EP0075437B1 - Verfahren zur Herstellung von Kohlenstoffasern - Google Patents

Verfahren zur Herstellung von Kohlenstoffasern Download PDF

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Publication number
EP0075437B1
EP0075437B1 EP19820304859 EP82304859A EP0075437B1 EP 0075437 B1 EP0075437 B1 EP 0075437B1 EP 19820304859 EP19820304859 EP 19820304859 EP 82304859 A EP82304859 A EP 82304859A EP 0075437 B1 EP0075437 B1 EP 0075437B1
Authority
EP
European Patent Office
Prior art keywords
yarn
fiber
fibers
cleaning
heat treatment
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
Application number
EP19820304859
Other languages
English (en)
French (fr)
Other versions
EP0075437A1 (de
Inventor
David Arthur Schulz
David Stuart Brookstein
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.)
Union Carbide Corp
Original Assignee
Union Carbide Corp
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 Union Carbide Corp filed Critical Union Carbide Corp
Publication of EP0075437A1 publication Critical patent/EP0075437A1/de
Application granted granted Critical
Publication of EP0075437B1 publication Critical patent/EP0075437B1/de
Expired 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
    • 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
    • D01D11/00—Other features of manufacture
    • 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
    • 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
    • D01F9/32—Apparatus therefor
    • 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
    • D01F9/322—Apparatus therefor for manufacturing filaments from pitch

Definitions

  • the invention relates to a process for producing carbon fibers and in particular to a process for cleaning the fibers.
  • the conventional process for producing a polyacrylonitrile (PAN) or pitch derived carbon fiber comprises the steps of spinning a fiber from PAN or mesophase pitch, infusibilizing the spun fiber by heating it in air, and carbonizing the infusible fiber by heating it in an inert gaseous environment.
  • PAN polyacrylonitrile
  • thermosetting step the infusible fiber is referred to as a "thermoset fiber”.
  • high quality commercial carbon fibers are made from PAN and mesophase pitch.
  • the pitch yarn comprises a plurality of pitch fibers whereas PAN yarn comprises a plurality of PAN fibers.
  • the subsequent operations are carried out on the yarn to produce a carbon yarn comprising a plurality of carbon fibers.
  • a mesophase pitch yarn typically can have 2,000 fibers. Each fiber typically has a diameter of about 14 pm or less.
  • US-A-3705236 describes a method of making carbon fibers having tensile strength improved by the application of vibrational energy during one or more heat treatment stages of the fiber production.
  • the vibrational energy is disclosed only for improving the degree of orientation of the molecules and hence, the tensile strength of the fiber, and it is only disclosed as occurring during the heat treatment steps so that the amplitude of the energy vibrations applied must be lower than that which will effect breakage or damage of the fibers whilst at the elevated temperatures of the heat treatment stages.
  • the cleaning step can be carried out subsequent to the fibers being thermoset.
  • the thermoset fibers are usually subjected to a coating step and the coating or "finish" can interfere with the effectiveness of the cleaning step according to the invention.
  • thermoset yarn is subjected to a first heat treatment at a temperature of about 1300°C in an inert atmosphere by the yarn being pulled through a heat chamber.
  • the first heat treatment substantially removes the finish and is sometimes called in the art "precarbonization", even though it is a carbonization step.
  • the yarn, after the first heat treatment is much stronger and can be handled with considerably less care.
  • the yarn is subjected to a second heat treatment at a temperature of from about 1500°C to about 3000°C in an inert atmosphere to produce the final product, carbon yarn.
  • thermosetting step Neither of the heat treatments remove the carbon black particles which were deposited on the fibers to improve the thermosetting step.
  • the instant invention is the use of high frequency mechanical vibrations applied directly to a substantially dry yarn or fiber.
  • the fiber can be mesophase pitch derived or PAN derived and preferably the mechanical vibrations are in the ultrasonic frequency range.
  • a yarn comprising a plurality of fibers having diameters of about 14 pm, typically about 2,000 fibers, can be used instead of a single fiber.
  • the cleaning step can be carried out subsequent to the first heat treatment.
  • the yarn after a first heat treatment is cleaned according to the invention immediately prior to the yarn entering into a chamber for carrying out the second heat treatment.
  • the yarn is extended generally along a linear path and presses against the horn of an ultrasonic source with an effective force of from about 0.098 to about 0.245 Newtons.
  • the ultrasonic source produces mechanical vibrations having an ultrasonic frequency of about 20,000 Hertz.
  • the range of suitable amplitudes and frequencies of the mechanical vibrations for cleaning according to the invention can be determined easily experimentally for the particular yarn being used. Some of the factors to be considered for yarns are the degree of cleaning which is acceptable, the speed at which the yarn is to be moved, the amount of yarn damage which can be tolerated, and the economics of the cleaning operation.
  • a mesophase pitch derived yarn 1 which has been thermoset exits a precarbonizing unit 2 which is operating at a maximum temperature of about 1300°C.
  • the yarn 1 has 2,000 fibers and each fiber has a diameter of about 10 11m.
  • Ultrasonic sources 3, 4 and 6 produce mechanical vibrations and clean the yarn 1 in accordance with the invention.
  • the yarn 1 moves at a rate of about 20 meters per minute and has a tension of about 5.39 Newtons.
  • Each of the ultrasonic sources 3, 4 and 6 has a frequency of about 20,000 Hertz and is a commercially available model.
  • Each of the horns, 7, 8 and 9 is the active output element of the respective ultrasonic sources 3, 4 and 6 and each horn has a surface about 1.3 centimeters long in contact with the yarn so that the residence time for the yarn 1 on each horn is about 0.04 second.
  • the yarn 1 is pressed with a force of from about 0.098 to about 0.245 Newtons.
  • the yarns cleaned by the invention showed significant improvements in the absence of particles as compared to yarns not cleaned.
  • a carbon yarn which had been cleaned according to the invention possessed tensile strength and Young's modulus comparable to those of a carbon yarn which had not been cleaned at all. This is important because it shows that the invention does not degrade these two important mechanical properties.
  • a carbon yarn made according to the invention as described for the Figure had fibers having an average tensile strength of 2.23 GPa and an average Young's modulus of 632 GPa whereas the carbon yarn which had not been cleaned at all had corresponding average values of 2.24 GPa and 600 GPa.
  • a higher degree of cleaning of the yarn can be obtained for predetermined output levels of the ultrasonic sources by increasing the number of ultrasonic sources and/or increasing the pressure of the yarn against the horn.
  • Commercially available ultrasonic sources usually have preset output levels.
  • the cleaning step was carried out in a separate experiment using a pressing force of about 0.49 Newtons for each of the three horns instead of from about 0.098 to about 0.245 Newtons.
  • the fibers of the carbon yarn produced had a tensile strength of about 2.25 GPa and a Young's modulus of about 612 GPa.
  • the particles being mechanically removed from the yarn during the cleaning step according to the invention appear in the form of visible clouds in the regions of the respective horns. Removal of the particles from the cleaning region can be accomplished with a suction device or the like. The largest cloud was present at the first horn, horn 7.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Fibers (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Claims (9)

1. Verfahren zur Herstellung von wenigstens einer Kohlenstoffaser, das umfaßt:
Spinnen wenigstens einer Faser, Hitzehärtung der Faser und Carbonisierung der Faser durch eine oder zwei Wärmebehandlungsstufen, und das gekennzeichnet ist durch Reinigung der Faser, indem die trockene Faser im Anschluß an den Wärmehärtungsschritt mechanischen Hochfrequenzschwingungen einer Amplitude und Frequenz, bei der Teilchen von der Oberfläche der Faser entfernt werden, unterworfen wird, wobei während der Wärmebehandlung zur Carbonisierung keine mechanischen Hochfrequenzschwingungen auf die Faser angewandt werden.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Faser von Polyacrylnitril oder Pech abgeleitet ist.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Faser von Mesophasenpech abgeleitet ist.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß eine Mehrzahl von Fasern gesponnen und zu einem Garn kombiniert ist.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß zumindest eine Ultraschallquelle zur Erzeugung der mechanischen Hochfrequenzschwingungen verwendet wird.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die Ultraschallquelle eine Frequenz von etwa 20.000 Hertz besitzt.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß eine Mehrzahl von Fasern gesponnen und zu einem Garn kombiniert ist und mindestens eine Ultraschallquelle zur Erzeugung der mechanischen Hochfrequenzschwingungen verwendet wird.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß das Garn durch eine erste Wärmebehandlung auf etwa 1300°C und eine anschließende zweite Wärmebehandlung auf eine Temperatur im Bereich zwischen 1500 und 3000°C carbonisiert wird und daß der Reinigungsschritt zwischen der ersten und der zweiten Wärmebehandlung erfolgt.
9. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß eine Mehrzahl von Fasern gesponnen und zu einem Garn kombiniert ist und daß ferner ein Schritt umfaßt wird, bei dem ein Teil der Oberflächen der Fasern mit Graphit- oder Rußpartikeln vor dem Wärmehärtungsschritt beschichtet wird.
EP19820304859 1981-09-17 1982-09-15 Verfahren zur Herstellung von Kohlenstoffasern Expired EP0075437B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US30318581A 1981-09-17 1981-09-17
US303185 1981-09-17

Publications (2)

Publication Number Publication Date
EP0075437A1 EP0075437A1 (de) 1983-03-30
EP0075437B1 true EP0075437B1 (de) 1986-06-04

Family

ID=23170894

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19820304859 Expired EP0075437B1 (de) 1981-09-17 1982-09-15 Verfahren zur Herstellung von Kohlenstoffasern

Country Status (3)

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EP (1) EP0075437B1 (de)
JP (1) JPS58109623A (de)
DE (1) DE3271564D1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3732947A1 (de) * 1987-09-30 1989-04-13 Henkel Kgaa Zur verwendung in wasch- und reinigungsmitteln geeignetes schaumregulierungsmittel
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

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3705236A (en) * 1969-11-01 1972-12-05 Nippon Carbon Co Ltd Method of producing carbon fibers
JPS5423730A (en) * 1977-07-21 1979-02-22 Sumitomo Electric Ind Ltd Production of glass fibers and its device
JPS584113B2 (ja) * 1979-03-01 1983-01-25 株式会社新和製作所 合成繊維の先端を細くする方法

Also Published As

Publication number Publication date
JPS628521B2 (de) 1987-02-23
JPS58109623A (ja) 1983-06-30
EP0075437A1 (de) 1983-03-30
DE3271564D1 (en) 1986-07-10

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