EP1179096B1 - Verfahren zur herstellung eines gewebes aus kohlenstofffasern durch kontinuierliche carbonisierung von geweben aus cellulosefasern - Google Patents

Verfahren zur herstellung eines gewebes aus kohlenstofffasern durch kontinuierliche carbonisierung von geweben aus cellulosefasern Download PDF

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Publication number
EP1179096B1
EP1179096B1 EP00985404A EP00985404A EP1179096B1 EP 1179096 B1 EP1179096 B1 EP 1179096B1 EP 00985404 A EP00985404 A EP 00985404A EP 00985404 A EP00985404 A EP 00985404A EP 1179096 B1 EP1179096 B1 EP 1179096B1
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EP
European Patent Office
Prior art keywords
fabric
temperature
range
lying
chamber
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Expired - Lifetime
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EP00985404A
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English (en)
French (fr)
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EP1179096A2 (de
Inventor
Pierre Olry
Mark Kazakov
Sylvie Loison
Marina Marakhovskaya
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Safran Ceramics SA
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SNECMA Moteurs SA
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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
    • D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate

Definitions

  • the invention relates to the manufacture of fabrics made of carbon from cellulosic cellulose fibers precursor carbon.
  • the invention aims more particularly, but not exclusively, the manufacture of carbon fiber fabric by carbonization of a fabric made of viscose fibers, especially rayon fibers.
  • Cellulosic precursor carbon fibers exhibit generally a porous structure formed of turbostratic carbon very disorganized, this structure being further disoriented by relative to the axial direction of the fibers and their pore network.
  • carbon fibers a low thermal conductivity, which makes them particularly suitable for formation of thermal protective coatings, such as ablative coatings for combustion chambers and nozzles thrusters.
  • a commonly used method is to perform a direct carbonization of a cellulosic fiber fabric, especially a viscose fabric.
  • the fabric is put in the form of a skein of a length from one to several hundred meters. It is precarbonized up to a temperature of about 400 ° C. Precarbonization is carried out in a container preferably in a neutral atmosphere, for example with nitrogen sweeping. Effluents from decomposition cellulose are sucked up and burned in a flare.
  • precarbonization can last up to 15 days, which is extremely long.
  • the pre-carbonization phase is followed by a treatment thermal at a temperature of about 1200 ° C for about 1 to 2 min.
  • a final treatment at high temperature, for example 2800 ° C, can be done to increase the conductivity of the carbon and close its porosity.
  • the precursor fabric for example viscose fibers is impregnated with an organosilicon compound which has the effect of maintain good mechanical properties for the fiber fabric of carbon obtained.
  • the organosilicon compound is chosen from the compounds from the group of polydimethylphenylallylsilanes, polysiloxanes, polymethylsiloxanes, polysilazanes, polyalumino-organosiloxanes.
  • the impregnated fabric is subjected to heat treatment in continuous under air at a temperature between 100 ° C and 300 ° C, plus particularly between 100 ° C and 150 ° C, to induce relaxation of constraints that exist in cellulosic fibers and eliminate water adsorbed by the fibers.
  • the carbonization is then carried out on the moving fabric in continuously in an enclosure under an inert atmosphere, raising the temperature gradually to 300 ° C to 600 ° C. Treatment at high temperature, maximum up to 280 ° C under inert atmosphere, is then realized.
  • the gaseous effluents of pyrolysis of the cellulose are sucked up and burned in a flare, the suction means being located in the enclosure where the maximum of degradation of cellulose.
  • This process makes it possible to obtain mechanical properties satisfactory for carbon fibers, but leads to deformations of the resulting fabric, such as disorganization of weaving and embossing.
  • the object of the invention is to avoid these drawbacks by proposing a process for obtaining carbon fiber fabric by carbonization of cellulosic fiber fabric, whereby a carbon fiber fabric obtained does not show any significant deformation.
  • the chain son that extend parallel to the scroll direction of the fabric in the room is not in isothermal.
  • the temperature at which the same wire is exposed varies between its portion exposed to the lowest temperature, before entering the room and the portion exposed to the highest temperature, at the other end of bedroom.
  • the temperature profile according to the method of the invention aims at answer a first concern, which is to induce on the weft threads a shrinkage to respect the geometry of the fabric during its withdrawal to avoid clogging or disruption of the fabric. Therefore, in an initial phase after entering the tissue into the enclosure, the elevation temperature is relatively fast, to impose an early withdrawal to the weft threads.
  • the temperature profile also aims to answer a second worry, which is to get a good mechanical quality of carbon threads resulting from carbonization. This is how, in a phase intermediate, where most of the decomposition of cellulose takes place, the temperature rise is slower to better respect the kinetics of decomposition. Choosing an average climb speed temperature between 2 ° C and 10 ° C can respond to this satisfactorily, without imposing a journey length excessive tissue.
  • the final stage of carbonization which aims essentially at to give carbon the desired structure, can be conducted with again a faster temperature rise, most of the shrinkage in chain and weft have been observed, in order to reduce the total duration of the carbonization, so the production costs.
  • the fabric is scrolled in the carbonization chamber through successive zones in each of which reigns a controlled temperature.
  • the residence time of the tissue in the room is between 20 min and 2 h. Carbonization so is extremely fast.
  • the tissue before carbonization, to a relaxation treatment at a temperature between 100 ° C and 250 ° C, preferably under air and for a duration for example between 15 min and 3 h.
  • a plant for the continuous carbonization of a fiber fabric Cellulosic is shown very schematically in Figure 1.
  • the carbonization is carried out on a fiber fabric T cellulose fibers, for example technical viscose fibers, to which added an organosilicon compound which acts, during the decomposition of the cellulose, so that the obtained carbon fibers retain good mechanical properties.
  • the organosilicon compound may be a siloxane resin, consisting of units of formula SiO 4 (designated Q 4 units ), units of formula SiO 3 -OH (so-called Q 3 units ) and units of formula O-Si-R 3 (referred to as M units), advantageously consisting of n 1 units Q 4 , n 2 units Q 3 and n 3 units M, with 2 ⁇ n 1 ⁇ 70, 3 ⁇ n 2 ⁇ 50 and 3 ⁇ n 3 ⁇ 50 and having a number average molecular weight of between 2,500 and 5,000.
  • Q 4 units units of formula SiO 3 -OH
  • M units units of formula O-Si-R 3
  • the organosilicon compound may also be chosen from oligomers of a partially hydrolysed organic silicate, advantageously selected from oligomers of a partially alkyl silicate hydrolyzed, and preferably selected from oligomers of ethyl silicate partially hydrolysed.
  • the impregnation is carried out by scrolling the fabric T in a tray 10 containing the selected organosilicon compound, in solution in a solvent such as a chlorinated solvent (for example tetrachlorethylene) or acetone. Impregnation of the fabric can be achieved by passing through a bath (as illustrated) and / or by spraying the compound solution organosilicon on the faces of the fabric. At the outlet of the tray 10, the impregnated fabric is expressed by passing between rollers 12 in order to leave a controlled amount of compound.
  • a solvent such as a chlorinated solvent (for example tetrachlorethylene) or acetone.
  • the impregnated fabric is then admitted to a dryer 14 so to eliminate the solvent.
  • the drying is carried out for example by air flow hot against the current of the fabric scrolling on embarrassments 16.
  • the impregnated and dried fabric is ready to be charred. he can be temporarily stored, for example by bambanning in a container or be admitted directly continuously to the carbonization station 18 itself.
  • the fabric may also have been impregnated with at least one mineral additive, acid or Lewis base, for example chosen from ammonium and sodium halides, sulphates and phosphates, urea and their mixtures and advantageously consists of in ammonium chloride (NH 4 Cl) or diammonium phosphate [(NH 4 ) 2 HPO 4 ].
  • at least one mineral additive for example chosen from ammonium and sodium halides, sulphates and phosphates, urea and their mixtures and advantageously consists of in ammonium chloride (NH 4 Cl) or diammonium phosphate [(NH 4 ) 2 HPO 4 ].
  • the carbonization comprises a moderate heat treatment of drying and relaxation of the tissue followed by passage in an oven where the carbonization is actually carried out.
  • the relaxation treatment is performed by admission of the tissue in a chamber 20 at atmospheric pressure and in ambient air.
  • the temperature in the chamber 20 is regulated to a value between 100 ° C and 250 ° C, for example about 130 ° C.
  • the residence time in the enclosure 20 is preferably between 15 min and 3 h.
  • the length of the path of the fabric in the enclosure, with passage on rolls of reference 22, is chosen to obtain the desired residence time depending the speed of scrolling of the fabric.
  • Relaxation heat treatment allows a relaxation of the internal stresses of the cellulosic fibers, and removal of water adsorbed by the fabric.
  • the carbonization is then carried out by admission of the fabric in an enclosure 30 enclosing a carbonization chamber 40.
  • the admission of the cellulosic fiber fabric into the chamber 40, at a end of it, and extracting the carbon fiber cloth out of the chamber 40, at the other end thereof, are made through sealing boxes 50, 52. At its entry into the box 50, the fabric is returned substantially at room temperature.
  • the carbonization chamber is a elongate chamber in which the fabric follows a horizontal straight path.
  • Other configurations of the carbonization chamber may be considered, for example a room with several adjacent parts consecutive horizontal or vertical in which the fabric is guided by return rollers.
  • the chamber 40 is delimited by the horizontal walls 42 has lower and upper 42b, and vertical side walls 42 c, 42 d, for example of graphite.
  • the chamber 40 is surrounded by an enclosure 30.
  • electrical heating resistors 34 are arranged near the outer faces of walls 42 a, 42 b.
  • the interior of the chamber 40 is kept under atmosphere neutral, for example under nitrogen injected by pipes 36 respectively near the entrance and the exit of the room.
  • atmosphere neutral for example under nitrogen injected by pipes 36 respectively near the entrance and the exit of the room.
  • of the products of decomposition of cellulose, during its carbonization, are extracts from the chamber through one or more chimneys 38.
  • the extraction chimneys are placed at a level of the oven where occurs mainly the decomposition of cellulose. Extracted products can be flared (not shown).
  • Sealing boxes 50, 52 prevent access to the interior of chamber 40 by ambient air, which would have the effect of disturbing the circulation of the gases inside chamber 40 and oxidizing the fabric charred. Sealing boxes 50, 52 also prevent polluting leakage of decomposition products of cellulose in the shelter building the enclosure 30. It is advantageous to use, at least for the box 50, a combination of static sealing by inflatable bead contacting the fabric with a minimum of friction, and dynamic barrier sealing formed by injection of neutral gas. An embodiment of such a sealing box is described in the patent application WO 01/42542.
  • the carbonization chamber 40 has an elongated rectangular profile (FIG. 2). Between the inlet and the outlet of the chamber 40, the fabric passes through a succession of adjacent zones separated from each other by transverse walls 44 a, 44 b.
  • the walls 44 for example graphite, are connected to top and side walls of the chamber 4, while the walls 44 b, for example also in graphite, are connected to the bottom and side walls of the chamber 40.
  • the ends facing walls 44 a and 44 b define therebetween a slit 46 for the passage of the fabric.
  • the division of the chamber 40 into several consecutive zones 40 1 , 40 2 , 40 3 ,... makes it possible to define different temperature zones between the inlet and the outlet of the chamber 40.
  • the temperature is regulated at a predetermined set value.
  • the currents in the resistors 34 are regulated by a control circuit 46 on the basis of information provided by temperature probes 48 arranged in the different zones 40 1 , 40 2 , 40 3 , ....
  • the initial phase aims at imposing an early withdrawal of the frame fabric so that it adapts to the geometry of the warp yarns.
  • the portion of each wire of chain entering the room is influenced by the part located in downstream exposed to a higher temperature. Imposing a rapid heating as soon as entering the chamber 40 allows the weft to "follow" the removal of the tissue and avoid the appearance of defects geometric in the fabric.
  • a rate of temperature rise relatively fast is chosen. It is on average between 10 ° C / min and 60 ° C / min, preferably between 10 ° C / min and 40 ° C / min.
  • the rate of rise in temperature may be higher at the beginning of the initial phase than at the end of it.
  • the tissue temperature at the end of the initial phase is included between 250 ° C and 350 ° C, preferably between 270 ° C and 300 ° C.
  • the intermediate phase is where most of the decomposition of cellulose.
  • this decomposition In order to keep fibers a good mechanical strength, this decomposition must be controlled, that is to say produce with a moderate rate of rise in temperature. In average, this speed is between 2 ° C / min and 10 ° C / min, preferably between 4 ° C / min and 6 ° C / min, being noted that too low a speed become economically disadvantageous.
  • the temperature of the tissue at the end of the intermediate phase is between 400 ° C and 450 ° C. This temperature is the temperature at which most of the decomposition of the cellulose is carried out.
  • the final phase is where the carbonization of the fibers is completed until the desired carbon structure is obtained.
  • the temperature of the fabric at the end of the final phase is included between 500 ° C. and 750 ° C., for example between 550 ° C. and 650 ° C. for reach a stage of charring sufficiently advanced.
  • the temperature rise can be faster than in the intermediate phase, since the decomposition of cellulose has been essentially achieved.
  • the constraints related to differential withdrawals between string and frame are smaller since most of the shrinkage occurred in both the warp and weft.
  • Speed average rise in temperature is chosen between 5 ° C / min and 40 ° C / min, for example between 25 ° C / min and 30 ° C / min.
  • a desired thermal profile for the tissue in the chamber of carbonization 40 is likely to be reproduced with even more that the number of zones in chamber 40 is high, with individual control of the temperature in each zone.
  • the number of zones is at least 3, preferably at least equal to 6.
  • the fabric passes between call rollers 54 before being stored for example in the form of a coil 56.
  • the call rollers are associated with means of training (not shown) to control the scrolling of the fabric at the desired speed. It should be noted that due to the removal of the warp threads during carbonization, the speed of entry of the fabric into the chamber 40 is greater than the output speed.
  • the residence time of the fabric in the chamber 40 is included between 20 minutes and 2 hours.
  • High temperature heat treatment can be realized on the carbonized fabric from the chamber 40.
  • This heat treatment is performed continuously by passing the fabric in a furnace 60.
  • This treatment thermal aims to achieve a structuring of carbon fibers. It is temperature above 1000 ° C, up to 2800 ° C, under a neutral atmosphere, for example under nitrogen.
  • the weather of residence of the fabric in the oven 60 is preferably between 1 min and 10 min, for example about 2 min.
  • the fabric is taken from the spool 56 and is stored, at the furnace outlet 60, on a coil 62, being called by rolls 64.
  • the carbon fabric directly from chamber 40 can also be carefully oxidized by exposure to water vapor or carbon dioxide, under conditions well known to elsewhere to obtain activated carbon fabric without heat treatment at high temperature.
  • a carbonization plant with a shared chamber is used in 8 zones 40 1 to 40 8 of equal lengths.
  • vent or chimneys for the decomposition products of the cellulose are located between the zones 40 5 and 40 6 .
  • the tissue was continuously treated at 1200 ° C under nitrogen for 90 s.
  • a rayon fiber fabric such as that of the examples above was carbonized continuously.
  • the same fabric was charred in similar conditions with the exception of the char profile, the temperature rise of the fabric having been carried out at a speed constant 7 ° C / min from room temperature to 650 ° C.
  • FIG. 4 shows the embossed appearance of the fabric obtained, due to a offset of the withdrawal between the chain and the frame.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatment Of Fiber Materials (AREA)
  • Inorganic Fibers (AREA)
  • Woven Fabrics (AREA)

Claims (9)

  1. Verfahren zur Herstellung eines Gewebes aus Kohlenstoffasern durch kontinuierliche Karbonisierung eines Gewebes aus Cellulosefasern, dadurch gekennzeichnet, daß ein sich kontinuierlich fortbewegendes Gewebe in einer Karbonisierungskammer einer Wärmebehandlung unterzogen wird, die folgendes umfaßt:
    eine Anfangsphase, um die Temperatur des Gewebes auf einen Wert zwischen 250 °C und 350 °C zu bringen, wobei die Anfangsphase einen Temperaturanstieg mit einer ersten Durchschnittsgeschwindigkeit aufweist, die zwischen 10 °C/Minute und 60 °C/Minute liegt,
    eine Zwischenphase, um die Temperatur des Gewebes bis auf einen Wert zu erhöhen, welcher zwischen 350 °C und 500 °C liegt, wobei die Zwischenphase einen Temperaturanstieg mit einer zweiten Durchschnittsgeschwindigkeit umfaßt, die geringer als die erste ist und zwischen 2 °C/Minute und 10 °C/Minute liegt, und
    eine Endphase, um die Temperatur des Gewebes bis auf einen Wert zwischen 500 °C und 750 °C zu bringen, wobei die Endphase einen Temperaturanstieg mit einer dritten Durchschnittsgeschwindigkeit umfaßt, die höher als die zweite ist und zwischen 5 °C/Minute und 40 °C/Minute liegt.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Gewebe in der Kammer durch aufeinanderfolgende Zonen geführt wird, in denen jeweils eine kontrollierte Temperatur herrscht.
  3. Verfahren nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, daß die Verweilzeit des Gewebes in der Kammer zwischen 20 Minuten und 2 Stunden liegt.
  4. Verfahren nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, daß das Gewebe vor der Karbonisierung einer Entspannungsbehandlung bei einer Temperatur zwischen 100 °C und 250 °C unterzogen wird.
  5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß die Entspannungsbehandlung unter Luft durchgeführt wird.
  6. Verfahren nach einem der Ansprüche 4 und 5, dadurch gekennzeichnet, daß die Entspannungsbehandlung während einer Dauer zwischen 15 Minuten und 3 Stunden durchgeführt wird.
  7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das karbonisierte Gewebe nach dem Transport in die Karbonisierungskammer einer Wärmebehandlung bei hoher Temperatur zwischen 1000 °C und 2800 °C unterzogen wird.
  8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß die Wärmebehandlung bei hoher Temperatur während einer Dauer zwischen einer 1 Minute und 10 Minuten durchgeführt wird.
  9. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das karbonisierte Gewebe einer Aktivierungsbehandlung unterzogen wird.
EP00985404A 1999-12-06 2000-12-05 Verfahren zur herstellung eines gewebes aus kohlenstofffasern durch kontinuierliche carbonisierung von geweben aus cellulosefasern Expired - Lifetime EP1179096B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9915330 1999-12-06
FR9915330A FR2801908B1 (fr) 1999-12-06 1999-12-06 Procede pour l'obtention de tissu en fibres de carbone par carbonisation en continu d'un tissu en fibres cellulosiques
PCT/FR2000/003385 WO2001042543A2 (fr) 1999-12-06 2000-12-05 Procede pour l'obtention de tissu en fibres de carbone par carbonisation en continu d'un tissu en fibres cellulosiques

Publications (2)

Publication Number Publication Date
EP1179096A2 EP1179096A2 (de) 2002-02-13
EP1179096B1 true EP1179096B1 (de) 2005-03-02

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EP00985404A Expired - Lifetime EP1179096B1 (de) 1999-12-06 2000-12-05 Verfahren zur herstellung eines gewebes aus kohlenstofffasern durch kontinuierliche carbonisierung von geweben aus cellulosefasern

Country Status (12)

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US (1) US6967014B1 (de)
EP (1) EP1179096B1 (de)
JP (1) JP4582566B2 (de)
AT (1) ATE290108T1 (de)
AU (1) AU2183101A (de)
BR (1) BR0007679B1 (de)
DE (1) DE60018406T2 (de)
FR (1) FR2801908B1 (de)
MX (1) MXPA01007953A (de)
RU (1) RU2257429C2 (de)
UA (1) UA68412C2 (de)
WO (1) WO2001042543A2 (de)

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Publication number Priority date Publication date Assignee Title
ATE361383T1 (de) * 2004-12-07 2007-05-15 Snecma Propulsion Solide Verfahren zur herstellung von garnen oder faserblättern aus kohlenstoff ausgehend von einem cellulosematerial
FR2909920B1 (fr) * 2006-12-15 2009-03-20 Snecma Propulsion Solide Sa Procede de realisation d'un ensemble carter-divergent
JP5271887B2 (ja) * 2009-05-08 2013-08-21 国防科学研究所 ライオセル系炭素繊維及び炭素織物の製造方法
RU2459893C1 (ru) * 2011-03-18 2012-08-27 Общество с ограниченной ответственностью Научно-производственный центр "УВИКОМ" (ООО НПЦ "УВИКОМ") Способ получения углеродного волокнистого материала
RU2506356C1 (ru) * 2012-07-13 2014-02-10 Открытое акционерное общество "Научно-исследовательский институт конструкционных материалов на основе графита "НИИграфит" Установка карбонизации волокнистых вискозных материалов для получения комбинированных углеродных нитей
US8777601B2 (en) * 2012-07-31 2014-07-15 Uht Unitech Co., Ltd. Manufacturing device of high modulus graphite fiber
RU2520982C1 (ru) * 2012-10-10 2014-06-27 Открытое акционерное общество "Научно-исследовательский институт конструкционных материалов на основе графита "НИИграфит" Способ карбонизации вискозных волокнистых материалов в процессе получения углеродных волокон
US20160201206A1 (en) * 2013-07-23 2016-07-14 Council Of Scientific & Industrial Research Conducting Carbon Cloth Electrode for Hydrogen Generation and Dye Sensitized Solar Cells
DE102014212241A1 (de) * 2014-06-25 2015-12-31 Siemens Aktiengesellschaft Carbonfasern mit modifizierter Oberfläche sowie Verfahren zur Modifizierung einer Carbonfaseroberfläche und Verwendung der Carbonfaser
US9657413B2 (en) * 2014-12-05 2017-05-23 Cytec Industries Inc. Continuous carbonization process and system for producing carbon fibers
CN105544022B (zh) * 2016-01-29 2018-06-05 合肥天玾环保科技有限公司 一种粘胶基活性碳纤维的生产装置及节能环保方法

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FR2760759B1 (fr) * 1997-03-14 1999-06-11 Carbone Ind Procede de realisation de textures activees en fibres de carbone

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FR2801908A1 (fr) 2001-06-08
WO2001042543A2 (fr) 2001-06-14
WO2001042543A3 (fr) 2001-11-29
JP2003516477A (ja) 2003-05-13
BR0007679B1 (pt) 2011-05-17
MXPA01007953A (es) 2003-07-14
UA68412C2 (en) 2004-08-16
RU2257429C2 (ru) 2005-07-27
DE60018406T2 (de) 2005-12-29
FR2801908B1 (fr) 2002-03-01
EP1179096A2 (de) 2002-02-13
JP4582566B2 (ja) 2010-11-17
AU2183101A (en) 2001-06-18
US6967014B1 (en) 2005-11-22
ATE290108T1 (de) 2005-03-15
DE60018406D1 (de) 2005-04-07
BR0007679A (pt) 2001-11-06

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