EP1179096A2 - 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

Info

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
English (en)
French (fr)
Other versions
EP1179096B1 (de
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SNECMA Moteurs SA filed Critical SNECMA Moteurs SA
Publication of EP1179096A2 publication Critical patent/EP1179096A2/de
Application granted granted Critical
Publication of EP1179096B1 publication Critical patent/EP1179096B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/16Carbon 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.

Landscapes

  • 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)
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 true EP1179096A2 (de) 2002-02-13
EP1179096B1 EP1179096B1 (de) 2005-03-02

Family

ID=9552915

Family Applications (1)

Application Number Title Priority Date Filing Date
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)

Country Link
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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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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Also Published As

Publication number Publication date
WO2001042543A2 (fr) 2001-06-14
US6967014B1 (en) 2005-11-22
RU2257429C2 (ru) 2005-07-27
UA68412C2 (en) 2004-08-16
ATE290108T1 (de) 2005-03-15
DE60018406T2 (de) 2005-12-29
DE60018406D1 (de) 2005-04-07
EP1179096B1 (de) 2005-03-02
BR0007679A (pt) 2001-11-06
JP2003516477A (ja) 2003-05-13
AU2183101A (en) 2001-06-18
BR0007679B1 (pt) 2011-05-17
FR2801908A1 (fr) 2001-06-08
MXPA01007953A (es) 2003-07-14
JP4582566B2 (ja) 2010-11-17
FR2801908B1 (fr) 2002-03-01
WO2001042543A3 (fr) 2001-11-29

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