US3886263A - Method for manufacture of heat-resistant fibers - Google Patents

Method for manufacture of heat-resistant fibers Download PDF

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US3886263A
US3886263A US329172A US32917273A US3886263A US 3886263 A US3886263 A US 3886263A US 329172 A US329172 A US 329172A US 32917273 A US32917273 A US 32917273A US 3886263 A US3886263 A US 3886263A
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fiber
fibers
atmosphere
heat
oxygen gas
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US329172A
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Akio Shindo
Yoichiro Nakanishi
Yoshihiro Sawada
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National Institute of Advanced Industrial Science and Technology AIST
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Agency of Industrial Science and Technology
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Priority claimed from JP1272872A external-priority patent/JPS4880898A/ja
Priority claimed from JP2960272A external-priority patent/JPS5040171B2/ja
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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
    • D01F9/145—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
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/24—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • D06M11/07—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 halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—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 halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • 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
    • D06M11/07—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 halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—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 halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/155—Halides of elements of Groups 2 or 12 of the Periodic Table
    • 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

Definitions

  • heatresistant fibers and flame-retardant fibers are proucked from organic fibers by heating the said organic fibers to a temperature between 180C and 350C in an atmosphere containing oxygen gas in a concentration of at least 25%, in a high oxygen content atmosphere containing acid vapor, or in a high oxygen content atmosphere and then in an acid-vapor containing, high-oxygen content atmosphere.
  • the heat-resistant fibers having higher heat-resistant property are produced by heating the said flame-retardant fibers to a temperature between 350C and 3,()00C in a non-oxidizing atmosphere or in vacuum.
  • the duration of the entire operation of heat treatment for producing the said heat resistant fibers can be shortened to a great extent while the said-heat treatment procedure enables the heat-resistant fibers produced to have quality favorably comparable with that of the heat-resistant fibers obtainable by the conventional method.
  • This invention relates to a method for the manufacture of heat-resistant fibers by the heat treatment of organic fibers.
  • heat-resistant fiber refers not only to carbon fiber and graphite fiber but equally to any fiber which has undergone a preliminary oxidation treatment or flame-retardation treatment which may be given prior to the carbonization treatment heretofore employed for the production of carbon fiber.
  • flame-retardation treatment may refers to the process which precedes the carbonization treatment.
  • An oxygen-containing atmosphere was heretofore used for the flame-retardation treatment in the manufacture of heat-resistant fibers. In actuality, however, it has invariably been air.
  • the carbon. fiber or graphite fiber has conventionally been produced by first heating in air at 180C 350C and then heating in an inert atmosphere at a temperature of 800C or above. In this case, the heat treatment given in air is required to last a long period of 5 to 6 hours.
  • a method for producing a carbon fiber by effecting the required carbonization in the acid containing atmosphere subsequent to the heat treatment in air. In this case, the use of the atmosphere containing acid vapor not in any way serve the purpose of shortening the time phase of the production.
  • the method of this invention performs the flameretardation heat treatment in an atmosphere containing oxygen gas at a higher concentration than air or in an atmosphere containing acid vapor in conjunction with oxygen gas present in a high concentration or in a high oxygen-content atmosphere and then in an acid containing, high oxygen-content atmosphere. Consequently the time requirement for the flame-retardation heat treatment given to the organic fiber can now be reduced to one-tenth or less.
  • FIGS. 1 through 6 are graphs showing the relation ship of yield, tensile strength and concentration of oxygen gas or acid vapor as observed with heat-resistant fibers manufactured in accordance with the method of the present invention.
  • the given organic fiber is treated in an atmosphere containing oxygen gas in a higher concentration than air or in an atmosphere containing acid vapor in conjection with oxygen gas contained in a high concentration, or the fiber is first treated in a high oxygen-content atmosphere and subsequently in an acid-containing high oxygen-content atmosphere.
  • oxygen-containing atmosphere has to date been used for the heat-resistant treatment of organic fibers
  • the oxygen source has invariably been limited to air which has a mild oxidizing effect.
  • none of the conventional methods has oxygen gas been used directly as the oxygen source. This is partly because oxygen gas or a high oxygen-content gas has too high oxidizing capacity to permit easy setting of appropriate treating conditions for conferring a suitable degree of oxidation upon the fiber in the process of the flameretardation treatment and partly because it is generally thought that the presence of oxygen gas rather entails heavy degradation of the mechanical properties or heat-resistant property of the fiber.
  • the inventors actually tested oxygen gas or a high oxygen-content gas as an atmosphere for the flame-retardation treatment and studied various heating conditions.
  • the fiber is heated in a high oxygen-content atmosphere until the fiber is partially oxidized and, thereafter, the partially oxidized fiber is further heated in an acid-containing, high oxygen-content atmosphere until the fiber undergoes suffi cient flame-retardation treatment.
  • the fiber may be carbonized by being heated to a higher temperature so as to afford a heat-resistant fiber, carbon fiber or graphite fiber, suited to the intended application.
  • the fibers to which the method of this invention is applicable include nitrogen-containing polymeric fibers, oxygen-containing polymeric fibers and organic fibers of hydrocarbon family.
  • the nitrogen-containing polymeric fibers include acrylic (polyacrylonitrile) fiber, polyamide fiber, oxathiazole fiber, thiadiazole fber, benzoxazole fiber, polyamide fibers containing aromatic rings, tetrabenzophenazine fiber, silk and wool.
  • the oxygen-containing polymeric fibers are polyvinyl alcoholic fibers and vinyl alcohol-vinyl chloride copolymer fiber. Formalized fiber is also included in the polyvinyl alcohol fibers.
  • Examples of the fibers of hydrocarbon family are those derived from pitches, dehydrated polyvinyl alcohol and poly-1,2- butadiene. Every exemplary fiber mentioned above refers to the fibers of polymer being composed of molecules containing the corresponding monomer as the main constituent in polymer form.
  • the various kinds of fibers mentioned above, even when they are in an insufficiently oxidized state, may be used as the starting materials for the method of this invention.
  • the aforesaid fibers to be used for the method of this invention can retain their fibrous shape when they are subjected to heat treatment in air at 200- 250C for four to ten hours and subsequently elevated in the atmosphere of argon up to 600C at a uniform rate of temperature rise of [00"C per hour according to the conventional procedure.
  • the atmosphere used for the flame-retardation treatment is required to contain oxygen gas by at least 25%.
  • This atmosphere is obtained by mixing the oxygen gas with an inert gas such as, for example, nitrogen or argon.
  • An atmosphere consisting wholly of oxygen gas can also be used for the treatment.
  • the acid to be incorporated in the vapor form in this atmosphere is a member selected from the group of Briinsted acids and Lewis acids such as hydrochloric acid (hydrogen chloride), hydrogen bromide and phosphorus pentachloride.
  • hydrochloric acid hydrochloric acid
  • the recommended acid content in the atmosphere is in the range of 0.5 50%.
  • the flame-retardation treatment in the case of this invention is carried out at temperatures in the range of 350C.
  • the heat treatment in the aforesaid atmosphere is desired to be started at temperatures below 230C.
  • the heat-resistant fiber as the end product can acquire improvements in tensile strength and Youngs modulus when the fiber is subjected to heat treatment under simultaneous application of tension.
  • the tension to be applied generally should not exceed l g/d, although it differs from one fiber to another.
  • the period of heating time is variable with the temperature of treatment, the composition of atmosphere and the kind of fiber, a period less than one hour proves sufficient. Satisfactory results can be obtained even with a period of heating time less than 30 minutes.
  • the heat resistant fiber obtained by the flameretardation treatment mentioned above are industrially utilizable.
  • the fiber is highly suitable for the production of packing materials for mechanical seals which are expected to make effective use of the fibers resistance to friction, heat and chemicals.
  • a heatresistant fiber (carbon or graphite fiber) excelling in flexibility, tensile strength and Young's modulus can be obtained in a high yield by heating the flame-retardant fiber in a non-oxidizing atmosphere or in vacuum. This fact clearly indicates that the flame-retardation treatment according to this invention is truly an excellent method for conferring heat-resisting property to the organic fiber.
  • the flame-retardant fibers can be converted into still more heat-resistant fibers, namely carbon or graphite fiber, which is possessed of improved tensile strength and Youngs modulus when the fiber is heated up to temperatures higher than 350C, such as 500C, 800C, l,500C or 3,000C, or up to a temperature intermediate between them in a non-oxidizing atmosphere or in vacuum.
  • heat-resistant fibers namely carbon or graphite fiber
  • EXAMPLE 1 Yarns composed of 2-Denier acrylic filaments were heated in a current of mixed gas consisting of oxygen and argon at 220C for 30 minutes, with the oxygen gas concentration varied from one run to another. Blackened heat-resistant fibers were obtained in runs in which the oxygen gas concentrations in the gas streams were higher than about These fibers were found to possess commercially utilizable flexibility. The yields invariably exceeded 96%. These fibers were heated up to l,000C in a current of argon. The relationship of the yield and the tensile strength of the carbon fibers obtained vs. the concentration of the oxygen gas present in the atmosphere used for the flame-retardation treatment is shown in FIG. 1.
  • the horizontal axis represents the concentration of the oxygen gas in the flameretardation treatment atmosphere
  • the vertical axis on the lefthand side the yield of fiber
  • the vertical axis on the righthand side the tensile strength respectively.
  • each solid line depicts the relationship between the oxygen gas concentration and the yield
  • each dotted line the relationship between the oxygen gas concentration and the tensile strength.
  • EXAMPLE 2 A yarn composed of 1.5-Denier acrylic filaments was heat-treated in a current of 100% oxygen gas at 220C for four minutes and subsequently elevated to 250C in a period of eight minutes. Consequently, there was obtained a blackened flame-retardant fiber having flexibility. When this fiber was further heated up to 500C and then to l,200C in a current of argon, it was converted into a flexible carbon fiber. This carbon fiber was found to have a tensile strength of 2 l0 kg/mm". A graphite fiber having a tensile strength of 180 kg/mm was obtained by heating the carbon fiber up to 2,850C in a current of argon.
  • EXAMPLE 4 Three fiber samples of a yarn composed of 4.0 Denier filaments of polyvinyl alcohol were heated at 200C for 6 minutes, heated to 240C in l2 minutes and held at 240C for 6 minutes, respectively in a current of argon containing oxygen gas in a concentration of 30%, or 80%, or in a current of air. Consequently, there were obtained blackish brown flame-retardant fibers having flexibility. When these fibers were further heated up to l,000C in a current of argon, there were obtained carbon fibers having 43, 52 and 18 kg/mm of tensile strength respectively. The yields of these fibers on the basis of the starting yarn were 28, 30 and 21%, suggesting that both tensile strength and yield would be improved by flame-retardation treating in currents of gases containing oxygen gas at a higher concentration than air.
  • EXAMPLE 5 Several fiber samples of a yarn composed of l.5- Denier acrylic filaments were heated at 220C for 30 minutes in respective currents of mixed gases containing 50% of oxygen gas, and argon and hydrogen chloride gas at different proportions. Consequently, there were obtained blackened fibers having flexibility. A part of every blackened fiber was heated to 700C, and another part to l,000C in a current of argon. The relationship of the yield based on the corresponding starting fiber, and the average tensile strength per filament for the carbon fibers obtained vs. the concentration of hydrochloric acid gas at the time of the flameretardation treatment is shown in Table l and FIG. 3.
  • curves A, B and C show the variation of yield of the l,000C fiber with the concentration of hydrochloric acid vapor, the tensile strength for the l,000C fibers, and the yield of the 700C fibers, respectively.
  • EXAMPLE 6 Several samples of yarn composed of 1.5-Denier acrylic filaments were heated at 220C for 30 minutes in respective currents of mixed gases containing oxygen gas and hydrochloric acid gas at different proportions. Consequently, there were obtained blackened flameretardant fibers having high flexibility. These dehydrogenated fibers were further heated up to l,00OC in a current of argon to produce carbon fibers. The yield of the carbon fibers thus obtained is shown as a function of the concentration of hydrochloric acid gas or oxygen gas in the flame-retardation treatment atmosphere in Table 2 and FIG. 4. The vertical axes and the horizontal axis in the figure have the same meanings as those in FIG. 1.
  • dehydrogenated fiber samples were heated up to 1,000C under the same conditions as mentioned above, except a tension of 0.08 g/d was applied to the fibers in the heating process.
  • the average tensile strength of the carbon fibers thus obtained is indicated in Table 2 and plotted as a dotted line in FIG. 4.
  • the yield of the l,000C fiber obtained was increased by 30% and the tensile strength by 50%, respectively. as compared with the l,0OOC fiber from the flame-retardant fiber obtained in the current of acid-free gas.
  • EXAMPLE 8 Several fiber samples of yarn composed of 2.0- Denier hydrocarbon filaments were heated at 180C for 5 minutes, heated from 180C to 325C in a period of 20 minutes and held at 325C for 5 minutes in respective currents of mixed gases containing oxygen gas and hydrochloric acid gas in different proportions. There were obtained blackened fibers having flexibility. These dehydrogenated fibers were further heated to l,0OOC in a current of argon. The yield, based on the starting yarn, for the l,000C fibers obtained are shown as a function of the concentrations of hydrochloric acid gas and oxygen gas in the flameretardation treatment atmosphere in Table 4 and as a solid line in FIG. 6.
  • EXAMPLE 10 An acrylic filament yarn having a total denier of 3,000 and a filament denier of 1.0 was heated separately for minutes at 220C in a current of air and a separate sample in a current of 100% oxygen gas using a continuous line, while the fiber yarn was held under tension. The same yarns as mentioned above were heated at 220C for 10 minutes in a current of 100% oxygen gas and for the next 10 minutes in a current of mixed gas consisting of 93% of oxygen gas and 7% of hydrochloric acid gas, being kept in continuous transfer through a heating zone. The yarns treated in the current of air turned yellow, while those treated in the current of 100% oxygen gas and those treated in the current of oxygen gas-acid vapor mixture both turned blackish brown.
  • EXAMPLE 11 A filamentary yarn, having a total denier of 4,000 and filament denier of 2.0, of hydrocarbon material (dehydrated polyvinyl alcohol) was heated from 180C to 220C and then held at 220C for 30 minutes in a current of air (1) while a separate sample was processed in a current of 100% oxygen gas (2) using in a continuous line. Another part of the same yarn of hydrocarbon as mentioned above was subjected to heat treatment at 220C for 15 minutes in an atmosphere of 100% oxygen gas and for the next 15 minutes in a dehydrogenating atmosphere consisting of 88% of oxygen gas and 12% of hydrochloric acid gas (3) by continuously passing through two atmosphere heating zones. In all cases, there were obtained fibers having flexibility.
  • hydrocarbon material dehydrated polyvinyl alcohol
  • EXAMPLE 12 A fiber sample of the same tows of pitch filaments as used in Example 9 was heated from 200C to 320C in a period of 15 minutes and then held at 320C for 15 minutes in a current of air while a separate sample was processed in a current of 100% oxygen gas. Another fiber sample of the same tows as stated above was separately heated from 200C to 320C in a period of 15 minutes and then held at the latter temperature for 5 minutes in a current of 100% oxygen gas and, thereafter, they were held at the same temperature for 10 minutes in a current of gas consisting of 20% of hydrogen bromide and of oxygen gas. All these fibers were heated up to 1,400C in an atmosphere of argon.
  • the carbon fibers obtained from the tow heated in air were so weak as to make the measurement of tensile strength difficult.

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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)
  • Adhesives Or Adhesive Processes (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
US329172A 1972-02-03 1973-02-02 Method for manufacture of heat-resistant fibers Expired - Lifetime US3886263A (en)

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Application Number Priority Date Filing Date Title
JP1272872A JPS4880898A (de) 1972-02-03 1972-02-03
JP2960272A JPS5040171B2 (de) 1972-03-23 1972-03-23

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4113847A (en) * 1975-09-01 1978-09-12 Japan Exlan Company Limited Process for producing carbon fibers
US4534950A (en) * 1982-08-13 1985-08-13 Nippon Oil Co., Ltd. Process for producing carbon fibers
US4731298A (en) * 1984-09-14 1988-03-15 Agency Of Industrial Science & Technology Carbon fiber-reinforced light metal composites
CN105040164A (zh) * 2015-08-24 2015-11-11 中国科学院宁波材料技术与工程研究所 一种以聚烯烃为基体制备活性碳纤维的方法
CN117684289A (zh) * 2023-11-30 2024-03-12 江苏恒科新材料有限公司 耐热油剂及其制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58169515A (ja) * 1982-03-31 1983-10-06 Nippon Oil Co Ltd 炭素繊維の製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3441378A (en) * 1966-05-10 1969-04-29 Union Carbide Corp Process for the manufacture of carbon textiles
US3529934A (en) * 1967-01-06 1970-09-22 Nippon Carbon Co Ltd Process for the preparation of carbon fibers
US3647770A (en) * 1968-11-21 1972-03-07 Celanese Corp Process for formation of a cyclized acrylic fibrous material
US3666417A (en) * 1969-05-17 1972-05-30 Kureha Chemical Ind Co Ltd Process for production of carbon fibers
US3671192A (en) * 1968-05-28 1972-06-20 Us Air Force Method of stabilizing acrylic polymer fibers prior to graphitization

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3441378A (en) * 1966-05-10 1969-04-29 Union Carbide Corp Process for the manufacture of carbon textiles
US3529934A (en) * 1967-01-06 1970-09-22 Nippon Carbon Co Ltd Process for the preparation of carbon fibers
US3671192A (en) * 1968-05-28 1972-06-20 Us Air Force Method of stabilizing acrylic polymer fibers prior to graphitization
US3647770A (en) * 1968-11-21 1972-03-07 Celanese Corp Process for formation of a cyclized acrylic fibrous material
US3666417A (en) * 1969-05-17 1972-05-30 Kureha Chemical Ind Co Ltd Process for production of carbon fibers

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4113847A (en) * 1975-09-01 1978-09-12 Japan Exlan Company Limited Process for producing carbon fibers
US4534950A (en) * 1982-08-13 1985-08-13 Nippon Oil Co., Ltd. Process for producing carbon fibers
US4731298A (en) * 1984-09-14 1988-03-15 Agency Of Industrial Science & Technology Carbon fiber-reinforced light metal composites
CN105040164A (zh) * 2015-08-24 2015-11-11 中国科学院宁波材料技术与工程研究所 一种以聚烯烃为基体制备活性碳纤维的方法
CN105040164B (zh) * 2015-08-24 2017-05-31 中国科学院宁波材料技术与工程研究所 一种以聚烯烃为基体制备活性碳纤维的方法
CN117684289A (zh) * 2023-11-30 2024-03-12 江苏恒科新材料有限公司 耐热油剂及其制备方法

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DE2305191B2 (de) 1977-12-15
GB1416366A (en) 1975-12-03
DE2305191C3 (de) 1978-08-17
DE2305191A1 (de) 1973-08-09

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