EP0443431A2 - Fibres de carbone creuses - Google Patents

Fibres de carbone creuses Download PDF

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Publication number
EP0443431A2
EP0443431A2 EP19910102053 EP91102053A EP0443431A2 EP 0443431 A2 EP0443431 A2 EP 0443431A2 EP 19910102053 EP19910102053 EP 19910102053 EP 91102053 A EP91102053 A EP 91102053A EP 0443431 A2 EP0443431 A2 EP 0443431A2
Authority
EP
European Patent Office
Prior art keywords
carbon fibers
ring
fibers according
weight
fibers
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.)
Withdrawn
Application number
EP19910102053
Other languages
German (de)
English (en)
Other versions
EP0443431A3 (en
Inventor
Erich Prof.Dr. Fitzer
Wolfgang Metzler
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.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0443431A2 publication Critical patent/EP0443431A2/fr
Publication of EP0443431A3 publication Critical patent/EP0443431A3/de
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor

Definitions

  • the invention relates to hollow carbon fibers based on polyacrylonitrile precursor fibers and their use for the production of high-performance composite materials.
  • Hollow carbon fibers based on pitch fibers and polyacrylonitrile fibers are known.
  • the cross-sectional area of the fibers is generally in the form of a uniform, closed ring.
  • High-performance composite materials that have been produced with such hollow fibers have the advantage of better fiber / matrix adhesion and higher compressive strength, based on the fiber weight, compared to those based on compact fibers.
  • it has been shown that the damage tolerance of such composite materials still needs improvement for some applications.
  • the invention was therefore based on the object of providing hollow carbon fibers which give high-performance composite materials with improved damage tolerance.
  • EP-A 232 051 describes carbon fibers with a cross-sectional area in the form of a ring that is not completely closed, the carbon fibers being produced from pitch fibers.
  • the explanations in this publication give the impression that carbon fibers shaped in this way cannot be produced from polyacrylonitrile fibers.
  • the hollow carbon fibers according to EP-A 232 051 have a diameter of more than 30 ⁇ m. Such fibers are not suitable for the production of high-performance composite materials because they do not have a sufficiently reinforcing effect in the composite.
  • EP-A 232 051 are correct insofar as it is not possible to produce carbon fibers with a cross-sectional area in the form of a not completely closed ring from the usual solution-spun polyacrylonitrile fibers using the processes described therein.
  • the preferred process for producing the hollow carbon fibers according to the invention is therefore based on melt-spun polyacrylonitrile precursor fibers.
  • Such fibers are e.g. in the as yet unpublished European patent application 89 11 5373.6 and in the publications cited therein.
  • the underlying polyacrylonitrile preferably consists of at least 85% by weight of acrylonitrile units; it can contain up to 15% by weight of units of conventional comonomers, e.g. Contain methyl acrylate, styrene, methyl methacrylate or itaconic acid.
  • this acrylonitrile polymer 100 parts by weight of this acrylonitrile polymer are mixed with 10-30 parts by weight of water, 5-30 parts by weight of acetonitrile or nitromethane, and optionally other organic liquids, e.g. 1-10 parts by weight of a C1-C4 alkanol mixed and melted.
  • the melt is pressed out through a nozzle head which has C-shaped nozzle openings.
  • a spatial extension is expediently provided at one end of the C-shaped nozzle opening (see FIG. 1) and serves as a reservoir for the polyacrylonitrile melt during the subsequent stretching.
  • the nozzles can have a diameter between 50 and 200 microns.
  • the hollow carbon fibers obtained preferably have an outer diameter of 5 to 20 ⁇ m and a wall thickness of 0.5 to 5 ⁇ m.
  • the distance between the ends of the non-closed ring depends on the size of the reservoir described above and on the stretching conditions.
  • the ring can either be completely open (FIG. 2), the distance between the ring ends being a maximum of 2 ⁇ m, preferably 0.1-1 ⁇ m, or the ring ends, which are rounded, can touch, so that the point of contact has a reduced wall thickness has (Figure 3).
  • polyacrylonitrile fibers are oxidized in a conventional manner at 200-300 ° C and carbonized at 1000-2000 ° C. It has been shown that these processes run much faster if the cross section of the stretched polyacrylonitrile fiber is in the form of an open ring. The fiber does not change its shape significantly during oxidation and carbonization, i.e. the shape of the cross-sectional area is retained.
  • the carbon hollow fibers according to the invention are outstandingly suitable for the production of specifically light, high-strength and rigid composite materials.
  • they are used in the form of rovings using customary methods thermosetting plastics, such as epoxy resins, bismaleimide resins or cyanate resins, or impregnated with thermoplastic plastics, such as polyether sulfones, polyether ketones or polyimides.
  • thermosetting plastics such as epoxy resins, bismaleimide resins or cyanate resins
  • thermoplastic plastics such as polyether sulfones, polyether ketones or polyimides.
  • the composite materials are characterized by particularly high resistance to buckling and buckling and have a higher damage tolerance than comparable composite materials based on carbon hollow fibers with a cross-sectional area in the form of a closed ring, that is to say the composite material can absorb higher loads without causing a load Damage comes. In terms of numbers, this is expressed in an increased fracture energy G 1c .

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Fibers (AREA)
  • Artificial Filaments (AREA)
EP19910102053 1990-02-22 1991-02-14 Hollow carbon fibres Withdrawn EP0443431A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4005530 1990-02-22
DE19904005530 DE4005530A1 (de) 1990-02-22 1990-02-22 Kohlenstoff-hohlfasern

Publications (2)

Publication Number Publication Date
EP0443431A2 true EP0443431A2 (fr) 1991-08-28
EP0443431A3 EP0443431A3 (en) 1992-02-19

Family

ID=6400695

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19910102053 Withdrawn EP0443431A3 (en) 1990-02-22 1991-02-14 Hollow carbon fibres

Country Status (2)

Country Link
EP (1) EP0443431A3 (fr)
DE (1) DE4005530A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002000973A1 (fr) * 2000-06-29 2002-01-03 R-R & D Centre N.V. Fibre synthetique, buse et procede de fabrication et d'utilisation associe
WO2006010401A1 (fr) * 2004-07-23 2006-02-02 Wabco Gmbh & Co. Ohg Fibre pour materiau isolant acoustique, en particulier pour des attenuateurs sonores dans des dispositifs a air comprime
US8006801B2 (en) 2004-07-24 2011-08-30 Wabco Gmbh Noise damper for a compressed air device
US8215448B2 (en) 2008-06-20 2012-07-10 Wabco Gmbh Sound damper for vehicle compressed air systems

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2945739A (en) * 1955-06-23 1960-07-19 Du Pont Process of melt spinning
US5149517A (en) * 1986-01-21 1992-09-22 Clemson University High strength, melt spun carbon fibers and method for producing same
US4935180A (en) * 1988-08-25 1990-06-19 Basf Aktiengesellschaft Formation of melt-spun acrylic fibers possessing a highly uniform internal structure which are particularly suited for thermal conversion to quality carbon fibers

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002000973A1 (fr) * 2000-06-29 2002-01-03 R-R & D Centre N.V. Fibre synthetique, buse et procede de fabrication et d'utilisation associe
WO2006010401A1 (fr) * 2004-07-23 2006-02-02 Wabco Gmbh & Co. Ohg Fibre pour materiau isolant acoustique, en particulier pour des attenuateurs sonores dans des dispositifs a air comprime
CN1989036B (zh) * 2004-07-23 2011-06-22 威伯科有限公司 用于隔音材料的热塑性材料纤维
US8006801B2 (en) 2004-07-24 2011-08-30 Wabco Gmbh Noise damper for a compressed air device
US8215448B2 (en) 2008-06-20 2012-07-10 Wabco Gmbh Sound damper for vehicle compressed air systems

Also Published As

Publication number Publication date
DE4005530A1 (de) 1991-08-29
EP0443431A3 (en) 1992-02-19

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