US3673035A - Method of manufacturing carbon fibres - Google Patents

Method of manufacturing carbon fibres Download PDF

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Publication number
US3673035A
US3673035A US816202A US3673035DA US3673035A US 3673035 A US3673035 A US 3673035A US 816202 A US816202 A US 816202A US 3673035D A US3673035D A US 3673035DA US 3673035 A US3673035 A US 3673035A
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US
United States
Prior art keywords
furnace
tapes
fibres
sheets
tape
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US816202A
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English (en)
Inventor
Ian Whitney
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rolls Royce PLC
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Rolls Royce PLC
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Publication date
Application filed by Rolls Royce PLC filed Critical Rolls Royce PLC
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Publication of US3673035A publication Critical patent/US3673035A/en
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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
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/14—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with organic compounds, e.g. macromolecular compounds
    • 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

Definitions

  • This invention relates to a method of manufacturing carbon fibres and provides a method by which tapes or sheets may be manufactured in a continuous, integrated process.
  • a method of manufacturing carbon fibre comprises continuously feeding a plurality of tapes or sheets of fibre of polyacrylonitrile or a copolymer thereof in parallel through a furnace or furnaces wherein the majority of the constituents other than carbon are driven off, said plurality comprising at least 105 fibres.
  • Said tapes may be fed initially through a pre-oxidising furnace in Which a temperature of between 150 C. and 300 C. is maintained in an atmosphere of an oxygencontaining gas.
  • said tapes may be fed to a carbonising furnace in which a temperature of between 500 C. and 1200 C. is maintained in an inert atmosphere.
  • the carbon fibre tapes are preferably subsequently resin impregnated.
  • Said resin impregnation is preferably effected by the transfer of resin from coated release paper to the tape by a combination of heat and pressure.
  • the invention also comprises the carbon fibre made by the method set out in any of the above statements.
  • FIG. 1 indicates a creel unit in which a plurality of creels 11 hold tows of polyacrylonitrile fibres of 11/2 denier.
  • this creel unit there is embodied a tape or sheetforming and retaining unit (not shown) such for instance as is described in our co-pending application Ser. No. 792,646 (now abandoned).
  • the creel unit produces tapes or sheets held together by a weft thread introduced at intervals into the warp fibres, each sheet being of approximately 18 inches width and each containing 50 tows, each tow comprising 104 fibres.
  • the eight tapes are maintained with a separation of some three inches between tapes, the tapes lying one above the other, and are fed into a roller unit generally indicated at 12.
  • the roller drive unit 12 comprises eight separate sets of four rollers, one of which is'indicatedA at 13. These sets of rollers are mounted in parallel so that each roller set receives a single tape lCe which then passes round the four driven rollers which comprise the set and then passes out from the drive unit horizontally aligned with its entry.
  • the eight tapes are brought closer together as shown at 14 and pass through closely fitting orifices at 15 into a pre-oxidisation furnace 16.
  • the atmosphere inside the furnace is maintained by a blower system and heater units (not shown) so that the ambient atmosphere within the furnace comprises air heated to a temperature of some 220 C.
  • a blower system 17 is provided to effect a controlled flow of air in the furnace.
  • the eight tapes pass over these rollers which cause them to move over a castellated path within the furnace, in this way achieving a long path length (40 feet) within a relatively compact furnace; the tapes are arranged to take some seven hours to pass through the furnace.
  • the fibres On emerging from the furnace through closely fitting orifices at 19 the fibres, still in their tape form, pass into a second roller drive unit 20, which is identical to that shown at 12.
  • the drive units 12 and 20 By arranging the drive units 12 and 20 at either end of the furnace 16 the fibre can be arranged to be held ⁇ under tension while it is being pre-oxidised. This prevents .the shrinkage which would otherwise take place during this stage of the process.
  • the tapes are brought together to form a single bunch and pass into a carbonising furnace 21 by way of a roller seal unit 22.
  • This seal unit makes use of a pair of roller seals as described in our copending application Ser. No. 771,466 (now abandoned) and prevents any considerable leakage from the furnace 21.
  • the fibre sheets are compacted at this stage to reduce the power required and to simplify the system; at this stage it is unnecessary to maintain the spacing which is required in the previous stages to allow purging of reaction products and dissipation of heat.
  • a nitrogen atmosphere is maintained, a duct 23 being provided for the influx of nitrogen while a duct 24 is provided for the efflux of nitrogen plus waste gases.
  • the tapes are suspended above a floor (not shown).
  • the temperature is arranged to rise steadily from room temperature adjacent to seal unit 22 up to approximately 1000 C. at a point 25.
  • the dimensions of the furnace are so chosen that at the point 25 the majority of the pyrolysis of the fibres has taken place; this being so there is no necessity to arrange for any additional purging of reaction products in the subsequent treatment.
  • the compacted fibres next pass through a higher temperature portion 26 of the furnace.
  • sectional area of this part of the furnace is reduced by wall assemblies 27 which comprise heating units; this reduction in area helps to reduce the power required to provide the higher temperature heating.
  • the fibres are further heated to a temperature in the region of 1600 C.
  • the compacted fibres finally emerge from the furnace 21 by way of a second seal unit 28 which again uses roller seals having an evacuated space therebetween to ensure complete removal of toxic reaction products.
  • the seal unit 28 On leaving the seal unit 28 the fibres pass into a further furnace 29. Although for convenience of drawing this furnace is shown as being separate from the furnace 21, it is in fact connected directly to the seal 28 and the entire apparatus forms a linear lay-out. Thus the seal 28 in fact divides the atmosphere within the furnace 21 from that in the furnace 29. Within the furnace 29 an atmosphere of argon is maintained and once again an input pipev 30 supplies argon while an output pipe 31 allows egress of argon and any products of reaction. Within the furnace 29 the libre is heated, still in its compacted form, to a temperature in this case of 2500 C., but which may be in the range of 1500 C. upwards. In this stage the structure of the carbon fibre is made more pseudo-graphitic. This stage can in fact be omitted completely and it is possible ⁇ to produce useful carbon libre with la carbonising furnace which merely heats the libre up to a temperature of 1000 C. to 1200 C.
  • the libre exits from the furnace 29 after some 1/2 hour residence time by way of a seal unit 32 which is given similar to the 4unit 28 and prevents large escape of gases from the furnace 29.
  • a seal unit 32 which is given similar to the 4unit 28 and prevents large escape of gases from the furnace 29.
  • the compacted libres pass between a pair of driven rollers 33 and after passing through these rollers the compacted libres are again split up into their eight discrete tapes into a resin impregnation unit generally indicated at 34.
  • the resin impregnation unit 34 is of the type described and claimed in our co-pending application Ser. No. 887,864 and uses coated paper as a transferring agent for an epoxy Novolac resin. For simplicity, the course of a single tape will be described; the remaining tapes follow an exactly similar course.
  • the upper tape first, on entering the unit 34 it passes between a pair of reels 35 and 36 of resin coated release paper.
  • the release paper is itself impregnated with a release agent which alfords the resin no permanent adhesion to the paper.
  • the reels 35 and 36 are mounted within a chamber 37 which is refrigerated so that the resin is maintained non-tacky.
  • the paper from the reels 35 and 36 is fed on to either side of the libre tape so that the coatedside of the paper is against the libre.
  • the sandwich thus formed passes from the chamber 37 into a second chamber 38 and between a pair of heated rollers 39. On passing between these rollers, the combined effect of the heat and pressure evolved causes the resin to transfer from the release paper to the libre tape, thus impregnating the tape with resin.
  • rollers 39 On leaving the rollers 39 the sheets come together in a stack, and pass through rollers 40.
  • the stacked sheets then pass through a conventional guillotine device 41 and are cut into sheets which are transported by a conveyor device 42 to be stacked at 43. They may alternatively be rolled on eight drums.
  • resin impregnation could be carried out by alternative methods such as immersion or spraying.
  • the present invention by using a multiplicity of fibres passing at a relatively slow speed through a series of furnaces enables a good output to be maintained with considerable advantages in ease of processing etc. It will be particularly noticed that the method of the present invention produces libres in sheet form; this form is generally highly convenient for the laying up of articles from the libres.
  • Y 4 f or a copolymer thereof the improvement comprising the stepsofv forming a lirst plurality of tapes or sheets from large numbers of individual continuous length libres formed from polyacrylonitrile or copolymer thereof, said plurality of said tapes or sheets comprising a total of at least libres, feeding said lirst plurality of said tapes or sheets, spaced apart and one above the other in generally parallel relationship, through a lirst furnace, heat treating said plurality of tapes or sheets while in said lirst furnace in an oxygen-containing atmosphere to a temperature between C. and 300 C.,

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Fibers (AREA)
  • Reinforced Plastic Materials (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
US816202A 1968-04-19 1969-04-15 Method of manufacturing carbon fibres Expired - Lifetime US3673035A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB1861768 1968-04-19

Publications (1)

Publication Number Publication Date
US3673035A true US3673035A (en) 1972-06-27

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Family Applications (1)

Application Number Title Priority Date Filing Date
US816202A Expired - Lifetime US3673035A (en) 1968-04-19 1969-04-15 Method of manufacturing carbon fibres

Country Status (8)

Country Link
US (1) US3673035A (fr)
JP (1) JPS5221090B1 (fr)
BE (1) BE731737A (fr)
CA (1) CA943316A (fr)
CH (1) CH516478A (fr)
DE (1) DE1919393C3 (fr)
FR (1) FR2006543A1 (fr)
GB (1) GB1257481A (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4065549A (en) * 1974-10-21 1977-12-27 Toray Industries, Inc. High tensile strength, high Young's modulus carbon fiber having excellent internal structure homogeneity, and process for producing the same
US4073870A (en) * 1975-04-02 1978-02-14 Toho Beslon Co., Ltd. Process for producing carbon fibers
USRE30414E (en) * 1974-10-21 1980-10-07 Toray Industries, Inc. Process for producing a high tensile strength, high Young's modulus carbon fiber having excellent internal structure homogeneity
US4534920A (en) * 1982-06-07 1985-08-13 Toray Industries, Inc. Process for producing carbonizable oxidized fibers and carbon fibers
US4588538A (en) * 1984-03-15 1986-05-13 Celanese Corporation Process for preparing tapes from thermoplastic polymers and carbon fibers
US4695415A (en) * 1985-01-24 1987-09-22 Mitsubishi Rayon Co., Ltd. Method for producing acrylic fiber precursors
US4856179A (en) * 1983-04-21 1989-08-15 Hoechst Celanese Corp. Method of making an electrical device made of partially pyrolyzed polymer
US4915926A (en) * 1988-02-22 1990-04-10 E. I. Dupont De Nemours And Company Balanced ultra-high modulus and high tensile strength carbon fibers
US5082701A (en) * 1987-12-09 1992-01-21 Quadrax Corporation Multi-directional, light-weight, high-strength interlaced material and method of making the material
US5229177A (en) * 1987-12-09 1993-07-20 Quadrax Corporation Multi-directional, light-weight, high-strength interlaced material
US20120111162A1 (en) * 2010-11-04 2012-05-10 Karl Mayer Malimo Textilmaschinenfabrik Gmbh Device and method for producing monoaxial or multiaxial scrims
JP2013147763A (ja) * 2012-01-18 2013-08-01 Mitsubishi Rayon Co Ltd 炭素繊維の製造方法

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2326488B2 (de) * 1972-06-01 1976-02-05 Toray Industries, Inc., Tokio Verfahren zur herstellung von kohlenstoff -fasern oder -faeden
DE2313284B2 (de) * 1973-03-16 1979-10-25 Robert Bosch Gmbh, 7000 Stuttgart Handwerkzeugmaschine
DE2964615D1 (en) * 1979-08-17 1983-03-03 Toray Industries Process for the manufacture of graphite fibres
US4501037A (en) * 1983-04-11 1985-02-26 Hitco Method for introducing heat-sensitive material into a hot environment
JPS60172655U (ja) * 1984-04-02 1985-11-15 東北金属工業株式会社 平面加工治具
JPH10121325A (ja) * 1996-10-14 1998-05-12 Toray Ind Inc 炭素繊維用前駆体繊維束とその製造方法および炭素繊維の製造方法
JP4740098B2 (ja) * 2006-12-04 2011-08-03 三菱レイヨン株式会社 炭素繊維の製造装置

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4065549A (en) * 1974-10-21 1977-12-27 Toray Industries, Inc. High tensile strength, high Young's modulus carbon fiber having excellent internal structure homogeneity, and process for producing the same
USRE30414E (en) * 1974-10-21 1980-10-07 Toray Industries, Inc. Process for producing a high tensile strength, high Young's modulus carbon fiber having excellent internal structure homogeneity
US4073870A (en) * 1975-04-02 1978-02-14 Toho Beslon Co., Ltd. Process for producing carbon fibers
US4534920A (en) * 1982-06-07 1985-08-13 Toray Industries, Inc. Process for producing carbonizable oxidized fibers and carbon fibers
US4856179A (en) * 1983-04-21 1989-08-15 Hoechst Celanese Corp. Method of making an electrical device made of partially pyrolyzed polymer
US4588538A (en) * 1984-03-15 1986-05-13 Celanese Corporation Process for preparing tapes from thermoplastic polymers and carbon fibers
US4695415A (en) * 1985-01-24 1987-09-22 Mitsubishi Rayon Co., Ltd. Method for producing acrylic fiber precursors
US5082701A (en) * 1987-12-09 1992-01-21 Quadrax Corporation Multi-directional, light-weight, high-strength interlaced material and method of making the material
US5229177A (en) * 1987-12-09 1993-07-20 Quadrax Corporation Multi-directional, light-weight, high-strength interlaced material
US4915926A (en) * 1988-02-22 1990-04-10 E. I. Dupont De Nemours And Company Balanced ultra-high modulus and high tensile strength carbon fibers
US20120111162A1 (en) * 2010-11-04 2012-05-10 Karl Mayer Malimo Textilmaschinenfabrik Gmbh Device and method for producing monoaxial or multiaxial scrims
JP2013147763A (ja) * 2012-01-18 2013-08-01 Mitsubishi Rayon Co Ltd 炭素繊維の製造方法

Also Published As

Publication number Publication date
CH516478A (fr) 1971-12-15
CA943316A (en) 1974-03-12
DE1919393A1 (de) 1970-03-05
DE1919393C3 (de) 1973-09-13
FR2006543A1 (fr) 1969-12-26
GB1257481A (fr) 1971-12-22
BE731737A (fr) 1969-10-01
JPS5221090B1 (fr) 1977-06-08

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