US20030025229A1 - Method for manufacturing pitch-based carbon fiber - Google Patents

Method for manufacturing pitch-based carbon fiber Download PDF

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Publication number
US20030025229A1
US20030025229A1 US10/210,131 US21013102A US2003025229A1 US 20030025229 A1 US20030025229 A1 US 20030025229A1 US 21013102 A US21013102 A US 21013102A US 2003025229 A1 US2003025229 A1 US 2003025229A1
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United States
Prior art keywords
pitch
carbon fiber
fiber
introduction hole
based carbon
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Abandoned
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US10/210,131
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English (en)
Inventor
Yutaka Arai
Tsutomu Nakamura
Hiroyuki Tadokoro
Osamu Katou
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Nippon Graphite Fiber Corp
Nippon Steel Corp
Eneos Corp
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Individual
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Assigned to NIPPON GRAPHITE FIBER CORPORATION, NIPPON OIL CORPORATION, NIPPON STEEL CORPORATION reassignment NIPPON GRAPHITE FIBER CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ARAI, YUTAKA;, KATOU, OSAMU, NAKAMURA, TSUTOMU, TADOKORO, HIROYUKI
Publication of US20030025229A1 publication Critical patent/US20030025229A1/en
Abandoned legal-status Critical Current

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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
    • D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
    • D01F9/15—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from coal pitch
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
    • D01F9/155—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from petroleum pitch

Definitions

  • the present invention relates to pitch-based carbon fiber and, in particular, to a method for manufacturing pitch-based carbon fiber having a high modulus of tensile elasticity and excellent tensile and compressive strength.
  • the pitch-based carbon fiber provided according to the present invention has a high modulus of elasticity and high strength
  • the carbon fiber is suitable as reinforcing fiber for composite materials used in a variety of industrial fields, to say nothing of the fields of sports, leisure, and space and aviation.
  • pitch-based carbon fiber carbon fiber using a mesophase pitch as a starting material has an advantage that carbon fiber having an extremely high modulus of tensile elasticity can be relatively easily manufactured.
  • the modulus of elasticity has attained a level on the order of 900 GPa substantially equal to the theoretical modulus of elasticity of graphite crystal, and carbon fiber having such a modulus of elasticity can be manufactured on an industrial scale.
  • a tensile strength on the order of 3 to 4 GPa is already available.
  • the practical properties such as flexural strength of a composite material are dependent on the compressive strength of fiber.
  • the compressive strength of pitch-based carbon fiber is significantly lower than PAN-based carbon fiber, and therefore, its use for a composite material has been restricted.
  • Japanese Unexamined Patent Publication No. H2-14023 discloses a method wherein carbon fiber is manufactured by spinning a pitch containing 5 to 40% of an optically anisotropic phase and having a spinning viscosity of several thousand poises, namely, a remarkably high spinning viscosity for melt spinning of pitch, thereby improving the compressive strength of the fiber.
  • Japanese Unexamined Patent Publication No. H3-816 discloses a method for improving compressive strength by implanting boron ions into pitch-based carbon fiber in a vacuum.
  • Japanese Unexamined Patent Publication Nos. S59-168127 and S60-194120 disclose a manufacturing method wherein pitch-based carbon fiber, without cracks in a cross section of the fiber, is manufactured by disposing an arcuate flow path on the upstream side of a discharge hole.
  • Japanese Unexamined Patent Publication No. H2-242918 discloses that strength is improved by changing the above-mentioned arcuate flow path to a rectangular flow path.
  • Japanese Unexamined Patent Publication No. H7-42025 discloses that compressive strength is improved depending on the shape of a portion approaching a discharge hole.
  • the object of the present invention is to provide a method for manufacturing carbon fiber having high tensile and high compressive strength and, in particular, to provide a method for manufacturing, on an industrial basis and in a simple and easy way, pitch-based carbon fiber having high strength even in a high-elasticity domain where the modulus of elasticity exceeds 600 GPa.
  • the gist of the present invention is as follows:
  • FIG. 1 is a schematic view showing a partial section of a spinning nozzle assembly used for the present invention.
  • FIG. 2 is an enlarged view showing a portion of the spinning nozzle assembly.
  • FIG. 3 is a view showing the relation between holes disposed in a straight line in an introduction hole entry portion and an introduction hole.
  • FIG. 4 consists of views showing examples of holes disposed in a substantially straight line in an introduction hole entry portion.
  • FIG. 4( a ) is a view showing one example
  • (b) is a view showing another example.
  • the strength of pitch-based carbon fiber is influenced by the fine structure of crystal grains of the fiber and also the strength changes depending on a macroscopic structure exhibited on a cross section of the fiber which is generally referred to as radial, random, onion or the like.
  • a structure exhibited on a cross section of fiber is substantially determined in the stage of melt spinning.
  • the present inventors have discovered that, in order to obtain a cross-sectional structure that increases strength, the method of spinning is required to satisfy the requirements stated below. It has also been made clear that, when the requirements stated below are satisfied, a remarkable improvement of physical properties is perceived as compared with conventional methods.
  • FIGS. 1 to 3 show partial sections of a spinning nozzle assembly used in the present invention.
  • Three or more contraction holes 1 are disposed in a substantially straight line in an introduction hole entry portion.
  • Melt spinning is performed as described below.
  • a flow of a molten material is passed through the plurality of contraction holes 1 disposed in a substantially straight line, then expanded in an introduction hole 2 , thereafter contracted in an approach portion (contraction portion) 3 extending from the introduction hole 2 to a discharge hole 5 (with an angle of inclination starting at the introduction hole 2 and ending at the discharge hole 5 being 60 to 150 degrees), and then passed through the discharge hole 5 having a circular cross-sectional shape disposed in a flat portion 4 formed at the terminal end of the approach portion 3 .
  • a shearing force acts on mesophase pitch in a plurality of contraction holes 1 and this shearing force makes domains finer while mutual interference of the flows of the mesophase pitch also leads to making the domains finer, thereby effectively improving the physical properties of the pitch.
  • the diameter D1 of the contraction hole 1 is 0.05 to 1 mm. Still more preferably, it is 0.1 to 0.7 mm. Further, all of the contraction holes 1 are not necessarily required to have the same diameter, and different diameters can be employed properly.
  • the number of contraction holes is 3 or more, preferably 3 to 20 , still preferably 4 to 10 . It is essential to dispose the contraction holes in a substantially straight line. Under normal conditions, it is preferable to dispose the contraction holes at equal intervals in such a manner that the diameter of the introduction hole is equally divided by the number of the contraction holes to be disposed; however, the contraction holes need not necessarily be disposed at equal intervals, but also other manners are allowable.
  • a substantially straight line here means that, as shown in (a) and (b) of FIG. 4, the group of a plurality of contraction holes 1 viewed from a direction normal to the cross section are arranged in a substantially straight line (refer to FIG. 4( b )), and also it can be said that holes arranged in zigzags in one direction, for example, are arranged in a substantially straight line (refer to FIG. 4( a )).
  • the value obtained by dividing the diameter D1 of each contraction hole 1 in the introduction hole entry portion by the mean value of interval W between contraction holes 1 is 3 or less, still preferably 2 or less. If this value exceeds 3 , the interference between contraction holes 1 is reduced, and accordingly its effect on the improvement of strength is lessened.
  • the diameter D2 of the introduction hole 2 is 0.5 to 10 mm, preferably 1.2 to 5 mm.
  • Residence time in the introduction hole 2 is designed to be 1 to 400 sec., preferably 4 to 200 sec. If the diameter D2 of the introduction hole 2 is smaller than 0.5 mm or larger than 10 mm, the compressive strength of obtained carbon fiber is decreased to some extent. Likewise, if the residence time is shorter than 1 sec. or longer than 400 sec., it becomes difficult to obtain an excellent strength improving effect.
  • the diameter D 3 of the flat portion 4 is not larger than 0.8 times the introduction hole diameter D2 and not smaller than 1.5 times the diameter D4 of the discharge hole 5 , and the effect of the present invention can be maximized under these conditions. Further, the diameter D4 of the discharge hole 5 is 0.05 to 0.5 mm, preferably 0.08 to 0.2 mm.
  • the introduction hole length L2 is 3 to 30 mm, still preferably 4 to 15 mm.
  • the length L3 of the discharge hole 5 is 0.05 to 3 mm, preferably 0.1 to 1 mm.
  • the orifice length L1 of each contraction hole in the introduction hole entry portion is 0.05 to 2 mm, preferably 0.1 to 0.5 mm.
  • the pitch used as the starting material of the carbon fiber according to the present invention includes various kinds of pitch such as: coal-based pitch such as coal tar and coal-tar pitch; liquefied coal pitch; ethylene-tar pitch; petroleum-based pitch such as decanted oil pitch obtained from the cracked residue of a fluidized catalytic cracking process; synthetic pitch made from naphthalene and the like by using a catalyst; and the like.
  • pitch such as: coal-based pitch such as coal tar and coal-tar pitch; liquefied coal pitch; ethylene-tar pitch; petroleum-based pitch such as decanted oil pitch obtained from the cracked residue of a fluidized catalytic cracking process; synthetic pitch made from naphthalene and the like by using a catalyst; and the like.
  • the mesophase pitch used for the carbon fiber according to the present invention is made by generating a mesophase in the above-mentioned pitch by using a publicly known prior art method. It is desirable that the mesophase pitch exhibits high orientation when spun into pitch fiber, and therefore, it is desirable for the mesophase content to be 60% or higher.
  • the mesophase pitch used for the present invention has a softening point of 200 to 400° C., still more preferably 250 to 350° C.
  • Pitch fiber is obtained by melt-spinning the above-mentioned mesophase pitch by using a spinning nozzle assembly according to the present invention.
  • pitch fiber of 5 to 20 ⁇ m in fiber diameter is obtained by drawing the above-mentioned mesophase pitch at a spinning speed of 100 to 2,000 m/min. while the mesophase pitch is extruded out of a discharge hole of 0.05 to 0.5 mm in diameter under a pressure on the order of 1 to 200 kg/cm 2 at a temperature for exhibiting a viscosity of 100 to 1,500 poises, preferably a temperature for exhibiting a viscosity of 200 to 800 poises.
  • the pitch fiber is subjected to an infusibilizing treatment in an atmosphere of oxidizing gas, normally at a temperature of 100 to 350° C., preferably at 130 to 320° C., and normally for 10 min. to 10 hr., preferably for 1 to 6 hr.
  • Oxygen, air, or a gas made by mixing either of them with nitrogen dioxide, chlorine or the like, is used as the oxidizing gas.
  • the infusibilized fiber is subjected to a baking treatment at a temperature of 1,000 to 3,000° C. in an atmosphere of inert gas such as nitrogen or argon, and then a pitch-based carbon fiber of improved strength can be obtained.
  • the carbon fiber thus obtained has few radial components in the surface layer of the fiber and exhibits a cross-sectional structure comprising two or more kinds of structures over the entire cross section of the fiber.
  • onion components appear relatively frequently in the cross-sectional structure of fiber.
  • onion components are not so conspicuous in the structure according to the present invention.
  • the cross section of fiber becomes relatively distorted and the uniformity of the cross-sectional structural of the fiber is lost.
  • such a cross-sectional structure is not exhibited in the case of the present invention.
  • the cross-sectional structure of the carbon fiber according to the present invention is observed to be different from that of conventional carbon fiber.
  • the difference in the structures observable by a microscope is observed even on the level of fine graphite crystals that may determine strength and this difference seems to provide high strength.
  • a nozzle structure having a contraction hole in an introduction hole entry portion is apt to develop pitch stagnating portions from its structural nature. It is known that, if pitch is caused to reside for a long time at a relatively high spinning temperature, in order to prevent pitch stagnating portions from developing, a change in pitch quality locally advances to induce the generation of degradable gas or a gelatinous substance leading to thread breakage. However, it is noted that stagnating portions are prevented from developing, in the present invention, by the influence of the plurality of contraction holes. The reason for this is unclear; however, it has been found that thread breakage is apparently reduced in actual spinning according to the present invention as compared with conventional methods, and at the same time, the effects of remarkably improving the productivity and the yield of carbon fiber are obtained.
  • Coal tar pitch as a raw material, having a softening point of 80° C. and cleared of quinoline insolubles, was directly hydrogenerated by using a catalyst.
  • the hydrogenated pitch was heat-treated at 490° C. under a reduced pressure, and then low-boiling point components were removed therefrom to obtain mesophase pitch.
  • This pitch has a softening point of 298° C., insoluble toluene of 85 wt. %, insoluble pyridine of 42 wt. %, and has a mesophase content of 80%.
  • a nozzle assembly was used having 3,000 discharge holes 5 and being equipped with a structure (refer to FIG. 2) made by placing a plate on the upper portions of unit nozzles.
  • Each of the unit nozzles has a discharge hole 5 having a diameter D4 of 0.10 mm and a length L3 of 0.15 mm, a flat portion 4 having a diameter D3 of 0.5 mm and an introduction hole 2 having a diameter D2 of 1.8 mm, an angle ⁇ 1 of 120 degrees, and a length L2 of 7 mm.
  • contraction holes 1 six holes per unit nozzle, each hole having a thickness L1 of 0.5 mm and a diameter D1 of 0.2 mm, are bored through the plate at equal hole intervals W of 0.16 mm in a straight line in a diametrical direction of the introduction hole 2 .
  • the mesophase pitch with a viscosity of 600 poises was spun by using this nozzle assembly at a pitch fiber drawing speed of 600 m/min. to obtain pitch fiber of 9 ⁇ m in single thread diameter, and the 3,000 pieces of pitch fiber were tied up in a bundle and housed in a can.
  • the frequency of breakage of one or more pieces of thread was measured during the spinning of the 3,000 pieces of pitch fiber, and resultantly, the frequency of thread breakage was 300 min./time/3,000 pieces on the average.
  • the temperature of the can housing the infusibilized fiber was increased to 390° C. at 10° C./min. in an atmosphere of gaseous nitrogen and held at 390° C. to primarily carbonize the infusibilized fiber. Then, the primarily carbonized fiber was further carbonized at a temperature of 1,200° C. and subsequently graphitized at a temperature of 2,700° C. to obtain carbon fiber.
  • This carbon fiber was 7 ⁇ m in fiber diameter, and the modulus of tensile elasticity thereof was 840 GPa, the tensile strength 4,800 MPa, and the compressive strength 950 MPa in terms of carbon fiber.
  • a single thread was taken out of the carbon fiber and its modulus of torsional elasticity was measured and found to be 9.4 GPa.
  • a cross section of the carbon fiber was observed by the use of a scanning electron microscope, and it was found that about 5% of the surface layer was composed of radial structures, about 20% of the middle portion was composed of onion-like structures, and the portion between the surface layer and the middle onion portion was composed of random structures.
  • a plate having a hole of 0.5 mm in diameter disposed substantially in the middle of the introduction hole was used in place of the plate used for Example 1.
  • Spinning was conducted under the same conditions as those of Example 1.
  • the frequency of thread breakage measured in the same way as Example 1 was 12 min./time/3,000 pieces on the average.
  • pitch fiber thus obtained was carbonized in the same way as Example 1 to obtain carbon fiber.
  • This carbon fiber was 7 ⁇ m in fiber diameter, and the modulus of tensile elasticity thereof was 800 GPa, the tensile strength 3,900 MPa, and the compressive strength 900 MPa in terms of carbon fiber.
  • a single thread was taken out of the carbon fiber and its modulus of torsional elasticity was measured and found to be 11.5 GPa.
  • a cross section of the carbon fiber was observed by the use of a scanning electron microscope, and it was found that about 10% of the surface layer was composed of radial structures, and other portions were composed of onion-like structures.
  • a plate having a rectangular slit of 0.2 mm in width and 1.5 mm in length disposed substantially in the middle of the introduction hole was used in place of the plate used for Example 1.
  • Spinning was conducted under the same conditions as those of Example 1.
  • the frequency of thread breakage measured in the same way as Example 1 was 30 min./time/3,000 pieces on the average.
  • pitch fiber thus obtained was carbonized in the same way as Example 1 to obtain carbon fiber.
  • This carbon fiber was 7 ⁇ m in fiber diameter, and the modulus of tensile elasticity thereof was 840 GPa, the tensile strength 4,100 MPa, and the compressive strength 900 MPa in terms of carbon fiber.
  • a single thread was taken out of the carbon fiber and its modulus of torsional elasticity was measured and found to be 10.0 GPa.
  • a cross section of the carbon fiber was observed by the use of a scanning electron microscope, and it was found that about 10% of the surface layer was composed of radial structures, and the other portions were composed of the mixture of onion structures and random structures.
  • Coal tar pitch as a raw material, having a softening point of 80° C. and cleared of quinoline insolubles, was directly hydrogenenated by using a catalyst.
  • the hydrogenated pitch was heat-treated at 490° C. under a reduced pressure, and then low-boiling point components were removed therefrom to obtain mesophase pitch.
  • This pitch has a softening point of 298° C., insoluble toluene of 85 wt. %, insoluble pyridine of 42 wt. %, and has a mesophase content of 80%.
  • a nozzle assembly was used having 3,000 discharge holes 5 and being equipped with a structure (refer to FIG. 2) made by placing a plate on the upper portions of unit nozzles.
  • Each of the unit nozzles has a discharge hole having a diameter D4 of 0.10 mm and a length of 0.15 mm, a flat portion having a diameter D3 of 0.5 mm and an introduction hole having a diameter D2 of 2.0 mm, an angle ⁇ 1 of 120 degrees, and a length L2 of 7 mm.
  • each hole having a thickness L1 of 0.5 mm and a diameter D1 of 0.25 mm, are bored through the plate at equal hole intervals W of 0.188 mm in a straight line in a diametrical direction of the introduction hole.
  • the mesophase pitch with a viscosity of 400 poises was spun by using this nozzle assembly at a pitch fiber drawing speed of 700 m/min. to obtain pitch fiber of 8 ⁇ m in single thread diameter, and the 3,000 pieces of pitch fiber were tied up in a bundle and housed in a can.
  • the frequency of breakage of one or more pieces of thread was measured during the spinning of the 3,000 pieces of the pitch fiber, and resultantly, the frequency of thread breakage was 180 min./time/3,000 pieces on the average.
  • an oxidizing gas made by adding gaseous nitrogen dioxide of 5 vol. % and water vapor of 5 vol. % to air was injected into the can from a lower portion of the can while the temperature in the can was increased from 150° C. to 300° C. at 1° C./min. and held at 300° C. for 30 minutes to obtain infusibilized fiber.
  • the temperature of the can housing the infusibilized fiber was increased to 390° C. at 10° C./min. in an atmosphere of gaseous nitrogen and held at 390° C. to primarily carbonize the infusibilized fiber.
  • the primarily carbonized fiber was further carbonized at a temperature of 1,200° C. and subsequently graphitized at a temperature of 2,700° C. to obtain carbon fiber.
  • This carbon fiber was 6 ⁇ m in fiber diameter, and the modulus of tensile elasticity thereof was 790 GPa, and the tensile strength 530 MPa.
  • a single thread was taken out of the carbon fiber and its modulus of torsional elasticity was measured and found to be 9.0 GPa.
  • a cross section of the carbon fiber was observed by the use of a scanning electron microscope, and it was found that about 5% of the surface layer was composed of radial structures, about 20% of the middle portion was composed of onion-like structures, and the portion between the surface layer and the middle onion portion was composed of random structures.
  • the strength of pitch-based carbon fiber can be improved by a technology easily applicable to industrial implementation, without requiring any special pitch or without requiring any special processing in manufacturing fiber, and carbon fiber can be obtained having a modulus of tensile elasticity on the order of 800 GPa and also excellent values of both tensile and compressive strength.
US10/210,131 2001-08-02 2002-08-01 Method for manufacturing pitch-based carbon fiber Abandoned US20030025229A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001-234830(PAT. 2001-08-02
JP2001234830A JP4601875B2 (ja) 2001-08-02 2001-08-02 炭素繊維の製造方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130277875A1 (en) * 2012-04-18 2013-10-24 Chong Chen Method and Apparatus for Producing Carbon Fiber

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US4426344A (en) * 1980-07-05 1984-01-17 Hoechst Aktiengesellschaft Coextrusion process and apparatus for manufacturing multi-layered flat films of thermoplastic materials
US4887957A (en) * 1986-10-09 1989-12-19 Idemitsu Kosan Co., Ltd. Nozzle for melt spinning of pitch and method for spinning pitch
US4923648A (en) * 1984-06-26 1990-05-08 Mitsubishi Kasei Corporation Process for the production of pitch-type carbon fibers
US5037589A (en) * 1988-11-18 1991-08-06 Nippon Steel Corporation Method of producing mesophase pitch type carbon fibers and nozzle for spinning same
US5169584A (en) * 1989-02-16 1992-12-08 E. I. Du Pont De Nemours And Company Method of making small diameter high strength carbon fibers
US5223276A (en) * 1989-09-01 1993-06-29 Er-We-Pa Machinenfabrik Gmbh Multilayer coextrusion apparatus
US5282731A (en) * 1990-04-27 1994-02-01 Hoechst Aktiengesellschaft Apparatus for the production of moldings from thermotropic, liquid-crystalline substances
US5578330A (en) * 1989-02-16 1996-11-26 Conoco Inc. Pitch carbon fiber spinning apparatus
US5968435A (en) * 1997-04-24 1999-10-19 Nippon Steel Corporation Process for manufacturing pitch-type carbon fiber

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JPS61113827A (ja) * 1984-11-06 1986-05-31 Teijin Ltd 高性能ピツチ系炭素繊維の製造方法
JPH07116643B2 (ja) * 1986-10-21 1995-12-13 株式会社ペトカ 炭素繊維の製造法
CA2009528C (en) * 1989-02-16 2001-01-09 Uel D. Jennings Pitch carbon fiber spinning process
JP3164704B2 (ja) * 1993-07-30 2001-05-08 新日本製鐵株式会社 ピッチ系高圧縮強度炭素繊維の製造方法

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Publication number Priority date Publication date Assignee Title
US4426344A (en) * 1980-07-05 1984-01-17 Hoechst Aktiengesellschaft Coextrusion process and apparatus for manufacturing multi-layered flat films of thermoplastic materials
US4923648A (en) * 1984-06-26 1990-05-08 Mitsubishi Kasei Corporation Process for the production of pitch-type carbon fibers
US4887957A (en) * 1986-10-09 1989-12-19 Idemitsu Kosan Co., Ltd. Nozzle for melt spinning of pitch and method for spinning pitch
US5037589A (en) * 1988-11-18 1991-08-06 Nippon Steel Corporation Method of producing mesophase pitch type carbon fibers and nozzle for spinning same
US5169584A (en) * 1989-02-16 1992-12-08 E. I. Du Pont De Nemours And Company Method of making small diameter high strength carbon fibers
US5578330A (en) * 1989-02-16 1996-11-26 Conoco Inc. Pitch carbon fiber spinning apparatus
US5223276A (en) * 1989-09-01 1993-06-29 Er-We-Pa Machinenfabrik Gmbh Multilayer coextrusion apparatus
US5282731A (en) * 1990-04-27 1994-02-01 Hoechst Aktiengesellschaft Apparatus for the production of moldings from thermotropic, liquid-crystalline substances
US5968435A (en) * 1997-04-24 1999-10-19 Nippon Steel Corporation Process for manufacturing pitch-type carbon fiber

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130277875A1 (en) * 2012-04-18 2013-10-24 Chong Chen Method and Apparatus for Producing Carbon Fiber

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JP2003049327A (ja) 2003-02-21

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