US3285696A - Method for the preparation of flexible carbon fibre - Google Patents

Method for the preparation of flexible carbon fibre Download PDF

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Publication number
US3285696A
US3285696A US270807A US27080763A US3285696A US 3285696 A US3285696 A US 3285696A US 270807 A US270807 A US 270807A US 27080763 A US27080763 A US 27080763A US 3285696 A US3285696 A US 3285696A
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fibre
acrylonitrile
mol percent
carbonized
preparation
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US270807A
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Tsunoda Yasugoro
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Tokai Denkyoku Seizo KK
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Tokai Denkyoku Seizo KK
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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
    • 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
    • D01F9/225—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 from stabilised 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
    • D01F9/20—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
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/34—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxygen, ozone or ozonides
    • 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

  • This invention relates to methods for the preparation of flexible heat resisting and corrosion resistant fibre.
  • the invention provides a method for the preparation of heat resisting and corrosion resistant fibre, characterized in that fibre, made of a material selected from the group consisting of acrylonitrile polymer and acrylonitrile copolymer prepared from less than 85 mol percent of acrylonitrile and not more than 15 mol percent of a monovinyl compound, is heated at a temperature from 180 to 550 C. in an oxygen-containing atmos phere for a time sufficient to blacken the fibre. Then the blackened material is carbonized and if necessary graphitized by a conventional method.
  • the fibrous carbon and graphite prepared by the methd mentioned. above are mechanically stronger and more flexible than those made by direct carbonization or graphitization without the pretreatment according to the invention.
  • a product such as -a filament, staple, or batting is made of the fibre which is made from acrylonitrile homopolymer or copolymer produced by copolymerizing not less than 85 mol percent of acrylonitrile with not more than 15 mol percent of a monovinyl compound such as methyl acrylate, methyl methacrylate, vinyl, acetate, vinyl chloride, vinylidine chloride, 2-methyl-5-vinyl pyridine or the like.
  • This product is heated for 5-60 minutes at 180-230 C. in an oxygen containing atmosphere such as air.
  • the temperature and time necessary for heating depend on the thickness of the fibre or woven fabric but, for convenience, it is determined by the degree of blackening of the fibre.
  • Polyacrylonitrile becomes yellowish, brown and black successively by heating in air, but yellowish and brown fibres are not suit-able for the purpose of this invention since their carbonized or graphitized products are brittle.
  • the blackened. fibre is carbonized at a temperature between 700-1200 C. for not less than 1 hour in an inert atmosphere to form a carbonized fibre. If a more heat resistant and corrosion resistant fibre is required, the carbonized fibre is graphitized at a temperature bep .JCC
  • tween 1200-3000 C. in an inert atmosphere to form a graphitized fibre.
  • Said inert atmosphere may be an inert gas or a packing material such as graphite, carbon black and silica.
  • Example I Staple of acrylonitrile copolymer containing 4 mol percent of methyl acrylate (yarn countings #48, two-ply) was heated in air at 220 C. for 3 hrs. in order to blacken it completely. Then the blackened fibre was heated in a nitrogen atmosphere at 1,000 C. for 1 hr. The product was not broken by bending, its tensile strength being above 60 g./yarn. The same staple was heated in air at 220 C. for 20 minutes and. a dark brown fibre was obtained. Then the fibre was heated in a nitrogen atmosphere at 1,000 C. for 1 hour.
  • the tensile strength of the product which was made merely by direct heating of the same fibre of polyacrylonitrile in a nitrogen atmosphere at 1,000 C. for 1 hr. was as small as about 6-11 g./yarn. The latter product was relatively'inflexible so that it too was readily broken by bending.
  • Example 3 A fibre made of copolymer of acrylonitrile 92 mol percent and 2-methyl-5-vinylpyridine 8 mol percent was treated in the manner mentioned in Examples 1 and 2. Substantially the same results were obtained.
  • Example 4 Woven fabric (plain weave; warp and woof yarn countings No. 48, two-ply) made of yarns of acrylonitrile copolymer containing 4 mol percent of methyl acrylate was heated in air at 220 C. for 1 hr. and then the blackened fibre was heated in nitrogen at 1,000 C. for 1 hr. The product was flexible and not broken even by bending to an angle of 180 degrees. The woven fabric heated solely at 1,000 C. for 1 hr. was broken by bending to angle of 15.
  • Example 5 The same yarn as that used in Example 1 was blackened by being heated in air at 220 C. for 30 minutes. Then it was buried in graphic powder and graphitized at 3,000 C. The product was flexible, its tensile strength being above 40 g./yarn. The same yarn was buried in graphite and graphitized at 3,000 C. The product obtained in this way was very brittle, its tensile strength being below 6 g./yarn.
  • a method for the preparation of flexible heat resistant and corrosion resistant fibre comprising pretreating a fibre, which is to be carbonized and which is selected from the group consisting of acrylonitrile homopolymer and acrylonitrile copolymer prepared from not less than 85 mol percent of acrylonitrile and not more than 15 mol percent of a monovinyl compound, by heating the fibre at a temperature of from 180 to 550 C. in an oxygen containing atmosphere for a time sufficient to blacken the fibre',and then carbonizing the blackened fibre at a temperature between 700 and 1200 C. for not less than one hour in an inert atmosphere to form a carbonized fibre.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Fibers (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Woven Fabrics (AREA)

Description

United States Patent '0.
3,285,696 METHOD FOR THE PREPARATION OF FLEXIBLE CARBON FIBRE Yasugoro Tsunoda, Kumamoto-ken, Japan, assignor to Tokai Denkyoku Seizo Kabushiki Kaisha, Tokyo, Japan No Drawing. Filed Apr. 5, 1963,'Ser. N0.270,807 Claims priority, application Japan, Aug. 25,1960, 35/ 36,145 3 Claims. (Cl. 23-209.1)
This application is a continuation-in-part of my earlier previously copending application, Ser. No. 97,461 filed March 22, 1961, now abandoned.
This invention relates to methods for the preparation of flexible heat resisting and corrosion resistant fibre.
The corrosion resistance of carbon and graphite against various chemicals and the heat resistance of carbon and graphite are substantially perfect excepting when these materials are placed in an oxidizing atmosphere. It has therefore been considered desirable to produce woven fabric made of carbon or graphite but which also has satisfactory mechanical strength It is known that if a fibre (for example, cotton or Orlon) containing carbon is heated at high temperatures (700-3,000 C.) in an inert gas atmosphere such as nitrogen or argon, the fibre retains the shape it had before-the heat treatment. Fibre obtained in this way is, however, so brittle that yarn and woven fabric made of such fibre are of no practical use.
It is an object of this invention to prepare fibrous carbon and graphite having improved properties.
Other objects and advantages of this invention will be apparent from the following description of some preferred embodiments.
The invention provides a method for the preparation of heat resisting and corrosion resistant fibre, characterized in that fibre, made of a material selected from the group consisting of acrylonitrile polymer and acrylonitrile copolymer prepared from less than 85 mol percent of acrylonitrile and not more than 15 mol percent of a monovinyl compound, is heated at a temperature from 180 to 550 C. in an oxygen-containing atmos phere for a time sufficient to blacken the fibre. Then the blackened material is carbonized and if necessary graphitized by a conventional method.
The fibrous carbon and graphite prepared by the methd mentioned. above are mechanically stronger and more flexible than those made by direct carbonization or graphitization without the pretreatment according to the invention.
According to the invention, a product such as -a filament, staple, or batting is made of the fibre which is made from acrylonitrile homopolymer or copolymer produced by copolymerizing not less than 85 mol percent of acrylonitrile with not more than 15 mol percent of a monovinyl compound such as methyl acrylate, methyl methacrylate, vinyl, acetate, vinyl chloride, vinylidine chloride, 2-methyl-5-vinyl pyridine or the like. This product is heated for 5-60 minutes at 180-230 C. in an oxygen containing atmosphere such as air. The temperature and time necessary for heating depend on the thickness of the fibre or woven fabric but, for convenience, it is determined by the degree of blackening of the fibre. Polyacrylonitrile becomes yellowish, brown and black successively by heating in air, but yellowish and brown fibres are not suit-able for the purpose of this invention since their carbonized or graphitized products are brittle.
Then the blackened. fibre is carbonized at a temperature between 700-1200 C. for not less than 1 hour in an inert atmosphere to form a carbonized fibre. If a more heat resistant and corrosion resistant fibre is required, the carbonized fibre is graphitized at a temperature bep .JCC
tween 1200-3000 C. in an inert atmosphere to form a graphitized fibre. Said inert atmosphere may be an inert gas or a packing material such as graphite, carbon black and silica. 1
Example I 'Staple of acrylonitrile copolymer containing 4 mol percent of methyl acrylate (yarn countings #48, two-ply) was heated in air at 220 C. for 3 hrs. in order to blacken it completely. Then the blackened fibre was heated in a nitrogen atmosphere at 1,000 C. for 1 hr. The product was not broken by bending, its tensile strength being above 60 g./yarn. The same staple was heated in air at 220 C. for 20 minutes and. a dark brown fibre was obtained. Then the fibre was heated in a nitrogen atmosphere at 1,000 C. for 1 hour. A carbonized fibre resulted which was so brittle that it was easily broken by bending and its tensile strength was 20 g./yarn. On the other hand, the tensile strength of the product which was made merely by direct heating of the same fibre of polyacrylonitrile in a nitrogen atmosphere at 1,000 C. for 1 hr. was as small as about 6-11 g./yarn. The latter product was relatively'inflexible so that it too was readily broken by bending.
Example 2 Batting of acrylonitrile polymer mol percent) was blackened by heating in air at 230 C. for 15 minutes. The blackened cotton obtained in this way was then heated in a nitrogen atmosphere at 1,000 C. for 1 hr. The product retained its original form and was flexible. On the other hand, the product which was made merely by heating the same batting in a nitrogen atmosphere at 1,000 C. for 1 hr. formed a conglomerate which was easily broken by a small force.
Example 3 A fibre made of copolymer of acrylonitrile 92 mol percent and 2-methyl-5-vinylpyridine 8 mol percent was treated in the manner mentioned in Examples 1 and 2. Substantially the same results were obtained.
Example 4 Woven fabric (plain weave; warp and woof yarn countings No. 48, two-ply) made of yarns of acrylonitrile copolymer containing 4 mol percent of methyl acrylate was heated in air at 220 C. for 1 hr. and then the blackened fibre was heated in nitrogen at 1,000 C. for 1 hr. The product was flexible and not broken even by bending to an angle of 180 degrees. The woven fabric heated solely at 1,000 C. for 1 hr. was broken by bending to angle of 15.
Example 5 The same yarn as that used in Example 1 was blackened by being heated in air at 220 C. for 30 minutes. Then it was buried in graphic powder and graphitized at 3,000 C. The product was flexible, its tensile strength being above 40 g./yarn. The same yarn was buried in graphite and graphitized at 3,000 C. The product obtained in this way was very brittle, its tensile strength being below 6 g./yarn.
What is claimed is:
1. A method for the preparation of flexible heat resistant and corrosion resistant fibre, comprising pretreating a fibre, which is to be carbonized and which is selected from the group consisting of acrylonitrile homopolymer and acrylonitrile copolymer prepared from not less than 85 mol percent of acrylonitrile and not more than 15 mol percent of a monovinyl compound, by heating the fibre at a temperature of from 180 to 550 C. in an oxygen containing atmosphere for a time sufficient to blacken the fibre',and then carbonizing the blackened fibre at a temperature between 700 and 1200 C. for not less than one hour in an inert atmosphere to form a carbonized fibre. Y
2. A method according to claim 1 wherein said carbonized fibre is then graphitized at a temperature between 1200 to 3000 C. in an inert atmosphere to form a graphitized fibre.
3. A method as claimed in claim 1, wherein the pretreatment heating is effected for 5-60 minutes..
7 4' References Cited by the Examiner UNiTED "STATES PATENTS 2,799,915 7/1957 Barnett et al. 8-115.5 X 3,011,981 12/1961 Soltes 252S02 3,027,222 3/ 1962 Wilkinson 8115.5 3,107,152, 10/1963 Ford et al. 23209'.2 X
-, MILTON WEISSMAN, Primary Examiner.
OSCAR R. VERTIZ, Examiner.
E. J. MEROS, Assistant Examiner.

Claims (1)

1. A METHOD FOR THE PREPARATION OF FLEXIBLE HEAT RESISTANT AND CORROSION RESISTANT FIBRE, COMPRISING PRETREATING A FIBRE, WHICH IS TO BE CARBONIZED AND WHICH IS SELECTED FROM THE GROUP CONSISTING OF ACRYLONITRILE HOMOPOLYMER AND ACRYLONITRILE COPOLYMER PREPARED FROM NOT LESS THAN 85 MOL PERCENT OF ACRYLONITRILE AND NOT MORE THAN 15 MOL PERCENT OOF A MONOVINYL COMPOUND, BY HEATING THE FIBRE AT A TEMPERATURE OF FROM MONOVINYL COMPOUND, BY HEATING THE OXYGEN CONTAINING ATMOSPHERE FOR A TIME SUFFICIENT TO BLACKEN THE FIBRE, AND THEN CARBONIZING THE BLACKENED FIBRE AT A TEMPERATURE BETWEEN 700* AND 1200*C. FOR NOT LESS THAN ONE HOUR IN AN INERT ATMOSPHERE TO FORM A CARBONIZED FIBRE.
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Cited By (45)

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Publication number Priority date Publication date Assignee Title
US3412062A (en) * 1964-04-24 1968-11-19 Nat Res Dev Production of carbon fibres and compositions containing said fibres
US3443899A (en) * 1966-07-22 1969-05-13 North American Rockwell Process for making graphitic-type fibers
US3449077A (en) * 1967-02-13 1969-06-10 Celanese Corp Direct production of graphite fibers
US3454362A (en) * 1965-03-16 1969-07-08 Union Carbide Corp Process for producing fibrous graphite
US3488151A (en) * 1967-09-01 1970-01-06 Union Carbide Corp Preparation of carbon fibers from polyvinyl alcohol base fibers
US3497318A (en) * 1967-09-01 1970-02-24 Union Carbide Corp Preparation of carbon textiles from polyacrylonitrile base textiles
US3508874A (en) * 1968-01-12 1970-04-28 Celanese Corp Production of carbon yarns
US3508871A (en) * 1963-05-29 1970-04-28 Carborundum Co Carbonizing fibrous materials
US3528774A (en) * 1967-03-14 1970-09-15 Us Air Force Formation of high modulus,high strength graphite yarns
US3529934A (en) * 1967-01-06 1970-09-22 Nippon Carbon Co Ltd Process for the preparation of carbon fibers
US3532466A (en) * 1965-11-16 1970-10-06 Nat Res Dev Production of carbon fibres
US3533741A (en) * 1967-05-26 1970-10-13 Courtaulds Ltd Process for the production of filamentary carbon
US3533743A (en) * 1968-05-28 1970-10-13 Great Lakes Carbon Corp Process for the manufacture of continuous high modulus carbon yarns and monofilaments
US3539295A (en) * 1968-08-05 1970-11-10 Celanese Corp Thermal stabilization and carbonization of acrylic fibrous materials
US3541582A (en) * 1966-07-08 1970-11-17 Nat Res Dev Manufacture of carbon cloth from polymeric fibre material
US3547584A (en) * 1967-12-18 1970-12-15 Celanese Corp Graphitization of fibrous polyamide resinous materials
US3607059A (en) * 1969-04-02 1971-09-21 Great Lakes Carbon Corp Process for the manufacture of filamentary carbon products
US3615212A (en) * 1968-03-06 1971-10-26 Rolls Royce Method of manufacturing carbon fibers
US3619139A (en) * 1968-02-02 1971-11-09 Morganite Research & Dev Ltd Manufacture of carbon filaments
US3635675A (en) * 1968-05-28 1972-01-18 Us Air Force Preparation of graphite yarns
US3648452A (en) * 1968-08-03 1972-03-14 Dunlop Holdings Ltd Method of forming reinforcing yarns or cords
US3650668A (en) * 1970-03-09 1972-03-21 Celanese Corp Thermally stabilized acrylic fibers produced by sulfation and heating in an oxygen-containing atmosphere
US3656903A (en) * 1969-04-10 1972-04-18 Celanese Corp Direct production of graphite fibrous materials from preoxidized acrylic fibrous materials
US3660018A (en) * 1969-08-04 1972-05-02 Rolls Royce Method of manufacturing carbon fibre
US3663170A (en) * 1968-02-02 1972-05-16 Morganite Research & Dev Ltd Manufacture of carbon filaments
US3699210A (en) * 1968-09-06 1972-10-17 Monsanto Res Corp Method of graphitizing fibers
US3716332A (en) * 1970-07-27 1973-02-13 Ducommun Inc Carbonization of wool
US3772173A (en) * 1969-12-04 1973-11-13 Xerox Corp Electroconductive paper
US3779789A (en) * 1971-04-20 1973-12-18 Celanese Corp Production of pervious low density carbon fiber reinforced composite articles
US3818082A (en) * 1971-02-03 1974-06-18 Celanese Corp Process for the production of carbonaceous tapes
US3862334A (en) * 1968-06-04 1975-01-21 Secr Defence Method of manufacturing carbon fibres
US3900556A (en) * 1968-11-20 1975-08-19 Celanese Corp Process for the continuous carbonization and graphitization of a stabilized acrylic fibrous material
US3914394A (en) * 1973-02-15 1975-10-21 Japan Exlan Co Ltd Process for producing carbon fibers
US3923950A (en) * 1971-11-18 1975-12-02 Celanese Corp Production of stabilized acrylic fibers and films
US3961888A (en) * 1968-09-18 1976-06-08 Celanese Corporation Acrylic fiber conversion utilizing a stabilization treatment conducted initially in an essentially inert atmosphere
US4237109A (en) * 1976-12-17 1980-12-02 Toray Industries, Inc. Process for producing carbon fabric
US4237108A (en) * 1976-12-09 1980-12-02 Toray Industries, Inc. Process for producing carbon fabric
US4284612A (en) * 1980-01-28 1981-08-18 Great Lakes Carbon Corporation Preparation of SiC whiskers
US4517169A (en) * 1982-06-02 1985-05-14 Toray Industries, Inc. Method of producing carbon fibers
US4541973A (en) * 1983-04-21 1985-09-17 Celanese Corporation Production of ferrimagnetic spinel fibers
EP0278139A1 (en) * 1984-10-12 1988-08-17 Zoltek Corporation Manufacture of controlled surface resistance carbon fibre sheet products
US4856179A (en) * 1983-04-21 1989-08-15 Hoechst Celanese Corp. Method of making an electrical device made of partially pyrolyzed polymer
US7534854B1 (en) 2005-03-29 2009-05-19 Ut-Battelle, Llc Apparatus and method for oxidation and stabilization of polymeric materials
US7649078B1 (en) 2005-03-29 2010-01-19 Ut-Battelle, Llc Apparatus and method for stabilization or oxidation of polymeric materials
US20110114342A1 (en) * 2008-03-14 2011-05-19 Kazuhiro Ono Fire barrier protection for airplanes comprising graphite films

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US3392216A (en) * 1963-11-01 1968-07-09 Kureha Chemical Ind Co Ltd Method for producing carbon structures from molten baked substances
US4571317A (en) * 1976-02-25 1986-02-18 United Technologies Corporation Process for producing binderless carbon or graphite articles
KR890002459A (en) * 1987-07-31 1989-04-10 오카다 모리오 Method of manufacturing flame resistant fiber
US7749479B2 (en) 2006-11-22 2010-07-06 Hexcel Corporation Carbon fibers having improved strength and modulus and an associated method and apparatus for preparing same

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US3011981A (en) * 1958-04-21 1961-12-05 Soltes William Timot Electrically conducting fibrous carbon
US3027222A (en) * 1957-09-03 1962-03-27 Du Pont Fireproof acrylonitrile copolymers
US3107152A (en) * 1960-09-12 1963-10-15 Union Carbide Corp Fibrous graphite

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US2799915A (en) * 1953-03-30 1957-07-23 Johns Manville Thermal modification of acrylonitrile polymers
US3027222A (en) * 1957-09-03 1962-03-27 Du Pont Fireproof acrylonitrile copolymers
US3011981A (en) * 1958-04-21 1961-12-05 Soltes William Timot Electrically conducting fibrous carbon
US3107152A (en) * 1960-09-12 1963-10-15 Union Carbide Corp Fibrous graphite

Cited By (49)

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Publication number Priority date Publication date Assignee Title
US3508871A (en) * 1963-05-29 1970-04-28 Carborundum Co Carbonizing fibrous materials
US3412062A (en) * 1964-04-24 1968-11-19 Nat Res Dev Production of carbon fibres and compositions containing said fibres
US3454362A (en) * 1965-03-16 1969-07-08 Union Carbide Corp Process for producing fibrous graphite
US3503708A (en) * 1965-03-16 1970-03-31 Union Carbide Corp Graphite yarn
US3532466A (en) * 1965-11-16 1970-10-06 Nat Res Dev Production of carbon fibres
US3541582A (en) * 1966-07-08 1970-11-17 Nat Res Dev Manufacture of carbon cloth from polymeric fibre material
US3443899A (en) * 1966-07-22 1969-05-13 North American Rockwell Process for making graphitic-type fibers
US3529934A (en) * 1967-01-06 1970-09-22 Nippon Carbon Co Ltd Process for the preparation of carbon fibers
US3449077A (en) * 1967-02-13 1969-06-10 Celanese Corp Direct production of graphite fibers
US3528774A (en) * 1967-03-14 1970-09-15 Us Air Force Formation of high modulus,high strength graphite yarns
US3533741A (en) * 1967-05-26 1970-10-13 Courtaulds Ltd Process for the production of filamentary carbon
US3497318A (en) * 1967-09-01 1970-02-24 Union Carbide Corp Preparation of carbon textiles from polyacrylonitrile base textiles
US3488151A (en) * 1967-09-01 1970-01-06 Union Carbide Corp Preparation of carbon fibers from polyvinyl alcohol base fibers
US3547584A (en) * 1967-12-18 1970-12-15 Celanese Corp Graphitization of fibrous polyamide resinous materials
US3508874A (en) * 1968-01-12 1970-04-28 Celanese Corp Production of carbon yarns
US3663170A (en) * 1968-02-02 1972-05-16 Morganite Research & Dev Ltd Manufacture of carbon filaments
US3619139A (en) * 1968-02-02 1971-11-09 Morganite Research & Dev Ltd Manufacture of carbon filaments
US3615212A (en) * 1968-03-06 1971-10-26 Rolls Royce Method of manufacturing carbon fibers
US3533743A (en) * 1968-05-28 1970-10-13 Great Lakes Carbon Corp Process for the manufacture of continuous high modulus carbon yarns and monofilaments
US3635675A (en) * 1968-05-28 1972-01-18 Us Air Force Preparation of graphite yarns
US3862334A (en) * 1968-06-04 1975-01-21 Secr Defence Method of manufacturing carbon fibres
US3648452A (en) * 1968-08-03 1972-03-14 Dunlop Holdings Ltd Method of forming reinforcing yarns or cords
US3539295A (en) * 1968-08-05 1970-11-10 Celanese Corp Thermal stabilization and carbonization of acrylic fibrous materials
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