US3702054A - Production of graphite fibers - Google Patents

Production of graphite fibers Download PDF

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Publication number
US3702054A
US3702054A US166448A US3702054DA US3702054A US 3702054 A US3702054 A US 3702054A US 166448 A US166448 A US 166448A US 3702054D A US3702054D A US 3702054DA US 3702054 A US3702054 A US 3702054A
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Prior art keywords
fibers
twisted
graphite
cross
yarn
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US166448A
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English (en)
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Tadashi Araki
Kiro Asano
Jun Yamada
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Kureha Corp
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Kureha 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
    • 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
    • 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 the production of graphite fibers, more particularly, to a method of producing graphite fibers of improved modulus of elasticity and strength as well as having various polygonal cross-sections.
  • FIG. 1 is a graphical representation showing crystal orientation of graphite fibers obtained under different conditions
  • FIG. 2 is an X-ray diffraction photograph of the graphite fiber according to the present invention.
  • FIGS. 3 and 5, respectively, are microphotographs showing the cross-section of the graphite fibers according to the present invention.
  • FIG. 4 is a microphotograph showing the cross-section of graphite fibers obtained by the ordinary method.
  • the cross-sectional shape of the heretofore known carbon fibers is determined by the manufacturing process of the raw material. Most common shapes are circles, ovals, cocoons, and stars.
  • carbon fibers of such cross-sectional shape are bundled and twisted into yarn (or thread), it is not possible to reduce space created among each of the fibers below a certain limit.
  • the space or porosity in' the twisted yarns reaches from 40 to 70 percent, or even higher, in a free state of no tension or compression being imparted thereto.
  • the carbon fibers are each in contact state mainly at various contact points, it is readily assumed that, when a pressure is imparted to the twisted yarns in the direction vertical thereto, there takes place a concentration of stress onto the contact points or tangential points of the fibers constituting the twisted yarns or threads. In the materials having high a Youngs modulus of elasticity such as carbon fibers, such concentration of stress is undesirable.
  • the characteristic feature of the present invention resides in having solved such difficult problems as mentioned above. That is, by treating carbon fibers of circular cross-section into a twisted yarn or thread under particular conditions, it has been found that the stress imparted to the fibers in the axial direction thereof at a high temperature is converted to a force which compresses the fibers in the direction vertical to the axis thereof. This is due to the pressure in which the fibers change from a state of being close to a state of line contact thereof to another state of being close to a state of plane contact thereof, or the fibers as a whole approximate a state of compactness from coarseness.
  • the cross-sectional shape of the raw material carbon fibers is, in general, circular or oval which is very close to a circle
  • the cross-section of the fibers after the deformation treatment according to the present invention converts the fibers into different polygonal cross-sections.
  • stress to be imparted to the carbon fibers at a temperature region of 2,000 C. and above is not only a negative pressure acting in the lengthwise direction of the fibers, but also a positive pressure along the cross-section of the twisted yarn.
  • the positive pressure along the cross-section of the twisted yarn changes the cross-section of the fibers into different polygonal cross-section by the mutual compressive action of the fibers with the consequence that the bundle fibers as a whole are brought to a state, wherein each and every fiber is mutually and compactly bundled due to the deformed cross-sections of the individual filaments.
  • This fact signifies that the individual fiber is not in point-contact with others along the lengthwise direction of the fiber as in the ordinary twisted yarn, but constitutes a linear or planar contact with each other.
  • the positive pressure along the cross-section of the fibers as described above increases the stretching force in the lengthwise direction of the twisted yarn as a compressive force to the individual fiber.
  • the fibers which are in the state of being readily subjected to plastic deformation are further elongated in their lengthwise direction by these two kinds of forces, at which time there takes place growth and orientation of the graphite crystallites resulting in remarkable increase in the modulus of elasticity during the stretching operation.
  • This increase in the modulus of elasticity may possibly exceed 700 depending on the elongation conditions.
  • the carbon fibers are still greatly increased rather than decreased in the mechanical strength.
  • the rate of increase in mechanical strength may reach almost 400 percent.
  • the measuredvalue in the mechanical strength is only about one-fifth to one-tenth of that of the theoretical value, even when the measured value of 200 T/cm in graphite whisker is compared. It is therefore assumed the mechanical strength of the carbon fibers and graphite fibers is governed by the defective portions existing'in the amorphous portion, surface portion as well as the internal portion of such fibers rather than in the crystalline portion thereof.
  • graphite fibers to be obtained by the present invention possess the above-described characters, it is possible to manufacture graphite fibers of superior quality such as, for example, fibers having mechanical strength of 37 T/cm and a modulus of 5 elasticity of 4,600 T/cm the values of which exceed those of boron fibers (mechanical strength of about'32 T/cm and modulus of elasticity of about 4,300 T/cm
  • the boron fibers have so far been regarded as having both mechanical strength and modulus of elasticity to the highest degree and in the most balanced state as the reinforcement material for composite materials.
  • the temperature for the carbon fibers to exhibit their plastic deformation is required to be higher than 2,000 C., or more preferably between 2,500 C. and 3,500 C. or so.
  • an inactive gas atmosphere such as argon, helium, etc. is used.
  • a temperature of more than 2,900 C. and a sufficient time for the heat-treatment be given so as not to damage the fibers.
  • it is preferable to impart to the fibers to be treated such a temperature, twisting condition, and
  • This heat-treatment may be carried out either in a single step or in a divided twostep process.
  • the raw material carbon fibers tobe subjected to the treatment in accordance with the present invention may be either carbonaceous or graphitic, but should be circular in the cross-section, possess a tensile strength of more than 7 T/cm, and contain carbon of more than percent by weight so as not to bring about lowering of strength during the high temperature treatment.
  • the average fiber length may be between 75 mm and mm to ,sufficiently attain this purpose. While the fiber length should of course be determined in terms of the number of fibers in the whole twisted yarn as well as the twisting conditions, the above specified figures are the shortest average lengths when the other conditions are in the most desirable ranges.
  • Carbon fibers satisfying the above mentioned conditions may be useful from whatever material and in whatever method they are produced. However, from the standpoint of the particular restriction in the present invention that the cross-sectional shape of the fibers should be circular, those carbon fibers obtained from pitch as the raw material are most preferable.
  • the stress imparted in the axial direction. of the twisted yarn may be converted to a compressive force in the direction perpendicular to the axis of the fiber, according to the present invention, there is required a process of giving proper twisting to a certain appropriate numbers of carbon filaments, and, if need be, a further twisting of such twisted yarns is necessary to give them double twisting.
  • EXAMPLE 1 treatment can be carried out at a practical treating tem- 5 perature and time without damaging the twisted fila- Pitch containing 96.2 percent by weight of carbon, ment within the above specified range of the converhaving mean molecular weight of 870, and a softening sion efficiency.
  • the Conversion efpetroleum naphtha at a high temperature is found to be appropriate between 0.07 and The pitch was melt-spun into fibers at various 0.2.
  • the rupture strength of the twisted spinning speeds and stretch ratios as shown in the folyam should not be lower than 0.5 T/cm (Fiber length lowing Table 1, and the thus obtained pitch fibers were of the test sample for measuring the rupture Strength of heat-treated in air starting from a room temperature up the twisted yarn is selected to be one half of the average I 5 o 250 at a mp r r ri r f -8 -Imin, fiber length of the constituent filament, or 300mm, after which the heat-treated (infusibilized) fibers were which ever is shorter). subjected to a carbonization treatment for 30 minutes When the twisted yarn of the above-described conat 1,000 C. in anitrogen atmosphere.
  • Nos 2 and 4 fiber samples were The fibers which have been compression-deformed heat-treated by fixing one end of the total fiber length under the above-mentioned conditions are intimately of 150 mm, and hanging a weight at the other end and compactly twisted as mentioned already, being thereof so as to impart a stress of 0.7 T/cm to the fibers close to the plane contact, with the result that rate of and to result in elongation of about 15 percent.
  • the heat-treatment was conducted tremely high degree.
  • the twisted graphite fibers obtained by the method of present invention (Sample No. 5) are recognized to have the following three major differences from the graphite fibers obtained by ordinary graphitization treatment.
  • the mechanical strength of the fibers are improved. This improvement in strength is considered due to the reduction on the defects existing in the fiber surface and fine pores present in the interior of the fiber itself as a result of the compressive force exerted among the fibers. This improvement can also be inferred from the difference in specific gravity of more than 0.2 g/cm among Sample Nos. 4, 4a and 5.
  • the method according to the present invention makes it possible to maintain a large elongation of the graphite fibers without losing the mechanical strength (vide: curve 5 in FIG. 1
  • curve 5 in FIG. 1 In the ordinary graphite fibers, when the fibers are oriented into crystals that such a modulus of elasticity of more than 3,500 T/cm is imparted thereto, it is usually difficult to obtain a mechanical strength higher than 22 T/cm. If obtainable, the elongation becomes only 0.5 percent or so.
  • the improvement in this respect results in particularly favorable pattern in the stress-strain curve of machine parts made of composite materials reinforced with the graphite fibers, which means that the reinforced composite materials can be used in a variety of machines because of their increased strength.
  • the fibers are mutually compressed to" deform their cross-sectional shape from the initial circular shape to a hexagonal or other polygonal shapes, whereby the bundle of the fibers are intimately and compactly combined as shown in FIG. 3.
  • the degree of compactness of the bundle of the fibers reaches 88%, while the graphite fibers obtained by the ordinary method has a'compactness of only 62 percent.
  • This fact is significant in that, when the fibers are used for composite materials, they can be mixed into the material to an extremely high degree.
  • EXAMPLE 2 The following eight kinds of raw material was used for manufacturing carbon fibers under the conditions as shown in Table 3 below.
  • Raw Material Preparation P-l Obtained by heating bottom oil resulting from naphtha cracking for ethylene production at a temperature of 360 C under presure of 10 mrnI-Ig to low boiling point fractions therein Obtained by heating tar resulting from a high temperature naphtha cracking at 380 C under 10 mmI-Ig to remove low boiling point fractions therein Obtained by first making heavy anthracene oil available in the general market through reaction with air at 200 C in the presence of 5% by weight of solid ammonium nitrate, and then removing the low boiling point fractions at 350 C under 10 mmH Obtained by removing low boiling point fractions of petroleum pitch at 380 C under 10 mmHg Obtained by treating coal pitch with chloroform to extract and remove low molecular weight substances, after which the coal pitch is heated at l50 C for 3 hours, then at 200 C for 3 hours, and further at 300 C for 1 hour under a reduced pressure Obtained by treating distilled bottom oil which is produced by partial hydrogenation of tar
  • Carbonization time 6 hours for each run.
  • Carbon fibers obtained from each raw material in the These carbon fibers were t kind percent P-ZA.
  • Table 3 contain more than 90 percent of carbon, and assume a substantially circular cross-sectional shape, or, oval in some parts.
  • the graphite fibers of Ex. Nos.1 and 2 showed a strength of about 14 T/cm and 18 T/cm respectively, and elongation of less than 0.9%, although the cross-section remained nearly a true circle.
  • the structure of the filament yarns used in this example are such .that vabout 300 monofilaments are subjected to the first-twisting, and then three-sets of the After the second step heat-treatment, the graphite yarn of Ex. No. 3 was loosened in such a manner that its twists are divided into the initial three sets. It was ob served that the yarn was heat-set in wavy form, though having a very gentle wave. When this yarn was again heat-treated at 3,000 C. applying a very small tension thereto, it returned to a straight form in appearance, although the filaments in the yarn still retained the their twisted appearance.
  • a method for the production of graphite fibers of a circular cross-section which comprises the steps of:
  • twisting carbon fibers having a strength of 7 T/cm and above at a ratio strength of from 0.03 to 0.5 times that of the original fibers with respect to the apparent rupture strength of the twisted yarn; and heat-treating the twisted yarn at a temperature of at least 2,000 C. in an inactive atmosphere, while imparting a tensile stress of at least 0.5 'T/cm to said twisted yarn, after the twisted yarn is brought into the state of being able to convert the tensile stress into a compressive force.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Inorganic Fibers (AREA)
  • Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
US166448A 1970-07-28 1971-07-27 Production of graphite fibers Expired - Lifetime US3702054A (en)

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FR (1) FR2103743A5 (OSRAM)
GB (1) GB1353764A (OSRAM)
SU (1) SU449482A3 (OSRAM)

Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3913828A (en) * 1971-09-02 1975-10-21 Avco Corp Reinforcing ultra-centrifuge rotors
US3971840A (en) * 1973-03-27 1976-07-27 The Carborundum Company Production of high strength carbide fibers by heat treatment
US3974264A (en) * 1973-12-11 1976-08-10 Union Carbide Corporation Process for producing carbon fibers from mesophase pitch
US3976729A (en) * 1973-12-11 1976-08-24 Union Carbide Corporation Process for producing carbon fibers from mesophase pitch
US3997654A (en) * 1974-04-24 1976-12-14 Bergwerksverband Gmbh Method for the production of carbonaceous articles, particularly strands
US4005183A (en) * 1972-03-30 1977-01-25 Union Carbide Corporation High modulus, high strength carbon fibers produced from mesophase pitch
US4051659A (en) * 1975-02-17 1977-10-04 Morganite Modmor Limited Production of carbon fibre
US4055583A (en) * 1974-04-24 1977-10-25 Bergwerksverband Gmbh Method for the production of carbonaceous articles, particularly strands
US4084399A (en) * 1976-03-31 1978-04-18 Nippon Carbon Kabushiki Kaisha Gut for racket
US4115527A (en) * 1969-03-31 1978-09-19 Kureha Kagaku Kogyo Kabushiki Kaisha Production of carbon fibers having high anisotropy
US4138525A (en) * 1976-02-11 1979-02-06 Union Carbide Corporation Highly-handleable pitch-based fibers
US4184942A (en) * 1978-05-05 1980-01-22 Exxon Research & Engineering Co. Neomesophase formation
US4197283A (en) * 1977-05-25 1980-04-08 The British Petroleum Company Limited Carbon fibres
US4197282A (en) * 1977-05-25 1980-04-08 The British Petroleum Company Limited Manufacture of carbon fibres
US4238547A (en) * 1973-03-27 1980-12-09 The Carborundum Company High strength yarn consisting of boron carbide fibers
US4265869A (en) * 1978-06-30 1981-05-05 Kureha Kagaku Kogyo Kabushiki Kaisha Method of and apparatus for making pitch fiber infusible
US4276278A (en) * 1979-01-29 1981-06-30 Union Carbide Corporation Spin size and thermosetting aid for pitch fibers
US4301135A (en) * 1979-12-26 1981-11-17 Union Carbide Corporation Process for spinning pitch fiber into a hot gaseous environment
US4356158A (en) * 1981-07-04 1982-10-26 Nippon Carbon Co., Ltd. Process for producing carbon fibers
US4496637A (en) * 1982-12-27 1985-01-29 Toyo Boseki Kabushiki Kaisha Electrode for flowcell
US4497789A (en) * 1981-12-14 1985-02-05 Ashland Oil, Inc. Process for the manufacture of carbon fibers
US4511625A (en) * 1982-09-30 1985-04-16 Union Carbide Corporation Physical conversion of latent mesophase molecules to oriented molecules
US4534950A (en) * 1982-08-13 1985-08-13 Nippon Oil Co., Ltd. Process for producing carbon fibers
US4671864A (en) * 1982-12-03 1987-06-09 Ashland Oil, Inc. Process for the manufacture of carbon fibers and feedstock therefor
US4746470A (en) * 1981-03-12 1988-05-24 Kureha Kagaku Kogo Kabushiki Kaisha Process for the preparation of carbon fibers having structure reflected in cross sectional view thereof as random mosaic
EP0296396A3 (en) * 1987-06-05 1989-11-23 Petoca Ltd. Mesophase pitch-based carbon fibres
US4892722A (en) * 1987-06-05 1990-01-09 Petoca Ltd. Method for producing high strength, high modulus mesophase-pitch-based carbon fibers
US4986893A (en) * 1987-07-08 1991-01-22 Kureha Kagaku Kogyo Kabushiki Kaisha Process for producing pitch for carbon materials
US5168004A (en) * 1988-08-25 1992-12-01 Basf Aktiengesellschaft Melt-spun acrylic fibers possessing a highly uniform internal structure which are particularly suited for thermal conversion to quality carbon fibers
US5238672A (en) * 1989-06-20 1993-08-24 Ashland Oil, Inc. Mesophase pitches, carbon fiber precursors, and carbonized fibers
US5272004A (en) * 1988-03-17 1993-12-21 Petoca Ltd. Carbon fibers and process for producing the same
US6740403B2 (en) * 2001-04-02 2004-05-25 Toyo Tanso Co., Ltd. Graphitic polyhederal crystals in the form of nanotubes, whiskers and nanorods, methods for their production and uses thereof
US20040173969A1 (en) * 2001-10-25 2004-09-09 Smith Walter J. Turbine brush seal
CN105358751A (zh) * 2013-07-22 2016-02-24 村田机械株式会社 丝线制造装置以及凝聚部

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3378999A (en) * 1965-06-17 1968-04-23 Brunswick Corp Metallic yarn structure
US3379000A (en) * 1965-09-15 1968-04-23 Roehr Prod Co Inc Metal filaments suitable for textiles
US3626041A (en) * 1968-11-13 1971-12-07 Monsanto Co Apparatus and process for making continuous filament
US3648452A (en) * 1968-08-03 1972-03-14 Dunlop Holdings Ltd Method of forming reinforcing yarns or cords

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3378999A (en) * 1965-06-17 1968-04-23 Brunswick Corp Metallic yarn structure
US3379000A (en) * 1965-09-15 1968-04-23 Roehr Prod Co Inc Metal filaments suitable for textiles
US3648452A (en) * 1968-08-03 1972-03-14 Dunlop Holdings Ltd Method of forming reinforcing yarns or cords
US3626041A (en) * 1968-11-13 1971-12-07 Monsanto Co Apparatus and process for making continuous filament

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4115527A (en) * 1969-03-31 1978-09-19 Kureha Kagaku Kogyo Kabushiki Kaisha Production of carbon fibers having high anisotropy
US3913828A (en) * 1971-09-02 1975-10-21 Avco Corp Reinforcing ultra-centrifuge rotors
US4005183A (en) * 1972-03-30 1977-01-25 Union Carbide Corporation High modulus, high strength carbon fibers produced from mesophase pitch
US4238547A (en) * 1973-03-27 1980-12-09 The Carborundum Company High strength yarn consisting of boron carbide fibers
US3971840A (en) * 1973-03-27 1976-07-27 The Carborundum Company Production of high strength carbide fibers by heat treatment
US3974264A (en) * 1973-12-11 1976-08-10 Union Carbide Corporation Process for producing carbon fibers from mesophase pitch
US3976729A (en) * 1973-12-11 1976-08-24 Union Carbide Corporation Process for producing carbon fibers from mesophase pitch
US3997654A (en) * 1974-04-24 1976-12-14 Bergwerksverband Gmbh Method for the production of carbonaceous articles, particularly strands
US4055583A (en) * 1974-04-24 1977-10-25 Bergwerksverband Gmbh Method for the production of carbonaceous articles, particularly strands
US4051659A (en) * 1975-02-17 1977-10-04 Morganite Modmor Limited Production of carbon fibre
US4138525A (en) * 1976-02-11 1979-02-06 Union Carbide Corporation Highly-handleable pitch-based fibers
US4084399A (en) * 1976-03-31 1978-04-18 Nippon Carbon Kabushiki Kaisha Gut for racket
US4197283A (en) * 1977-05-25 1980-04-08 The British Petroleum Company Limited Carbon fibres
US4197282A (en) * 1977-05-25 1980-04-08 The British Petroleum Company Limited Manufacture of carbon fibres
US4184942A (en) * 1978-05-05 1980-01-22 Exxon Research & Engineering Co. Neomesophase formation
US4265869A (en) * 1978-06-30 1981-05-05 Kureha Kagaku Kogyo Kabushiki Kaisha Method of and apparatus for making pitch fiber infusible
US4276278A (en) * 1979-01-29 1981-06-30 Union Carbide Corporation Spin size and thermosetting aid for pitch fibers
US4301135A (en) * 1979-12-26 1981-11-17 Union Carbide Corporation Process for spinning pitch fiber into a hot gaseous environment
US4746470A (en) * 1981-03-12 1988-05-24 Kureha Kagaku Kogo Kabushiki Kaisha Process for the preparation of carbon fibers having structure reflected in cross sectional view thereof as random mosaic
US4356158A (en) * 1981-07-04 1982-10-26 Nippon Carbon Co., Ltd. Process for producing carbon fibers
US4497789A (en) * 1981-12-14 1985-02-05 Ashland Oil, Inc. Process for the manufacture of carbon fibers
US4534950A (en) * 1982-08-13 1985-08-13 Nippon Oil Co., Ltd. Process for producing carbon fibers
US4511625A (en) * 1982-09-30 1985-04-16 Union Carbide Corporation Physical conversion of latent mesophase molecules to oriented molecules
US4671864A (en) * 1982-12-03 1987-06-09 Ashland Oil, Inc. Process for the manufacture of carbon fibers and feedstock therefor
US4496637A (en) * 1982-12-27 1985-01-29 Toyo Boseki Kabushiki Kaisha Electrode for flowcell
EP0296396A3 (en) * 1987-06-05 1989-11-23 Petoca Ltd. Mesophase pitch-based carbon fibres
US4892722A (en) * 1987-06-05 1990-01-09 Petoca Ltd. Method for producing high strength, high modulus mesophase-pitch-based carbon fibers
US4986893A (en) * 1987-07-08 1991-01-22 Kureha Kagaku Kogyo Kabushiki Kaisha Process for producing pitch for carbon materials
US5272004A (en) * 1988-03-17 1993-12-21 Petoca Ltd. Carbon fibers and process for producing the same
US5168004A (en) * 1988-08-25 1992-12-01 Basf Aktiengesellschaft Melt-spun acrylic fibers possessing a highly uniform internal structure which are particularly suited for thermal conversion to quality carbon fibers
US5238672A (en) * 1989-06-20 1993-08-24 Ashland Oil, Inc. Mesophase pitches, carbon fiber precursors, and carbonized fibers
US5614164A (en) * 1989-06-20 1997-03-25 Ashland Inc. Production of mesophase pitches, carbon fiber precursors, and carbonized fibers
US6740403B2 (en) * 2001-04-02 2004-05-25 Toyo Tanso Co., Ltd. Graphitic polyhederal crystals in the form of nanotubes, whiskers and nanorods, methods for their production and uses thereof
US20040173969A1 (en) * 2001-10-25 2004-09-09 Smith Walter J. Turbine brush seal
CN105358751A (zh) * 2013-07-22 2016-02-24 村田机械株式会社 丝线制造装置以及凝聚部

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SU449482A3 (ru) 1974-11-05
CA937374A (en) 1973-11-27
GB1353764A (en) 1974-05-22
DE2137614C3 (de) 1975-07-10
DE2137614B2 (de) 1974-11-28
DE2137614A1 (de) 1972-02-03
FR2103743A5 (OSRAM) 1972-04-14

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