US3723609A - Process for the production of carbon fibers - Google Patents

Process for the production of carbon fibers Download PDF

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US3723609A
US3723609A US00078943A US3723609DA US3723609A US 3723609 A US3723609 A US 3723609A US 00078943 A US00078943 A US 00078943A US 3723609D A US3723609D A US 3723609DA US 3723609 A US3723609 A US 3723609A
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solution
percent
process according
carbon
fiber
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M Mansmann
G Winter
G Pampus
N Schon
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Bayer AG
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Bayer AG
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    • 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
    • D01F9/18—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from proteins, e.g. from wool
    • 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
    • D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
    • 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
    • D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
    • D01F9/17—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate from lignin
    • 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
    • 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
    • D01F9/245—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 from polyurethanes
    • 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
    • D01F9/26—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 from polyesters
    • 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
    • D01F9/28—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 from polyamides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/19—Inorganic fiber

Definitions

  • the spun-filaments are converted to solid fibrous material, and the fibrous material is carbonized
  • the improvement which comprises including in said solution at least one fiber-forming high polymer at a con centration of about 0.001 to 10 percent by weight and a greater amount of a carbon source comprising at least one carbon-containing organic material having a softening or melting point in excess of about 80 C., whereby the solution of said carbon containing material is rendered spinnable by addition of said fiber-forming high polymer, said carbon containing organic material serving as the source of carbon for the carbon fiber; the fiber may thereafter be graphitized.
  • the spinning solution used for fiber production is preferably a solution in a volatile solvent so that it may be dry spun.
  • the carbon source in said solvent by itself would not be spinnable and may be a monomer or low polymer.
  • Carbon fibers are generally produced through carbonizing an organic starting material in the form of fibers by a thermal treatment in an inert gas.
  • the carbon fibers thus produced are converted into graphite fibers by further heating to temperatures of up to about 3 ,000 C.
  • the starting fibers must not only be readily producible but also fulfil the following important requirements:
  • the carbon residue should be as high as possible.
  • the original fiber In order to obtain high volume/time yields in the production process, the original fiber must be able to withstand a rapid temperature increase without loss in strength and flexibility of the resulting carbon fibers.
  • the starting material must be readily available in a fibrous form. The starting material should be inexpensive.
  • Carbon and graphite fibers have been obtained, for example, by the carbonization and, where indicated, the graphitization of natural or regenerated cellulose, polyacrylonitrile, polyvinyl alcohol, polyvinyl chloride and specially pretreated woolen fibers (0. Vohler, E. Sperk: Ber. Dtsch. Keram. Ges. 43 [1966] pages 199208).
  • molten bitumen or tar pitch is spun into fibers at temperatures of at least 240 C., and these fibers are then used as starting fibers for the production of carbon and graphite fibers.
  • the object of this process is this process is to enable inexpensive fiber materials to be used as starting materials for carbon fibers, which are not normally available in fibrous form.
  • the starting material must first be adjusted to a quite specific C/H ratio in a separate process step, and the tar fibers must be rendered infusible before the carbonization by pretreating them with ozone or peroxides, followed by oxidation in air.
  • carbonization is understood to mean the heat treatment of an organic substance to temperatures below 2,000" C., preferably to about 1,000 C., heating being carried out at a temperature of at least about 400 C. in an inert gas at normal or reduced pressure.
  • Graphitization is understood to mean a heat treatment at temperatures of between 2,000 C. and about 3,000 C. under a protective gas atmosphere.
  • the process according to the invention for the production of carbon and graphite fibers by carbonization, and if indicated graphitization, of starting fibers which contain carbon is characterized in that the starting fibers which contain carbon are produced by spinning solutions, which, in addition to at least one organic substance which has a melting or softening point above approximately C. and which can be decomposed to carbon by a carbonization treatment, also contain 0.001 to 10 percent by weight of at least one fiber-forming high polymer substance which has a chain structure and which is soluble in the solvent.
  • a solution of an organic substance which is suitable as a starting material for the production of carbon fibers i.e. which can be decomposed into carbon by a carbonization treatment but which is not spinnable as such (hereinafter termed the carbon source or source of carbon) can be rendered spinnable in a simple manner by the presence of small quantities of high molecular weight linear polymers (hereinafter referred to as fiber-forming substances) or fiber-forming high polymers.
  • the fiber-forming substances are added in quantities of about 0.001 to 10 percent by weight, preferably about 0.01 to 5 percent by weight. For allpractical purposes, these concentrations are sufficient for achieving spinnability.
  • spinning can be carried out with inexpensive carbon sources, which are by-products or waste products ofother processes, with addition of high polymer fiberforming substances in only very small'amountwith obviouseconomic advantage.
  • the concentration of the carbon source in the'solution can vary within wide limits. Solutions having concentrations of from about 5 to 60 percent can be used but the concentration of the carbon source in the solutions used for spinning is generally between about and 40 percent by weight.
  • the process enables carbon and graphite fibers to be obtained for the first time from numerous organic starting materials which could not hitherto be used since they could not be obtained in the form of fibers.
  • the necessary condition for the suitability of an organic material is a sufficiently high carbon residue in the carbonization process which of course depends upon the initial carbon content and should preferably be at least about 10 percent by weight of the starting material.
  • the material must not pass through a liquid or tacky state in the course of carbonization. This is ensured whenever the melting point is substantially above the decomposition temperature.
  • Carbohydrate derivatives such as starch, partly degraded or oxidized starch, dextrin, hemicellulose, cellulose derivatives such as methyl cellulose, vegetable gums, polymeric sugar derivatives such as polyuronic acids, e.g. pectin, pectinic acid or alginic acid, proteins such as casein, gelatine or fish glue, organic acid derivatives which are capable of internal salt formation such as glycocol or betaine, sulfonic acids, their substitution products and their salts, especially ammonium slats, lignin, ligninsulfonic acid and its salts, in particular ammonium lignin sulfonate.
  • polyuronic acids e.g. pectin, pectinic acid or alginic acid
  • proteins such as casein, gelatine or fish glue
  • organic acid derivatives which are capable of internal salt formation such as glycocol or betaine, sulfonic acids, their substitution products and their salts, especially ammonium
  • substances whose melting or softening point is below the decomposition temperature may also be used as carbon sources provided the fibers spun from them are treated so that they will maintain their fibrous character during the actual carbonization, e.g. as by being rendered in-. fusible.
  • the melting or softening point of the substances used as carbon sources should not be substantially below about 80 C. Numerous measures are already known in the literature by which fiber materials which soften before their decomposition can be rendered infusible.
  • a process for producing carbon or graphite fibrous material from a starting material which contains wool has been claimed in German Auslegeschrift 1,255,629. Since the starting material which contains wool would lose its fibrous structure by a heat treatment, this must be prevented by special measures which comprise heating the starting material to about 200 C. with access of air at such a rate that the temperature rises by from 5 to 50 C. per hour. Heating is then continued to a temperature of about 300 C. under a restricted air supply and at a rate of temperature increase of 1 to 10 C. per hour, and the temperature is then raised to about l,000 C. with exclusion of air at a rate of temperature increase of 10 to 100 C. per hour, and'heating is carried out at least partly in an atmosphere which contains formaldehyde, ammonia and/or carbon dioxide.
  • tar fibers can be rendered infusible by a treatment with ozone or peroxides followed by oxidation in air.
  • fibers of vinyl chloride copolymers, polyvinyl alcohol derivatives and/or polyvinyl alcohol are rendered infusible by a treatment with acid condensing agents below the softening temperature of the fibers.
  • the condensing agents used are preferably concentrated sulfuric acid or difluoroand hexa-fluorophosphoric acid.
  • Polyvinyl alcohol which melts at about 230 C. in inert gas, can be rendered infusible simply by a preliminary oxidation with air.
  • Carbon sources in accordance with this invention are therefore any low molecular weight or higher molecular weight organic substances which have melting or softening points above approximately C., are soluble in a solvent and can be decomposed to carbon by a carbonization treatment.
  • Carbon sources include especially those substances which in addition to having the above mentioned features have a spinnability of less than 10 cm as 10 percent solutions.
  • the carbon residue from carbonization should be at least about 10 percent by weight of the carbon source.
  • the process according to the invention makes it possible for the first time to convert molecular disperse solutions and those of low polymers, in particular those which have a degree of polymerization below about 50, into fibers by a dry spinning process (as defined in Ullmanns'Encyklopadie der ischen Chemie 7 [1956] page 263) and hence make them available as starting materials for carbon fibers.
  • a dry spinning process as defined in Ullmanns'Encyklopadie der ischen Chemie 7 [1956] page 263
  • Compounds of this type frequently have the advantage over macromolecular substances of being more soluble so that they can be used in higher concentrations in solutions.
  • the fiber-forming substances which are used according to the invention are characterized not only by their linear polymer structure but also by'their degree of polymerization or molecular weight. It is only above a certain degree of polymerization that solutions of high polymers manifest the property of spinnability at concentrations below 5 percent.
  • the choice of the fiberforming substance depends on the particular solvent used. For aqueous solutions, water-soluble high polymers are used, preferably polyethylene oxide, polyacrylamide or acrylic acid/acrylamide copolymers and the like. In organic media, one may use not only the substances mentioned above but also other high polymer substances such as polystyrene, polyisobutylene, polymethylmethacrylate, polyisoprene, and the like.
  • Solutions of linear polymeric substances have been in use for a long time in spinning processes of the manmade fiber industry. These solutions also have the property of spinnability but the molecular weights and degrees of polymerization of the substances used for these purposes are substantially lower than in the substances used according to the invention. These solutions are not sufficiently spinnable until they have concentrations in the region of 25 to 45 percent.
  • a 25 percent solution of a polyacrylonitrile having a molecular weight of 35,000 to 50,000, which cor responds to a degree of polymerization of 660 to 950 is spun in dimethyl formamide (Ullmanns Encyklopadie der ischen Chemie, 7 [1956]). If such substances are made up into 0.01 to 5 percent solutions in a suitable solvent, they are not spinnable. When extruded through a nozzle, they only form a series of droplets but no coherent fibers.
  • 2 percent aqueous solutions of polyethylene oxide may achieve various values of spinnability depending on the molecular weight or degree of polymerization.
  • the solution of a polyethylene oxide A having a degree of polymerization DP of 5,450 has a spinnability of only 30 cm
  • the solution of a polyethylene oxide B (DP 17,000) has a spinnability of 130 cm
  • polyethylene oxide C (DP 68,200) a spinnability of 225 cm
  • the spinnability of a polyethylene oxide D with DP 136,400 is already far above 300 cm.
  • the limiting viscosity number also known as the intrinsic viscosity is defined as follows:
  • polyacrylamides or acrylamide/acrylic acid copolymers and salts thereof are also suitable.
  • a copolymer of acrylamide and acrylic acid which consists to an extent of percent of polyacrylamide and which has a degree of polymerization of 14,080 has a spinnability of 300 cm when present as a 1.7 percent aqueous solution.
  • a higher molecular weight product with a degree of polymerization of 70,400 has a spinnability of 300 cm when its concentration in water is only 0.25 percent.
  • the inherent viscosity (In 1 r)/c (determined in water, 25 C., pH 7; 0,05 percent solution with 0.1 percent NaCl at 'r 0.98 dyn/cm where c is the concentration in gram per ml. of the solvent) of this product is 35.
  • the proportion of acrylamide to acrylic acid in' the copolymers may have any value between 0 l and 1 0.
  • a copolymer containing 2.5 percent of acrylamide (97.5 percent of acrylic acid) has a spinnability of 210 cm when present as a 0.8 percent solution.
  • high spinnability is also achieved if the acrylic acid of TABLE 2 Substance Degree of Concentration Spinnability polymerization Percent by (cm) wt. in CH,C1,
  • Polyethylene oxide which can be spun in the form of an aqueous solution also manifests this property in organic solvents such as CH Cl
  • An increase in spinnability with the degree of polymerization is again observed here. The effect is even greater in CH Cl than in water.
  • Polyethylene oxide with a degree of polymerization of 6,800 has a spinnability of 300 cm already at a concentration of only 0.2 percent.
  • polyesters polyamides, polypeptides, polysaccharides,
  • Fiber-forming substances within the meaning of the present invention are therefore high polymer organic soluble compounds which have a linear polymeric structure. They preferably have degrees of polymerization above approximately 2,000.
  • the usual commercial solvents may be used. Their choice will depend on the solubility of the carbon source. It is advantageous to use solvents with boiling points below about 200 C.
  • the solvent used is preferably water.
  • a solution of the fiber-forming substance is added to the solutions of the carbon source until the solution iscapable of producing fibers, i.e. until sufficient spinnability is obtained, which generally occurs in the region of from 0.01 to 2 percent by weight of the fiber-forming substance based on the total amount of the solution.
  • the carbon source may also be dissolved directly inthe solution of the fiber-forming substance.
  • the concentration of the carbon source may vary within wide limits. At high concentrations, a lower concentration of the fiberforming substance is generally sufficient whereas at lower concentrations of the carbon source it is necessary to use larger quantities of the fiber-forming substance. The quantity also depends on the nature of the solution, more highly viscous solutions generally requiring less fiber-forming substance than thin, very liquid solutions.
  • the spinnability of the solution should be at least above 50, advantageously at least above 100 and preferably at least above 200.
  • the known inorganic acids especially hydrohalic acids,-may be added.
  • organic monoor polycarboxylic acids such as formic acid, acetic acid or oxalic acid, advantageously in quantities of from about 1 to 60 percent.
  • the spinning solutions thus obtained have numerous advantageous properties. Apart from having good spin-v nability, the relatively low viscosity and the ease with which they can therefore be handled are added advantages.
  • the viscosity of these solutions may lie between about 0.1 to 100 poise but preferably from about 1 to 10 poise, therefore below the values usually required for spinning processes.
  • the spinning solutions are therefore easily to be filtered, easily to be degasified, and'can easily be pumped through pipes.
  • Spinning may be carried out by either the wet or the dry spinning process but a conventional dry spinning process is preferably employed.
  • the solutions are spun from a multiaperture spinning die substantially at temperatures below the boiling point of the solvent used.
  • the filaments pass through a spinning column which can be heated to several hundred degrees centigrade, depending on the solvent used, and which may be traversed by a current of air or inert gas in the usual manner. In the column, the fibers are drawn out to a diameter of from about 50 to about 1 micron. At the same time, most of the solvent is removed.
  • the filament which is at first highly fluid, is concentrated in the process and is converted into the gel state via a highly viscous state. At the stage of gel formation, the filaments may still contain some solvent. After leaving the spinning column, the filaments are collected. These filaments are the actual starting material for the production of carbon and graphite fibers.
  • the fibrous starting material is now converted in the conventional manner either continuously or intermittently into fibers consisting substantially of more than 97 percent of carbon by increasing the temperature to about l,000 C. 2,000 C.; heating must be carried out in a stream of an inert gas at a temperature of at least about 400 C.
  • the starting fibers are pretreated before the actual carbonization process. This pretreatment may consist of a special gas treatment, for example with HCl, C1 N0 or 0 either to improve the behavior during carbonization or to render the fibers infusible.
  • the temperature treatment depends on the starting material used for providing the carbon.
  • the measures described in the patent literature for the known processes for the production of carbon fibers may be used as a guide for successful carbonization.
  • Carbon fibers may also be graphitized by a thermal treatment at a temperature from about 2,000 C. to about 3,000 C. under a protective gas.
  • the carbon and graphite fibers produced according to the invention may be used for numerous purposes. Yarns, woven fabrics, felts and wadding can be produced by conventional processes, and these products may be used, for example, for high temperature insulation, as filters for hot, corrosive gases and liquids, as reinforcing components in composite materials and as catalysts and catalyst carriers.
  • Example 1 300 g of an aqueous 40 percent ammonium lignin sulfonate solution (SAP/N of Zellstoff Waldhof) were mixed with 100 g of a 2 percent aqueous polyethylene oxide solution (WSR 301 of UCC with [1;] 9.15) and 45 g of water. The solution was homogenized with the introduction of ammonia gas up to a pH of 10. The filtered spinning solution which contained 27 percent of ammonium lignin sulfonate and 0.45 percent of polyethylene oxide was spun in a column which was heated to 80 C. and washed with dry air. The spun filaments were taken up on a rotating drum. The spinning cake removed from the drum was heated from 100 to 250 C. in air in the course of 1 hour.
  • SAP/N of Zellstoff Waldhof a 2 percent aqueous polyethylene oxide solution
  • the fibers were then heated in a stream of nitrogen, first to 400 C. at a rate of temperature increase of 40 per hour and finally to 1,000 C. at a rate of temperature increase of 150 per hour.
  • Flexible carbon fibers were obtained (carbon yield: 36 percent).
  • a part of the carbon fibers was subjected to a graphitization treatment by heating for 2 hours to 2,600 C. under an argon atmosphere.
  • Example 2 300 g of dextrin, 300 g of glacial acetic acid and 300 g of water were boiled until completely dissolved. 430 g of the filtered solution were concentrated by evaporation to 320 g and mixed with 214 g of a 2 percent aqueous solution of a copolymer of acrylic acid and acrylamide (Praestol 2935 of Stockhausen having an inherent viscosity of (In 1 r)/c 35.0) to form a spinning solution which contained 24 percent dextrin and 0.8 percent of acrylic acid/acrylamide copolymer. This solution was spun as described in Example 1. The dextrin filaments were kept under nitrogen at 220 C. for hours. The fibers were then heated in a stream of nitrogen to 400 C.
  • Example 4 300 g of gelatine were dissolved in 300 g of hot water and mixed with 300 g of glacial acetic acid and 600 g of a 2 percent aqueous solution of an acrylic acid/acrylamide copolymer (Praestol 2935 of Stockhausen, viscosity (ln '1 .r)/c 35.0). The solution, which contained 0.8 percent of an acrylic acid/acrylamide copolymer in addition to 20 percent of gelatine, was spun into gelatine filaments as in Example 1.
  • the gelatine fibers were converted into carbon fibers (carbon yield: 21 percent) by carbonization in a stream of nitrogen (5 hours kept at 220 C., heated up to 400 C. at'a rate of temperature increase of 30 per hour, and up to 1,000 C. at a rate of increase of 150 per hour).
  • a 10 percent gelatine solution prepared in a similar manner without the fiber-forming substance is not spinnable.
  • Example 5 v A spinning solution containing 8.8 percent of alginic acid and 0.5 percent of acrylic acid/acrylamide copolymer was obtained by dissolving g of alginic acid in 560 g of formamide and then thoroughly homogenizing this solution with 680 g of a 1 percent solution in formamide of the acrylic acid/acrylamide copolymer used in Examples 2 and 4, and the resulting product was spun as in the previous examples to produce alginic acid filaments. Carbon fibers could be obtained from these filaments by carbonization in a manner analogous to Example 2. Without the fiberforming substance, an 8.8 percent alginic acid solution in formamide was not spinnable.
  • Example 6 33 g of starch (amylium solubile of Merck), 33 g of water and 33 g of glacial acetic acid were concentrated by boiling to 62 g. After the addition of 15.5 g of water,
  • Example 8 Polyvinyl acetate having a degree of polymerization of about 430 was made up into a 30 percent solution in methylene chloride. This solution was not spinnable. By the addition of 20 g of 3 percent solution of polymethylmethacrylate (degree of polymerization DP 15,000) in methylenechloride to l g of the polyvinyl acetate solution, a spinning solution was obtained which contained 25 percent of polyvinyl acetate and 0.5 percent of polymethylmethacrylate. This spinning solution was spun as in Example 1 to produce polyvinyl acetate filaments. Since polyvinyl acetate melts above approximately 100 C., the spun filaments first had to be rendered infusible.
  • a spinning solution containing 24.8 percent of naphthol-l-disulfonic acid- (3,8) and 0,57 percent of polyethylene oxide was obtained by the addition of 41 g of a 2 percent aqueous polyethylene oxide solution, using the same polyethylene oxide as in Examples 1, 3 and 7.
  • This spinning solution was spun into filaments in a manner analogous to Example 1.
  • Carbonization under nitrogen rate of heating to 400 C.: 57 C./h and between 400 C. and 1,000 C.: 170 C./h
  • the improvement which comprises forming said solution by dissolving in a solvent to a concentration of about 0.001 to 10 percent by weight at least one fiber-forming linear high polymer having a degree of polymerization in excess of about 2,000, and a greater amount of a carbon source comprising at least one carbonizable carbon-containing organic material having a softening or melting point in excess of about 80 C.'and a degree of polymerization below about 2,000, whereby said fibenforming linear high polymer imparts to said solution a spinnability of at least 50 cm.
  • said carbon source is a material leaving a carbon residue after carbonization which is at least about 10 percent by weight of the original material and, when dissolved alone in said solvent to a concentration of 10 percent, has a spinnability of less than about 10 cm.
  • said carbon source is at least one of lignin, derivatives of lignin, carbohydrate derivatives and proteins.
  • said carbon source comprises a monomer or a polymer having a degree of polymerization less than about 50.
  • said carbon source is selected from vinyl polymers, polyethers, polyesters, polyanhydrides, polyurethanes, polyureas, polyamides, phenol formaldehyde resins, polyolefins, and mixtures, derivatives or copolymers thereof.
  • said fiber-forming high polymer is at least one of polystyrene, polyisobutylene, polymethylmethacrylate, polyisoprene, vinyl polymers and copolymers, diolefin polymers, polydienes, polyethylene oxide, substituted polyethers and thioethers, polyesters, polyamides, polypeptides, polysaccharides, polysiloxanes, and polyacrylamide or acrylic acid/acrylamide copolymers or their alkali metal or ammonium salts.
  • said fiberforming high polymer is selected from polyethylene oxide, polyacrylamide, and acrylic acid/acrylamide copolymers or their alkali metal ammonium salts or substituted ammonium salts having an inherent viscosity (In 1; r)/c above 4 (determined at a shearing stress r 0.98 dynlcm' 25 C., pH 7, 0.05 percent solution with 0.1 percent NaCl).
  • said fiber-forming high polymer is at least one of polystyrene, polyisobutylene, polymethylmethacrylate, polyisoprene, vinyl polymers and copolymers, diolefin polymers, polydienes, polyethylene oxide, substituted polyethers and thioethers, polyesters, polyamides, polypeptides, polysaccharides, polysiloxanes, polyacrylamide, and acrylic acid/acrylamide copolymers or their alkali metal, ammonium, and substituted ammonium salts present in the solution in a

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US00078943A 1969-10-17 1970-10-07 Process for the production of carbon fibers Expired - Lifetime US3723609A (en)

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Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3852428A (en) * 1970-09-08 1974-12-03 Coal Industry Patents Ltd Manufacture of carbon fibres
US3903220A (en) * 1972-12-04 1975-09-02 Carborundum Co Method for producing carbon fibers
US3966887A (en) * 1971-11-08 1976-06-29 Charbonnages De France Process for production of carbon fibers and the resultant fibers
US4002426A (en) * 1971-01-25 1977-01-11 Celanese Corporation Production of stabilized non-burning acrylic fibers and films
US4020145A (en) * 1973-01-18 1977-04-26 Celanese Corporation Carbon fiber production
US4070446A (en) * 1973-02-01 1978-01-24 Sumitomo Chemical Company, Limited Process for production of carbon fiber
US4793912A (en) * 1986-06-02 1988-12-27 Mitsubishi Oil Co., Ltd. Process for producing a pitch having a low softening point
EP0304010A3 (en) * 1987-08-21 1990-02-28 Mitsui Mining Company, Limited Process for producing carbon materials
US5217701A (en) * 1987-08-21 1993-06-08 Mitsui Mining Company, Limited Process for producing carbon materials
US5340511A (en) * 1992-08-17 1994-08-23 Enerkom (Proprietary Limited Production of carbon fibre
US20080317661A1 (en) * 2007-06-25 2008-12-25 Weyerhaeuser Co. Carbon fibers from kraft softwood lignin
US20110274612A1 (en) * 2009-01-15 2011-11-10 Fraunhofer Geseiischaft Zur Forderung Der Angewandten Forschung E.V. Lignin derivative, shaped body comprising the derivative and carbon fibers produced from the shaped body
WO2012003070A1 (fr) * 2010-06-30 2012-01-05 Weyerhaeuser Nr Company Dopes contenant de la lignine et du polyacrylonitrile, fibres, et leurs procédés de fabrication
WO2012112108A1 (fr) * 2011-02-14 2012-08-23 Innventia Ab Procédé de fabrication d'une fibre de lignine
EP2216431A4 (fr) * 2007-11-27 2012-08-29 Univ Sevilla Procédé permettant la fabrication à température ambiante de micro et de nanofibres de lignine et d'autres composés résineux
WO2013020919A1 (fr) * 2011-08-05 2013-02-14 Sgl Carbon Se Fibres de précurseur à base de matières premières renouvelables
US20130214443A1 (en) * 2012-02-17 2013-08-22 E I Du Pont De Nemours And Company Process for the production of carbon fibers from poly(alpha(1->3) glucan) fibers
EP2644758A1 (fr) 2012-03-29 2013-10-02 Honda R&D Europe (Deutschland) GmbH Stabilisation de fibres de carbone de lignine avec des agents de réticulation
CN103451777A (zh) * 2013-09-10 2013-12-18 北京梦狐宇通竹纤维研究开发中心 制备中间相木质素及其碳纤维的工艺方法
CN103748271A (zh) * 2011-05-18 2014-04-23 斯托拉恩索公司 制造含木质素的前体纤维和碳纤维的方法
WO2014076612A1 (fr) * 2012-11-13 2014-05-22 Stora Enso Oyj Produit intermédiaire thermoplastique thermoréactif et son procédé de fabrication
WO2015143497A1 (fr) * 2014-03-28 2015-10-01 The University Of Queensland Fibres de carbone obtenues à partir de matières premières biopolymères
US9850603B2 (en) * 2010-10-20 2017-12-26 Fitesa Simpsonville, Inc. Nonwoven fabric, a laminated fabric, a nonwoven fabric product, a multicomponent fibre, a web, and a method of producing the nonwoven fabric
US11040882B2 (en) * 2018-03-23 2021-06-22 Kabushiki Kaisha Toyota Chuo Kenkyusho Carbon material precursor, carbon material precursor composition containing the same, and method for producing carbon material using these
US11286582B2 (en) * 2012-01-23 2022-03-29 Rise Innventia Ab Method for stabilizing lignin fiber for further conversion to carbon fiber
WO2024013370A1 (fr) 2022-07-14 2024-01-18 Technikum Laubholz Gmbh Fibres précurseurs de fibres de carbone à base de lignine, leur production et leur utilisation

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2118488A1 (de) * 1971-04-16 1972-10-26 Farbenfabriken Bayer Ag, 5090 Lever Kusen Stabile Ligmnfasern, Kohlenstoff fasern und Verfahren zu deren Herstellung
JPS5966518A (ja) * 1982-10-08 1984-04-16 Toho Rayon Co Ltd 黒鉛繊維の製造法

Citations (5)

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US3443899A (en) * 1966-07-22 1969-05-13 North American Rockwell Process for making graphitic-type fibers
US3488151A (en) * 1967-09-01 1970-01-06 Union Carbide Corp Preparation of carbon fibers from polyvinyl alcohol base fibers
US3552923A (en) * 1966-06-28 1971-01-05 William George David Carpenter Production of carbon fibers
US3552922A (en) * 1966-08-03 1971-01-05 Nippon Carbon Co Ltd Method for the manufacture of carbon fiber
US3595946A (en) * 1968-06-04 1971-07-27 Great Lakes Carbon Corp Process for the production of carbon filaments from coal tar pitch

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3552923A (en) * 1966-06-28 1971-01-05 William George David Carpenter Production of carbon fibers
US3443899A (en) * 1966-07-22 1969-05-13 North American Rockwell Process for making graphitic-type fibers
US3552922A (en) * 1966-08-03 1971-01-05 Nippon Carbon Co Ltd Method for the manufacture of carbon fiber
US3488151A (en) * 1967-09-01 1970-01-06 Union Carbide Corp Preparation of carbon fibers from polyvinyl alcohol base fibers
US3595946A (en) * 1968-06-04 1971-07-27 Great Lakes Carbon Corp Process for the production of carbon filaments from coal tar pitch

Cited By (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3852428A (en) * 1970-09-08 1974-12-03 Coal Industry Patents Ltd Manufacture of carbon fibres
US4002426A (en) * 1971-01-25 1977-01-11 Celanese Corporation Production of stabilized non-burning acrylic fibers and films
US3966887A (en) * 1971-11-08 1976-06-29 Charbonnages De France Process for production of carbon fibers and the resultant fibers
US3903220A (en) * 1972-12-04 1975-09-02 Carborundum Co Method for producing carbon fibers
US4020145A (en) * 1973-01-18 1977-04-26 Celanese Corporation Carbon fiber production
US4070446A (en) * 1973-02-01 1978-01-24 Sumitomo Chemical Company, Limited Process for production of carbon fiber
US4793912A (en) * 1986-06-02 1988-12-27 Mitsubishi Oil Co., Ltd. Process for producing a pitch having a low softening point
EP0304010A3 (en) * 1987-08-21 1990-02-28 Mitsui Mining Company, Limited Process for producing carbon materials
US5217701A (en) * 1987-08-21 1993-06-08 Mitsui Mining Company, Limited Process for producing carbon materials
US5340511A (en) * 1992-08-17 1994-08-23 Enerkom (Proprietary Limited Production of carbon fibre
US20080317661A1 (en) * 2007-06-25 2008-12-25 Weyerhaeuser Co. Carbon fibers from kraft softwood lignin
WO2009002785A1 (fr) 2007-06-25 2008-12-31 Weyerhaeuser Company Fibres de carbone à base d'alcali-lignine de bois tendre
US7678358B2 (en) 2007-06-25 2010-03-16 Weyerhaeuser Nr Company Carbon fibers from kraft softwood lignin
EP2216431A4 (fr) * 2007-11-27 2012-08-29 Univ Sevilla Procédé permettant la fabrication à température ambiante de micro et de nanofibres de lignine et d'autres composés résineux
US20110274612A1 (en) * 2009-01-15 2011-11-10 Fraunhofer Geseiischaft Zur Forderung Der Angewandten Forschung E.V. Lignin derivative, shaped body comprising the derivative and carbon fibers produced from the shaped body
WO2012003070A1 (fr) * 2010-06-30 2012-01-05 Weyerhaeuser Nr Company Dopes contenant de la lignine et du polyacrylonitrile, fibres, et leurs procédés de fabrication
CN103080390A (zh) * 2010-06-30 2013-05-01 韦尔豪泽Nr公司 含木质素/聚丙烯腈的纺丝液、纤维及其制备方法
JP2013532238A (ja) * 2010-06-30 2013-08-15 ウェヤーハウザー・エヌアール・カンパニー リグニン／ポリアクリロニトリルを含有するドープおよび繊維、ならびにこれらの製造方法
CN103080390B (zh) * 2010-06-30 2015-09-02 韦尔豪泽Nr公司 含木质素/聚丙烯腈的纺丝液、纤维及其制备方法
US8771832B2 (en) 2010-06-30 2014-07-08 Weyerhaeuser Nr Company Lignin/polyacrylonitrile-containing dopes, fibers, and methods of making same
US9133568B2 (en) 2010-06-30 2015-09-15 Weyerhaeuser Nr Company Lignin/polyacrylonitrile-containing dopes, fibers, and methods of making same
US9850603B2 (en) * 2010-10-20 2017-12-26 Fitesa Simpsonville, Inc. Nonwoven fabric, a laminated fabric, a nonwoven fabric product, a multicomponent fibre, a web, and a method of producing the nonwoven fabric
WO2012112108A1 (fr) * 2011-02-14 2012-08-23 Innventia Ab Procédé de fabrication d'une fibre de lignine
US9446955B2 (en) 2011-02-14 2016-09-20 Innventia Ab Method for producing a lignin fiber
CN103748271A (zh) * 2011-05-18 2014-04-23 斯托拉恩索公司 制造含木质素的前体纤维和碳纤维的方法
CN103748271B (zh) * 2011-05-18 2017-10-20 斯托拉恩索公司 制造含木质素的前体纤维和碳纤维的方法
WO2013020919A1 (fr) * 2011-08-05 2013-02-14 Sgl Carbon Se Fibres de précurseur à base de matières premières renouvelables
US11286582B2 (en) * 2012-01-23 2022-03-29 Rise Innventia Ab Method for stabilizing lignin fiber for further conversion to carbon fiber
US20130214443A1 (en) * 2012-02-17 2013-08-22 E I Du Pont De Nemours And Company Process for the production of carbon fibers from poly(alpha(1->3) glucan) fibers
US9096956B2 (en) * 2012-02-17 2015-08-04 E I Du Pont De Nemours And Company Process for the production of carbon fibers from poly(α(1-→3) glucan) fibers
EP2644758A1 (fr) 2012-03-29 2013-10-02 Honda R&D Europe (Deutschland) GmbH Stabilisation de fibres de carbone de lignine avec des agents de réticulation
WO2014076612A1 (fr) * 2012-11-13 2014-05-22 Stora Enso Oyj Produit intermédiaire thermoplastique thermoréactif et son procédé de fabrication
US10941297B2 (en) 2012-11-13 2021-03-09 Stora Enso Oyj Thermally reactive thermoplastic intermediate product and method of manufacturing thereof
CN103451777B (zh) * 2013-09-10 2015-06-17 北京梦狐宇通竹纤维研究开发中心 制备中间相木质素及其碳纤维的工艺方法
CN103451777A (zh) * 2013-09-10 2013-12-18 北京梦狐宇通竹纤维研究开发中心 制备中间相木质素及其碳纤维的工艺方法
WO2015143497A1 (fr) * 2014-03-28 2015-10-01 The University Of Queensland Fibres de carbone obtenues à partir de matières premières biopolymères
US11040882B2 (en) * 2018-03-23 2021-06-22 Kabushiki Kaisha Toyota Chuo Kenkyusho Carbon material precursor, carbon material precursor composition containing the same, and method for producing carbon material using these
WO2024013370A1 (fr) 2022-07-14 2024-01-18 Technikum Laubholz Gmbh Fibres précurseurs de fibres de carbone à base de lignine, leur production et leur utilisation
DE102022117670A1 (de) 2022-07-14 2024-01-25 Technikum Laubholz Gmbh Precursor-Fasern von Lignin-basierten Carbonfasern, deren Herstellung und Verwendung
JP2025522096A (ja) * 2022-07-14 2025-07-10 テクニカム ラウプホルツ ゲーエムベーハー リグニン系炭素繊維の前駆体繊維、その製造及び使用

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GB1323765A (en) 1973-07-18
CH540852A (de) 1973-08-31
NL7015164A (fr) 1971-04-20
DE1952388B2 (de) 1977-02-03
DE1952388A1 (de) 1971-05-13
CA938416A (en) 1973-12-18
BE757620A (fr) 1971-04-16
AT310343B (de) 1973-09-25
ES384640A1 (es) 1973-01-16

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