EP2475812B1 - Stabilisation de fils de précurseurs en poly-acrylonitrile - Google Patents

Stabilisation de fils de précurseurs en poly-acrylonitrile Download PDF

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Publication number
EP2475812B1
EP2475812B1 EP10749843.8A EP10749843A EP2475812B1 EP 2475812 B1 EP2475812 B1 EP 2475812B1 EP 10749843 A EP10749843 A EP 10749843A EP 2475812 B1 EP2475812 B1 EP 2475812B1
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EP
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Prior art keywords
application space
yarn
precursor yarn
electromagnetic waves
temperature
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EP10749843.8A
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German (de)
English (en)
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EP2475812A1 (fr
Inventor
Bernd Wohlmann
Michael WÖLKI
Christian Hunyar
Rudolf Emmerich
Mathias Kaiser
Matthias Graf
Lukas Alberts
Klaus-Dieter Nauenburg
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Teijin Carbon Europe GmbH
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Toho Tenax Europe GmbH
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Classifications

    • 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
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • 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
    • 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
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/06—Inorganic compounds or elements
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
    • D06M2101/28—Acrylonitrile; Methacrylonitrile

Definitions

  • the invention relates to a method for stabilizing polyacrylonitrile yarns.
  • Stabilized polyacrylonitrile multifilament yarns are needed in the production of carbon fibers.
  • Today's carbon fibers are predominantly made of polyacrylonitrile fibers, i. made of polyacrylonitrile precursor yarns.
  • the polyacrylonitrile precursor yarns are first subjected to stabilization by an oxidation treatment before the stabilized precursor yarns are subsequently carbonized at temperatures of at least 1200 ° C. in a nitrogen atmosphere and, if appropriate, graphitized in a further step at temperatures up to about 2800 ° C., thus carbon fibers to obtain.
  • the stabilization of polyacrylonitrile precursor yarns is generally understood to mean the conversion of the yarns via chemical stabilization reactions, in particular via cyclization reactions and dehydrogenation reactions, from a thermoplastic state into an oxidized, infusible and simultaneously flame-resistant state.
  • the stabilization is carried out today usually in conventional convection ovens at temperatures between 200 and 300 ° C and under an oxygen-containing atmosphere (see, eg F. Fourné: "Synthetic Fibers", Carl Hanser Verlag Kunststoff Vienna 1995, chapter 5.7 ).
  • a stepwise conversion of the Precursorgarns of a thermoplastic into an oxidized, infusible fiber instead of ( J.-B.
  • the yarn passes through differently tempered oven stages, by means of which a slow heating of the yarn can be set and thus sufficient removal of the exothermic heat from the yarn material can be achieved.
  • the stabilization can be carried out, for example, in a conventional convection oven with three oven stages, wherein in the first stage at temperatures in the range of 200 to 300 ° C usually a residence time of at least 20 minutes is required to perform the stabilization to the extent that the density of the precursor yarn is increased by about 0.03 g / cm 3 .
  • the precursor yarn based on a polyacrylonitrile polymer submitted in the process according to the invention is a yarn which contains at least 85% of polymerized acrylonitrile.
  • the polyacrylonitrile polymer may also contain portions of comonomers, such as e.g. of vinyl acetate, methyl acrylate, methyl methacrylate, vinyl chloride, vinylidene chloride, styrene or itaconic acid (ester).
  • thermoplastic polyacrylonitrile precursor yarn prepared may be a yarn which has not yet been subjected to any stabilization.
  • the precursor yarn presented can also be a polyacrylonitrile yarn which has already been subjected to partial stabilization, in which case the stabilization proceeds further in the process according to the invention.
  • the method according to the invention is not limited to stabilizing the precursor yarn completely by the method according to the invention, but it can also be carried out so that the yarn is only stabilized to a certain degree.
  • the method according to the invention is therefore suitable for partially or completely stabilizing an untreated polyacrylonitrile precursor yarn.
  • the inventive method comprises the further partial or complete stabilization of an already partially stabilized Precursorgarns. In this case, the previous partial stabilization and / or a subsequent completion of the stabilization can also be done under Use of the method according to the invention or by known methods in conventional convection ovens.
  • the applicator When carrying out the process according to the invention, e.g. generated in a magnetron high-frequency electromagnetic waves, which are guided via suitable means, preferably via a waveguide or a coaxial into the application space.
  • the applicator has a generally channel-shaped application space with a wall of a conductive material, which is traversed by the precursor yarn to be stabilized and into which the electromagnetic waves are fed.
  • the wall surrounding the application space can be, for example, a continuous metal wall. However, it is also possible to form the wall of a conductive grid-shaped material.
  • the application space preferably has a circular, oval or rectangular contour transversely to the feedthrough direction of the precursor yarn and thus transversely to the propagation direction of the electromagnetic waves.
  • the applicator is a rectangular waveguide.
  • the application space furthermore comprises, in its interior surrounded by the wall, a conductive element, which is preferably a metal rod.
  • a conductive element extends coaxially to the longitudinal axis of the application space, i. in the propagation direction of the electromagnetic waves, whereby a coaxial conductor is formed.
  • the conductive element is arranged in the center of the application space. In such coaxial conductors, it is advantageous if the application space has a circular contour transversely to the propagation direction of the electromagnetic waves.
  • the application space can at its inlet end, at which the Precursorgarn enters the applicator and / or at its outlet end, from which the Precursor yarn leaves the applicator, have diaphragms through which the precursor yarn is passed. These diaphragms hold the high-frequency electromagnetic waves in the application space.
  • the applicator e.g. a tube which is connected via an elbow with the application space, wherein the precursor yarn to be stabilized is guided in the region of the elbow by the wall into the application space.
  • the maximum electric field strength of the high-frequency electromagnetic waves in the application space is set to a level in the range from 3 to 150 kV / m.
  • the level of the field strength refers to the unladen state of the applicator, ie. to a state where the precursor yarn to be stabilized does not pass through the applicator.
  • microwaves High-frequency electromagnetic waves of a frequency of 300 MHz to 300 GHz, which are generally referred to as microwaves, are preferred for carrying out the method according to the invention. Particularly preferred are microwaves in the range of 300 MHz to 45 GHz and in a particular embodiment microwaves in the range of 900 MHz to 5.8 GHz. By default, microwaves are used with a frequency of 915 MHz and 2.45 GHz, which are suitable for carrying out the invention Method are best suited.
  • the process gas may be an inert gas, for example nitrogen, argon or helium.
  • nitrogen is used as the inert gas.
  • the process gas used in the process according to the invention is an oxygen-containing gas. It has been shown that can be achieved in the stabilization by means of an oxygen-containing gas higher carbon yields.
  • an oxygen-containing gas is understood as meaning a gas which contains molecular oxygen, the concentration of molecular oxygen in the oxygen-containing gas preferably being less than 80% by volume. Most preferably, the oxygen-containing gas is air.
  • the critical minimum temperature T crit is the temperature above which the high-frequency electromagnetic waves couple sufficiently into the precursor yarn passing through the application device, ie above which the electromagnetic waves are sufficiently absorbed by the yarn and the conversion reactions take place. It has been shown that the atmosphere surrounding the precursor yarn in the application space and thus the precursor yarn passing through the application space itself must exceed a certain threshold temperature, ie the critical minimum temperature, so that the high-frequency electromagnetic waves couple so strongly into the precursor yarn that the conversion reactions or chemical stabilization reactions, ie in particular cyclization reactions, dehydrogenation reactions and oxidation reactions can proceed to stabilize the yarn.
  • the high-frequency electromagnetic waves may already be coupled into the yarn below the critical minimum temperature, the coupled-in electromagnetic waves do not yet result in a temperature increase in the yarn sufficient for initiating the conversion reactions, since at the same time cooling takes place due to the process gas flowing relative to the yarn the yarn is done.
  • the critical minimum temperature T crit can be determined in a simple way for the precursor yarn guided in each case by the application device. As stated, above the critical minimum temperature, the electromagnetic waves are sufficiently absorbed by the precursor yarn and, as a result of the resulting temperature increase in the yarn, initiates the conversion reactions leading to the stabilization of the yarn. As a result, among other HCN gas is released.
  • the HCN gas can be measured by conventional analytical methods such as gas chromatography, mass spectrometry or electrochemical HCN sensors in the gas outlet, via which the process gas introduced into the applicator is removed from the applicator.
  • the minimum temperature is understood to be that temperature above which the electromagnetic waves couple so strongly or are absorbed so strongly by the yarn that the conversion reactions in the yarn, ie in particular the cyclization reaction, take place and as a result HCN gas is released becomes.
  • the conversion reactions may take place on the basis of the HCN cleavage associated cyclization can be detected by IR spectroscopy.
  • the maximum temperature T max is to be understood as meaning the temperature which is 20 ° C. below the decomposition temperature of the precursor yarn introduced into the application device.
  • the process gas in the application space has a temperature in the range between (T crit + 20 ° C) and (T max - 20 ° C).
  • the decomposition temperature can be easily determined by thermogravimetric measurements. In this case, the decomposition temperature is that temperature at which a sample of the precursor yarn presented in the method according to the invention loses 5% of its mass within a time of less than 5 minutes.
  • the respective critical minimum temperature T crit and the maximum temperature T max is dependent on the precursor material, ie, for example, of concrete polyacrylonitrile polymer.
  • the polyacrylonitrile Precursorgarne commonly used for the purpose of carbon fiber production can be used in the inventive method.
  • the critical minimum temperature and the maximum temperature can be influenced by additives which may be added to the polyacrylonitrile.
  • the precursor yarn may contain additives which bring about an improvement in the absorption capacity of the precursor yarn with respect to high-frequency electromagnetic waves.
  • these additives are polyethylene glycol, carbon black or carbon nanotubes.
  • the critical minimum temperature and the maximum temperature are also dependent on the degree of stabilization of the Precursorgarns submitted in the process according to the invention. This shows that with increasing degree of stabilization, the critical minimum temperature shifts to higher values. It is likewise evident that increasing stabilization has the effect of increasing thermal stability and, as a result, increasing decomposition temperatures, and thus also of increasing maximum temperatures in the context of the present invention.
  • the adjustment of the temperature of the process gas flowing through the application space can be effected for example by supplying a gas heated to the required temperature into a heat-insulated application space.
  • a process gas which is initially tempered to a lower temperature level may be present in the application space or in a heat exchanger upstream of the application space, e.g. be heated by means of suitable heating elements or by means of IR radiation to the required temperature.
  • a combination of different methods is possible to set the required temperature of the process gas in the application room.
  • the density of, for example, originally about 1.19 g / cm 3 by the stabilization ultimately increases to a value of up to about 1.40 g / cm 3 .
  • the degree of stabilization can thus also be determined on the basis of the density of the precursor material.
  • the process gas fed into the application space has, on the one hand, the task of ensuring a temperature level at the yarn, at which a sufficient coupling of the high-frequency electromagnetic waves into the yarn takes place.
  • the task of the process gas is to transport the released during the conversion reactions volatile degradation products such as HCN, NH 3 or H 2 O, on the other hand but also the resulting heat of reaction and to provide a temperature level in particular in the range Precursorgarns, the is below the maximum temperature T max .
  • an oxygen-containing gas is used as the process gas, this gas finally also has the task of providing the required amount of oxygen for the conversion or oxidation reactions leading to stabilization in the precursor yarn.
  • the process gas is guided through the application space such that it has a flow velocity of at least 0.1 m / s relative to the precursor yarn passing through the application space.
  • the flow rate is above 0.1 m / s relative to the Precursorgarn set so that the aforementioned requirements are met.
  • limits are set up to the extent that too high a flow velocity of the gas lead to instabilities in the yarn path of the precursor yarn and thus there is a risk of yarn breakage or tearing of the yarn.
  • the process gas is introduced into the application space and discharged therefrom so that it flows through the application space perpendicular to the precursor yarn, wherein the flow velocity is perpendicular to the precursor yarn in the range of 0.1 to 2 m / s.
  • the process gas is introduced into the application space and removed therefrom so that the process gas parallel to the Precursorgarn the application space or in countercurrent to the transport direction of Precursorgarns with a related to the free cross section of the application space average flow velocity of 0.1 to 20 m / s flows through relative to the application space passing through the precursor yarn.
  • the flow rate is particularly preferably in the range between 0.5 and 5 m / s.
  • the precursor yarn in the applicator is kept under a defined tension.
  • the precursor yarn is preferably passed through the applicator under a thread tension in the range from 0.125 to 5 cN / tex. Particularly preferred is a thread tension in the range of 0.5 to 3.5 cN / tex.
  • the residence time of the precursor yarn in the application space is at least 20 s.
  • An upper limit of the residence time results from e.g. the desired degree of stabilization, which is to be achieved after passing through the yarn by the applicator or from device-technical boundary conditions, for example with regard to the displayable length of the applicator.
  • the precursor yarn is passed through one after the other through a plurality of application devices, ie, through at least two application devices arranged one behind the other.
  • each of these application devices can be equipped with their own means for generating a field of high-frequency electromagnetic waves, but it is also possible that all the application devices have a common microwave generator, for example.
  • the series connection of several application devices offers the advantage that in each of the application devices taking into account, for example, the current degree of stabilization of the respective application device passing precursor yarn independent adjustment with respect to the optimal process parameters can be done, such as in terms of field strength, temperature, the flow velocity of the process gas, the oxygen content of the optionally used oxygen-containing gas, the residence time, the yarn tension, etc ..
  • the frequency is e.g.
  • the microwaves are technically determined by the availability of low-cost high-performance sources to specific areas.
  • the field distribution in the application space is determined by its geometry and by the frequency and the power of the supplied electromagnetic waves. In the application space, this results in the expression of field maxima, the distance of which is determined inter alia by the geometry of the application space.
  • the precursor yarn to be stabilized in the application space passes through the stationary field maxima in a rhythm predetermined by the yarn speed.
  • a pronounced heating or heating of the yarn takes place in the region of the maxima and cooling takes place in the region of the minima due to the process gas flowing in the fiber.
  • this can lead to the stabilization process gets into an unstable area.
  • the high intensity of the coupled-in electromagnetic waves can lead to a large extent to the described exothermic conversion reactions, which in turn lead to an increase in temperature in the yarn material.
  • This in turn results in an improved coupling of the electromagnetic waves and thus an intensification of the exothermic reactions, combined with a further increase in the temperature in the yarn.
  • the heat generated by the inflowing process gas can only be dissipated to a limited extent, so that the stabilization process becomes unstable. A stabilization of the process can be achieved in such cases, for example via a temporal change in field strength.
  • the field strength in the application space has a periodically varying intensity over time, the period being determined primarily by the yarn speed and by the distance of the stationary field maxima.
  • the intensity changes sinusoidally or in the form of pulses, wherein in the case of a pulsed change in intensity, the field strength can change, for example, between two non-zero levels or between zero and a non-zero level.
  • the polyacrylonitrile precursor yarn 8 to be stabilized is withdrawn from a bobbin 9, introduced into the applicator 2 after looping around a deflection roller 10 via an aperture 11 in the elbow 6 and passed through the application space 3.
  • the precursor yarn 8 treated in the applicator 2 leaves the application device 1 via an elbow 13 connected to the outlet end 12 of the applicator 2 through an aperture 14.
  • the yarn tension of the precursor yarn can be adjusted by the drive speeds of the deflection rollers 10, 15.
  • the process gas required in the process of the invention is introduced into the application space 3 and passes through the application space 3 in the illustrated case in direct current to Precursorgarn 8 via a attached to the elbow 13 outlet nozzle 19, the process gas together with the volatile degradation products due to in the application space 3 in the yarn 8 occurring conversion reactions have arisen, discharged from the applicator 2.
  • the elbow 13 at the outlet end 12 of the applicator 2 is connected in the illustrated case with a pipe section 20 which is closed at its free end with a metal plate 21. This ensures that the electromagnetic waves are reflected back into the application space 3.
  • An untreated polyacrylonitrile precursor yarn was prepared as it is suitable for the production of carbon fibers, the precursor yarn having 12,000 filaments with a filament diameter of about 8 ⁇ m.
  • the density of the precursor yarn was 1.18 g / cm 3 .
  • the application device used for microwave treatment corresponded in structure to the in FIG. 1 illustrated device.
  • a microwave generator microwaves having a wavelength of 2.45 GHz were generated and led via a rectangular waveguide connected to the microwave generator via an elbow in the application space (R 26 rectangular waveguide), which had a length of 120 cm.
  • R 26 rectangular waveguide In the rectangular waveguide hot air at a temperature of 190 ° C was supplied via a side-mounted nozzle and passed in direct current to the precursor yarn through the application space, the volume flow was so dimensioned that resulted in the application space, an average flow rate of 2 m / s.
  • the application space was tempered by heating elements arranged in the wall to a temperature of 170 ° C., so that an air temperature of 170 ° C. prevailed in the application space. In the application room, a maximum electric field strength of 30 kV / m was set.
  • the polyacrylonitrile precursor org was introduced into the application device and passed through the applicator continuously at a speed of 30 m / h and under a thread tension of 0.9 cN / tex. In the area of an elbow connected to the outlet of the applicator, the yarn was led out of the application device.
  • Example 2 The same application device as in Example 1 was used.
  • the process parameters were also the same as in Example 1.
  • a polyacrylonitrile Precursorgam was submitted, which had already been subjected in a conventional process in a convection oven of a partial stabilization.
  • the yarn presented in this example had a density of 1.19 g / cm 3 and had a yellow color.
  • the density of the yarn was increased to 1.20 g / cm 3 and the yarn had turned a dark brown color.
  • Example 2 The same application device was used as in Example 1, except that the applicator, unlike Example 1, had a length of 1.0 m.
  • a partially stabilized yarn was introduced, which had a density of 1.21 g / cm 3 and a dark brown to black color due to the partial stabilization.
  • the temperature of the supplied hot air and the temperature of the arranged in the wall of the applicator heating elements was set to 170 ° C, so that the hot air in the application room also had a temperature of 170 ° C.
  • the yarn speed was 10 m / h, the yarn tension 1.25 cN / tex.
  • a pulsating microwave field was set by switching the magnetron on / off, in which the maximum electric field strength was 25 kV / m (15 s) and zero kV / m (6 s).
  • the color of the yarn leaving the application device had changed in the direction of a black color.
  • the density had increased to 1.24 g / cm 3 .
  • Example 1 An application device was used as in Example 1, whereby the same process parameters as in Example 1 were set.
  • the yarn was used, which was also used in Example 1. Notwithstanding Example 1, however, the yarn was treated several times in succession in the application device by being passed a total of three times through the application device. The partially stabilized precursor yarn of the previous pass through the application device served as a template for the following pass.
  • the total residence time in the application device was about 7.5 min.
  • the precursor yarn thus treated three times had a density of 1.22 g / m 3 .
  • the originally white precursor yarn had a dark brown to black color after treatment.
  • Example 3 The procedure was as in Example 3, but the maximum electric field strength was set to a constant value of 30 kV / m.
  • yarn there was a partially stabilized polyacrylonitrile Precursorgarn having a density of 1.26 g / cm 3.
  • the treated yarn After passing through the application device, ie after a residence time of 6 min at a Yarn speed of 10 m / h, the treated yarn had a density of 1.40 g / cm 3 .
  • Example 2 In a conventional multi-stage convection oven for stabilizing polyacrylonitrile precursor yarns for the production of carbon fibers, stabilization was carried out on an unstabilized precursor yarn as presented in Example 1. Air was passed through the convection oven. In the first stage of the furnace, a temperature of about 230 ° C was set.
  • the partially stabilized precursor yarn After a residence time of 23 minutes, the partially stabilized precursor yarn left the first furnace stage.
  • the partially stabilized precursor yarn had a dark brown to black color and a density of 1.21 g / cm 3 .

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Fibers (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (14)

  1. Procédé de stabilisation de fils en polyacrylonitrile au moyen de réactions de stabilisation chimiques, comportant les étapes suivantes :
    - mise en place d'un fil à traiter à base d'un polymère du type polyacrylonitrile,
    - mise à disposition d'un dispositif d'application destiné au traitement du fil à traiter au moyen d'ondes électromagnétiques à haute fréquence, ce dispositif comprenant un élément d'application doté d'un espace d'application, de moyens de génération des ondes électromagnétiques à haute fréquence ainsi que de moyens d'introduction des ondes électromagnétiques à haute fréquence dans l'espace d'application,
    - génération d'un champ d'ondes électromagnétiques à haute fréquence dans l'espace d'application, qui comprend des zones d'intensité de champ électrique minimale et des zones d'intensité de champ électrique maximale et réglage de l'intensité maximale de champ électrique dans l'espace d'application qui se situe dans la plage comprise entre 3 kV/m et 150 kV/m,
    - introduction en continu du fil à traiter et passage du fil à traiter dans l'espace d'application et dans le champ d'ondes électromagnétiques à haute fréquence, à cette occasion l'introduction d'un gaz de traitement dans l'espace d'application et passage du gaz de traitement dans l'espace d'application à une vitesse d'écoulement relative, d'au moins 0,1 m/s par rapport au fil à traiter en cours de passage dans l'espace d'application, la température du gaz de traitement étant ainsi réglée dans une plage comprise entre 150°C et 300°C, de telle sorte qu'elle se situe au-dessus de la température critique minimum Tkrit et au-dessous de la température maximum Tmax, et la température critique minimum Tkrit étant la température au-dessus de laquelle les ondes électromagnétiques à haute fréquence provoquent un couplage dans le fil à traiter en cours de passage dans l'espace d'application et font se dérouler les réactions de stabilisation chimiques et la température maximale Tmax étant la température qui se situe 20°C au-dessous de la température de décomposition du fil à traiter introduit dans le dispositif d'application.
  2. Procédé selon la revendication 1 caractérisé en ce qu'une intensité de champ électrique maximum des ondes électromagnétiques à haute fréquence de 5 à 50 kV/m est produite dans l'espace d'application.
  3. Procédé selon la revendication 1 ou 2 caractérisé en ce que le fil à traiter passe dans l'applicateur sous une tension de fil comprise de 0,125 cN/tex à 5 cN/tex.
  4. Procédé selon une ou plusieurs des revendications 1 à 3 caractérisé en ce que le gaz de traitement traverse l'espace d'application perpendiculairement au fil à traiter avec une vitesse d'écoulement comprise de 0,1 m/s à 2 m/s.
  5. Procédé selon une ou plusieurs des revendications 1 à 3 caractérisé en ce que le gaz de traitement traverse l'espace d'application parallèlement au fil à traiter avec une vitesse d'écoulement moyenne rapportée à la section libre de l'espace d'application, comprise de 0,1 m/s à 20 m/s par rapport au fil à traiter qui traverse l'espace d'application.
  6. Procédé selon une ou plusieurs des revendications 1 à 5 caractérisé en ce que le gaz de traitement est un gaz contenant de l'oxygène.
  7. Procédé selon la revendication 6 caractérisé en ce que le gaz contenant de l'oxygène est de l'air.
  8. Procédé selon une ou plusieurs des revendications 1 à 7 caractérisé en ce que le fil à traiter contient des additifs destinés à l'amélioration de la capacité d'absorption du fil à traiter vis-à-vis des ondes électromagnétiques à haute fréquence.
  9. Procédé selon la revendication 8 caractérisé en ce qu'en ce qui concerne les additifs il s'agit du polyéthylène glycol, de la rouille, ou de nanotubes de carbone.
  10. Procédé selon une ou plusieurs des revendications 1 à 9 caractérisé en ce que les ondes électromagnétiques à haute fréquence ont une fréquence comprise entre 0,3 GHz et 45 GHz.
  11. Procédé selon une ou plusieurs des revendications 1 à 10 caractérisé en ce que le temps de séjour du fil à traiter dans l'espace d'application est d'au moins 20 s.
  12. Procédé selon une ou plusieurs des revendications 1 à 11 caractérisé en ce que le gaz de traitement présente dans l'espace d'application une température se situant dans la plage comprise entre (Tkrit + 20°C) et (Tmax - 20°C).
  13. Procédé selon une ou plusieurs des revendications 1 à 12 caractérisé en ce que l'intensité de champ dans l'espace d'application est une intensité qui varie périodiquement en fonction du temps.
  14. Procédé selon une ou plusieurs des revendications 1 à 13 caractérisé en ce que le fil à traiter passe dans au moins deux dispositifs d'application disposés l'un à la suite de l'autre.
EP10749843.8A 2009-09-11 2010-08-31 Stabilisation de fils de précurseurs en poly-acrylonitrile Active EP2475812B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10749843.8A EP2475812B1 (fr) 2009-09-11 2010-08-31 Stabilisation de fils de précurseurs en poly-acrylonitrile

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP09170059 2009-09-11
PCT/EP2010/062674 WO2011029745A1 (fr) 2009-09-11 2010-08-31 Stabilisation de fils précurseurs en polyacrylnitrile
EP10749843.8A EP2475812B1 (fr) 2009-09-11 2010-08-31 Stabilisation de fils de précurseurs en poly-acrylonitrile

Publications (2)

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EP2475812A1 EP2475812A1 (fr) 2012-07-18
EP2475812B1 true EP2475812B1 (fr) 2013-06-05

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US (1) US20120137446A1 (fr)
EP (1) EP2475812B1 (fr)
JP (1) JP5538545B2 (fr)
CN (1) CN102612576B (fr)
AR (1) AR078361A1 (fr)
AU (1) AU2010294347B2 (fr)
BR (1) BR112012005159A2 (fr)
CA (1) CA2772580A1 (fr)
DK (1) DK2475812T3 (fr)
ES (1) ES2426612T3 (fr)
PT (1) PT2475812E (fr)
TW (1) TWI480443B (fr)
WO (1) WO2011029745A1 (fr)

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US10834820B2 (en) 2013-08-06 2020-11-10 Bedrock Automation Platforms Inc. Industrial control system cable
US9727511B2 (en) 2011-12-30 2017-08-08 Bedrock Automation Platforms Inc. Input/output module with multi-channel switching capability
WO2013144123A1 (fr) 2012-03-28 2013-10-03 Toho Tenax Europe Gmbh Dérivé de lignine fusible et fibre produite à partir de ce dérivé de lignine
US9725829B2 (en) * 2013-03-15 2017-08-08 Ut-Battelle, Llc Magneto-carbonization method for production of carbon fiber, and high performance carbon fibers made thereby
US9771669B2 (en) 2013-11-08 2017-09-26 Georgia Tech Research Corporation Use, stabilization and carbonization of polyacrylonitrile/carbon composite fibers
US20170275786A1 (en) * 2014-10-08 2017-09-28 Georgia Tech Research Corporation High strength and high modulus carbon fibers
TWI695096B (zh) * 2018-01-29 2020-06-01 永虹先進材料股份有限公司 氧化纖維製造方法
TWI695099B (zh) * 2018-01-29 2020-06-01 永虹先進材料股份有限公司 氧化纖維
TWI665349B (zh) * 2018-01-29 2019-07-11 永虹先進材料股份有限公司 Fiber pre-oxidation equipment
CN109944057A (zh) * 2019-03-08 2019-06-28 常熟市翔鹰特纤有限公司 一种聚丙烯腈长丝微波致密化装置

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Publication number Publication date
EP2475812A1 (fr) 2012-07-18
WO2011029745A1 (fr) 2011-03-17
TW201129743A (en) 2011-09-01
JP2013504696A (ja) 2013-02-07
ES2426612T3 (es) 2013-10-24
JP5538545B2 (ja) 2014-07-02
AU2010294347A1 (en) 2012-03-08
CN102612576A (zh) 2012-07-25
TWI480443B (zh) 2015-04-11
BR112012005159A2 (pt) 2016-05-03
PT2475812E (pt) 2013-09-03
CN102612576B (zh) 2014-01-15
DK2475812T3 (da) 2013-09-08
AU2010294347B2 (en) 2014-06-26
US20120137446A1 (en) 2012-06-07
AR078361A1 (es) 2011-11-02
CA2772580A1 (fr) 2011-03-17

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