US3699210A - Method of graphitizing fibers - Google Patents

Method of graphitizing fibers Download PDF

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US3699210A
US3699210A US757964A US3699210DA US3699210A US 3699210 A US3699210 A US 3699210A US 757964 A US757964 A US 757964A US 3699210D A US3699210D A US 3699210DA US 3699210 A US3699210 A US 3699210A
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fibers
yarn
fiber
temperature
heating
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Robert C Binning
Leo P Parts
Robert J Peresie
Margaret L Rodenburg
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Monsanto Research Corp
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Monsanto Research Corp
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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
    • D01F9/20—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
    • D01F9/20—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
    • D01F9/30—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 from aromatic polyamides
    • 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
    • D01F9/32—Apparatus therefor
    • 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

  • ABSTRACT A method for carbonizing and/or graphitizing precursor fibers selected from the group consisting of po1yacry1onitri1e and aromatic polyamide fibers,
  • the fibers are pretreated with an oxygen-containing atmosphere at 180-550C. and thereafter heated in a laser beam in a non-oxidizing atmosphere at 700l,200C. for carbonizing and at 1,2003,600 C. for graphitizing.
  • the invention pertains to a process for preparing carbonized and/or graphitized fibers by heating suitable precursors in a laser beam, and particularly provides a continuous process for carbonizing or graphitizing a precursor yarn.
  • carbonized or graphitic fibers have been prepared by thermal degradation of variousfibcrs, e.g., cellulose, polyacrylonitrile, aromatic polyamide, etc. (see Ezekiel and Spain, Preparation of Graphite Fibers from Polymeric Fibers, Journal of Polymer Science, Part C, No. 19, pp. 249-265 (1967)).
  • the process of pretreating an acrylonitrile precursor by heating in an oxygen-containing atmosphere and thereafter carbonizing at 7001200C. and graphitizing at l200-3600C. was disclosed by Tsunoda in US. Pat. No. 3,285,696, issued Nov. 15, 1966.
  • a process for continuously graphitizing a carbonaceous thread by passing an electric current through it to heat it is disclosed by Cranch and Shinko in US. Pat. No. 3,313,597, issued Apr. 11, 1967.
  • An object of this invention is to provide a process for preparing flexible carbonized or graphitized fibers by a process utilizing a laser beam, said fibers being useful in reinforcing plastic composites.
  • R and R are selected from the group consisting of hydrogen, lower alkyl of up to three carbon atoms, phenyl, lower alkoxy containing up to three carbon atoms and nitro, and wherein the R groups can be the same or different and the R groups must be the same, and wherein X and Y are selected from the group consisting of hydrogen, lower alkyl containing up to three carbon atoms and phenyl, the phenylene radicals of said general formula being oriented other than ortho, which comprises (a) pretreating the fiber by heating at a temperature of from 180 to 550C.
  • the present method for preparing graphitized fibers comprises the additional step of (c) heating in a laser beam in a non-oxidizing atmosphere at a temperature between about 1,200 and 3,600C. for a period of time greater than one-tenth of a second, said time being dependent upon the temperature.
  • carbon-base fibers are useful in reinforced plastic composites (see Schmidt and Jones, Carbon-Base Fiber Reinforced Plastics, Chemical Engineering Progress, Vol. 58, No. 10, pp. 42-50 (1962)).
  • the fibers be flexible and have a high tensile strength and elastic modulus.
  • graphitized carbon fibers are preferred over carbonized fibers for their greater mechanical strength, higher modulus, and higher thermal stability.
  • carbon-base fibers includes a wide range of materials varying in chemical composition within the range -100 percent carbon, and varying considerably in crystal structure, e.g., from a highly disordered or essentially amorphous structure in the carbonized fibers to a more ordered but not highly crystalline structure characterizing the graphitized fibers (see Franklin, The Structure of Graphitic Carbons, Acta Crystallographica, Vol. 4, pp. 253-261 (1951)) and representing a point in the continuum from amorphous carbon to highly crystalline three-dimensionally ordered graphite.
  • carbonized fibers isv used herein for fibers containing at least 90 percent carbon, but showing essentially no (002) reflection of graphite by X-ray diffraction analysis.
  • Graphitized fibers refers to fibers containing at least percent carbon and showing at least some degree of ordering .by X-ray diffraction analysis, e.g., the (002), (004) and reflections of the graphitic carbons. Generally, such fibers do not show the highly ordered structure of crystalline graphite.
  • the present process for carbonizing or graphitizing fibers generally yields fibers having tensile strengths of over 100 X 10 p.s.i. and elastic moduli of over 20 X 10 p.s.i.
  • Such fibers find ready application in plastic composites for structural members, filament-wound tanks, ablative nose cones, rocket exhaust nozzles, electric brushes, etc., where they may be employed with epoxy, phenolic, silicone, polyimide, and other resin systems.
  • lasers have become available during the recent years.
  • Some types of lasers e.g., the CO laser, convert electrical energy with high efficiency to intense, collimated beams of electromagnetic radiation.
  • the laser output beams can be readily focused with great efficiency onto objects for generating high temperatures.
  • the improvement of the present invention over older methods of carbonizing and graphitizing fibers lies in the use of laser radiation for effecting the chemical and physical changes in the fibers.
  • the lasers offer advantages for this operation as compared with conventional methods of heating, viz. l convenience in startup and shut-down without significant time lag, (2) rapid response and sensitive control of power output by simple optical, electronic, and electrical means, and (3) efficient energy utilization and optical manipulation inherent in utilizing a collimated beam of coherent radiation for heating.
  • the beam is readily manipulated by optical means so as to generate desired energy flux densities and density gradients, using lenses or reflectors.
  • the temperature of fibers exposed to the radiation is readily controlled either by changing the energy output of the laser or by changing the energy flux density in the irradiated zone by optical means.
  • Laser heating permits carbonizing and graphitizing fibers to be conducted as-a continuous process. Fast production rates can be attained by the use of lasers which provide high power output.
  • precursor fibers which are preferably either acrylonitrile homopolymer or copolymers, or. an aromatic polyamide (previously disclosed in U.S. Pat. No. 3,232,9l0, issued Feb. 1, 1966), are first pretreated by heating in an oxygen-containing atmosphere at between 180 and 550C. for a time sufficient to. partially oxidize and blacken the fibers, and are then carbonized by heating in a laser beam in a nonoxidizing atmosphere at between 700C. and about l,200C.
  • the time of exposure of the fibers to the laser beam during carbonizing varies with the temperature
  • cellulose in either its natural or regenerated form e.g., rayon
  • copolymers of acrylonitrile with up to mol percent of a-monovinyl compound such as methyl acrylate, methyl methacrylate, vinyl acetate, vinyl chloride, vinylidine chloride, 2-methyl-2-vinyl pyridine, etc.
  • Catalysts may be incorporated in the fiber, to lower the decomposition temperature; e.g., in cellulose fibers there may be used ammonium phosphates, boric acid, zinc chloride, etc.
  • the fibers may be used as single fibers or as monofilaments, or loose bundles or in the form of roving.
  • thepreferred form is yarn.
  • Other forms which are adaptable to the process are tape, woven fabric, matted fibers, paper, etc.
  • the precursor fibers may be heated in the pretreating step in. the oxygen-containing atmosphere by conventional, relatively low-temperature, heating methods; viz. resistance-heating, flame-heating, radiative-heating, etc. well-known in the art.
  • the pretreating may be done in bulk, in a batch operation, or in a continuous operation.
  • precursor fibers which have been pretreated and carbonized are graphitized by heating in a laser beam in a non-oxidizing atmosphere at between about l,200 and 3,600C.
  • the time of exposure of the fibers to laser radiation during graphitizing varies with the temperature, being about 3 minutes at 2,27 0C. The optimum time is readily determined by experimentation. Excessive exposure at high temperatures (above 3,000C.) is to be avoided, as causing weakening of the fibers through sublimation of the graphitized carbon.
  • the carbonized fibers may be heated at I temperatures above 1,200C.they are preferably surrounded by a non-oxidizing atmosphere such asnitrogen, hydrogen, helium, methane, etc. or mixtures thereof.
  • a non-oxidizing atmosphere such asnitrogen, hydrogen, helium, methane, etc. or mixtures thereof.
  • small amounts of air, chlorine, hydrogen chloride, etc. may be added as desired.
  • -it may be desirable to perform one or more of the operations in a partial or full vacuum or even under increased pressure, any of which are permitted through the convenience of laser irradiation.
  • Means may be provided for rotating the fibers around their longitudinal axis.
  • laser-irradiative heating during the carbonizing and graphitizing steps, it may also be employed for the pretreating or oxidation step.
  • a plurality of laser beams may be employed, or a single laser beam may be split by the use of partly transmitting beam-splitters.
  • a surface of a bonded fibrous body may be graphitized without affecting its interior structure; such a graphitized surface may provide a useful bearing surface having lubricating properties.
  • a fibrous mat e.g., a sheet of paper, or a woven cloth may be exposed to a laser beam so as to carbonize precise areas for decorative or aesthetic purposes in various degrees of blackening, to simulate black or grey tones of a charcoal drawing, by suitably controlling the energy of the beam and the time of exposure at each area.
  • paper or cloth may be carbonized in very specific and narrowly defined areas, to produce symbols, letters, figures, bits of information, etc. for the purpose of communication.
  • FIGS. 1 and 2 are representations of two embodiments of a continuous process for carbonizing or graphitizing organic fibers by laser-heating.
  • FIG. 1 there is shown a laser beam, focused by a condensing lens, impinging upon a .yarn of organic fibers.
  • the laser beam 1 emanates from Co -laser tube 2 through infrared radiation-transmitting lens 3. It passes through water-cooled germanium condensing lens 4, thence through infrared radiation-transmitting window 5 in housing 6, and impinges upon yarn 7.
  • the feedstock yarn isunwound from supply reel 8 which is turned by an unreeling motor controlled by dancer 9. .
  • the dancer consists of apulley which floats on the yarn and operates a microswitch.
  • housing 6 is provided with an entry port 12 for gases which may be non-oxidizing, e.g., nitrogen,
  • Housing 6 is also provided with a second infrared radiation-transmitting window 13 so that laser radiation which is not intercepted and absorbed by the yarn may be transmitted outside of the housing and subsequently harmlessly absorbed.
  • Windows 5 and 13 are sealed against'housing 6 by O-rings 14 and suitable clamping means.
  • FIG. 2 there is shown a modification in which a hollow cylindrical reflector directs the fraction of laser radiation not absorbed from the incident beam back onto the fibers.
  • a condensing lens may or may not be used to concentrate the laser beam; in this embodiment it has been omitted.
  • the collimated laser beam 21 emanates from laser tube 22 through radiation-transmitting lens 23. It passes through infrared radiationtransmitting window 24 in housing 25 and impinges upon yarn 26.
  • Means are provided for moving yarn 26 at a controlled rate under tension through laser beam 21, as for example by the method illustrated in FIG. 1 or by simply employing a motor-driven take-up reel at the upper end of the yarn and by hanging a weight on the lower 'end.
  • Cylindrical reflector 27 is a polished infrared radiation-reflecting hollow cylinder having a hole cut in its front wall for the entering beam. It is supported by rod 28 which passes through plate 29 and is manipulated for focusing and alignment by handle 30. For maximum utilization of the reflected energy the cylinder is positioned so that the yarn is in the focal plane, which is parallel to the rear wall and spaced therefrom by a distance equal to one-half of the radius of the' cylinder. Reflectors of other configurations, such as parabolic, can also be used for focusing the radiation the oxygen content was about 22 percent by difference.
  • yarn guides 31 which are rods, e.g., glass, graphite, Teflon, etc., equipped with smooth notches.
  • Bottom plate 32 is provided with gas entry port 33.
  • O-ring 34 are employed for seals as in FIG. 1.
  • EXAMPLE 1 This example illustrates carbonization at a temperature below 1,200C.
  • the apparatus was essentially as represented in H6. 2 in which a reflector 27 having an internal diameter of 23 mm. was employed.
  • the upper end of the yarn went to a motor-driven take-up reel.
  • Tension was applied to the yarn by attaching a l0-gram weight to the lower end of yarn 26.
  • the feedstock consisted of preoxidized acrylonitrile homopolymer yarn having about 250 fibers in the bundle.
  • the yarn was wrapped on a thin-walled glass cylinder taking care not to overlap the yarn.
  • the yarn was then heated in an aircirculating oven in which the temperature was raised from 25to 280C. during 2 hours and thereafter held at 280C. for 3 hours.
  • the now-blackened yarn was cooled, and washed in distilled water at the boil for 1
  • the laser beam was produced by a C0 laser made by Korad Corp., Model K-G3, wavelength 10.6;t, operating at up to about watts output.
  • the yarn was heated by two passes through the laser beam at an average temperature of about 1,060C. Residence time in the heated zone was about 1.6 minutes for each pass. Argon was blown through the housing.
  • the physical properties of the partially graphitized carbon fibers were determined on single fibers. For these as well as the products obtained in the remaining examples, the tests and method used were as follows: tensile strength and modulus were determined by the method of S. Schulman reported in the Journal of Polymer Science, Part C, Polymer Symposia, High Temperature Resistant Fibers,No. 19, pp. 211-225 (1967): Methods of Single Fiber Evaluation. The data reported here are the average of replicate determinations, usually six or more.
  • the apparatus consisted of a modification of that represented by FIG. 1: the yarn supply reel 8 and dancer 9 were removed and tension was applied to the yarn simply by attaching a 5-gram weight to the lower end of the yarn 7.
  • a condensing lens 4 having a focal length of 6 inches was used.
  • the feedstock consisted of preoxidized acrylonitrile homopolymer yarn prepared as described in Example
  • the yarn was passed repeatedly through the laser beam, increasing the power of the laser generator after each second pass so that the yarn attained the following observed temperatures (C): 820, 890, 1,010, 1,340, 1,890 and 1,930.
  • the power output for the highest temperature was watts.
  • argon was blown through the housing.
  • the yarn moved at a rate of 0.37 inches per minute.
  • the residence time for the yarn in the heated zone was about 13.8 seconds for each pass when the lens was at a distance of 6.87 inches from the yarn.
  • the yarn was rotated after the first pass at each temperature.
  • EXAMPLE 3 The apparatus and method were essentially the same as in Example 2. The tension was applied by a IO-gram weight.
  • the feedstock consisted of preoxidized and precarbonized' acrylonitrile homopolymer yarn.
  • the preoxidation conditions were the same as in Example 1.
  • the yarn was heated by a conventional, relatively low-temperature, method in a furnace at 950C. for about 6 minutes in a nitrogen atmosphere.
  • Laser irradiation was then applied to heating the yarn by successive passes through the laser beam, with two passes at-each of the following temperatures (C.): 1,160, 1,340, 1,950 and 1,990.
  • C. temperatures
  • the 6-inch focal length condensing lens was at a distance of 6.87 inches.
  • argon was blown through the housing.
  • EXAMPLE 4 This example illustrates the use of a reflector, with stepwise heating in sevenv steps to a maximum of 1,420C.
  • the apparatus was essentially as represented in FIG. 2 in which a reflector 27 was employed.
  • the upper end of the yarn went to a motor-driven take-up reel.
  • Tension was applied to the yarn by attaching a lO-gram weight to the lower end of the yarn 26.
  • the condensing lens was not used.
  • the feedstock consisted of preoxidized acrylonitrile homopolymer yarn prepared as in Example 1.
  • the yarn was heated by successive passes through the laser beam with two passes at each of the following temperatures (C.): ca. 400, ca. 500,890, 1,000, 1,210, 1,320 and 1,420.
  • Argon was blown through the housmg.
  • Example 5-B Elastic modulus In Example 5-B, the yarn was heated by one pass at an average temperature of about 2,170C.
  • the apparatus was the same as in Example 4.
  • the feedstock was preoxidized acrylonitrile homopolymer prepared as in Example 1.
  • the yarn was heated by two passes through the laser beam at each temperature: first at about 1,030C., then atabout 2,270C. Residence time in the heated zone was about 1.6 minutes for each pass. Argon was blown through the housing.
  • the product was found by chemical analysis to be 97.76 percent carbon.
  • EXAMPLE 7 This example illustrates the use of a condensing lens and reflector in combination.
  • the apparatus consisted of the lasersource and con-v densing lens as represented in FIG. 1, and the reflector and housing as represented in; FIG. 2.
  • the upper end of the yarn went to a motor-driven take-up reel.
  • Tension was applied to the yarn by av IO-gram weight.
  • the yarn moved at a rate of-0.37 inches per minute.
  • the residence time for the yarn in the heated zone was about 66 seconds for each pass when the lens was at a distance of 10.5 inches.
  • the feedstock consisted of preoxidized acrylonitrile homopolymer yarn prepared as in Example 1.
  • the yarn was heated by successive passes through thelaser beam with two passes at each of the following temperatures I (C.): ca. 500, 1,000, 1,330, 1,530, 1,690, 1,930 and 2,080.
  • Argon was blown through the housing.
  • the yarn was heated by eight passes through the laser beam, as the temperature was raised in stages from l,520 to 2,500C.
  • EXAMPLE 9 This example illustrates graphitizing the surface of a bonded fibrous body.
  • a layer of an epoxy resin-bonded carbon fiber composite is built up on ,a steel shaft by winding a carbon yarn liberally coated with curable epoxy resin.
  • the composite is cured to a hard tough condition.
  • the outer surface of the composite which is substantially cylindrical in shape, is then exposed to laser radiation in an inert atmosphere.
  • the surface layers of carbon yarn are graphitized.
  • the shaft is found to turn smoothly because of the graphitized surface which results in a decreased coefficient of friction.
  • pretreating the fiber by heating at a temperature of from 180 to 550C. in an oxygen-containing atmosphere for a time sufficient to blacken the fiber;
  • the improvement in the carbonizing and graphitizing heating steps comprises irradiating substantially all sides of the fiber at least once in a C0 laser beam the time of exposure being dependent upon the temperature.
  • a method for preparing a graphitized fiber from a precursor fiber as disclosed in claim 1 having the steps of a. pretreating the fiber by heating at a temperature of from 180 to 550C. in an oxygen containing atmosphere for a time sufficient to blacken the fiber; and thereafter b. heating the blackened fiber in a non-oxidizing atmosphere at a temperature between 700C. and about 1,200C. to carbonize the fiber;
  • the improvement further comprising the further step of irradiating at least once substantially all sides of the carbonized fiber with a C0 laser beam in a non-oxidiz- 5 ing atmosphere at a temperature between about l,200

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Fibers (AREA)
  • Carbon And Carbon Compounds (AREA)
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US4070412A (en) * 1976-09-08 1978-01-24 The United States Of America As Represented By The Secretary Of The Navy Method for production of acetylene by laser irradiation
US4115280A (en) * 1970-11-12 1978-09-19 Massachusetts Institute Of Technology Apparatus for altering the biological and chemical activity of molecular species
US4370141A (en) * 1981-05-18 1983-01-25 Celanese Corporation Process for the thermal stabilization of acrylic fibers
US4473372A (en) * 1983-05-12 1984-09-25 Celanese Corporation Process for the stabilization of acrylic fibers
DE10057867C1 (de) * 2000-11-21 2002-02-14 Freudenberg Carl Kg Verfahren zum Graphitieren eines carbonisierten Flächengebildes und Verwendung der nach diesen Verfahren hergestellten carbonisierten Verfahren
EP1260619A1 (de) * 2001-05-22 2002-11-27 Polymatech Co., Ltd. Pulver aus Kohlenstofffasern, Herstellungsverfahren und thermisch leitende Zusammensetzung
US20040025261A1 (en) * 2000-11-21 2004-02-12 Birgit Severich Method for the carbonization of an at least inherently stable two-dimensional textile structure
US7534854B1 (en) 2005-03-29 2009-05-19 Ut-Battelle, Llc Apparatus and method for oxidation and stabilization of polymeric materials
EP2105406A1 (de) * 2008-03-25 2009-09-30 Korea Institute of Energy Research Kohlenstoffmaterial mit Graphitnanoschicht und entsprechendes Syntheseverfahren
US7649078B1 (en) 2005-03-29 2010-01-19 Ut-Battelle, Llc Apparatus and method for stabilization or oxidation of polymeric materials
CN102517693A (zh) * 2011-11-21 2012-06-27 圣欧（苏州）安全防护材料有限公司 芳纶基碳纤维的制备方法
AU2010331411B2 (en) * 2009-12-17 2015-06-18 Toray Industries, Inc. Layered carbon-fiber product, preform, and processes for producing these
CN106521718A (zh) * 2015-09-09 2017-03-22 通用汽车环球科技运作有限责任公司 制造具有增强可模塑性的复合材料过程中对连续碳纤维的改性
EP3246436A1 (de) 2016-05-19 2017-11-22 DWI - Leibniz-Institut für Interaktive Materialien e.V. Verfahren zur herstellung hochporöser kohlenstofffasern durch schnelle karbonisierung von kohlenstoffvorläuferfasern
WO2018011524A1 (fr) * 2016-07-13 2018-01-18 Centre National De La Recherche Scientifique Procede de preparation d'un materiau carbone massif localement graphite
WO2018186958A1 (en) * 2017-04-03 2018-10-11 The George Washington University Methods and systems for the production of crystalline flake graphite from biomass or other carbonaceous materials
US10358767B2 (en) 2016-07-15 2019-07-23 GM Global Technology Operations LLC Carbon fiber pre-pregs and methods for manufacturing thereof
US10427349B2 (en) 2016-09-23 2019-10-01 GM Global Technology Operations LLC Components molded with moldable carbon fiber and methods of manufacturing thereof
US10612163B2 (en) 2017-08-24 2020-04-07 GM Global Technology Operations LLC Modification of continuous carbon fibers during precursor formation for composites having enhanced moldability
US10941510B2 (en) 2017-12-08 2021-03-09 GM Global Technology Operations LLC Equipment for perforated pre-impregnated reinforcement materials
CN113981569A (zh) * 2021-10-27 2022-01-28 因达孚先进材料(苏州)有限公司 一种催化石墨化生产石墨纤维的方法
US11498318B2 (en) 2019-12-05 2022-11-15 GM Global Technology Operations LLC Class-A components comprising moldable carbon fiber

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US4856179A (en) * 1983-04-21 1989-08-15 Hoechst Celanese Corp. Method of making an electrical device made of partially pyrolyzed polymer
DE102015221701A1 (de) * 2015-11-05 2017-05-11 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Anlage zur Herstellung von Kohlenstofffasern

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US4115280A (en) * 1970-11-12 1978-09-19 Massachusetts Institute Of Technology Apparatus for altering the biological and chemical activity of molecular species
US4070412A (en) * 1976-09-08 1978-01-24 The United States Of America As Represented By The Secretary Of The Navy Method for production of acetylene by laser irradiation
US4370141A (en) * 1981-05-18 1983-01-25 Celanese Corporation Process for the thermal stabilization of acrylic fibers
US4473372A (en) * 1983-05-12 1984-09-25 Celanese Corporation Process for the stabilization of acrylic fibers
US20040025261A1 (en) * 2000-11-21 2004-02-12 Birgit Severich Method for the carbonization of an at least inherently stable two-dimensional textile structure
DE10057867C1 (de) * 2000-11-21 2002-02-14 Freudenberg Carl Kg Verfahren zum Graphitieren eines carbonisierten Flächengebildes und Verwendung der nach diesen Verfahren hergestellten carbonisierten Verfahren
US20040029471A1 (en) * 2000-11-21 2004-02-12 Birgit Severich Method for graphitising a carbonised fabric
WO2002042533A1 (de) * 2000-11-21 2002-05-30 Carl Freudenberg Kg Verfahren zum graphitieren eines carbonisierten flächengebildes
EP1260619A1 (de) * 2001-05-22 2002-11-27 Polymatech Co., Ltd. Pulver aus Kohlenstofffasern, Herstellungsverfahren und thermisch leitende Zusammensetzung
US20030064017A1 (en) * 2001-05-22 2003-04-03 Masayuki Tobita Carbon fiber powder, a method of making the same, and thermally conductive composition
US7649078B1 (en) 2005-03-29 2010-01-19 Ut-Battelle, Llc Apparatus and method for stabilization or oxidation of polymeric materials
US7534854B1 (en) 2005-03-29 2009-05-19 Ut-Battelle, Llc Apparatus and method for oxidation and stabilization of polymeric materials
US7786253B2 (en) 2005-03-29 2010-08-31 Ut-Battelle, Llc Apparatus and method for oxidation and stabilization of polymeric materials
US20090263295A1 (en) * 2005-03-29 2009-10-22 Ut-Battelle, Llc Apparatus and method for oxidation and stabilization of polymeric materials
EP2105406A1 (de) * 2008-03-25 2009-09-30 Korea Institute of Energy Research Kohlenstoffmaterial mit Graphitnanoschicht und entsprechendes Syntheseverfahren
US20090246511A1 (en) * 2008-03-25 2009-10-01 Korea Institute Of Energy Research Cellulose carbide material having graphite nanolayer and synthesis method thereof
US8414861B2 (en) * 2008-03-25 2013-04-09 Korea Institute Of Energy Research Carbonized cellulose material having graphite nanolayer and synthesis method thereof
EP2514587A4 (de) * 2009-12-17 2017-01-11 Toray Industries, Inc. Geschichtetes kohlenstofffaserprodukt, vorform und herstellungsverfahren dafür
AU2010331411B2 (en) * 2009-12-17 2015-06-18 Toray Industries, Inc. Layered carbon-fiber product, preform, and processes for producing these
CN102517693A (zh) * 2011-11-21 2012-06-27 圣欧（苏州）安全防护材料有限公司 芳纶基碳纤维的制备方法
US10113250B2 (en) * 2015-09-09 2018-10-30 GM Global Technology Operations LLC Modification of continuous carbon fibers during manufacturing for composites having enhanced moldability
CN106521718B (zh) * 2015-09-09 2018-12-21 通用汽车环球科技运作有限责任公司 用于具有增强可模塑性的复合材料中的连续碳纤维的制造方法
CN106521718A (zh) * 2015-09-09 2017-03-22 通用汽车环球科技运作有限责任公司 制造具有增强可模塑性的复合材料过程中对连续碳纤维的改性
EP3246436A1 (de) 2016-05-19 2017-11-22 DWI - Leibniz-Institut für Interaktive Materialien e.V. Verfahren zur herstellung hochporöser kohlenstofffasern durch schnelle karbonisierung von kohlenstoffvorläuferfasern
FR3053964A1 (fr) * 2016-07-13 2018-01-19 Centre Nat Rech Scient Procede de preparation d'un materiau carbone massif localement graphite
WO2018011524A1 (fr) * 2016-07-13 2018-01-18 Centre National De La Recherche Scientifique Procede de preparation d'un materiau carbone massif localement graphite
US10358767B2 (en) 2016-07-15 2019-07-23 GM Global Technology Operations LLC Carbon fiber pre-pregs and methods for manufacturing thereof
US10427349B2 (en) 2016-09-23 2019-10-01 GM Global Technology Operations LLC Components molded with moldable carbon fiber and methods of manufacturing thereof
WO2018186958A1 (en) * 2017-04-03 2018-10-11 The George Washington University Methods and systems for the production of crystalline flake graphite from biomass or other carbonaceous materials
US11380895B2 (en) 2017-04-03 2022-07-05 The George Washington University Methods and systems for the production of crystalline flake graphite from biomass or other carbonaceous materials
US10612163B2 (en) 2017-08-24 2020-04-07 GM Global Technology Operations LLC Modification of continuous carbon fibers during precursor formation for composites having enhanced moldability
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US11498318B2 (en) 2019-12-05 2022-11-15 GM Global Technology Operations LLC Class-A components comprising moldable carbon fiber
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IL32949A0 (en) 1969-11-30
DE1945145A1 (de) 1970-03-12
IL32949A (en) 1972-09-28
GB1241937A (en) 1971-08-04

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