which the fiber is under tension.
  • the fiber When placed under tension, the fiber can be extended at least 1.2 times, typically from 2 to 4 times, the length of the fiber in its relaxed non-deflected spring-like configuration.
  • the spring-like fiber can thus be deflected (elongated or stretched) to a substantially linear shape or configuration. If the modulus of elasticity of the fiber per se is not approached or exceeded, that is to say the fiber is not put under tension beyond that necessary to straighten the fiber to a substantially linear shape, the fiber is capable of returning from the linear to its relaxed spring-like shape over many cycles of stress elongation and relaxation without either breaking or substantially altering the dimensions or physical structure of the fiber.
  • the prior art has generally taught the manufacture of filaments from pitch based (petroleum and/or coal tar) compositions by the conventional technique of melt spinning the composition into continuous filaments which can then be stabilized by oxidation. Such filaments are taught to be useful per se.
  • the continuous filament may be chopped or stretch-broken into what the art refers to as a "staple" fiber. Such "staple" fiber can be converted into a yarn by drafting, drawing and twisting, (referred to as spinning in the industry).
  • the continuous filaments can also be made into a tow formed from a plurality of continuous mono-filaments. The resulting yarn or threads are used per se or may be woven into cloth-like articles and used as such.
  • a woven article may be carbonized to produce a graphite or graphite-like cloth.
  • a tow per se may be carbonized, without weaving the tow into a cloth, and thereafter used as a reinforcement material for synthetic resinous materials e.g. "pre-preg", and the like.
  • polyacrylonitrile can be wet spun into filaments; the filaments assembled into filament tow; the filaments or tow stabilized by oxidation; the filaments or tow made into staple by chopping or stretch breaking; the staple spun into yarn; the yarn knitted or woven into a cloth or fabric; and, if desired, the resulting fabric carbonized at a temperature of greater than 1400°C.
  • PAN polyacrylonitrile
  • These materials in their pre-carbonized woven state, have been used as a non-combustible reinforcing material for metallized fire fighting suits. In their unwoven carbonized form, these materials have also been used as a reinforcement material for synthetic resinous materials such as golf club shafts, and the like.
  • a knitted fabric cannot be deknitted without special care and such a deknitted yarn cannot thereafter be carded to convert the fibers in the yarn into a wool-like fluffy material without causing severe destruction, i.e. breakage, of the fibers.
  • the resulting short and broken fibers do not have sufficient length or crimp to produce a well entangled fluff.
  • the prior art also generally discloses carbonized filaments having a high tensile strength or a high surface area.
  • Such filaments are of a highly "graphitic" nature and necessitate the utilization of high temperatures to obtain a high degree of carbonization.
  • the filaments produced by such a high temperature treatment are very brittle and incapable of standing up to stress such as repeated bending of the filaments, particularly when they have been subjected to a temperature above about 1000°C, and more so when they have been subjected to a temperature of above about 1400°C.
  • Exemplary of a high temperature treatment of filaments derived from stabilized mesophase pitch can be found in U.S. Patent No.
  • GB-A-1190269 (corresponding to FR-A-1539755) discloses carbonizing a woven cloth of oxidized PAN or other polymeric fiber filament yarn.
  • the fibers are essentially linear and do not have a spring-like structural configuration (as defined above). There is no reference to disassembling the carbonized cloth into fibers except for extraction of fibers to test their physical properties.
  • US-A-4423675 discloses a carbon spring obtained by carbonizing a length of organic linear material in the form of a coiled spring.
  • Specified organic linear materials include pitches and PAN. The material usually is extruded to a diameter of at least 100 micrometers and it appears to be essential that the coil is maintained under tension whilst being carbonized.
  • JP-A-44-2512 discloses the carbonation of Ishimeuchi or Admishiroushi woven cord or cloth formed from organic fiber yarn and subsequent removal of the warp fiber yarn to leave a resilient article.
  • the resilience in said article arises from the arrangement of the constituent fiber yarns and not from the resilience of the fibers themselves.
  • the fiber yarns have essentially linear portions between sharp return angle bends and hence the fibers do not have a spring-like configuration (as defined above). There is no reference to disassembling the resilient article into fibers.
  • JP-A-53-98423 discloses the formation of carbon fiber elements for use in incandescent lamps by carbonizing a coil of polymer fibers and subsequently graphitizing the set fiber coil.
  • the coil is maintained under tension during carbonization and said carbonization is conducted at a temperature of at least 1500°C.
  • the coil can be formed of a monofilament or a plurality, eg 400 to 1000, of monofilaments twisted together or formed into a cord.
  • US-A-4193252 discloses a method of producing carbon or graphite yarn from a fabric of knitted precursor yarn by carbonization, firing and graphitization of the yarn.
  • the fabric can be deknitted after carbonization or firing and the deknitted yarn subjected to the subsequent heating step(s).
  • the only exemplified precursor material is rayon and there is no reference to the carbonization of monofilaments or tows.
  • fiber or “filament” interchangeably refers to a fine threadlike body or structure of a natural or synthetic material in the conventional usage. Included herein are filaments made by melt spinning a pitch based composition such as petroleum or coal tar, or fibers which are made by wet spinning a synthetic resinous material such as polyacrylonitrile.
  • Fiber assembly refers to a multiplicity of filaments commonly referred to in the textile industry as a tow. Fiber assemblies are made of common polymeric textile fibers or filaments, but are also applicable to carbonaceous fibers or filaments which have been stablized and treated in accordance with the following teaching and examples.
  • spring-like “spring-like structure”, or “spring-like structural configuration” are interchangeably used herein to designate a fiber or tow that is physically deformed from a substantially linear configuration into a coil-like, sinusoidal, or other multi-curvilinear form or configuration having no acute angular bends.
  • nK n is a numerical value in increments of 1000 filaments.
  • staple refers to non-continuous fibers which may be "spun” into yarns.
  • stabilized herein applies for example to fibers or tows which have been oxidized at a specific temperature, typically less than about 250°C for PAN fibers or, in some instances, oxidized by chemical oxidants at lower temperatures.
  • spun herein applies to a continuous strand of twisted fibers.
  • spun yarn refers to a continuous strand of staple fibers which has been drafted, drawn and twisted into a yarn.
  • carding refers to a procedure in which fibers are combed or brushed with a toothed apparatus, e.g. a wire tooth brush, to effect at least a partial alignment of the fibers into an entangled web or sliver.
  • a toothed apparatus e.g. a wire tooth brush
  • garnettted refers to a process for reducing various textile waste materials to fiber by passing them through a machine called a garnett, which is similar to a card.
  • knitting herein includes single Jersey knit, Rib knit, Pearl knit, Interlock knit, Double knit, and similar methods of knitting a fiber, yarn or tow into a cloth.
  • reversible deflection or “working deflection” is used herein as it applies to a helical or sinusoidal compression spring to mean the extent, expressed as a ratio of extended to free spring length, to which a spring can repeatedly be extended and, on release of the extending force, return to its original (ie. free) length.
  • a helical or sinusoidal compression spring to mean the extent, expressed as a ratio of extended to free spring length, to which a spring can repeatedly be extended and, on release of the extending force, return to its original (ie. free) length.
  • Carbonaceous precursor starting materials which have the capability of forming the spring-like structural configuration carbonaceous fiber of the invention are selected from starting materials such as pitch (petroleum or coal tar), polyacetylene, polyacrylonitrile (PANOX or GRAFIL), polyphenylene, polyvinylidene chloride (SARAN), and the like. GRAFIL, PANOX and SARAN are Trade Marks.
  • Preferred precursor materials are prepared by melt spinning or wet spinning in a manner to yield a monofilament or multi-filament assembly.
  • the filaments are stabilized and then converted into a tow, or a woven cloth or knitted cloth by any of a number of commercially available techniques.
  • a partially carbonized or substantially completely carbonized fiber derived from a continuous precursor fiber or tow of a stabilized, carbonaceous precursor material, said precursor fiber having a diameter of up to 30 micrometers, characterised in that the fiber has a permanently set multi-curvilinear structural configuration with no sharp bends and a reversible deflection ratio of greater than 1.2:1.
  • the fiber has a diameter of from 4 to 20 micrometers.
  • a method of forming a fiber of the invention comprising the steps of imparting and setting a multi-curvilinear shape having no sharp bends to a continuous precursor fiber or tow of a stabilized, carbonaceous material, said precursor fiber having a diameter of up to 30 micrometers; and heating the set fiber in a relaxed state under non-oxidizing conditions and at a temperature sufficient to impart a permanent setting of said shape to said fiber and at least partially carbonize the fiber.
  • a unique article is prepared from such a carbonaceous precursor material which is made into a carbonaceous fiber or tow of fibers by stabilizing the fiber or tow and then providing it with a spring-like structural configuration, imparting to the fiber or tow flexible, resilient, elongatable and deflectable characteristics, without altering the spring-like configuration of the fiber over many cycles of elongation and contraction.
  • Fibers made from PAN are generally oxidation stabilized at a temperature of from 200°C to 250°C and typically have a nominal diameter of from 10 to 20 micrometers.
  • Fibers made from mesophase pitches are oxidation stabilized at a temperature of from 250° to 400°C, preferably at a temperature of from 300° to 390°C, as described in U.S. Patent No. 4005183.
  • Fibers made from SARAN are stabilized by dehydrochlorination in which the SARAN fiber loses its thermoplastic nature and begins to take on a thermoset-like behavior. It will be understood that fibers having a somewhat larger diameter of, for example, 30 micrometers may be employed where stiffer fibers are desired, depending upon the particular end use to which such heavier and stiffer fibers are to be applied.
  • a multiplicity of continuous fibers are associated into a tow which is then stabilized by oxidation in conventional manner.
  • the stabilized tow is thereafter, and in accordance with the present invention, formed into a coil-like structural configuration as, for example, by winding the tow on a cylindrical rod or mandrel, or is formed into a sinusoidal form or other multi-curvilinear form by knitting the tow into a fabric or cloth (recognizing that other fabric forming and coil forming methods can be employed). It is convenient to form the sinusoidal structure on a standard textile knitting machine (e.g. Flat bed knitting machine, or a tubular knitting machine) or in a rounded tooth gear-box that will not impart any sharp or acute angular bends to the fibers.
  • a standard textile knitting machine e.g. Flat bed knitting machine, or a tubular knitting machine
  • the coil-like or sinusoidally shaped fiber, tow or the knitted cloth is thereafter heat treated in a relaxed state at a temperature of from 150°C to 1550°C. At a temperature of above about 250°C, the fiber, tow or cloth is heat treated in an inert atmosphere. If the desired end product requires subsequent mechanical treatment, ie. carding or deknitting of the fabric, it is preferable to subject the fiber, tow or cloth to a temperature below about 550°C in an inert atmosphere.
  • the fibers are provided with a temporary set and have not yet acquired the high degree of brittleness associated with "graphite" fibers.
  • the fibers are, ab initio, provided with a permanent set.
  • Such permanent set is accompanied by some degree of brittleness which can lead to breakage of some fibers during subsequent treatment of the fibers.
  • the fiber not be heated to a temperature above about 275°C, while under tension. Above this temperature, the fiber begins to lose weight and shrink in coilure diameter and the tension resulting from such shrinkage and weight loss causes non-annealable stress cracks and weak points in the fiber.
  • the fiber or tow may be initially heat treated at the higher temperature range up to 1550°C so long as the heat treatment is conducted while the fiber is in a relaxed state (spring-like configuration) under an inert, non-oxidizing atmosphere.
  • a permanent set spring-like structural configuration is imparted to the fiber.
  • the resulting fibers or tow having such spring-like structural configuration may be used per se, or in the case of a knitted cloth, may be deknitted to form a sinusoidal or other multi-curvilinear tow.
  • the tow or the cloth per se may then be further subjected to a carding or garnetting operation or any of a number of other methods of mechanical treatment known in the art to create an entangled wool-like fluffy material in which, the fibers are separated into an entangled mass of fibers and in which the individual fibers retain their spring-like configuration.
  • the fibers of the invention have a density of less than 2.5 gm/cm3 and/or a Young's modulus of from 7 to 380 GPa.
  • the fibers, tow or the knitted cloth or the wool-like fluff produced by a heat treatment at a temperature of no higher than about 550°C, in a relaxed state (which has placed a temporary set spring-like configuration into the fibers, tow or thread) may then be further heat treated in a relaxed state and under a non-oxidizing atmosphere to a temperature of from 550°C to 1500°C to impart a permanent set, spring-like structural configuration to the fiber.
  • various lower degrees of electrical resistivity are imparted to the fibers, such resistivity being preferably less than about 1010 ohm-cm.
  • the diameter of the fibers is reduced when treated at a higher temperature up to about 1550°C. Although higher temperature treatment results in a gradually increasing brittleness, the fibers still retain their spring-like configuration.
  • the precursor materials are of a nature believed to lose their non-carbon moieties upon heating and form a conjugated bond structure within the carbon to carbon backbones which are believed to convert to an aromatic, fused, ring-like form.
  • brittle fibers produced at the higher temperatures of above 1000°C may still be useful as, for example, a structural reinforcement material for various synthetic resinous materials, as a filler material for rendering synthetic resinous materials antistatic, as electrical conductors (e.g. automobile ignition systems), as a thermal insulating material, or the like.
  • the stabilized fibers or tow when heat-set into the desired spring-like structural configuration, e.g. by knitting, and thereafter heating in a relaxed state at a temperature of from 550°C to 1550°C retain their resilient and reversible, deflectable characteristics in accordance with Hooke's Law. If the tow has been knitted and heat treated in a relaxed state at a temperature between 550°C and 1000°C to "perm-set" the spring-like configuration in the tow, it may then be deknitted, carded, garnetted or otherwise mechanically treated to convert the deknitted tow to an entangled wool-like fluffy material which still retains a resilience similar to that found in wool.
  • a predetermined length of fiber or tow made into a spring-like structural configuration in accordance with the above described manner will exhibit a reversible deflection in excess of 1.2 times, generally greater than twice, of its relaxed, non-elongated, spring-like configuration.
  • a fiber or tow which has been provided with a permanently set spring-like configuration can be stretched or elongated to a length of at least 1.2 times of its coiled, i.e. contracted, relaxed spring-like structural configuration length.
  • the knitting parameters such as the number of loops per unit length or the number of turns on a rod or mandrel
  • a greater extension or elongation of the spring-like fiber or tow is possible.
  • the tightness or looseness of the non-linear, coil or curl in the fiber, e.g. the loops per centimeter in a knitted cloth, therefor governs the extent of the elongation of the spring-like fiber or tow.
  • the reversible deflection could be much greater than twice the length of a fiber or tow when in a relaxed state, spring-like configuration.
  • an assembly e.g. a bundle of fibers is obtained, by spinning a carbonaceous precursor material into a fiber, stabilizing the fiber, assembling a multiplicity of mono-filaments or fibers into a tow, and knitting the tow into a cloth.
  • the fibers in the cloth are "set", i.e. temporarily formed into a coil-like or sinusoidal structure, by treating the knitted cloth at a temperature of from 150°C to 550°C.
  • the fibers in the knitted cloth are formed into a permanently set, spring-like structure at a temperature of from 550°C to 1550°C and most preferably at a temperature of less than 1000°C, under an inert atmosphere and in a relaxed condition.
  • the fibers in the knitted cloth may then be carbonized at a temperature in excess of 1000°C to impart other desirable properties into the fibers, noted hereinabove.
  • the fiber tow having the spring-like configuration or even the knitted fabric may be carded, garnetted, or otherwise mechanically treated either before or after treatment at a temperature of less than 1550°C, preferably less than 1000°C, and most preferably at a temperature of below about 650°C, when preparing a wool-like, fluffy material.
  • the perm set (550°C to 1000°C) fiber, tow or cloth can be further heat treated to a temperature above 1000°C, e.g. up to 3000°C.
  • fibers treated at a temperature above 1550°C become extremely brittle and do not readily lend themselves to a deknitting, carding or garnetting treatment. Accordingly, such carding and/or garnetting treatment should be accomplished prior to heat treatment to temperatures up to 1550°C for continuous fiber or fiber tows.
  • Fibers made from carbonaceous precursor materials normally have a surface area of from 0.5 to 1600 m2/gm, preferably less than 15m2/gm when produced according to the procedures set forth above. However, it is known that such fibers can have imparted to them a surface area of greater than this by rapidly heating the fibers to a high temperature thereby converting the non-carbon moieties to gases which, on leaving the fiber, disrupt the surface.
  • Other techniques known in the art for producing high surface area, high porousity fibers include oxidation of the fiber surface.
  • Such high porousity fibers can be prepared from the materials of the present invention by the same techniques after the spring-like structural configuration has been imparted into the fibers.
  • the continuous fibers or tows may be chopped into discrete lengths and made into non-woven products employing present day techniques for preparing such non-woven products.
  • the deknitted tow was cut into various lengths of from 5 to 25 cm, and fed into a Platts Shirley (Trade Mark) Analyzer.
  • the fibers of the tow were separated by a carding treatment into a wool-like fluff, that is to say, the resulting product resembled an entangled wool-like mass or fluff in which the fibers had a high interstitial spacing and a high degree of interlocking as a result of the coiled and spring-like configuration of the fibers.
  • the fiber lengths of each such treatment were measured and the results of these measurements set forth in Table I.
  • a fabric was knitted from a 3K or 6K PANOX (R.K. Textiles) continuous stabilized filament tow on a Singer flat bed knitting machine and heat treated at the temperatures set forth in Table II and under an inert atmosphere of nitrogen. The fabric was then deknitted and the tow having a spring-like structural configuration fed directly into a carding machine. The resulting wool-like mass was collected onto a rotating drum and had sufficient integrity to enable it to be easily handled. The length of the fibers ranged from 2 to 15 cm.
  • the wool-like mass treated at a temperature of 950°C was highly conductive and had a resistance of less than 75 ohms at any probe length taken at widely separated distances up to 60 cm in the wool-like mass.
  • a 3K PANOX stabilized tow was knitted on a Singer flat bed knitting machine at a rate of 4 stitches/cm and was then heat treated at a temperature of 950°C and under an inert atmosphere of nitrogen.
  • the cloth was deknitted and the tow (which had a coil elongation or reversible deflection ratio of greater than 2:1) cut into 7.5 cm lengths.
  • the cut yarn was then carded on a Platt Minature Carding machine to produce a wool-like fluff having fibers ranging from 3.5 to 6.5 cm in length with an average length of about 5 cm.
  • the wool-like fluff had a high electrical conductivity over any length of up to 60 cm tested.
  • Example 3 In a similar manner to Example 3 a portion from the same knitted cloth was heat treated at a temperature of 1550°C and under an inert atmosphere of nitrogen. The cloth itself and the deknitted tow had a very high electrical conductivity. On carding 15 cm lengths of cut tow, a fluff was obtained which had fibers of lengths 2.5 to 9.5 cm with average lengths of 5 cm. Thus, carding of a deknitted, continuous filament tow, fabric which has been subjected to a temperature of above 1000°C is still capable of producing a wool-like fluffy product.
  • a staple 2 ply singles 10's stabilized polyacrylonitrile PANOX yarn was knitted into a tubular sock at a rate of 4 loops per cm and thereafter heat treated at a temperature of 1550°C under an inert atmosphere of nitrogen and the yarn was then cut into 10 cm lengths.
  • the cut yarn was carded in a carding machine.
  • the resulting product was collected with difficulty. Only short fibers having a length of from 0.5 to 1.25 cm were obtained along with a high level of dust. The difficulty of fiber recovery resulted from the high degree of twist and fiber entanglement which is typically found in spun yarns. Similar results were obtained when this example was repeated starting with a similar spun yarn sample of Grafil-01 obtained from Hysol-Grafil Ltd., Coventry, England.
  • the temperature of the furnace was gradually increased from room temperature to about 550°C over a three hour period with the higher temperatures being achieved by 50°C increments every 10-15 min.
  • the material was held at the desired temperature for about 1 hour, the furnace opened and allowed to cool while purging with nitrogen.
  • Representative of the furnace temperatures at the above preset incremental temperature schedule is that for a 6K yarn and shown in Table III following: TABLE III Time Temp. °C 0720 200 0810 270 0820 300 0830 320 0840 340 0850 360 0900 370 0905 380 0935 420 0950 450 1005 500 1010 550 1025 590 1035 650 1045 700 1100 750 1400 750
  • the specific resistivity of the fibers was calculated from measurements made on each sample using a measured average of six measurements, one made from fibers removed at each corner of the sample and one made from fibers removed from each edge approximately at the middle of the sample.
  • the results are set forth in Table IV following: TABLE IV Final Temp. in °C % wt. loss Log Specific Resistivity 500 - 4.849 550 33 - 600 - 2.010 650 34 - 700 - - 750 37 - 1.21 850 38 - 2.02 900 42 - 2.54 950 45 - 2.84 1000 48 - 3.026 1800 51 - 3.295
  • the carbonized and permanently set fibers of the invention when treated at temperatures sufficiently high to render the fibers electrically conductive and yet sufficiently low where the fibers still exhibit resilient, flexible, and non- brittle characteristics, are particularly suitable for blending with standard carpet fibers or yarn to produce a yarn having static dissipation properties.
  • a carpet/yarn blend may incorporate at least 0.25 weight percent carbonized fibers in the carpet yarn.
  • the weight ratio of synthetic carpet fibers to carbonized fibers is preferably greater than 100:1 to 200:1.
  • a carpet employing the carbonized fibers of the invention exhibited static discharge properties to 0 percent of an applied electrostatic charge in less than 1 second.
  • Monsanto 1879 nylon (trilobal) staple was blended with 0.5 percent by weight of a conductive fiber prepared in accordance with the present invention.
  • the conductive fiber was prepared by heating an oxidatively stabilized polyacrylonitrile multifilament fiber tow which had been knitted into a cloth, heat treated at about 1500°C, deknitted and cut into staple approximately 18 cm in length.
  • the blended staple was carded and the resulting sliver was pin drafted three times, recombination ratios were 10:1, 3:1, and 5.1, respectively.
  • the resulting drafted sliver was spun into a single ply yarn with an average twist of about 4.75.
  • the resulting carbonaceous fiber containing singles yarn was plied with a nylon yarn made in the same fashion but containing no carbonaceous fiber.
  • the 3.00/2 ply yarn which was heat set on a Suessen (Trade Mark) heat setting apparatus was thereafter tufted into a 1/8 inch (3 mm) gauge, 27 on (765 gm), 9.5 mm pile height carpet (a cut loop form) with approximately 3 stitches per cm.
  • the ratio of carbonaceous fiber to yarn containing no carbonaceous yarn in the tufting operation was 1:5 respectively.
  • a portion of the carpet was backed with a commercial non-conductive latex carpet backing.
  • the resulting carpet was tested for static discharge properties by charging the carpet to 5000 volts while in an atmosphere having a relative humidity of less than 20 percent.
  • the static charge was dissipated to 0 percent of original charge in less than one second, and some of the samples discharged in less than 1/2 second.
  • the standard for the industry is a discharge to 0 percent in 2 seconds or less.
  • Example 6 100 grams of the same precursor acrylonitrile fiber tow as described in Example 6 was used. However, the precurser fiber was heat treated after knitting at a temperature of 950°C. All other aspects of handling the carbonaceous material were the same.
  • the carbonized fiber was blended with 45 kg of the Monsanto 1879 nylon yarn as in Example 6.
  • the resulting yarn contained 0.02 percent carbonized fibers which were substantially evenly distributed throughout the yarn.
  • the yarn was tufted to prepare a carpet in a similar manner to Example 6. Thus, each tufted end has the carbonized fibers. Results were similar to the results obtained in Example 6.
  • Knitted fiber tows which have been heat treated to a temperature above 1000°C, and thus been rendered electrically conductive, have also found special utility in the manufacture of electrodes for a non-aqueous secondary energy storage device such as described in GB-A-2150741.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Fibers (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Nonwoven Fabrics (AREA)
  • Chemical Treatment Of Fibers During Manufacturing Processes (AREA)

Claims (31)

  1. Fibre partiellement carbonisée ou quasiment carbonisée en totalité dérivée d'une fibre ou d'une mèche précurseur continue d'un matériau carboné stabilisé précurseur, ladite fibre précurseur ayant un diamètre allant jusqu'à 30 micromètres, caractérisée en ce que la fibre a une configuration structurelle, fixée de façon permanente, muticurvilinéaire sans aucun pli aigu et un rapport de déflexion réversible supérieur à 1,2/1.
  2. Fibre selon la revendication 1, dans laquelle ladite fibre a été stabilisée par oxydation.
  3. Fibre selon la revendication 2, dans laquelle ladite fibre précurseur est une fibre de polyacrylonitrile.
  4. Fibre selon la revendication 3, dans laquelle le log de la résistivité spécifique de ladite fibre carbonisée est supérieur à -2,84.
  5. Fibre selon la revendication 1, dans laquelle ladite fibre précurseur est une fibre de chlorure de polyvinylidène stabilisée par déshydrochloration.
  6. Fibre selon l'une quelconque des revendications précédentes, dans laquelle ledit diamètre est de 4 à 20 micromètres.
  7. Fibre selon l'une quelconque des revendications précédentes, dans laquelle ledit rapport de déflexion réversible est supérieur à 2/1.
  8. Fibre selon l'une quelconque des revendications précédentes, ayant une résistivité électrique spécifique inférieure à 10¹⁰ ohm-cm.
  9. Fibre selon l'une quelconque des revendications précédentes, dans laquelle la densité de la fibre est inférieure à 2,5 g/cm³.
  10. Fibre selon l'une quelconque des revendications précédentes, dans laquelle le module de Young de la fibre est de 7 GPa à 380 GPa.
  11. Fibre selon l'une quelconque des revendications précédentes, dans laquelle la surface spécifique de ladite fibre carbonisée est de 0,5 à 1 600 m²/g.
  12. Fibre selon la revendication 11, dans laquelle ladite surface spécifique est 0,5 à 15 m²/g.
  13. Peluche analogue à de la laine comprenant une multiplicité emmêlée de fibres carbonisées selon l'une quelconque des revendications précédentes.
  14. Peluche selon la revendication 13, dans laquelle la résistance électrique mesurée à travers la peluche analogue à de la laine à une distance d'épreuve de 60 cm est inférieure à 75 ohms.
  15. Article comprenant des fibres carbonisées selon l'une quelconque des revendications 1 à 12.
  16. Article selon la revendication 15, dans lequel ledit article est non tissé.
  17. Procédé de formation d'une fibre selon la revendication 1, comprenant les étapes consistant à communiquer et à fixer une forme multicurvilinéaire n'ayant aucun pli aigu à une fibre ou mèche précurseur continue d'un matériau stabilisé carboné, ladite fibre précurseur ayant un diamètre allant jusqu'à 30 micromètres; et à chauffer la fibre fixée à l'état détendu dans des conditions non-oxydantes à une température suffisante pour communiquer une fixation permanente de ladite forme à ladite fibre et à carboniser au moins partiellement la fibre.
  18. Procédé selon la revendication 17, comprenant l'étape de chauffage de ladite fibre stabilisée formée à l'état détendu dans des conditions non-oxydantes à une température allant de 150°C à 550°C pour communiquer une fixation temporaire de ladite forme à la fibre.
  19. Procédé selon la revendication 17 ou 18, dans lequel ladite fibre stabilisée formée est chauffée à une température allant de 550°C à 1550°C dans des conditions non-oxydantes pour communiquer une fixation permanente de ladite forme.
  20. Procédé selon l'une quelconque des revendications 17, 18 et 19, dans lequel une multiplicité desdites fibres précurseurs stabilisées sont assemblées dans une mèche de fibres, ladite forme multicurvilinéaire est communiquée à ladite mèche de fibres, et ladite mèche de fibres formée est chauffée à l'état détendu dans des conditions non-oxydantes pour fixer de façon permanente ladite forme et carboniser au moins partiellement la mèche de fibres.
  21. Procédé selon la revendication 20, dans lequel la mèche de fibres stabilisée est enroulée autour d'une baguette ou d'un mandrin cylindrique, la mèche de fibres enroulée est chauffée à une température allant de 150°C à 300°C dans une atmosphère non-oxydante, la mèche de fibres est déroulée de la baguette ou du mandrin cylindrique, et chauffée à l'état détendu dans une atmosphère inerte à une température allant de 550°C à 1 550°C.
  22. Procédé selon l'une quelconque des revendications 17 à 20, dans lequel ladite forme multicurvilinéaire est communiquée en tricotant la fibre en un tissu, ledit tissu est chauffé dans des conditions non-oxydantes à une température au moins suffisante pour communiquer une fixation temporaire de la forme de la fibre tricotée et le tissu fixé est détricoté.
  23. Procédé selon la revendication 22, dans lequel le tissu tricoté est chauffé à une température allant de 150°C à 550°C pour communiquer une fixation temporaire aux fibres dans le tissu, et le tissu fixé temporairement est détricoté.
  24. Procédé selon la revendication 23, dans lequel les fibres du tissu détricoté sont chauffées à une température allant de 550°C à 1 000°C pour fixer de façon permanente les fibres.
  25. Procédé selon l'une quelconque des revendications 17 à 24, dans lequel la fibre fixée est traitée mécaniquement pour former une peluche analogue à de la laine.
  26. Procédé selon l'une quelconque des revendications 17 à 25, dans lequel la fibre formée est chauffée à une température inférieure à 1000°C pour la rendre conductrice de l'électricité.
  27. Procédé selon l'une quelconque des revendications 17 à 26, dans lequel la fibre formée est chauffée à une température supérieure à 1000°C pour la rendre plus fortement conductrice de l'électricité.
  28. Procédé selon la revendication 27, dans lequel la fibre conductrice de l'électricité est incorporée dans une résine synthétique.
  29. Procédé selon l'une quelconque des revendications 17 à 28, dans lequel la fibre carbonisée est chauffée dans une atmosphère non-oxydante à une température allant jusqu'à 3 000°C pour rendre la fibre conductrice de l'électricité.
  30. Procédé selon l'une quelconque des revendications 17 à 29, dans lequel la fibre précurseur est définie comme dans l'une quelconque des revendications 2 à 6.
  31. Procédé selon l'une quelconque des revendications 17 à 30, dans lequel les conditions du traitement sont telles qu'il est fourni une fibre définie comme dans l'une quelconque des revendications 7 à 12.
EP86302959A 1985-04-18 1986-04-18 Fibres du genre carbone ayant des propriétés de déflexion réversible comme un ressort et méthode de préparation Expired - Lifetime EP0199567B1 (fr)

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US72444085A 1985-04-18 1985-04-18
US724440 1985-04-18
US82756786A 1986-02-10 1986-02-10
US827567 1986-02-10

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EP0199567A2 EP0199567A2 (fr) 1986-10-29
EP0199567A3 EP0199567A3 (en) 1988-01-13
EP0199567B1 true EP0199567B1 (fr) 1992-08-26

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EP (1) EP0199567B1 (fr)
JP (4) JPH0670286B2 (fr)
KR (1) KR890000129B1 (fr)
AU (1) AU590879B2 (fr)
BR (1) BR8606634A (fr)
CA (1) CA1284858C (fr)
DE (1) DE3686504T2 (fr)
WO (1) WO1986006110A1 (fr)

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JPS63503000A (ja) * 1986-10-14 1988-11-02 ザ　ダウ　ケミカル　カンパニー 防音および断熱材
JP2648711B2 (ja) * 1986-11-07 1997-09-03 株式会社 ペトカ ピッチ系炭素繊維三次元織物の製造法
US4868038A (en) * 1987-10-23 1989-09-19 The Dow Chemical Company Carbonaceous fiber reinforced composites
US4950533A (en) * 1987-10-28 1990-08-21 The Dow Chemical Company Flame retarding and fire blocking carbonaceous fiber structures and fabrics
US4950540A (en) * 1987-10-28 1990-08-21 The Dow Chemical Company Method of improving the flame retarding and fire blocking characteristics of a fiber tow or yarn
US4879168A (en) * 1987-10-28 1989-11-07 The Dow Chemical Company Flame retarding and fire blocking fiber blends
US4844974A (en) * 1987-11-18 1989-07-04 The Dow Chemical Company Antistatic, antislosh, flame arresting structure for use in containers holding flammable fluids
US4869962A (en) * 1988-01-29 1989-09-26 The Dow Chemical Company Asbestos-like structures
US4857394A (en) * 1988-01-29 1989-08-15 The Dow Chemical Company Flame retardant foams
US5028477A (en) * 1988-03-04 1991-07-02 The Dow Chemical Company Carbonaceous fiber or fiber assembly with inorganic coating
KR970001582B1 (ko) * 1988-03-04 1997-02-11 더 다우 케미칼 캄파니 조밀한 탄소상 섬유 구조체
US4902563A (en) * 1988-03-04 1990-02-20 The Dow Chemical Company Carbonaceous fiber or fiber assembly with inorganic coating
US4944999A (en) * 1988-03-04 1990-07-31 The Dow Chemical Company Carbonaceous fiber or fiber assembly with inorganic coating
US4956235A (en) * 1988-03-04 1990-09-11 The Dow Chemical Company Carbonaceous fiber or fiber assembly with inorganic coating
US5034267A (en) * 1988-03-04 1991-07-23 The Dow Chemical Company Carbonaceous fiber or fiber assembly with inorganic coating
US4978571A (en) * 1988-03-04 1990-12-18 The Dow Chemical Company Carbonaceous fiber or fiber assembly with inorganic coating
US4897303A (en) * 1988-03-07 1990-01-30 The Dow Chemical Company Buoyant coated fibers
JPH0811863B2 (ja) * 1988-03-15 1996-02-07 チッソ株式会社 繊維マット及びその製造方法
JP2838140B2 (ja) * 1988-03-17 1998-12-16 株式会社ペトカ よじれを有する炭素繊維及びその製造方法
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JP3737849B2 (ja) * 1996-03-31 2006-01-25 大阪瓦斯株式会社 炭素繊維３次元構造体の製造方法
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GB2477531B (en) * 2010-02-05 2015-02-18 Univ Leeds Carbon fibre yarn and method for the production thereof
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AU5635986A (en) 1986-10-23
AU590879B2 (en) 1989-11-23
CA1284858C (fr) 1991-06-18
JPH0327123A (ja) 1991-02-05
EP0199567A2 (fr) 1986-10-29
JPS62500600A (ja) 1987-03-12
BR8606634A (pt) 1987-08-04
EP0199567A3 (en) 1988-01-13
JPH0670286B2 (ja) 1994-09-07
JPH0327122A (ja) 1991-02-05
JPH0663138B2 (ja) 1994-08-17
DE3686504T2 (de) 1993-01-21
WO1986006110A1 (fr) 1986-10-23
JPH0663137B2 (ja) 1994-08-17
KR890000129B1 (ko) 1989-03-08
JPH0327121A (ja) 1991-02-05
DE3686504D1 (de) 1992-10-01
KR880700109A (ko) 1988-02-15

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