EP1845179B1 - Continuous process for the production of carbon fibres - Google Patents

Continuous process for the production of carbon fibres Download PDF

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Publication number
EP1845179B1
EP1845179B1 EP06007926A EP06007926A EP1845179B1 EP 1845179 B1 EP1845179 B1 EP 1845179B1 EP 06007926 A EP06007926 A EP 06007926A EP 06007926 A EP06007926 A EP 06007926A EP 1845179 B1 EP1845179 B1 EP 1845179B1
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EP
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Prior art keywords
fibres
process according
coaxial conductor
conductor
fibers
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EP06007926A
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German (de)
French (fr)
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EP1845179A1 (en
Inventor
Mathias Dr. Kaiser
Rudolf Dr. Emmerich
Ralf Dreher
Lukas Dr. Alberts
Christian Dr. Hunyar
Peter Dr. Elsner
Frank Dr. Henning
Klaus-Dieter Dr. Nauenburg
Bernd Dr. Wohlmann
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Teijin Ltd
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Toho Tenax Co Ltd
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Priority to DE502006007528T priority Critical patent/DE502006007528D1/en
Application filed by Toho Tenax Co Ltd filed Critical Toho Tenax Co Ltd
Priority to EP06007926A priority patent/EP1845179B1/en
Priority to ES06007926T priority patent/ES2348590T3/en
Priority to AT06007926T priority patent/ATE475728T1/en
Priority to US12/226,325 priority patent/US20090277772A1/en
Priority to PCT/EP2007/002909 priority patent/WO2007118596A1/en
Priority to CA2649131A priority patent/CA2649131C/en
Priority to BRPI0710157A priority patent/BRPI0710157B1/en
Priority to AU2007237521A priority patent/AU2007237521B2/en
Priority to CN2007800135079A priority patent/CN101421448B/en
Priority to JP2009504606A priority patent/JP5191004B2/en
Priority to TW096112685A priority patent/TWI372798B/en
Priority to ARP070101532A priority patent/AR060505A1/en
Publication of EP1845179A1 publication Critical patent/EP1845179A1/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
    • D01F9/32—Apparatus therefor
    • D01F9/328—Apparatus therefor for manufacturing filaments from polyaddition, polycondensation, or polymerisation products
    • 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
    • D01F9/20—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
    • D01F9/225—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 from stabilised polyacrylonitriles

Definitions

  • the invention relates to a method for the continuous production of carbon fibers, wherein stabilized precursor fibers are carbonized and graphitized with the aid of high-frequency electromagnetic waves.
  • Stabilized precursor fibers are fibers which have been converted into infusible fibers by methods known per se. Only such infusible fibers are suitable for the subsequent carbonation steps required to produce carbon fibers.
  • Fibers, yarns and strands of stabilized precursor fibers are poor electrical conductors and moderate absorbers of high-frequency electromagnetic Waves such as microwaves. With the irradiation of the high-frequency electromagnetic waves, the transition to complete carbonization and increasing graphitization begins, resulting in a large increase in the electrical conductivity of the treated fibers.
  • the fiber behaves like a wire in the waveguide and leads to strong distortions and disturbances of the electric field in the waveguide or in the resonator arrangement. Without control, inhomogeneities and perturbations occur that affect the homogeneity and process stability of the graphitization, or in extreme cases can lead to the ignition of discharges and arcing or the thermal vaporization of the fiber.
  • the object of the present invention is to provide a simple process for the continuous production of carbon fibers, in which stabilized precursor fibers are carbonized and graphitized with the aid of high-frequency electromagnetic waves, which can be carried out economically and with reasonable outlay in terms of process control.
  • the stabilized precursor fibers are continuously fed as an inner conductor of a coaxial conductor consisting of outer conductor and inner conductor and through a treatment zone, in the treatment zone the stabilized precursor fibers high-frequency electromagnetic waves are supplied, which absorb the Precursorfasern whereby the precursor fibers are heated and converted into carbon fibers, and that the stabilized precursor fibers or the carbon fibers are conducted under a protective gas atmosphere through the coaxial conductor and the treatment zone.
  • the high-frequency electromagnetic waves are preferably microwaves.
  • the decoupling of microwave energy from a rectangular waveguide is for example off DE 10 2004 021 016 A1 known, wherein both the outer conductor and the inner conductor are fixed components of the coaxial conductor.
  • This type of coupling is used to bring microwave energy into hot process spaces, since with the help of coaxial conductors microwave power can be transmitted with high power density.
  • the microwave energy which is supplied from a waveguide, coupled via a suitable device, for example via a coupling cone in the coaxial conductor.
  • a protective gas atmosphere around the stabilized precursor fibers in the outcoupling region and in the coaxial conductor can be maintained in a simple manner, for example, by arranging a tube permeable to the energy of the high-frequency electromagnetic waves or microwaves within the outer conductor of the coaxial conductor and the treatment zone and the stabilized precursor fibers as Inner conductor as well as the protective gas are passed through this tube.
  • the resulting carbon fibers become increasingly more conductive, decoupling the microwave energy more and more into the coaxial junction and preventing further treatment of the carbon fibers.
  • the coupled-out microwave energy already starts the treatment of the stabilized precursor fibers in the coaxial conductor, so that when the stabilized precursor fibers are passed through the coaxial conductor, a self-regulating system is established.
  • the method according to the invention is characterized in that the stabilized precursor fibers are guided through the coaxial conductor at such a speed that they carbonize or graphitise on leaving the coaxial conductor and thus are carbon fibers.
  • pre-carbonated precursor fibers are used to carry out the process according to the invention.
  • stabilized precursor fibers produced very particularly from polyacrylonitrile are particularly suitable for this purpose.
  • gas used is nitrogen.
  • the speed with which the stabilized precursor fibers are guided through the coaxial conductor is controlled by measuring the electrical resistance of the resulting carbon fiber. It has been found that the level of electrical resistance can draw conclusions about the quality of the carbon fibers.
  • precursor fibers which are already precarbonized still have an electrical resistance which is in the region of 30 M ⁇ , while carbon fibers with good properties in terms of strength, elongation and modulus have an electrical resistance which is within the range of a few ⁇ , for example in the range of 10 to 50 ⁇ .
  • the measurement of the electrical resistance is carried out via two copper electrodes, which are arranged on the fibers at a distance of 50 cm.
  • oxygen is added to the protective gas atmosphere.
  • the treatment step of the oxidation which is usually carried out after completion of the carbonization or graphitization, can be carried out in the process according to the invention directly during carbonization.
  • the addition of oxygen can be effected, for example, by the fact that the air contained between the fibers in the supplied precursor fibers is not removed before introduction into the coaxial conductor. But it is also readily possible to supply oxygen in a targeted uniform dosage of the inert gas atmosphere.
  • the process according to the invention can be carried out particularly advantageously when the stabilized precursor fibers are separated by two or more arranged consisting of coaxial conductor and treatment zone reactors are performed.
  • stabilized precursor fibers 1 are guided as an inner conductor 2 through a coaxial conductor with an outer conductor 3.
  • a tube 4 Arranged around the inner conductor 2 and within the outer conductor 3 and inside the resonator 9 is a tube 4 which is permeable to high-frequency electromagnetic waves or microwaves and into which protective gas is injected to produce a protective gas atmosphere.
  • the microwave energy supplied in a waveguide 5 is transmitted via coupling cone 6 (FIG. FIG. 1 ) or via a cavity resonator 9 (FIG. FIG.
  • the microwave supply via a coaxial conductor the inner conductor 11 is T-shaped and electrically conductive, whereby the microwave to the treatment zone 10th is redirected.
  • This inner conductor 11 may for example be tubular.
  • carbon fibers 7 are produced from the stabilized precursor fibers 1.
  • a field distribution of the microwave energy in the form of standing waves in the coaxial conductor is achieved.
  • Further embodiments which are suitable for carrying out the method according to the invention are, for example, in DE 26 16 217 . EP 0 508 867 or WO 00/075 955 described.
  • the stabilized precursor fibers used were stabilized precursor polycarboxylate-precursor fibers, which were precarbonated, which were combined into a strand of 12,000 filaments.
  • a cylindrical resonator For coupling the microwave energy, a cylindrical resonator became similar FIG. 2 used with walls made of aluminum Muegge Electronics GmbH. This has a diameter of 100 mm and is designed to connect rectangular waveguide R 26 type with a microwave generator with a microwave power of 3 kW. The microwave energy generated is decoupled into a coaxial conductor whose outer jacket has an inner diameter of 100 mm.
  • the precarbonated stabilized precursor fibers were passed through the apparatus described above under a protective gas atmosphere using nitrogen, wherein the resulting carbon fibers were withdrawn from the apparatus at different rates.
  • the used Microwave energy was set to 2 kW.
  • the obtained carbon fibers had the following properties off speed tensile strenght module elongation m / h MPa GPa % 50 3200 220 1.4 150 3100 218 1.4 240 3500 217 1.5 420 2700 180 1.4

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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)

Description

Die Erfindung betrifft ein Verfahren zur kontinuierlichen Herstellung von Kohlenstofffasern, wobei stabilisierte Precursorfasern unter Zuhilfenahme von hochfrequenten elektromagnetischen Wellen karbonisiert und graphitisiert werden.The invention relates to a method for the continuous production of carbon fibers, wherein stabilized precursor fibers are carbonized and graphitized with the aid of high-frequency electromagnetic waves.

Stabilisierte Precursorfasern sind Fasern, die durch an sich bekannte Verfahrensmaßnahmen in unschmelzbare Fasern umgewandelt wurden. Nur derartige unschmelzbare Fasern eigen sich für die sich anschließenden Karbonisierungsschritte, die zur Erzeugung von Kohlenstofffasern erforderlich sind.Stabilized precursor fibers are fibers which have been converted into infusible fibers by methods known per se. Only such infusible fibers are suitable for the subsequent carbonation steps required to produce carbon fibers.

Ein derartiges Verfahren zur Herstellung von Kohlenstofffasern aus Pech unter Zuhilfenahme von Mikrowellen ist aus US 4,197,282 bekannt geworden. Allerdings wird zu diesem Verfahren ausgeführt, dass die Mikrowellenbehandlung erst nach einer vorbereitenden Hitzebehandlung durchgeführt werden kann. Die Hitzebehandlung bewirkt gemäß US 4,197,282 , dass die Precursorfasern bereits so weit umgewandelt werden (Mesophase bei Pechfasern), dass sie durch die hohe Frequenz der Mikrowelle angeregt werden können. Ein Hinweis, in welcher Weise die Mikrowelle auf die stabilisierten Precursorfasern einwirken soll, kann dieser Schrift nicht entnommen werden.Such a method for the production of carbon fibers from pitch with the aid of microwaves is out US 4,197,282 known. However, it is stated in this method that the microwave treatment can be performed only after a preliminary heat treatment. The heat treatment effected according to US 4,197,282 in that the precursor fibers are already transformed so far (mesophase in pitch fibers) that they can be excited by the high frequency of the microwave. An indication of how the microwave should act on the stabilized Precursorfasern can not be found in this document.

Fasern, Garne und Stränge aus stabilisierten Precursorfasern sind schlechte elektrische Leiter und mäßige Absorber von hochfrequenten elektromagnetischen Wellen wie beispielsweise Mikrowellen. Mit der Bestrahlung mit den hochfrequenten elektromagnetischen Wellen beginnt der Übergang zur vollständigen Karbonisierung und zunehmender Graphitisierung, was zu einem starken Anwachsen der elektrischen Leitfähigkeit der behandelten Fasern führt.Fibers, yarns and strands of stabilized precursor fibers are poor electrical conductors and moderate absorbers of high-frequency electromagnetic Waves such as microwaves. With the irradiation of the high-frequency electromagnetic waves, the transition to complete carbonization and increasing graphitization begins, resulting in a large increase in the electrical conductivity of the treated fibers.

Ist die Graphitisierung abgeschlossen, verhält sich die Faser wie ein Draht im Hohlleiter und führt zu starken Verzerrungen und Störungen des elektrischen Feldes im Hohlleiter oder in der Resonatoranordnung. Ohne Regelung treten Inhomogenitäten und Störungen auf, die die Homogenität und die Prozessstabilität der Graphitisierung beeinflussen, oder im Extrem zur Zündung von Entladungen und Lichtbögen oder der thermischen Verdampfung der Faser führen können.Once the graphitization has been completed, the fiber behaves like a wire in the waveguide and leads to strong distortions and disturbances of the electric field in the waveguide or in the resonator arrangement. Without control, inhomogeneities and perturbations occur that affect the homogeneity and process stability of the graphitization, or in extreme cases can lead to the ignition of discharges and arcing or the thermal vaporization of the fiber.

Für die Prozesskontrolle der homogenen und kontinuierlichen Faserbehandlung mit Mikrowellenenergie war bisher eine aufwändige Messapparatur und Regelungstechnik erforderlich. Dies mag der Grund sein, warum das Verfahren großtechnisch bisher nicht eingesetzt wurde.For the process control of the homogeneous and continuous fiber treatment with microwave energy, a complex measuring apparatus and control technology was previously required. This may be the reason why the process has not yet been used on a large scale.

Aufgabe der vorliegenden Erfindung ist es, ein einfaches Verfahren zur kontinuierlichen Herstellung von Kohlenstofffasern, bei dem stabilisierte Precursorfasern unter Zuhilfenahme von hochfrequenten elektromagnetischen Wellen karbonisiert und graphitisiert werden, zur Verfügung zu stellen, welches wirtschaftlich und mit vertretbarem Aufwand hinsichtlich der Prozesskontrolle durchführbar ist.The object of the present invention is to provide a simple process for the continuous production of carbon fibers, in which stabilized precursor fibers are carbonized and graphitized with the aid of high-frequency electromagnetic waves, which can be carried out economically and with reasonable outlay in terms of process control.

Diese Aufgabe wird durch ein Verfahren der eingangs genannten Art dadurch gelöst, dass die stabilisierten Precursorfasern kontinuierlich als Innenleiter eines aus Außenleiter und Innenleiter bestehenden Koaxialleiters und durch eine Behandlungszone geführt werden, in der Behandlungszone den stabilisierten Precursorfasern hochfrequente elektromagnetische Wellen zugeführt werden, welche die Precursorfasern absorbieren, wodurch sich die Precursorfasern erhitzen und zu Kohlenstofffasern umgewandelt werden, und dass die stabilisierten Precursorfasern beziehungsweise die Kohlenstofffasern unter Schutzgasatmosphäre durch den Koaxialleiter und die Behandlungszone geführt werden.This object is achieved by a method of the type mentioned in that the stabilized precursor fibers are continuously fed as an inner conductor of a coaxial conductor consisting of outer conductor and inner conductor and through a treatment zone, in the treatment zone the stabilized precursor fibers high-frequency electromagnetic waves are supplied, which absorb the Precursorfasern whereby the precursor fibers are heated and converted into carbon fibers, and that the stabilized precursor fibers or the carbon fibers are conducted under a protective gas atmosphere through the coaxial conductor and the treatment zone.

Bevorzugt sind die hochfrequenten elektromagnetischen Wellen Mikrowellen.The high-frequency electromagnetic waves are preferably microwaves.

Überraschender Weise kann bei Durchführung des erfindungsgemäßen Verfahrens beobachtet werden, dass sich im Auskoppelungsbereich, in dem die Energie von hochfrequenten elektromagnetischen Wellen beziehungsweise die Energie von Mikrowellen ausgekoppelt wird, eine kurze , meist wenige Zentimeter aufweisende Reaktionszone bildet, in welcher zumindest überwiegend die Reaktion zur Umwandlung der Kohlenstofffaser erfolgt.Surprisingly, it can be observed when carrying out the process according to the invention that in the decoupling region, in which the energy is decoupled from high-frequency electromagnetic waves or the energy from microwaves, a short, usually a few centimeters, reaction zone is formed, in which at least predominantly the reaction for conversion the carbon fiber takes place.

Die Auskoppelung von Mikrowellenenergie aus einem Rechteckhohlleiter ist beispielsweise aus DE 10 2004 021 016 A1 bekannt, wobei sowohl der Außenleiter als auch der Innenleiter feste Bestandteile des Koaxialleiters sind. Diese Art der Koppelung wird dazu benutzt, Mikrowellenenergie in heiße Prozessräume einzubringen, da mit Hilfe von Koaxialleitern Mikrowellenenergie mit hoher Leistungsdichte übertragen werden kann. Hierbei wird die Mikrowellenenergie, die aus einem Hohlleiter zugeführt wird, über eine geeignete Vorrichtung, beispielsweise über einen Koppelkegel in den Koaxialleiter ausgekoppelt.The decoupling of microwave energy from a rectangular waveguide is for example off DE 10 2004 021 016 A1 known, wherein both the outer conductor and the inner conductor are fixed components of the coaxial conductor. This type of coupling is used to bring microwave energy into hot process spaces, since with the help of coaxial conductors microwave power can be transmitted with high power density. Here, the microwave energy, which is supplied from a waveguide, coupled via a suitable device, for example via a coupling cone in the coaxial conductor.

Eine Schutzgasatmosphäre um die stabilisierten Precursorfasern im Auskopplungsbereich und im Koaxialleiter kann in einfacher Weise beispielsweise dadurch aufrecht erhalten werden, dass eine für die Energie der hochfrequenten elektromagnetischen Wellen bzw. Mikrowellen durchlässige Röhre innerhalb des Außenleiters des Koaxialleiters und der Behandlungszone angeordnet wird und die stabilisierten Precursorfasern als Innenleiter wie auch das Schutzgas durch diese Röhre hindurch geführt werden.A protective gas atmosphere around the stabilized precursor fibers in the outcoupling region and in the coaxial conductor can be maintained in a simple manner, for example, by arranging a tube permeable to the energy of the high-frequency electromagnetic waves or microwaves within the outer conductor of the coaxial conductor and the treatment zone and the stabilized precursor fibers as Inner conductor as well as the protective gas are passed through this tube.

Überraschender Weise konnte festgestellt werden, dass bei Anwendung einer solchen Koppelungsvorrichtung derart, dass der Innenleiter des Koaxialleiters durch die durch den Koaxialleiter sich bewegenden und zu karbonisierenden stabilisierten Precursorfasern ersetzt wird, diese stabilisierten Precursorfasern auf einfache Weise in Kohlenstofffasern umgewandelt werden können. Da die stabilisierten Precursorfasern eine sehr geringe Leitfähigkeit aufweisen, bewirkt die Mikrowellenenergie, dass die stabilisierten Precursorfasern über Absorption im Auskoppelungsbereich erwärmt werden. Mit zunehmender Erwärmung wandeln sich die stabilisierten Precursorfasern in ein Material um, das zunächst besser absorbiert und sich dadurch noch besser erwärmt und infolge der steigenden Erwärmung auch karbonisiert und graphitisiert, wodurch aus den stabilisierten Precursorfasern nunmehr Kohlenstofffasern entstanden sind. Durch diese Umwandlung werden die entstehenden Kohlenstofffasern zunehmend leitfähiger, wodurch die Mikrowellenenergie immer mehr in den Koaxialübergang ausgekoppelt wird, und wodurch eine weitere Behandlung der Kohlenstofffasern verhindert wird. Die ausgekoppelte Mikrowellenenergie startet im Koaxialleiter bereits die Behandlung der stabilisierten Precursorfasern, so dass beim Hindurchführen der stabilisierten Precursorfasern durch den Koaxialleiter sich ein selbstregulierendes System einstellt.Surprisingly, it has been found that when such a coupling device is used such that the inner conductor of the coaxial conductor is replaced by the stabilized precursor fibers moving and to be carbonized by the coaxial conductor, these stabilized precursor fibers can be easily converted into carbon fibers. Since the stabilized precursor fibers have a very low conductivity, the microwave energy causes the stabilized precursor fibers to be heated via absorption in the decoupling region. With increasing warming, the stabilized precursor fibers are transformed into a material that initially absorbs better and thereby heats even better and also carbonized and graphitized as a result of increasing heating, as a result of which carbon fibers have now been formed from the stabilized precursor fibers. As a result of this transformation, the resulting carbon fibers become increasingly more conductive, decoupling the microwave energy more and more into the coaxial junction and preventing further treatment of the carbon fibers. The coupled-out microwave energy already starts the treatment of the stabilized precursor fibers in the coaxial conductor, so that when the stabilized precursor fibers are passed through the coaxial conductor, a self-regulating system is established.

Insbesondere zeichnet sich das erfindungsgemäße Verfahren dadurch aus, dass die stabilisierten Precursorfasern mit einer solchen Geschwindigkeit durch den Koaxialleiter geführt werden, dass sie beim Verlassen des Koaxialleiters karbonisiert beziehungsweise graphitisiert und somit Kohlenstofffasern sind.In particular, the method according to the invention is characterized in that the stabilized precursor fibers are guided through the coaxial conductor at such a speed that they carbonize or graphitise on leaving the coaxial conductor and thus are carbon fibers.

Auch kann es von Vorteil sein, wenn zur Durchführung des erfindungsgemäßen Verfahrens vorkarbonisierte Precursorfasern eingesetzt werden. Obwohl bei dem erfindungsgemäßen Verfahren praktisch alle bekannten stabilisierten Precursorfasern eingesetzt werden können, eignen sich hierfür ganz besonders aus Polyacrylnitril hergestellte stabilisierte Precursorfasern. Weiterhin hat es sich als Vorteil herausgestellt, wenn das für die Erzeugung der Schutzgasathmosphäre, durch welche die stabilisierten Precursorfasern im Koaxialleiter geführt werden, verwendete Gas Stickstoff ist.It may also be advantageous if pre-carbonated precursor fibers are used to carry out the process according to the invention. Although virtually all known stabilized precursor fibers can be used in the process according to the invention, stabilized precursor fibers produced very particularly from polyacrylonitrile are particularly suitable for this purpose. Furthermore, it has proven to be an advantage if that for the generation of the Inert gas atmosphere, through which the stabilized precursor fibers are guided in the coaxial conductor, gas used is nitrogen.

Besonders günstig ist es, wenn die Geschwindigkeit, mit welcher die stabilisierten Precursorfasern durch den Koaxialleiter geführt werden, über die Messung des elektrischen Widerstandes der entstandenen Kohlenstofffaser gesteuert wird. Es hat sich nämlich herausgestellt, dass die Höhe des elektrischen Widerstandes Rückschlüsse hinsichtlich der Qualität der Kohlenstofffasern ziehen lassen. Bei Durchführung des erfindungsgemäßen Verfahrens konnte ermittelt werden, dass Precursorfasern, die bereits vorkarbonisiert sind noch einen elektrischen Widerstand aufweisen, welcher im Bereich von 30 MΩ liegt, während Kohlenstofffasern mit guten Eigenschaften hinsichtlich Festigkeit, Dehnung und Modul einen elektrischen Widerstand aufweisen, die im Bereich von wenigen Ω, beispielsweise im Bereich von 10 bis 50 Ω liegen. Die Messung des elektrischen Widerstandes erfolgt hierbei über zwei Kupferelektroden, die an den Fasern in einem Abstand von 50 cm angeordnet sind.It is particularly favorable if the speed with which the stabilized precursor fibers are guided through the coaxial conductor is controlled by measuring the electrical resistance of the resulting carbon fiber. It has been found that the level of electrical resistance can draw conclusions about the quality of the carbon fibers. When carrying out the method according to the invention, it was possible to determine that precursor fibers which are already precarbonized still have an electrical resistance which is in the region of 30 MΩ, while carbon fibers with good properties in terms of strength, elongation and modulus have an electrical resistance which is within the range of a few Ω, for example in the range of 10 to 50 Ω. The measurement of the electrical resistance is carried out via two copper electrodes, which are arranged on the fibers at a distance of 50 cm.

Von besonderem Vorteil ist es, wenn in die Schutzgasatmosphäre geringe Mengen an Sauerstoff beigegeben wird. Auf diese Weise kann der in der Regel nach Abschluss der Karbonisierung beziehungsweise Graphitisierung vorgenommene Behandlungsschritt der Oxidierung bei dem erfindungsgemäßen Verfahren direkt beim Karbonisieren durchgeführt werden. Die Zugabe von Sauerstoff kann beispielsweise dadurch bewirkt werden, dass bei den zugeführten Precursorfasern die zwischen den Fasern enthaltene Luft vor Einführung in den Koaxialleiter nicht entfernt wird. Es ist aber auch ohne weiteres möglich, Sauerstoff in gezielter gleichmäßiger Dosierung der Schutzgasatmosphäre zuzuführen.It is particularly advantageous if small amounts of oxygen are added to the protective gas atmosphere. In this way, the treatment step of the oxidation, which is usually carried out after completion of the carbonization or graphitization, can be carried out in the process according to the invention directly during carbonization. The addition of oxygen can be effected, for example, by the fact that the air contained between the fibers in the supplied precursor fibers is not removed before introduction into the coaxial conductor. But it is also readily possible to supply oxygen in a targeted uniform dosage of the inert gas atmosphere.

Besonders günstig lässt sich das erfindungsgemäße Verfahren durchführen, wenn die stabilisierten Precursorfasern durch zwei oder mehr hintereinander angeordnete aus Koaxialleiter und Behandlungszone bestehende Reaktoren geführt werden.The process according to the invention can be carried out particularly advantageously when the stabilized precursor fibers are separated by two or more arranged consisting of coaxial conductor and treatment zone reactors are performed.

Im nachfolgenden werden zur Durchführung des erfindungsgemäßen Verfahrens geeignete Vorrichtungen näher beschrieben.In the following, suitable devices for carrying out the method according to the invention will be described in more detail.

Es zeigen:

Figur 1
den schematischen Aufbau einer Vorrichtung, bei welcher die Auskopplung der Mikrowellenenergie über einen Koppelkegel erfolgt,
Figur 2
den schematischen Aufbau einer Vorrichtung, bei welcher ein Hohlraumresonator zur Auskopplung der Mikrowellenenergie eingesetzt ist.
Figur 3
den schematischen Aufbau einer Vorrichtung, bei welcher eine koaxiale Mikrowellenzuführung zur Auskopplung der Mikrowellen eingesetzt ist.
Show it:
FIG. 1
the schematic structure of a device in which the coupling out of the microwave energy via a coupling cone,
FIG. 2
the schematic structure of a device in which a cavity resonator for coupling the microwave energy is used.
FIG. 3
the schematic structure of a device in which a coaxial microwave feed is used for coupling the microwaves.

Zur Durchführung des erfindungsgemäßen Verfahrens werden stabilisierte Precursorfasern 1 als Innenleiter 2 durch einen Koaxialleiter mit einem Außenleiter 3 geführt. Um den Innenleiter 2 und innerhalb des Außenleiters 3 und innerhalb des Resonators 9 ist ein für hochfrequente elektromagnetische Wellen beziehungsweise Mikrowellen durchlässiges Rohr 4 angeordnet, in welches Schutzgas zur Erzeugung einer Schutzgasatmosphäre eingeblasen wird. Die in einem Hohlleiter 5 zugeführte Mikrowellenenergie wird über Koppelkegel 6 (Figur 1) beziehungsweise über einen Hohlraumresonator 9 (Figur 2) in den aus Innenleiter 2 und Außenleiter 3 bestehenden Koaxialleiter in einer sich bildenden Behandlungszone 10 zugeführt und infolge der Umwandlung in Kohlenstofffasern in den Koaxialleiter 2,3 ausgekoppelt. Gemäß Figur 3 erfolgt die Mikrowellenzuführung über einen Koaxialleiter, dessen Innenleiter 11 T-förmig und elektrisch leitend ausgebildet ist, wodurch die Mikrowelle zur Behandlungszone 10 umgeleitet wird. Dieser Innenleiter 11 kann beispielsweise rohrförmig ausgebildet sein. Beim Verlassen des Innenleiters 11 am Übergang 12 übernehmen die stabilisierten Precursorfasern die Funktion des Innenleiters 2 des Koaxialleiters dessen Außenleiter mit 3 bezeichnet ist.To carry out the method according to the invention, stabilized precursor fibers 1 are guided as an inner conductor 2 through a coaxial conductor with an outer conductor 3. Arranged around the inner conductor 2 and within the outer conductor 3 and inside the resonator 9 is a tube 4 which is permeable to high-frequency electromagnetic waves or microwaves and into which protective gas is injected to produce a protective gas atmosphere. The microwave energy supplied in a waveguide 5 is transmitted via coupling cone 6 (FIG. FIG. 1 ) or via a cavity resonator 9 (FIG. FIG. 2 ) are fed into the coaxial conductor consisting of inner conductor 2 and outer conductor 3 in a forming treatment zone 10 and decoupled into the coaxial conductor 2, 3 as a result of the conversion into carbon fibers. According to FIG. 3 the microwave supply via a coaxial conductor, the inner conductor 11 is T-shaped and electrically conductive, whereby the microwave to the treatment zone 10th is redirected. This inner conductor 11 may for example be tubular. When leaving the inner conductor 11 at the transition 12, the stabilized precursor fibers assume the function of the inner conductor 2 of the coaxial conductor whose outer conductor is designated 3.

Nach Verlassen der Behandlungszone 10 sind aus den stabilisierten Precursorfasern 1 Kohlenstofffasern 7 entstanden. Durch einen koaxialen Abschluss 8 wird eine Feldverteilung der Mikrowellenenergie in Form von stehenden Wellen im Koaxialleiter erreicht. Weitere Ausführungsformen, die für die Durchführung des erfindungsgemäßen Verfahrens geeignet sind, sind beispielsweise in DE 26 16 217 , EP 0 508 867 oder WO 00/075 955 beschrieben.After leaving the treatment zone 10, carbon fibers 7 are produced from the stabilized precursor fibers 1. By means of a coaxial termination 8, a field distribution of the microwave energy in the form of standing waves in the coaxial conductor is achieved. Further embodiments which are suitable for carrying out the method according to the invention are, for example, in DE 26 16 217 . EP 0 508 867 or WO 00/075 955 described.

Die Erfindung wird anhand der nachfolgenden Beispiele näher erläutert.The invention will be explained in more detail with reference to the following examples.

Als stabilisierte Precursorfasern wurden aus Polyacylnitril hergestellte und stabilisierte Precursorfasern, welche vorkarbonisiert waren, eingesetzt, die zu einem Strang von 12.000 Filamenten zusammengefasst waren.The stabilized precursor fibers used were stabilized precursor polycarboxylate-precursor fibers, which were precarbonated, which were combined into a strand of 12,000 filaments.

Zur Einkoppelung der Mikrowellenenergie wurde ein zylindrischer Resonator ähnlich Figur 2 mit Wänden aus Aluminium der Firma Muegge Electronics GmbH eingesetzt. Dieser weist einen Durchmesser von 100 mm auf und ist darauf ausgelegt, Rechteckhohlleiter des Typs R 26 mit einem Mikrowellengenerator mit einer Mikrowellenleistung von 3 kW zu verbinden. Die erzeugte Mikrowellenenergie wird in einen Koaxialleiter, dessen Außenmantel einen Innendurchmesser von 100 mm aufwies, ausgekoppelt.For coupling the microwave energy, a cylindrical resonator became similar FIG. 2 used with walls made of aluminum Muegge Electronics GmbH. This has a diameter of 100 mm and is designed to connect rectangular waveguide R 26 type with a microwave generator with a microwave power of 3 kW. The microwave energy generated is decoupled into a coaxial conductor whose outer jacket has an inner diameter of 100 mm.

Die vorkarbonisierten stabilisierten Precursorfasern wurden durch die oben beschriebene Apparatur unter Schutzgasatmosphäre unter Verwendung von Stickstoff geleitet, wobei die entstandenen Kohlenstofffasern mit unterschiedlichen Geschwindigkeiten aus der Apparatur abgezogen wurden. Die eingesetzte Mikrowellenenergie war auf 2 kW eingestellt. Die erhaltenen Kohlenstofffasern hatten folgende Eigenschaften Abzugsgeschwindigkeit Zugfestigkeit Modul Bruchdehnung m/h MPa GPa % 50 3.200 220 1,4 150 3.100 218 1,4 240 3.500 217 1,5 420 2.700 180 1,4 The precarbonated stabilized precursor fibers were passed through the apparatus described above under a protective gas atmosphere using nitrogen, wherein the resulting carbon fibers were withdrawn from the apparatus at different rates. The used Microwave energy was set to 2 kW. The obtained carbon fibers had the following properties off speed tensile strenght module elongation m / h MPa GPa % 50 3200 220 1.4 150 3100 218 1.4 240 3500 217 1.5 420 2700 180 1.4

Claims (9)

  1. A process for continuous production of carbon fibres whereby stabilised precursor fibres are carbonised and graphitised with the help of high-frequency electromagnetic waves, characterised in that the stabilised precursor fibres are continuously conveyed, as the inner conductor of a coaxial conductor consisting of an outer and an inner conductor, through the coaxial conductor and a treatment zone; that the stabilised precursor fibres are irradiated in the treatment zone with high-frequency electromagnetic waves that are absorbed by the precursor fibres, which are thereby heated and converted into carbon fibres; and that the stabilised precursor fibres or carbon fibres are conveyed under an inert gas atmosphere through the coaxial conductor and the treatment zone.
  2. Process according to Claim 1, characterised in that microwaves are used as the high-frequency electromagnetic waves.
  3. Process according to Claim 1 or 2, characterised in that the stabilised precursor fibres are conveyed through the coaxial conductor at such a speed that on leaving the coaxial conductor they have been carbonised or graphitised and are therefore carbon fibres.
  4. Process according to one or more of Claims 1 to 3, characterised in that precarbonised precursor fibres are used.
  5. Process according to one or more of Claims 1 to 4, characterised in that the stabilised precursor fibres are made from polyacrylonitrile.
  6. Process according to one or more of Claims 1 to 5, characterised in that the gas used for producing the inert atmosphere through which the stabilised precursor fibres are conveyed is nitrogen.
  7. Process according to one or more of Claims 1 to 6, characterised in that the speed at which the stabilised precursor fibres are conveyed through the coaxial conductor is controlled via measurement of the electrical resistance of the carbon fibres formed.
  8. Process according to one or more of Claims 1 to 7, characterised in that small amounts of oxygen are added to the inert gas atmosphere.
  9. Process according to one or more of Claims 1 to 8, characterised in that the stabilised precursor fibres are conveyed through two or more successive reactors, each consisting of a coaxial conductor and treatment zone.
EP06007926A 2006-04-15 2006-04-15 Continuous process for the production of carbon fibres Active EP1845179B1 (en)

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EP06007926A EP1845179B1 (en) 2006-04-15 2006-04-15 Continuous process for the production of carbon fibres
ES06007926T ES2348590T3 (en) 2006-04-15 2006-04-15 PROCEDURE FOR CONTINUOUS CARBON FIBER PRODUCTION.
AT06007926T ATE475728T1 (en) 2006-04-15 2006-04-15 METHOD FOR CONTINUOUSLY PRODUCING CARBON FIBERS
DE502006007528T DE502006007528D1 (en) 2006-04-15 2006-04-15 Process for the continuous production of carbon fibers
BRPI0710157A BRPI0710157B1 (en) 2006-04-15 2007-03-31 process for the continuous production of carbon fibers
CA2649131A CA2649131C (en) 2006-04-15 2007-03-31 Process for continuous production of carbon fibres
US12/226,325 US20090277772A1 (en) 2006-04-15 2007-03-31 Process for Continous Production of Carbon Fibres
AU2007237521A AU2007237521B2 (en) 2006-04-15 2007-03-31 Process for continuous production of carbon fibers
CN2007800135079A CN101421448B (en) 2006-04-15 2007-03-31 Continuous process for the production of carbon fibres
JP2009504606A JP5191004B2 (en) 2006-04-15 2007-03-31 Continuous production method of carbon fiber
PCT/EP2007/002909 WO2007118596A1 (en) 2006-04-15 2007-03-31 Method for the continuous production of carbon fibers
TW096112685A TWI372798B (en) 2006-04-15 2007-04-11 Process for continuous production of carbon fibres
ARP070101532A AR060505A1 (en) 2006-04-15 2007-04-11 PROCESS FOR THE CONTINUOUS PRODUCTION OF CARBON FIBERS

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AU2007237521B2 (en) 2011-01-20
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TW200745395A (en) 2007-12-16

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