EP1179096A2 - Method for obtaining a carbon fiber fabric by continuous carbonization of a fabric consisting of cellulosic fibers - Google Patents

Method for obtaining a carbon fiber fabric by continuous carbonization of a fabric consisting of cellulosic fibers

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Publication number
EP1179096A2
EP1179096A2 EP00985404A EP00985404A EP1179096A2 EP 1179096 A2 EP1179096 A2 EP 1179096A2 EP 00985404 A EP00985404 A EP 00985404A EP 00985404 A EP00985404 A EP 00985404A EP 1179096 A2 EP1179096 A2 EP 1179096A2
Authority
EP
European Patent Office
Prior art keywords
fabric
temperature
carbonization
chamber
carried out
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP00985404A
Other languages
German (de)
French (fr)
Other versions
EP1179096B1 (en
Inventor
Pierre Olry
Mark Kazakov
Sylvie Loison
Marina Marakhovskaya
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Safran Ceramics SA
Original Assignee
SNECMA Moteurs SA
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Application filed by SNECMA Moteurs SA filed Critical SNECMA Moteurs SA
Publication of EP1179096A2 publication Critical patent/EP1179096A2/en
Application granted granted Critical
Publication of EP1179096B1 publication Critical patent/EP1179096B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/16—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 carbon fiber fabrics from fiber fabrics of carbon precursor cellulosic material.
  • the invention relates more particularly, but not exclusively, to the manufacture of carbon fiber fabric by carbonization of a fabric made of viscose fibers, in particular rayon fibers.
  • Carbon fibers with a cellulose precursor generally have a porous structure formed from highly disorganized turbostratic carbon, this structure being furthermore very disoriented with respect to the axial direction of the fibers and their network of pores.
  • carbon fibers a low thermal conductivity, which makes them particularly suitable for the formation of thermal protective coatings, such as ablative coatings for combustion chambers and propellant nozzles.
  • a commonly used method consists in carrying out a direct carbonization of a fabric made of cellulosic fibers, in particular a viscose fabric.
  • the fabric is put in the form of a skein with a length of one to several hundred meters. It is precarbonized up to a temperature of around 400 ° C. Precarbonisation is carried out in a container preferably in a neutral atmosphere, for example with nitrogen sweep. The effluents from the decomposition of cellulose are sucked and burned in a flare.
  • precarbonization can last up to 15 days, which is extremely long.
  • the pre-carbonization phase is followed by a heat treatment at a temperature of about 1200 ° C for about 1 to 2 min.
  • a final treatment at high temperature which can for example reach 2800 ° C., can be carried out to increase the conductivity of the carbon and to close its porosity.
  • a method and an installation making it possible to obtain a carbon fiber fabric by continuous carbonization of a cellulose fiber fabric, with a much shorter heat treatment duration, are described in patents RU 2 005 829, RU 2 045 472 and RU 2 047 674.
  • the precursor fabric for example in technical viscose fibers, is impregnated with an organosilicon compound having the effect of retaining good mechanical properties for the fabric of carbon fibers obtained.
  • the organosilicon compound is chosen from compounds from the group of polydimethylphenylallylsilanes, polysiloxanes, polymethylsiloxanes, polysilazanes, polyalumino-organosiloxanes.
  • the impregnated fabric is subjected to a continuous heat treatment in air at a temperature between 100 ° C and 300 ° C, more particularly between 100 ° C and 150 ° C, to induce a relaxation of the stresses which exist in cellulosic fibers and remove the water adsorbed by the fibers.
  • the carbonization is then carried out on the continuously passing fabric in an enclosure under an inert atmosphere, gradually raising the temperature to 300 ° C to 600 ° C.
  • a treatment at high temperature, at most up to 280 ° C. under an inert atmosphere, is then carried out.
  • the gaseous effluents from the pyrolysis of the cellulose are sucked and burnt in a flare, the suction means being located at the level of the enclosure where the maximum degradation of the cellulose occurs. This process makes it possible to obtain satisfactory mechanical properties for the carbon fibers, but leads to deformations of the fabric obtained, such as disorganization of the weaving and embuvage.
  • the object of the invention is to avoid these drawbacks by proposing a process for obtaining carbon fiber fabric, by carbonization of cellulose fiber fabric, by which a carbon fiber fabric obtained does not shows no significant deformation.
  • an initial phase for bringing the temperature of the fabric to a value between 250 ° C and 350 ° C the initial phase comprising a rise in temperature at a first average speed of between 10 ° C / min and 60 ° C / min,
  • an intermediate phase to raise the temperature of the fabric to a value between 350 ° C and 500 ° C, the intermediate phase comprising a rise in temperature at a second average speed lower than the first and between 2 ° C / min and 10 ° C / min, and
  • a final phase to raise the temperature of the fabric to a value between 500 ° C and 750 ° C, the final phase comprising a rise in temperature at a third average speed greater than the second and between 5 ° C / min and 40 ° C / min.
  • the choice of this particular temperature profile during carbonization responds to the concern of finding the best compromise between the quality of the carbonization, on which depends in particular the mechanical strength of the fibers, the quality of the appearance of the fabric, that is to say the absence of significant baking and respect for the warp / weft geometry, and the keeping production costs at an acceptable level.
  • a thread made of cellulosic fibers undergoes a significant shrinkage. This can reach 30 to 40% when the thread is free of any tension.
  • a favorable situation for obtaining a carbon fiber fabric without excessive fogging and without deformation of geometry would be that where, along the path in the chamber, the shrinkage affects in the same way the weft threads and the threads chain.
  • each weft thread is in isothermal
  • the warp threads which extend parallel to the direction of travel of the fabric in the chamber are not in isothermal.
  • the temperature to which the same warp wire is exposed varies between its portion exposed to the lowest temperature, before entering the chamber and the portion exposed to the highest temperature, at the other end of the chamber.
  • the temperature profile according to the process of the invention aims to respond to a first concern, which is to induce on the weft yarns a shrinkage making it possible to respect the geometry of the fabric during its shrinkage to avoid bogging or disorganization fabric.
  • a first concern which is to induce on the weft yarns a shrinkage making it possible to respect the geometry of the fabric during its shrinkage to avoid bogging or disorganization fabric.
  • the temperature profile also aims to respond to a second concern, which is to obtain good mechanical quality of carbon wires resulting from carbonization.
  • the temperature rise is slower to best respect the decomposition kinetics.
  • the choice of an average temperature rise speed of between 2 ° C and 10 ° C makes it possible to respond to this concern satisfactorily, without imposing an excessive path length on the fabric.
  • the final carbonization phase which essentially aims to give the desired structure to the carbon, can be carried out again with a faster rise in temperature, most of the warp and weft removal having been observed, in order to reduce the total time. carbonization, so production costs.
  • the fabric is passed through the carbonization chamber through successive zones in each of which a controlled temperature prevails.
  • the residence time of the fabric in the chamber is between 20 min and 2 h. Carbonization is therefore extremely rapid.
  • the fabric is subjected, before carbonization, to a relaxation treatment at a temperature between 100 ° C. and 250 ° C., preferably in air and for a duration for example between 15 min and 3 h.
  • - Figure 2 is a cross-sectional view along the plane ll-ll of Figure 1;
  • - Figure 3 illustrates a range of thermal profile of a fabric inside a carbonization chamber according to a method according to the invention.
  • FIG. 4 shows a fabric obtained by implementing a method other than that of the invention.
  • FIG. 1 An installation for the continuous carbonization of a fabric of cellulosic fibers is shown very schematically in FIG. 1.
  • the carbonization is carried out on a fabric T of cellulosic fibers, for example of technical viscose fibers, to which has been added an organosilicon compound which acts, during the decomposition of the cellulose, so that the carbon fibers obtained retain good mechanical properties.
  • the viscose fabric T in the dry state and free of any size, is impregnated by passage through a bath containing said organosilicon compound in solution.
  • the organosilicon compound can be chosen from polysiloxanes.
  • a polysiloxane chosen from the families defined in the French patent applications filed simultaneously with the present application, and by the same applicant, entitled “carbonization of fibrous cellulosic materials in the presence of an organosilicon compound", and the contents are incorporated here by reference, these families being:
  • R represents hydrogen or an alkyl radical, linear or branched, comprising from 1 to 10 carbon atoms, different R being capable of occurring in the same unit, when y>2;
  • R ' represents, independently of R, hydrogen or an alkyl radical, linear or branched, comprising from 1 to 10 carbon atoms, different R' being capable of occurring in the same unit, when z>2; Being heard that : . for oligomers which have a number average molecular mass of less than 1000, it is az # 0, in said formula SiO x R y (OR ') z ; and
  • the organosilicon compound may be a siloxane resin, consisting of units of formula Si0 4 (said units Q), of units of formula Si ⁇ 3 -OH (said units Q 3 ) and of units of formula 0-Si-R 3 (so-called M units), advantageously consisting of ni Q units, n 2 Q 3 units and n 3 M units, with 2 ⁇ ni ⁇ 70, 3 ⁇ n 2 ⁇ 50 and 3 ⁇ n 3 ⁇ 50 and having an average molecular weight in number between 2,500 and 5,000.
  • siloxane resin consisting of units of formula Si0 4 (said units Q), of units of formula Si ⁇ 3 -OH (said units Q 3 ) and of units of formula 0-Si-R 3 (so-called M units), advantageously consisting of ni Q units, n 2 Q 3 units and n 3 M units, with 2 ⁇ ni ⁇ 70, 3 ⁇ n 2 ⁇ 50 and 3 ⁇ n 3 ⁇ 50 and having an average mole
  • the organosilicon compound can also be chosen from the oligomers of a partially hydrolyzed organic silicate, advantageously chosen from the oligomers of a partially hydrolyzed alkyl silicate, and preferably chosen from the oligomers of partially hydrolyzed ethyl silicate.
  • the impregnation is carried out by passing the fabric T through a tank 10 containing the chosen organosilicon compound, in solution in a solvent such as a chlorinated solvent (tetrachlorethylene for example) or acetone.
  • a solvent such as a chlorinated solvent (tetrachlorethylene for example) or acetone.
  • the fabric can be impregnated by passing it through a bath (as illustrated) and / or by spraying the solution of organosilicon compound onto the faces of the fabric. Leaving tray 10, the impregnated fabric is expressed by passing between rollers 12 in order to leave a controlled amount of compound.
  • the impregnated fabric is then admitted into a dryer 14 in order to remove the solvent.
  • the drying is carried out, for example, by a current of hot air against the current of the moving fabric on the fittings 16.
  • the impregnated and dried fabric is ready to be charred. It can be temporarily stored, for example by bamboo in a container or be admitted directly continuously to the carbonization station 18 itself. It will be noted that the fabric may also have been impregnated with at least one mineral, acid or Lewis base additive, for example chosen from halides, sulfates and phosphates of ammonium, sodium, urea and their mixtures and advantageously consists ammonium chloride (NH 4 CI) or diammonium phosphate [(NH) 2 HP0 4 ].
  • the carbonization includes a moderate heat treatment for drying and relaxing the fabric, followed by passage through an oven where the carbonization is effectively carried out.
  • the relaxation treatment is carried out by admitting the tissue into an enclosure 20 at atmospheric pressure and under ambient air.
  • the temperature in the enclosure 20 is regulated at a value between 100 ° C and 250 ° C, for example around 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, passing over return rollers 22, is chosen to obtain the desired residence time as a function of the speed of movement of the fabric.
  • the thermal relaxation treatment allows the internal stresses of the cellulosic fibers to be relaxed, and the water adsorbed by the tissue to be eliminated.
  • the carbonization is then carried out by admitting the tissue into an enclosure 30 enclosing a carbonization chamber 40. Admission of the tissue of cellulosic fibers into the chamber 40, at one end thereof, and extraction of the tissue from carbon out of the chamber 40, at the other end of the latter, are produced through sealing boxes 50, 52. When it enters the box 50, the fabric has returned substantially to ambient temperature.
  • the carbonization chamber is an elongated chamber in which the fabric follows a horizontal rectilinear path.
  • Other configurations of the carbonization chamber could be envisaged, for example a chamber with several adjacent adjacent horizontal or vertical parts in which the fabric is guided by deflection rollers.
  • the chamber 40 is delimited by lower horizontal walls 42a and upper 42b, and vertical lateral walls 42c, 42d, for example made of graphite.
  • the chamber 40 is surrounded by an enclosure 30. Inside the enclosure 30, electrical heating resistors 34 are arranged, near the external faces of the walls 42a, 42b.
  • the interior of the chamber 40 is maintained under a neutral atmosphere, for example under nitrogen injected through pipes 36 respectively near the inlet and the outlet of the chamber.
  • Decomposition products of the cellulose during its carbonization, are extracted from the chamber through one or more chimneys 38.
  • the extraction chimney or chimneys are placed at a level in the oven where the cellulose decomposition mainly occurs.
  • the extracted products can be burned in a flare (not shown).
  • the sealing boxes 50, 52 prevent access to the interior of the chamber 40 by the ambient air, which would have the effect of disturbing the circulation of the gases inside the chamber 40 and of oxidizing the fabric. charred.
  • the sealing boxes 50, 52 also prevent a polluting leak of cellulose decomposition products in the building housing the enclosure 30.
  • sealing box for an enclosure for continuous treatment of thin product in a strip , in particular for a continuous carbonization furnace of fibrous substrates ", the content of which is incorporated here by reference.
  • the carbonization chamber 40 has an elongated rectangular profile ( Figure 2). Between the entry and exit of the chamber 40, the fabric crosses a succession of adjacent zones separated from each other by transverse walls 44a, 44b.
  • the walls 44a for example in graphite, are connected to the upper and lateral walls of the chamber 4, while the walls 44b, for example also in graphite, are connected to the lower and lateral walls of the chamber 40.
  • the ends facing each other walls 44a and 44b define between them a slot 46 for the passage of the fabric.
  • the division of the chamber 40 into several consecutive zones 40 ⁇ , 40 2 , 40 3 , ... makes it possible to define different temperature zones between the entry and the exit of the chamber 40.
  • the temperature is regulated to a predetermined set value.
  • the currents in the resistors 34 are regulated by a control circuit 46 on the basis of information supplied by temperature probes 48 arranged in the different zones 40 ⁇ , 40 2 , 40 3
  • the temperatures in the different zones of the carbonization chamber are determined, as well as the speed of movement of the fabric, as a function of the length of said zones, so that the heat treatment applied to the fabric comprises:
  • the final phase during which the temperature of the fabric is brought to a value between 500 ° C and 750 ° C, the final phase comprising a rise in temperature at a third speed on average greater than the second and between 5 ° C / min and
  • FIG. 3 The corresponding range of thermal profile of the fabric is illustrated in FIG. 3 in solid lines.
  • curve C in dashed lines illustrates a "typical" profile.
  • the initial phase aims to impose an early removal of the weft from the fabric so that it adapts to the geometry of the warp threads.
  • the portion of each warp thread entering the chamber is influenced by the part located downstream exposed to a higher temperature. Imposing rapid heating upon entry into chamber 40 allows the weft to "follow" the withdrawal of the fabric and to avoid the appearance of geometric defects in the fabric.
  • a relatively rapid temperature rise rate 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 temperature rise may be higher at the start of the initial phase than at the end of it.
  • the temperature of the tissue at the end of the initial phase is between 250 ° C and 350 ° C, preferably between 270 ° C and 300 ° C.
  • the intermediate phase is that where most of the cellulose decomposition takes place. In order to maintain good mechanical strength in the fibers, this decomposition must be controlled, that is to say occur with a moderate rate of temperature rise. On average, this speed is between 2 ° C / min and 10 ° C / min, preferably between 4 ° C / min and 6 ° C / min, it being noted that too low a speed would become disadvantageous economically.
  • the temperature of the fabric at the end of the intermediate phase is between 400 ° C and 450 ° C. This temperature is the temperature at which most of the cell's decomposition is carried out.
  • the final phase is where 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 between 500 ° C and 750 ° C, for example between 550 ° C and 650 ° C to reach a sufficiently advanced carbonization stage.
  • the temperature rise may be faster than in the intermediate phase, since the decomposition of cellulose has essentially been carried out.
  • the average speed of temperature rise 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 fabric in the carbonization chamber 40 can be reproduced with all the more precision as the number of zones in the chamber 40 is high, with individual control of the temperature in each zone.
  • the number of zones is at least equal to 3, preferably at least equal to 6.
  • the fabric passes between take-up rollers 54 before being stored, for example in the form of a reel 56.
  • the take-up rollers are associated with drive means (not shown) to control the scrolling of the fabric at the desired speed. It will be noted that due to the withdrawal of the warp threads during carbonization, the speed of entry of the fabric into the chamber 40 is greater than the speed of exit.
  • the residence time of the fabric in chamber 40 is between 20 min and 2 h.
  • a heat treatment at high temperature can be carried out on the charred fabric coming from the chamber 40.
  • This heat treatment is carried out continuously by passing the fabric through an oven 60.
  • This heat treatment aims to achieve structuring of the carbon fibers. It is carried out at a temperature above 1000 ° C., which can range up to 2800 ° C., under a neutral atmosphere, for example under nitrogen.
  • the residence time of the fabric in the oven 60 is preferably between 1 min and 10 min, for example around 2 min.
  • the fabric is taken from the spool 56 and is stored, at the outlet of the oven 60, on a spool 62, being called up by rollers 64.
  • the carbon fabric directly originating from chamber 40 can also be oxidized in a controlled manner by exposure to water vapor or to carbon dioxide, under conditions well known elsewhere for obtaining activated carbon fabric, without treatment. thermal at high temperature.
  • a carbonization installation is used with a chamber divided into 8 zones 40 ⁇ to 40 8 of equal length.
  • Different strips of the same technical rayon fabric consisting of 3600 dtex threads with 11 threads / cm in warp and weft have were carbonized in this installation after having been impregnated with an organosilicon compound constituted by a polyhydromethylsiloxane resin sold by the French company Rhodia Silicones under the reference "RHODORSIL RTV 141 B", and a drying and relaxation treatment at 170 ° C. for 90 min .
  • the chimney (s) for evacuating cellulose decomposition products are located between zones 40 5 and 40 ⁇ .
  • Rayon fiber fabric such as that of the above examples was continuously charred.
  • the same fabric was carbonized under similar conditions with the exception of the carbonization profile, the temperature rise of the fabric having been carried out at a constant speed of 7 ° C / min from room temperature to 650 ° vs.
  • FIG. 4 shows the embossed appearance of the fabric obtained, due to an offset in the shrinkage between the warp and the weft.

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

Abstract

The carbonization of cellulose fiber fabric comprises an initial stage of heat treatment up to 250° C. to 350° C., with a relatively high mean temperature rise speed of 10° C./min to 60° C./min, an intermediate stage up to 350° C. to 500° C. with a lower mean temperature rise speed of 2° C./min to 10° C./min, and a final stage up to 500° C. to 750° C. with a mean temperature rise speed that is again raised to 5° C./min to 40° C./min.

Description

PROCEDE POUR L'OBTENTION DE TISSϋ EN FIBRES DE CARBONE PAR CARBONISATION EN CONTINU D'UN TISSU EN FIBRES CELLULOSIQUESPROCESS FOR OBTAINING CARBON FIBER TISSUE BY CONTINUOUS CARBONIZATION OF A CELLULOSIC FIBER TISSUE
Domaine de l'inventionField of the invention
L'invention concerne la fabrication de tissus en fibres de carbone à partir de tissus en fibres en matériau cellulosique précurseur du carbone.The invention relates to the manufacture of carbon fiber fabrics from fiber fabrics of carbon precursor cellulosic material.
L'invention vise plus particulièrement, mais non exclusivement, la fabrication de tissu en fibres de carbone par carbonisation d'un tissu en fibres de viscose, notamment en fibres de rayonne.The invention relates more particularly, but not exclusively, to the manufacture of carbon fiber fabric by carbonization of a fabric made of viscose fibers, in particular rayon fibers.
Arrière-plan de l'inventionInvention background
Les fibres de carbone à précurseur cellulosique présentent généralement une structure poreuse formée de carbone turbostratique très désorganisé, cette structure étant en outre très désorientée par rapport à la direction axiale des fibres et à leur réseau de pores.Carbon fibers with a cellulose precursor generally have a porous structure formed from highly disorganized turbostratic carbon, this structure being furthermore very disoriented with respect to the axial direction of the fibers and their network of pores.
Ces caractéristiques confèrent aux fibres de carbone une faible conductivité thermique, ce qui les rend particulièrement aptes à la formation de revêtements de protection thermique, tels que des revêtements ablatifs pour des chambres de combustion et tuyères de propulseurs.These characteristics give carbon fibers a low thermal conductivity, which makes them particularly suitable for the formation of thermal protective coatings, such as ablative coatings for combustion chambers and propellant nozzles.
D'autres applications ont été envisagées pour les tissus en fibres de carbone à précurseur cellulosique, notamment la réalisation de résistances chauffantes, la réalisation d'électrodes de batteries ou de supports de catalyseurs, ou la formation de tissus activés utilisés comme matériaux adsorbants.Other applications have been envisaged for carbon fiber fabrics with a cellulose precursor, in particular the production of heating resistors, the production of battery electrodes or catalyst supports, or the formation of activated fabrics used as adsorbent materials.
Des procédés d'obtention de tissus en fibres de carbone à précurseur cellulosique sont connus. On pourra se référer notamment aux brevets US 3 053 775, US 3 107 152, US 3 305 315 et US 3 663 173.Processes for obtaining carbon fiber fabrics with a cellulose precursor are known. We can refer in particular to US Patents 3,053,775, US 3,107,152, US 3,305,315 and US 3,663,173.
Un procédé couramment utilisé consiste à réaliser une carbonisation directe d'un tissu en fibres cellulosiques, notamment un tissu de viscose. Le tissu est mis sous forme d'un écheveau d'une longueur d'une à plusieurs centaines de mètres. Il est précarbonisé jusqu'à une température d'environ 400°C. La précarbonisation est réalisée dans un conteneur de préférence sous atmosphère neutre, par exemple avec balayage par de l'azote. Les effluents provenant de la décomposition de la cellulose sont aspirés et brûlés dans une torchère.A commonly used method consists in carrying out a direct carbonization of a fabric made of cellulosic fibers, in particular a viscose fabric. The fabric is put in the form of a skein with a length of one to several hundred meters. It is precarbonized up to a temperature of around 400 ° C. Precarbonisation is carried out in a container preferably in a neutral atmosphere, for example with nitrogen sweep. The effluents from the decomposition of cellulose are sucked and burned in a flare.
La montée en température est très lente, pour respecter la cinétique de décomposition de la cellulose, afin d'obtenir un rendement correct en carbone, et pour éviter un emballement de la réaction de décomposition, qui est exothermique, un tel emballement pouvant anéantir les propriétés mécaniques des fibres de carbone obtenues. A titre d'exemple, pour un echeveau de 100 mètres, la précarbonisation peut durer jusqu'à 15 jours, ce qui est extrêmement long. La phase de pré-carbonisation est suivie par un traitement thermique à une température d'environ 1200°C pendant environ 1 à 2 min. Un traitement final à haute température, pouvant par exemple atteindre 2800°C, peut être effectué pour augmenter la conductibilité du carbone et fermer sa porosité. Un procédé et une installation permettant d'obtenir un tissu en fibres de carbone par carbonisation en continu d'un tissu en fibres cellulosiques, avec une durée de traitement thermique beaucoup moins longue, sont décrits dans les brevets RU 2 005 829, RU 2 045 472 et RU 2 047 674. Le tissu précurseur, par exemple en fibres de viscose technique, est imprégné par un composé organosilicié ayant pour effet de conserver de bonnes propriétés mécaniques pour le tissu en fibres de carbone obtenu. Le composé organosilicié est choisi parmi les composés du groupe des polydiméthylphénylallylsilanes, polysiloxanes, polyméthyl- siloxanes, polysilazanes, polyalumino-organosiloxanes.The rise in temperature is very slow, to respect the kinetics of decomposition of the cellulose, in order to obtain a correct carbon yield, and to avoid a runaway of the decomposition reaction, which is exothermic, such runaway can destroy the properties. mechanics of the carbon fibers obtained. For example, for a skein of 100 meters, precarbonization can last up to 15 days, which is extremely long. The pre-carbonization phase is followed by a heat treatment at a temperature of about 1200 ° C for about 1 to 2 min. A final treatment at high temperature, which can for example reach 2800 ° C., can be carried out to increase the conductivity of the carbon and to close its porosity. A method and an installation making it possible to obtain a carbon fiber fabric by continuous carbonization of a cellulose fiber fabric, with a much shorter heat treatment duration, are described in patents RU 2 005 829, RU 2 045 472 and RU 2 047 674. The precursor fabric, for example in technical viscose fibers, is impregnated with an organosilicon compound having the effect of retaining good mechanical properties for the fabric of carbon fibers obtained. The organosilicon compound is chosen from compounds from the group of polydimethylphenylallylsilanes, polysiloxanes, polymethylsiloxanes, polysilazanes, polyalumino-organosiloxanes.
Le tissu imprégné est soumis à un traitement thermique en continu sous air à une température comprise entre 100°C et 300°C, plus particulièrement entre 100°C et 150°C, pour provoquer une relaxation des contraintes qui existent dans les fibres cellulosiques et éliminer l'eau adsorbée par les fibres.The impregnated fabric is subjected to a continuous heat treatment in air at a temperature between 100 ° C and 300 ° C, more particularly between 100 ° C and 150 ° C, to induce a relaxation of the stresses which exist in cellulosic fibers and remove the water adsorbed by the fibers.
La carbonisation est ensuite réalisée sur le tissu défilant en continu dans une enceinte sous atmosphère inerte, en élevant la température progressivement jusqu'à 300°C à 600°C. Un traitement à haute température, au maximum jusqu'à 280C°C sous atmosphère inerte, est ensuite réalisé. Lors de la carbonisation, les effluents gazeux de pyrolyse de la cellulose sont aspirés et brûlés en torchère, les moyens d'aspiration étant localisés au niveau de l'enceinte où se produit le maximum de dégradation de la cellulose. Ce procédé permet d'obtenir des propriétés mécaniques satisfaisantes pour les fibres de carbone, mais conduit à des déformations du tissu obtenu, telles que désorganisation du tissage et embuvage.The carbonization is then carried out on the continuously passing fabric in an enclosure under an inert atmosphere, gradually raising the temperature to 300 ° C to 600 ° C. A treatment at high temperature, at most up to 280 ° C. under an inert atmosphere, is then carried out. During carbonization, the gaseous effluents from the pyrolysis of the cellulose are sucked and burnt in a flare, the suction means being located at the level of the enclosure where the maximum degradation of the cellulose occurs. This process makes it possible to obtain satisfactory mechanical properties for the carbon fibers, but leads to deformations of the fabric obtained, such as disorganization of the weaving and embuvage.
De telles déformations ne sont pas acceptables, notamment lorsque le tissu doit être utilisé pour la réalisation de préformes de pièces en matériau composite, car elles entraînent une hétérogénéité de répartition des fibres dans la préforme, ce qui affecte la tenue des pièces en matériau composite renforcées par ces tissus.Such deformations are not acceptable, in particular when the fabric is to be used for the production of preforms of parts made of composite material, because they lead to a heterogeneity of distribution of the fibers in the preform, which affects the behavior of the parts made of reinforced composite material. by these fabrics.
Objet et résumé de l'invention L'invention a pour but d'éviter ces inconvénients en proposant un procédé d'obtention de tissu en fibres de carbone, par carbonisation de tissu en fibres cellulosiques, grâce auquel un tissu en fibres de carbone obtenu ne présente pas de déformation sensible.OBJECT AND SUMMARY OF THE INVENTION The object of the invention is to avoid these drawbacks by proposing a process for obtaining carbon fiber fabric, by carbonization of cellulose fiber fabric, by which a carbon fiber fabric obtained does not shows no significant deformation.
Ce but est atteint grâce à un procédé selon lequel on soumet un tissu défilant en continu dans une chambre de carbonisation à un traitement thermique comprenant :This object is achieved by a process according to which a continuously moving fabric is subjected in a carbonization chamber to a heat treatment comprising:
- une phase initiale pour amener la température du tissu à une valeur comprise entre 250°C et 350°C, la phase initiale comprenant une montée en température à une première vitesse moyenne comprise entre 10°C/min et 60°C/min,an initial phase for bringing the temperature of the fabric to a value between 250 ° C and 350 ° C, the initial phase comprising a rise in temperature at a first average speed of between 10 ° C / min and 60 ° C / min,
- une phase intermédiaire pour élever la température du tissu jusqu'à une valeur comprise entre 350°C et 500°C, la phase intermédiaire comprenant une montée en température à une deuxième vitesse moyenne inférieure à la première et comprise entre 2°C/min et 10°C/min, et- an intermediate phase to raise the temperature of the fabric to a value between 350 ° C and 500 ° C, the intermediate phase comprising a rise in temperature at a second average speed lower than the first and between 2 ° C / min and 10 ° C / min, and
- une phase finale pour élever la température du tissu jusqu'à une valeur comprise entre 500°C et 750°C, la phase finale comprenant une montée en température à une troisième vitesse moyenne supérieure à la deuxième et comprise entre 5°C/min et 40°C/min. Le choix de ce profil particulier de température lors de la carbonisation répond au souci de rechercher le meilleur compromis entre la qualité de la carbonisation, de laquelle dépend notamment la tenue mécanique des fibres, la qualité d'aspect du tissu, c'est-à-dire l'absence d'embuvage notable et le respect de la géométrie chaîne/trame, et le maintien des coûts de production à un niveau acceptable. Lors de sa carbonisation, un fil en fibres cellulosiques subit un retrait important. Celui-ci peut atteindre 30 à 40 % lorsque le fil est libre de toute tension.- a final phase to raise the temperature of the fabric to a value between 500 ° C and 750 ° C, the final phase comprising a rise in temperature at a third average speed greater than the second and between 5 ° C / min and 40 ° C / min. The choice of this particular temperature profile during carbonization responds to the concern of finding the best compromise between the quality of the carbonization, on which depends in particular the mechanical strength of the fibers, the quality of the appearance of the fabric, that is to say the absence of significant baking and respect for the warp / weft geometry, and the keeping production costs at an acceptable level. During its carbonization, a thread made of cellulosic fibers undergoes a significant shrinkage. This can reach 30 to 40% when the thread is free of any tension.
Dans le cas d'un tissu subissant un processus de carbonisation en continu, le retrait des fils de trame est pratiquement libre et atteint donc quasiment la valeur maximale.In the case of a fabric undergoing a process of continuous carbonization, the withdrawal of the weft threads is practically free and therefore reaches almost the maximum value.
Le retrait des fils de trame entre l'entrée et la sortie de la chambre impose une convergence (rapprochement progressif) des fils de chaîne. Une situation favorable à l'obtention d'un tissu en fibres de carbone sans embuvage excessif et sans déformation de géométrie serait celle où, le long du trajet dans la chambre, le retrait affecte sensiblement de la même façon les fils de trame et les fils de chaîne.The withdrawal of the weft threads between the inlet and the outlet of the chamber imposes a convergence (progressive approximation) of the warp threads. A favorable situation for obtaining a carbon fiber fabric without excessive fogging and without deformation of geometry would be that where, along the path in the chamber, the shrinkage affects in the same way the weft threads and the threads chain.
Toutefois, alors que chaque fil de trame est en isothermie, les fils de chaîne qui s'étendent parallèlement à la direction de défilement du tissu dans la chambre ne sont pas en isothermie. La température à laquelle un même fil de chaîne est exposée varie entre sa portion exposée à la température la plus basse, avant entrée dans la chambre et la portion exposée à la température la plus élevée, à l'autre extrémité de la chambre.However, while each weft thread is in isothermal, the warp threads which extend parallel to the direction of travel of the fabric in the chamber are not in isothermal. The temperature to which the same warp wire is exposed varies between its portion exposed to the lowest temperature, before entering the chamber and the portion exposed to the highest temperature, at the other end of the chamber.
En outre, alors que le retrait des fils de trame est pratiquement libre, celui des fils de chaîne reste plus ou moins légèrement inférieur à la valeur maximale possible en raison de la tension exercée inévitablement sur les fils de chaîne par les moyens de support et d'entraînement du tissu en défilement continu.In addition, while the withdrawal of the weft threads is practically free, that of the warp threads remains more or less slightly lower than the maximum possible value due to the tension inevitably exerted on the warp threads by the support means and d entrainment of the fabric in continuous scrolling.
Le profil de température selon le procédé de l'invention vise à répondre à un premier souci, qui est d'induire sur les fils de trame un retrait permettant de respecter la géométrie du tissu lors de son retrait pour éviter l'embuvage ou la désorganisation du tissu. C'est ainsi que, dans une phase initiale après entrée du tissu dans l'enceinte, l'élévation de température est relativement rapide, pour imposer un retrait précoce aux fils de trame. Le profil de température vise aussi à répondre à un deuxième souci, qui est d'obtenir une bonne qualité mécanique de fils de carbone résultant de la carbonisation. C'est ainsi que, dans une phase intermédiaire, où se produit l'essentiel de la décomposition de la cellulose, l'élévation de température est plus lente pour respecter au mieux la cinétique de décomposition. Le choix d'une vitesse moyenne de montée en température comprise entre 2°C et 10°C permet de répondre à ce souci de façon satisfaisante, sans imposer une longueur de trajet excessive au tissu. La phase finale de carbonisation, qui vise essentiellement à conférer au carbone la structure désirée, peut être conduite avec à nouveau une élévation de température plus rapide, l'essentiel du retrait en chaîne et en trame ayant été observé, afin de réduire la durée totale de la carbonisation, donc les coûts de production. Selon une particularité du procédé, on fait défiler le tissu dans la chambre de carbonisation à travers des zones successives dans chacune desquelles règne une température contrôlée.The temperature profile according to the process of the invention aims to respond to a first concern, which is to induce on the weft yarns a shrinkage making it possible to respect the geometry of the fabric during its shrinkage to avoid bogging or disorganization fabric. Thus, in an initial phase after entry of the fabric into the enclosure, the temperature rise is relatively rapid, in order to impose an early withdrawal on the weft threads. The temperature profile also aims to respond to a second concern, which is to obtain good mechanical quality of carbon wires resulting from carbonization. Thus, in an intermediate phase, where most of the decomposition of the cellulose takes place, the temperature rise is slower to best respect the decomposition kinetics. The choice of an average temperature rise speed of between 2 ° C and 10 ° C makes it possible to respond to this concern satisfactorily, without imposing an excessive path length on the fabric. The final carbonization phase, which essentially aims to give the desired structure to the carbon, can be carried out again with a faster rise in temperature, most of the warp and weft removal having been observed, in order to reduce the total time. carbonization, so production costs. According to a particular feature of the process, the fabric is passed through the carbonization chamber through successive zones in each of which a controlled temperature prevails.
Selon une autre particularité du procédé, le temps de séjour du tissu dans la chambre est compris entre 20 min et 2 h. La carbonisation est donc extrêmement rapide.According to another particular feature of the process, the residence time of the fabric in the chamber is between 20 min and 2 h. Carbonization is therefore extremely rapid.
Selon encore un autre particularité du procédé, on soumet le tissu, avant carbonisation, à un traitement de relaxation à une température comprise entre 100°C et 250°C, de préférence sous air et pendant une durée par exemple comprise entre 15 min et 3 h.According to yet another particular feature of the process, the fabric is subjected, before carbonization, to a relaxation treatment at a temperature between 100 ° C. and 250 ° C., preferably in air and for a duration for example between 15 min and 3 h.
Brève description des dessinsBrief description of the drawings
D'autres particularités et avantages de l'invention ressortiront à la lecture de la description, faite ci-après à titre indicatif mais non limitatif, en référence aux dessins annexés sur lesquels : - la figure 1 est une vue très schématique en coupe longitudinale d'une installation de carbonisation en continu pour l'obtention de tissus en fibres de carbone ;Other features and advantages of the invention will emerge on reading the description, given below for information but not limitation, with reference to the accompanying drawings in which: - Figure 1 is a very schematic view in longitudinal section d '' a continuous carbonization installation for obtaining carbon fiber fabrics;
- la figure 2 est une vue en coupe transversale selon le pian ll-ll de la figure 1 ; - la figure 3 illustre une plage de profil thermique d'un tissu à l'intérieur d'une chambre de carbonisation selon un procédé conforme à l'invention ; et- Figure 2 is a cross-sectional view along the plane ll-ll of Figure 1; - Figure 3 illustrates a range of thermal profile of a fabric inside a carbonization chamber according to a method according to the invention; and
- la figure 4 montre un tissu obtenu par mise en oeuvre d'un procédé autre que celui de l'invention.- Figure 4 shows a fabric obtained by implementing a method other than that of the invention.
Description détaillée de modes de réalisation de l'inventionDetailed description of embodiments of the invention
Une installation de carbonisation en continu d'un tissu en fibres cellulosiques est montrée très schématiquement sur la figure 1. La carbonisation est effectuée sur un tissu T en fibres cellulosiques, par exemple en fibres de viscose technique, auquel a été ajouté un composé organosilicié qui agit, lors de la décomposition de la cellulose, pour que les fibres de carbone obtenues conservent de bonnes propriétés mécaniques. A cet effet, le tissu de viscose T, à l'état sec et débarrassé de tout ensimage, est imprégné par passage dans un bain contenant ledit composé organosilicié en solution. Comme indiqué plus haut, le composé organosilicié peut être choisi parmi des polysiloxanes. De préférence, on utilise un polysiloxane choisi dans les familles définies dans les demandes de brevet français déposées simultanément avec la présente demande, et par la même déposante, intitulées "carbonisation de matériaux fibreux cellulosiques en présence d'un composé organosilicié", et dont les contenus sont incorporés ici par référence, ces familles étant :An installation for the continuous carbonization of a fabric of cellulosic fibers is shown very schematically in FIG. 1. The carbonization is carried out on a fabric T of cellulosic fibers, for example of technical viscose fibers, to which has been added an organosilicon compound which acts, during the decomposition of the cellulose, so that the carbon fibers obtained retain good mechanical properties. To this end, the viscose fabric T, in the dry state and free of any size, is impregnated by passage through a bath containing said organosilicon compound in solution. As indicated above, the organosilicon compound can be chosen from polysiloxanes. Preferably, a polysiloxane chosen from the families defined in the French patent applications filed simultaneously with the present application, and by the same applicant, entitled "carbonization of fibrous cellulosic materials in the presence of an organosilicon compound", and the contents are incorporated here by reference, these families being:
- celle des polyhydrosiloxanes, cycliques, linéaires ou ramifiés, substitués par des groupes méthyles et/ou phényles, dont la masse moléculaire moyenne en nombre est comprise entre 250 et 10 000, avantageusement entre 2 500 et 5 000 ; et- that of polyhydrosiloxanes, cyclic, linear or branched, substituted by methyl and / or phenyl groups, the number average molecular mass of which is between 250 and 10,000, advantageously between 2,500 and 5,000; and
- celle des oligomères et résines, réticulés, cycliques ou ramifiés, qui présentent une masse moléculaire en nombre comprise entre 500 et 10 000 et qui sont constitués de motifs de formule Si04 (dits motifs Q4) et de motifs de formule SiOxRy(OR')z dans laquelle : . x, y et z sont des nombres entiers, tels que x + y + z = 4 et 1 < x < 3 0 < y < 3 0 < z < 3 ; . R représente l'hydrogène ou un radical alkyle, linéaire ou ramifié, comportant de 1 à 10 atomes de carbone, des R différents étant susceptibles d'intervenir dans un même motif, lorsque y > 2 ;- that of oligomers and resins, crosslinked, cyclic or branched, which have a number-average molecular mass between 500 and 10,000 and which consist of units of formula Si0 4 (said units Q 4 ) and of units of formula SiO x R y (OR ') z in which: . x, y and z are whole numbers, such that x + y + z = 4 and 1 <x <3 0 <y <3 0 <z <3; . R represents hydrogen or an alkyl radical, linear or branched, comprising from 1 to 10 carbon atoms, different R being capable of occurring in the same unit, when y>2;
. R' représente, indépendamment de R, l'hydrogène ou un radical alkyle, linéaire ou ramifié, comportant de 1 à 10 atomes de carbone, des R' différents étant susceptibles d'intervenir dans un même motif, lorsque z > 2 ; étant entendu que : . pour les oligomères qui présentent une masse molé- culaire moyenne en nombre inférieure à 1 000, on a z # 0, dans ladite formule SiOxRy(OR')z ; et. R 'represents, independently of R, hydrogen or an alkyl radical, linear or branched, comprising from 1 to 10 carbon atoms, different R' being capable of occurring in the same unit, when z>2; Being heard that : . for oligomers which have a number average molecular mass of less than 1000, it is az # 0, in said formula SiO x R y (OR ') z ; and
. pour les résines qui présentent une masse moléculaire moyenne en nombre supérieure à 2 000, on a y # 0, dans ladite formule SiOxRy(OR')z. En particulier, le composé organosilicié peut être une résine siloxane, constituée de motifs de formule Si04 (dits motifs Q ), de motifs de formule Siθ3-OH (dits motifs Q3) et de motifs de formule 0-Si-R3 (dits motifs M), avantageusement constituée de n-i motifs Q , n2 motifs Q3 et n3 motifs M, avec 2 < n-i < 70, 3 < n2 < 50 et 3 < n3 < 50 et présentant une masse moléculaire moyenne en nombre comprise entre 2 500 et 5 000.. for resins which have a number average molecular mass greater than 2,000, there is # 0, in said formula SiO x R y (OR ') z . In particular, the organosilicon compound may be a siloxane resin, consisting of units of formula Si0 4 (said units Q), of units of formula Siθ 3 -OH (said units Q 3 ) and of units of formula 0-Si-R 3 (so-called M units), advantageously consisting of ni Q units, n 2 Q 3 units and n 3 M units, with 2 <ni <70, 3 <n 2 <50 and 3 <n 3 <50 and having an average molecular weight in number between 2,500 and 5,000.
Le composé organosilicié peut aussi être choisi parmi les oligomères d'un silicate organique partiellement hydrolyse, avantageusement choisi parmi les oligomères d'un silicate d'alkyle partiellement hydrolyse, et de préférence choisi parmi les oligomères du silicate d'éthyle partiellement hydrolyse.The organosilicon compound can also be chosen from the oligomers of a partially hydrolyzed organic silicate, advantageously chosen from the oligomers of a partially hydrolyzed alkyl silicate, and preferably chosen from the oligomers of partially hydrolyzed ethyl silicate.
L'imprégnation est réalisée en faisant défiler le tissu T dans un bac 10 contenant le composé organosilicié choisi, en solution dans un solvant tel qu'un solvant chloré (tétrachloréthylène par exemple) ou de l'acétone. L'imprégnation du tissu peut être réalisée par passage dans un bain (comme illustré) et/ou par projection de la solution de composé organosilicié sur les faces du tissu. En sortie du bac 10, le tissu imprégné est exprimé par passage entre des rouleaux 12 afin de laisser subsister une quantité contrôlée de composé.The impregnation is carried out by passing the fabric T through a tank 10 containing the chosen organosilicon compound, in solution in a solvent such as a chlorinated solvent (tetrachlorethylene for example) or acetone. The fabric can be impregnated by passing it through a bath (as illustrated) and / or by spraying the solution of organosilicon compound onto the faces of the fabric. Leaving tray 10, the impregnated fabric is expressed by passing between rollers 12 in order to leave a controlled amount of compound.
Le tissu imprégné est ensuite admis dans un séchoir 14 afin d'éliminer le solvant. Le séchage est réalisé par exemple par courant d'air chaud à contre-courant du tissu défilant sur des embarrages 16.The impregnated fabric is then admitted into a dryer 14 in order to remove the solvent. The drying is carried out, for example, by a current of hot air against the current of the moving fabric on the fittings 16.
Le tissu imprégné et séché est prêt à être carbonisé. Il peut être provisoirement stocké, par exemple par bambannage dans un conteneur ou être admis directement en continu au poste de carbonisation 18 proprement dit. On notera que le tissu pourra avoir été aussi imprégné d'au moins un additif minéral, acide ou base de Lewis, par exemple choisi parmi les halogénures, sulfates et phosphates d'ammonium, de sodium, l'urée et leurs mélanges et consiste avantageusement en le chlorure d'ammonium (NH4CI) ou le phosphate diammonique [(NH )2HP04]. La carbonisation comprend un traitement thermique modéré de séchage et de relaxation du tissu suivi du passage dans un four où la carbonisation est effectivement réalisée.The impregnated and dried fabric is ready to be charred. It can be temporarily stored, for example by bamboo in a container or be admitted directly continuously to the carbonization station 18 itself. It will be noted that the fabric may also have been impregnated with at least one mineral, acid or Lewis base additive, for example chosen from halides, sulfates and phosphates of ammonium, sodium, urea and their mixtures and advantageously consists ammonium chloride (NH 4 CI) or diammonium phosphate [(NH) 2 HP0 4 ]. The carbonization includes a moderate heat treatment for drying and relaxing the fabric, followed by passage through an oven where the carbonization is effectively carried out.
Le traitement de relaxation est effectué par admission du tissu dans une enceinte 20 à la pression atmosphérique et sous air ambiant. La température dans l'enceinte 20 est régulée à une valeur comprise entre 100°C et 250°C, par exemple environ 130°C. Le temps de séjour dans l'enceinte 20 est de préférence compris entre 15 min et 3 h. La longueur du trajet du tissu dans l'enceinte, avec passage sur des rouleaux de renvoi 22, est choisie pour obtenir le temps de séjour désiré en fonction de la vitesse de défilement du tissu. Le traitement thermique de relaxation permet un relâchement des contraintes internes des fibres cellulosiques, et une élimination de l'eau adsorbée par le tissu.The relaxation treatment is carried out by admitting the tissue into an enclosure 20 at atmospheric pressure and under ambient air. The temperature in the enclosure 20 is regulated at a value between 100 ° C and 250 ° C, for example around 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, passing over return rollers 22, is chosen to obtain the desired residence time as a function of the speed of movement of the fabric. The thermal relaxation treatment allows the internal stresses of the cellulosic fibers to be relaxed, and the water adsorbed by the tissue to be eliminated.
La carbonisation est ensuite réalisée par admission du tissu dans une enceinte 30 renfermant une chambre de carbonisation 40. L'admission du tissu de fibres cellulosiques dans la chambre 40, à une extrémité de celle-ci, et l'extraction du tissu de fibres de carbone hors de la chambre 40, à l'autre extrémité de celle-ci, sont réalisées à travers des boîtes d'étanchéité 50, 52. A son entrée dans la boîte 50, le tissu est revenu sensiblement à la température ambiante. Dans l'exemple illustré, la chambre de carbonisation est une chambre allongée dans laquelle le tissu suit un trajet rectiligne horizontal. D'autres configurations de la chambre de carbonisation pourront être envisagées, par exemple une chambre avec plusieurs parties adjacentes consécutives horizontales ou verticales dans lesquelles le tissu est guidé par des rouleaux de renvoi. La chambre 40 est délimitée par des parois horizontales inférieure 42a et supérieure 42b, et des parois latérales verticales 42ç, 42d, par exemple en graphite. La chambre 40 est entourée par une enceinte 30. A l'intérieur de l'enceinte 30, des résistances électriques de chauffage 34 sont disposées, à proximité des faces externes des parois 42a, 42b.The carbonization is then carried out by admitting the tissue into an enclosure 30 enclosing a carbonization chamber 40. Admission of the tissue of cellulosic fibers into the chamber 40, at one end thereof, and extraction of the tissue from carbon out of the chamber 40, at the other end of the latter, are produced through sealing boxes 50, 52. When it enters the box 50, the fabric has returned substantially to ambient temperature. In the example illustrated, the carbonization chamber is an elongated chamber in which the fabric follows a horizontal rectilinear path. Other configurations of the carbonization chamber could be envisaged, for example a chamber with several adjacent adjacent horizontal or vertical parts in which the fabric is guided by deflection rollers. The chamber 40 is delimited by lower horizontal walls 42a and upper 42b, and vertical lateral walls 42c, 42d, for example made of graphite. The chamber 40 is surrounded by an enclosure 30. Inside the enclosure 30, electrical heating resistors 34 are arranged, near the external faces of the walls 42a, 42b.
L'intérieur de la chambre 40 est maintenu sous atmosphère neutre, par exemple sous azote injecté par des canalisations 36 respectivement à proximité de l'entrée et de la sortie de la chambre. Des produits de décomposition de la cellulose, lors de sa carbonisation, sont extraits de la chambre à travers une ou plusieurs cheminées 38. La ou les cheminées d'extraction sont placées à un niveau du four où se produit principalement la décomposition de la cellulose. Les produits extraits peuvent être brûlés en torchère (non représentée).The interior of the chamber 40 is maintained under a neutral atmosphere, for example under nitrogen injected through pipes 36 respectively near the inlet and the outlet of the chamber. Decomposition products of the cellulose, during its carbonization, are extracted from the chamber through one or more chimneys 38. The extraction chimney or chimneys are placed at a level in the oven where the cellulose decomposition mainly occurs. The extracted products can be burned in a flare (not shown).
Les boîtes d'étanchéité 50, 52 évitent un accès à l'intérieur de la chambre 40 par l'air ambiant, ce qui aurait pour effet de perturber la circulation des gaz à l'intérieur de la chambre 40 et d'oxyder le tissu carbonisé. Les boîtes d'étanchéité 50, 52 évitent aussi une fuite polluante de produits de décomposition de la cellulose dans le bâtiment abritant l'enceinte 30. On utilise avantageusement, au moins pour la boîte d'étanchéité d'entrée 50, une combinaison d'étanchéité statique par boudin gonflable venant au contact du tissu avec un minimum de frottement, et d'étanchéité dynamique par barrière formée par injection de gaz neutre. Un mode de réalisation d'une telle boîte d'étanchéité est décrit dans la demande de brevet français déposée simultanément avec la présente demande et par la même déposante, intitulée "boîte d'étanchéité pour une enceinte de traitement en continu de produit mince en bande, notamment pour four de carbonisation en continu de substrats fibreux", et dont le contenu est incorporé ici par référence.The sealing boxes 50, 52 prevent access to the interior of the chamber 40 by the ambient air, which would have the effect of disturbing the circulation of the gases inside the chamber 40 and of oxidizing the fabric. charred. The sealing boxes 50, 52 also prevent a polluting leak of cellulose decomposition products in the building housing the enclosure 30. Advantageously, at least for the inlet sealing box 50, a combination of static sealing by inflatable tube coming into contact with the fabric with a minimum of friction, and dynamic sealing by barrier formed by injection of neutral gas. One embodiment of such a sealing box is described in the French patent application filed simultaneously with the present application and by the same applicant, entitled "sealing box for an enclosure for continuous treatment of thin product in a strip , in particular for a continuous carbonization furnace of fibrous substrates ", the content of which is incorporated here by reference.
En coupe transversale, la chambre de carbonisation 40 présente un profil rectangulaire allongé (figure 2). Entre l'entrée et la sortie de la chambre 40, le tissu traverse une succession de zones adjacentes séparées les unes des autres par des parois transversales 44a, 44b. Les parois 44a, par exemple en graphite, se raccordent aux parois supérieure et latérales de la chambre 4, tandis que les parois 44b, par exemple également en graphite, se raccordent aux parois inférieure et latérales de la chambre 40. Les extrémités se faisant face des parois 44a et 44b délimitent entre elles une fente 46 pour le passage du tissu.In cross section, the carbonization chamber 40 has an elongated rectangular profile (Figure 2). Between the entry and exit of the chamber 40, the fabric crosses a succession of adjacent zones separated from each other by transverse walls 44a, 44b. The walls 44a, for example in graphite, are connected to the upper and lateral walls of the chamber 4, while the walls 44b, for example also in graphite, are connected to the lower and lateral walls of the chamber 40. The ends facing each other walls 44a and 44b define between them a slot 46 for the passage of the fabric.
Le partage de la chambre 40 en plusieurs zones consécutives 40ι, 402, 403, ... permet de définir différentes zones de température entre l'entrée et la sortie de la chambre 40. Dans chaque zone, la température est régulée à une valeur de consigne prédéterminée. A cet effet, les courants dans les résistances 34 sont régulés par un circuit de commande 46 à partir d'informations fournies par des sondes de température 48 disposées dans les différentes zones 40ι, 402, 403 The division of the chamber 40 into several consecutive zones 40ι, 40 2 , 40 3 , ... makes it possible to define different temperature zones between the entry and the exit of the chamber 40. In each zone, the temperature is regulated to a predetermined set value. To this end, the currents in the resistors 34 are regulated by a control circuit 46 on the basis of information supplied by temperature probes 48 arranged in the different zones 40ι, 40 2 , 40 3
Selon l'invention, les températures dans les différentes zones de la chambre de carbonisation sont déterminées, ainsi que la vitesse de défilement du tissu, fonction de la longueur desdites zones, pour que le traitement thermique appliqué au tissu comprenne :According to the invention, the temperatures in the different zones of the carbonization chamber are determined, as well as the speed of movement of the fabric, as a function of the length of said zones, so that the heat treatment applied to the fabric comprises:
- une phase initiale au cours de laquelle la température du tissu est amenée à une valeur comprise entre 250°C et 350°C, avec une montée en température du tissu à une première vitesse en moyenne comprise entre 10°C/min et 60°C/min,- an initial phase during which the temperature of the fabric is brought to a value between 250 ° C and 350 ° C, with a rise in temperature of the fabric at a first speed on average between 10 ° C / min and 60 ° C / min,
- une phase intermédiaire au cours de laquelle la température du tissu est amenée jusqu'à une valeur comprise entre 350°C et 500°C, avec une montée en température du tissu à une deuxième vitesse en moyenne inférieure à la première et comprise entre 2°C/min et 10°C/min, et- an intermediate phase during which the temperature of the fabric is brought to a value between 350 ° C and 500 ° C, with a rise in temperature of the fabric at a second speed on average lower than the first and between 2 ° C / min and 10 ° C / min, and
- une phase finale au cours de laquelle la température du tissu est amenée à une valeur comprise entre 500°C et 750°C, la phase finale comprenant une montée en température à une troisième vitesse en moyenne supérieure à la deuxième et comprise entre 5°C/min et- a final phase during which the temperature of the fabric is brought to a value between 500 ° C and 750 ° C, the final phase comprising a rise in temperature at a third speed on average greater than the second and between 5 ° C / min and
40°C/min.40 ° C / min.
La plage correspondante de profil thermique du tissu est illustrée par la figure 3 en traits pleins. Sur cette figure 3, la courbe C en traits mixtes illustre un profil "typique". La phase initiale vise à imposer un retrait précoce de la trame du tissu afin que celle-ci s'adapte à la géom étrie des fils de chaîne. En effet, alors que les fils de trame s'échauffent progressivement après leur entrée dans la chambre de combustion, la portion de chaque fil de chaîne pénétrant dans la chambre est influencée par la partie située en aval exposée à une température plus élevée. Le fait d'imposer un échauffement rapide dès l'entrée dans la chambre 40 permet à la trame de "suivre" le retrait du tissu et d'éviter l'apparition de défauts géométriques dans le tissu.The corresponding range of thermal profile of the fabric is illustrated in FIG. 3 in solid lines. In this FIG. 3, curve C in dashed lines illustrates a "typical" profile. The initial phase aims to impose an early removal of the weft from the fabric so that it adapts to the geometry of the warp threads. In Indeed, while the weft threads gradually heat up after entering the combustion chamber, the portion of each warp thread entering the chamber is influenced by the part located downstream exposed to a higher temperature. Imposing rapid heating upon entry into chamber 40 allows the weft to "follow" the withdrawal of the fabric and to avoid the appearance of geometric defects in the fabric.
C'est pourquoi une vitesse de montée en température relativement rapide est choisie. Elle est en moyenne comprise entre 10°C/min et 60°C/min, de préférence entre 10°C/min et 40°C/min. La vitesse de montée en température pourra être plus élevée au début de la phase initiale qu'à la fin de celle-ci.This is why a relatively rapid temperature rise rate 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 temperature rise may be higher at the start of the initial phase than at the end of it.
La température du tissu en fin de phase initiale est comprise entre 250°C et 350°C, de préférence entre 270°C et 300°C. La phase intermédiaire est celle où se produit l'essentiel de la décomposition de la cellulose. Afin de conserver aux fibres une bonne tenue mécanique, cette décomposition doit être contrôlée, c'est-à-dire se produire avec une vitesse modérée de montée en température. En moyenne, cette vitesse est comprise entre 2°C/min et 10°C/min, de préférence entre 4°C/min et 6°C/min, étant noté qu'une trop faible vitesse deviendrait pénalisante au plan économique.The temperature of the tissue at the end of the initial phase is between 250 ° C and 350 ° C, preferably between 270 ° C and 300 ° C. The intermediate phase is that where most of the cellulose decomposition takes place. In order to maintain good mechanical strength in the fibers, this decomposition must be controlled, that is to say occur with a moderate rate of temperature rise. On average, this speed is between 2 ° C / min and 10 ° C / min, preferably between 4 ° C / min and 6 ° C / min, it being noted that too low a speed would become disadvantageous economically.
La température du tissu en fin de phase intermédiaire est comprise entre 400°C et 450°C. Cette température est celle à laquelle l'essentiel de la décomposition de la cellule est réalisé. La phase finale est celle où la carbonisation des fibres est achevée jusqu'à obtention de la structure de carbone souhaitée.The temperature of the fabric at the end of the intermediate phase is between 400 ° C and 450 ° C. This temperature is the temperature at which most of the cell's decomposition is carried out. The final phase is where carbonization of the fibers is completed until the desired carbon structure is obtained.
La température du tissu en fin de phase finale est comprise entre 500°C et 750°C, par exemple comprise entre 550°C et 650°C pour atteindre un stade de carbonisation suffisamment avancé. Lors de la phase finale, la montée en température peut être plus rapide que dans la phase intermédiaire, puisque la décomposition de cellulose a été pour l'essentiel réalisée. En outre, les contraintes liées à des retraits différentiels entre chaîne et trame sont moindres puisque l'essentiel du retrait s'est produit tant en chaîne qu'en trame. La vitesse moyenne de montée en température est choisie entre 5°C/min et 40°C/min, par exemple entre 25°C/min et 30°C/min. Un profil thermique souhaité pour le tissu dans la chambre de carbonisation 40 est susceptible d'être reproduit avec d'autant plus de précision que le nombre de zones dans la chambre 40 est élevé, avec contrôle individuel de la température dans chaque zone. En pratique, le nombre de zones est au minimum égal à 3, de préférence au minimum égal à 6.The temperature of the fabric at the end of the final phase is between 500 ° C and 750 ° C, for example between 550 ° C and 650 ° C to reach a sufficiently advanced carbonization stage. During the final phase, the temperature rise may be faster than in the intermediate phase, since the decomposition of cellulose has essentially been carried out. In addition, the constraints linked to differential withdrawals between warp and weft are less since the main part of the withdrawal occurred both in warp and weft. The average speed of temperature rise 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 fabric in the carbonization chamber 40 can be reproduced with all the more precision as the number of zones in the chamber 40 is high, with individual control of the temperature in each zone. In practice, the number of zones is at least equal to 3, preferably at least equal to 6.
En sortie de la boîte d'étanchéité 52, le tissu passe entre des rouleaux d'appel 54 avant d'être stocké par exemple sous forme d'une bobine 56. Les rouleaux d'appel sont associés à des moyens d'entraînement (non représentés) pour commander le défilement du tissu à la vitesse souhaitée. On notera qu'en raison du retrait des fils de chaîne lors de la carbonisation, la vitesse d'entrée du tissu dans la chambre 40 est supérieure à la vitesse de sortie.At the outlet of the sealing box 52, the fabric passes between take-up rollers 54 before being stored, for example in the form of a reel 56. The take-up rollers are associated with drive means (not shown) to control the scrolling of the fabric at the desired speed. It will be noted that due to the withdrawal of the warp threads during carbonization, the speed of entry of the fabric into the chamber 40 is greater than the speed of exit.
Le temps de séjour du tissu dans la chambre 40 est compris entre 20 min et 2 h.The residence time of the fabric in chamber 40 is between 20 min and 2 h.
Un traitement thermique à température élevée peut être réalisé sur le tissu carbonisé issu de la chambre 40. Ce traitement thermique est effectué en continu par passage du tissu dans un four 60. Ce traitement thermique vise à réaliser une structuration des fibres de carbone. Il est effectué à une température supérieure à 1 000°C, pouvant aller jusqu'à 2 800°C, sous une atmosphère neutre, par exemple sous azote. Le temps de séjour du tissu dans le four 60 est de préférence compris entre 1 min et 10 min, par exemple environ 2 min. Le tissu est repris de la bobine 56 et est stocké, en sortie du four 60, sur une bobine 62, en étant appelé par des rouleaux 64.A heat treatment at high temperature can be carried out on the charred fabric coming from the chamber 40. This heat treatment is carried out continuously by passing the fabric through an oven 60. This heat treatment aims to achieve structuring of the carbon fibers. It is carried out at a temperature above 1000 ° C., which can range up to 2800 ° C., under a neutral atmosphere, for example under nitrogen. The residence time of the fabric in the oven 60 is preferably between 1 min and 10 min, for example around 2 min. The fabric is taken from the spool 56 and is stored, at the outlet of the oven 60, on a spool 62, being called up by rollers 64.
Le tissu de carbone directement issu de la chambre 40 peut aussi être oxydé de façon ménagée par exposition à de la vapeur d'eau ou à du dioxyde de carbone, dans des conditions bien connues par ailleurs pour obtenir du tissu de carbone activé, sans traitement thermique à température élevée.The carbon fabric directly originating from chamber 40 can also be oxidized in a controlled manner by exposure to water vapor or to carbon dioxide, under conditions well known elsewhere for obtaining activated carbon fabric, without treatment. thermal at high temperature.
Exemple 1Example 1
On utilise une installation de carbonisation avec une chambre partagée en 8 zones 40ι à 408 d'égales longueurs. Différentes bandes d'un même tissu de rayonne technique constitué de fils de 3 600 dtex avec 11 fils/cm en chaîne et en trame ont été carbonisées dans cette installation après avoir subi une imprégnation par un composé organosilicié constitué par une résine polyhydrométhylsiloxane commercialisée par la société française Rhodia Silicones sous la référence "RHODORSIL RTV 141 B", et un traitement de séchage et relaxation à 170°C pendant 90 min.A carbonization installation is used with a chamber divided into 8 zones 40ι to 40 8 of equal length. Different strips of the same technical rayon fabric consisting of 3600 dtex threads with 11 threads / cm in warp and weft have were carbonized in this installation after having been impregnated with an organosilicon compound constituted by a polyhydromethylsiloxane resin sold by the French company Rhodia Silicones under the reference "RHODORSIL RTV 141 B", and a drying and relaxation treatment at 170 ° C. for 90 min .
Différentes températures régulées dans les zones du four et différentes vitesses de défilement ont été choisies de sorte que les températures et les vitesses de montée en température du tissu dans les différentes zones de la chambre de carbonisation 40 se situent dans les plages indiquées dans le tableau ci-dessous. Les limites de température sont représentées par des courbes en tirets sur la figure 3. Les durées totales de carbonisation étaient comprises entre 30 min et 70 min.Different regulated temperatures in the areas of the oven and different running speeds have been chosen so that the temperatures and rates of temperature rise of the fabric in the different areas of the carbonization chamber 40 are within the ranges indicated in the table below. -Dessous. The temperature limits are represented by dashed curves in FIG. 3. The total charring times were between 30 min and 70 min.
Dans ce four, la ou les cheminées d'évacuation des produits de décomposition de la cellulose sont situées entre les zones 405 et 40β.In this oven, the chimney (s) for evacuating cellulose decomposition products are located between zones 40 5 and 40β.
Dans tous les cas, on observe une absence de plis sur le tissu en sortie de la chambre de carbonisation, grâce au profil thermique conforme à l'invention. Après carbonisation, le tissu a subi un traitement en continu àIn all cases, there is an absence of folds on the fabric leaving the carbonization chamber, thanks to the thermal profile according to the invention. After charring, the fabric underwent continuous treatment at
1200°C sous azote pendant 90 s.1200 ° C under nitrogen for 90 s.
Des essais de traction ont été effectués sur les différentes bandes de tissu de carbone obtenues. Des valeurs comprises entre 30 et 70 daN/cm en chaîne, et entre 30 et 50 daN/cm en trame ont été mesurées pour un poids de tissu au m2 compris entre 310 et 330 g. Au niveau du filament en carbone, cela correspond à une résistance à rupture comprise entre 1000 et 1300 MPa et un module d'Young compris entre 30 et 50 GPa. Exemple comparatifTensile tests were carried out on the various strips of carbon fabric obtained. Values between 30 and 70 daN / cm in warp, and between 30 and 50 daN / cm in weft were measured for a weight of fabric per m 2 between 310 and 330 g. At the level of the carbon filament, this corresponds to a breaking strength of between 1000 and 1300 MPa and a Young's modulus of between 30 and 50 GPa. Comparative example
Un tissu en fibres de rayonne tel que celui des exemples ci-dessus a été carbonisé en continu.Rayon fiber fabric such as that of the above examples was continuously charred.
A titre de comparaison, un même tissu a été carbonisé dans des conditions semblables à l'exception du profil de carbonisation, la montée en température du tissu ayant été réalisée à une vitesse constante de 7°C/min de la température ambiante à 650°C.By way of comparison, the same fabric was carbonized under similar conditions with the exception of the carbonization profile, the temperature rise of the fabric having been carried out at a constant speed of 7 ° C / min from room temperature to 650 ° vs.
La figure 4 montre l'aspect gaufré du tissu obtenu, dû à un décalage du retrait entre la chaîne et la trame. FIG. 4 shows the embossed appearance of the fabric obtained, due to an offset in the shrinkage between the warp and the weft.

Claims

REVENDICATIONS
1. Procédé d'obtention d'un tissu en fibres de carbone par carbonisation en continu d'un tissu en fibres cellulosiques, caractérisé en ce que l'on soumet un tissu défilant en continu dans une chambre de carbonisation à un traitement thermique comprenant :1. A process for obtaining a carbon fiber fabric by continuous carbonization of a cellulose fiber fabric, characterized in that a continuously moving fabric is subjected in a carbonization chamber to a heat treatment comprising:
- une phase initiale pour amener la température du tissu à une valeur comprise entre 250°C et 350°C, la phase initiale comprenant une montée en température à une première vitesse moyenne comprise entre 10°C/min et 60°C/min,an initial phase for bringing the temperature of the fabric to a value between 250 ° C and 350 ° C, the initial phase comprising a rise in temperature at a first average speed of between 10 ° C / min and 60 ° C / min,
- une phase intermédiaire pour élever la température du tissu jusqu'à une valeur comprise entre 350°C et 500°C, la phase intermédiaire comprenant une montée en température à une deuxième vitesse moyenne inférieure à la première et comprise entre 2°C/min et 10°C/min, et- an intermediate phase to raise the temperature of the fabric to a value between 350 ° C and 500 ° C, the intermediate phase comprising a rise in temperature at a second average speed lower than the first and between 2 ° C / min and 10 ° C / min, and
- une phase finale pour élever la température du tissu jusqu'à une valeur comprise entre 500°C et 750°C, la phase finale comprenant une montée en température à une troisième vitesse moyenne supérieure à la deuxième et comprise entre 5°C/min et 40°C/min. - a final phase to raise the temperature of the fabric to a value between 500 ° C and 750 ° C, the final phase comprising a rise in temperature at a third average speed greater than the second and between 5 ° C / min and 40 ° C / min.
2. Procédé selon la revendication 1 , caractérisé en ce que l'on fait défiler le tissu dans la chambre à travers des zones successives dans chacune desquelles règne une température contrôlée.2. Method according to claim 1, characterized in that the fabric is scrolled through the chamber through successive zones in each of which prevails a controlled temperature.
3. Procédé selon l'une quelconque des revendications 1 et 2, caractérisé en ce que le temps de séjour du tissu dans la chambre est compris entre 20 min et 2 h.3. Method according to any one of claims 1 and 2, characterized in that the residence time of the fabric in the chamber is between 20 min and 2 h.
4. Procédé selon l'une quelconque des revendications 1 et 2, caractérisé en ce qu'avant carbonisation, on soumet le tissu à un traitement de relaxation à une température comprise entre 100°C et 250°C. 4. Method according to any one of claims 1 and 2, characterized in that before carbonization, the fabric is subjected to a relaxation treatment at a temperature between 100 ° C and 250 ° C.
5. Procédé selon la revendication 4, caractérisé en ce que le traitement de relaxation est effectué sous air.5. Method according to claim 4, characterized in that the relaxation treatment is carried out in air.
6. Procédé selon l'une quelconque des revendications 4 et 5, caractérisé en ce que le traitement de relaxation est effectué pendant une durée comprise entre 15 min et 3 h. 6. Method according to any one of claims 4 and 5, characterized in that the relaxation treatment is carried out for a period of between 15 min and 3 h.
7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que l'on soumet le tissu carbonisé à un traitement thermique à haute température comprise entre 1 000°C et 2 800°C, après passage dans la chambre de carbonisation.7. Method according to any one of claims 1 to 6, characterized in that the charred fabric is subjected to a treatment high temperature thermal between 1000 ° C and 2800 ° C, after passing through the carbonization chamber.
8. Procédé selon la revendication 7, caractérisé en ce que le traitement thermique à haute température est réalisé pendant une durée comprise entre 1 min et 10 min.8. Method according to claim 7, characterized in that the high temperature heat treatment is carried out for a period of between 1 min and 10 min.
9. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que l'on soumet le tissu carbonisé à un traitement d'activation. 9. Method according to any one of claims 1 to 6, characterized in that the charred tissue is subjected to an activation treatment.
EP00985404A 1999-12-06 2000-12-05 Method for obtaining a carbon fiber fabric by continuous carbonization of a fabric consisting of cellulosic fibers Expired - Lifetime EP1179096B1 (en)

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FR9915330 1999-12-06
FR9915330A FR2801908B1 (en) 1999-12-06 1999-12-06 PROCESS FOR OBTAINING CARBON FIBER TISSUE BY CONTINUOUS CARBONIZATION OF A CELLULOSIC FIBER TISSUE
PCT/FR2000/003385 WO2001042543A2 (en) 1999-12-06 2000-12-05 Method for obtaining a carbon fiber fabric by continuous carbonization of a fabric consisting of cellulosic fibers

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JP5271887B2 (en) * 2009-05-08 2013-08-21 国防科学研究所 Method for producing lyocell-based carbon fiber and carbon fabric
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FR2801908B1 (en) 2002-03-01
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