EP3931381B1 - Procédé d'irradiation ionisante de fibres textiles en polyacrylonitrile et leur utilisation comme précurseur de la fibre de carbone - Google Patents

Procédé d'irradiation ionisante de fibres textiles en polyacrylonitrile et leur utilisation comme précurseur de la fibre de carbone Download PDF

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EP3931381B1
EP3931381B1 EP20709517.5A EP20709517A EP3931381B1 EP 3931381 B1 EP3931381 B1 EP 3931381B1 EP 20709517 A EP20709517 A EP 20709517A EP 3931381 B1 EP3931381 B1 EP 3931381B1
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Prior art keywords
pan
irradiation
temperature
oxidative
fibers
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EP3931381C0 (fr
EP3931381A1 (fr
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Simon König
Elisabeth Giebel
Michael R. Buchmeiser
Andreas Jürgen WEGO
Christian Herbert
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Deutsche Institute fuer Textil und Faserforschung Stuttgart
Deutsche Institute fuer Textil und Faserforschung Denkendorf DITF
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Deutsche Institute fuer Textil und Faserforschung Stuttgart
Deutsche Institute fuer Textil und Faserforschung Denkendorf DITF
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • D01F9/225—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles from stabilised polyacrylonitriles
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected

Definitions

  • the invention relates to a method for electron beam irradiation of textile polyacrylonitrile fibers and their use for the production of carbon moldings, in particular carbon fibers.
  • carbon fibers Flexible, elongate molded bodies containing at least 92% by weight of carbon and produced from organic polymeric precursors are referred to as carbon fibers.
  • the primary precursor used in carbon fiber production is polyacrylonitrile, the polymer of acrylonitrile.
  • polyacrylonitrile fibers are first stabilized by oxidation and then carbonized. If necessary, the carbon fiber is then graphitized.
  • the polyacrylonitrile is cyclized and dehydrated, ie converted into a polyaromatic structure at temperatures of 200 to 300° C. in air. This temperature range is referred to below as the cycling temperature.
  • the resulting polyaromatic structure is called Ox-PAN in the following.
  • the polyaromatic structure of the Ox-PAN enables the high carbon yield in the subsequent carbonization. At this will convert the Ox-PAN into a turbostratic modification of the carbon by pyrolysis, with the elimination of CO2 and HCN.
  • polyacrylonitrile not only the homopolymer of acrylonitrile is usually referred to as polyacrylonitrile, but also co- and terpolymers consisting of acrylonitrile and comonomers such as vinyl acetate, methyl acrylate, methyl methacrylate, itaconic acid, acrylic acid, acrylamide and others.
  • high-molecular terpolymers consisting of mostly more than 95% by weight of acrylonitrile and up to 5% by weight of other comonomers, primarily methyl acrylate and itaconic acid, with a number-average molecular weight of about 120,000 to 1,500,000 have proven suitable for carbon fibers g/mol as particularly suitable precursor polymers, which are referred to below as CF-PAN.
  • CF-PAN particularly suitable precursor polymers
  • T onset-Z onset temperature of the cyclization reaction, measured in air, referred to below as T onset-Z , analogous to T ei,r in DIN EN ISO 11357-5:2014-7.
  • Typical values for Tonset -Z for a CF-PAN are 200 to 240°C, depending on the composition of the CF-PAN.
  • T peak Z Another parameter is the temperature of the highest exotherm, measured under air, referred to below as T peak Z , analogous to T p,r in DIN EN ISO 11357-5:2014-7.
  • T peak Z is typically 280-300°C for CF-PANs.
  • the distance between Tonset -Z and T peak-Z should be as large as possible to avoid overheating or even burning of the fiber during the oxidative stabilization. For CF-PAN this is typically >60°C.
  • Polyacrylonitrile is mostly converted into fiber form by wet or dry spinning.
  • the productivity of the spinning plant correlates with molecular weight and comonomer content in such a way that a higher molecular weight or a lower comonomer content reduces productivity.
  • Polyacrylonitrile fibers are currently used not only for carbon fiber production, but also to a significant extent for textiles, especially for home and Outdoor textiles as well as work and sportswear.
  • polyacrylonitrile with a lower number-average molecular weight of about 30,000 to 250,000 g/mol and a comonomer content of up to 15% by weight is usually used in favor of productivity, referred to below as textile PAN.
  • Vinyl acetate, methyl acrylate and others are usually used as comonomers in textile PAN.
  • Comonomers with carboxyl groups are rarely used because, as already mentioned, they lead to a lower Tonset Z.
  • a low T onset Z is usually not desired for textile PAN, since the cyclization reactions are accompanied by a color change.
  • Textile PAN In the case of textile PAN, comonomers containing carboxyl groups would therefore lead to undesirable discolouration at elevated temperatures, for example when ironing. Textile PAN's low molecular weight and high comonomer content enables higher dope concentrations and thus higher productivity. Textile PAN fibers are therefore about 50% cheaper per kilogram than CF PAN fibers. Since the precursor, i.e. CF-PAN fibers, accounts for about half the cost of the resulting carbon fiber in state-of-the-art carbon fiber production, the use of textile PAN fibers would potentially reduce the cost of carbon fiber production by about 25%.
  • Tonset -Z is typically 240 to 300°C.
  • the use of textile PAN leads to higher energy costs when tempering the oxidative stabilization.
  • the distance between Tonset -Z and T peak-Z is smaller. The difference is usually between 10°C and 50°C.
  • This narrower temperature window of the cyclization reaction leads to problems when handling the stabilization step, since even small temperature fluctuations in the stabilization furnace lead to a significantly higher exothermic nature of the cyclization reaction.
  • Overheating of a multifilament with a large overall diameter, such as a "heavy tow" (50,000 filaments) customary in industry, is also conceivable due to precisely that exothermicity.
  • One way of changing the thermal properties of PAN is to irradiate the PAN with high-energy radiation, such as gamma rays or electron beams. Radicals are generated in the backbone of the polymer by this radiation. The amount of radicals generated correlates with the dose of irradiation. This enables shorter stabilization times. This was already 1996 in the JPH0827619A described. In this document, fibers irradiated with electrons are stabilized and carbonized in air, with the stabilization time being shortened compared to stabilization without prior irradiation. A CF-PAN with 0.1-10% by weight of comonomer containing carboxylic acid was used.
  • the resulting carbon fibers achieve the usual tensile strengths of 3.0-3.5 GPa and 220 to 250 GPa modulus of elasticity for CF-PAN. According to the technical teaching disclosed in this document, costs are saved in the stabilization step, but the much more decisive precursor costs are unchanged because of the use of CF-PAN instead of textile PAN.
  • the invention is therefore based on the object of proposing a method which is characterized in that it can be used in a practicable and economical manner, in particular for the production of carbon fibers from textile PAN.
  • the mechanical properties of the carbon fibers produced from textile PAN should clearly surpass those of the prior art and be comparable with carbon fibers made from CF-PAN, so that the savings potential of around 25% of the carbon fiber production costs can be exploited.
  • the object on which the invention is based is achieved by a method for the irradiation and oxidative stabilization of PAN fibers for the production of a precursor fiber of carbon fibers, characterized in that (1) the PAN fibers are based on a homopolymer or copolymer of PAN, wherein the PAN homopolymer or copolymer has a Tonset -z temperature of at least 245° C., measured in air (according to DIN EN ISO 11357-5:2014-07), a number-average molecular weight of 20,000 to 250,000 g/mol polymethyl methacrylate -Molar mass equivalents (determined according to DIN 55672-2:2016-03) and a comonomer content of not more than 15.0% by weight, (2) the PAN fibers are subjected to ionizing radiation with electron beams in an inert gas atmosphere with a radiation dose from 10 to 5000 kGy, (3) the reduced Tonset -z temperature of the E-PAN fibers obtained by irradi
  • the PAN has a number average molecular weight of from 30,000 to 150,000 g/mol, in particular from 50,000 to 120,000 g/mol. It is also considered an advantage that the comonomer content of PAN is 0.0 to 15.0% by weight, in particular 0.0 to 12.0% by weight and particularly preferably 0.0 to 7.5% by weight. -% amounts to.
  • the comonomer of PAN is a vinyl compound, in particular vinyl acetate, vinyl propionate, methyl acrylate, methyl methacrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, sodium methallyl sulfonate, sodium vinyl sulfonate, acrylamide, methacrylamide and/or vinyl acetamide. It is particularly preferred if the PAN fibers are textile PAN fibers.
  • the ionizing irradiation takes place with electron beams in an inert gas atmosphere, in particular in a nitrogen atmosphere.
  • an inert gas atmosphere compared to air leads to better mechanical properties of the resulting carbon fibers under otherwise identical process conditions.
  • the radiation dose for the ionizing radiation is 70 to 2500 kGy, in particular 300 to 1000 kGy.
  • the acceleration voltage is preferably 100 to 900 kV, in particular 160 to 600 kV, with the range from 180 to 400 kV being particularly preferred.
  • the current intensity during the ionizing irradiation with electron beams is 0.1 to 100 mA, in particular 1 to 50 mA and particularly preferably 2 to 10 mA.
  • the oxidative heat stabilization to be used in the invention is accessible to a variety of advantageous configurations: It is preferred that the starting temperature in the oxidative heat stabilization Tonset -Z E-PAN is ⁇ 20°C, in particular ⁇ 10°C.
  • the end temperature of the oxidative thermal stabilization T Peak-Z E-PAN is preferably ⁇ 30°C, in particular ⁇ 20°C.
  • the oxidative thermal stabilization is carried out up to a density of the oxidatively thermally stabilized PAN (Ox-PAN) of 1.30 to 1.5 g/cm 3 , in particular of 1.35 to 1.39 g/cm 3 becomes. It has been shown that the end temperature of the oxidative heat stabilization is preferably between 250 and 300.degree. C., in particular between 260 and 290.degree.
  • the oxidative thermal stabilization particularly preferably takes place immediately after the ionizing irradiation. It is preferred that the storage time between ionizing radiation and carbonization is less than one day, preferably less than one hour. In particular, it is preferred that the ionizing radiation occurs immediately before the oxidative thermal stabilization in the case of a continuous thread run.
  • the product obtained according to the invention can be put to advantageous uses.
  • the use of those obtained according to the invention is preferred oxidatively thermally stabilized PAN fibers (Ox-PAN) for the production of carbon fibers by carbonization, optionally with subsequent graphitization.
  • Ox-PAN oxidatively thermally stabilized PAN fibers
  • the object on which the invention is based is therefore achieved by an advantageous method for stabilizing shaped bodies, in particular fibers, consisting in particular of textile PAN.
  • the shaped bodies, in particular the fibers are irradiated with ionizing radiation, preferably with electron beams, preferably in an inert gas atmosphere, particularly preferably in a nitrogen atmosphere, followed by oxidative thermal stabilization, which preferably takes place immediately after the irradiation and which has a temperature profile , which is tailored to the thermal properties of the particularly irradiated textile PAN.
  • the shaped bodies or fibers thus stabilized according to the invention can be carbonized and optionally graphitized by conventional methods.
  • the properties of the carbon fibers produced according to the invention correspond to typical carbon fibers made from CF-PAN.
  • a fiber made of "textile PAN” is used as the starting fiber.
  • the properties of this PAN are explained below in connection with the term “textile PAN”.
  • the textile PAN preferably has a number-average molecular weight of from 20,000 to 250,000 g/mol, in particular from 30,000 to 150,000 g/mol of polymethyl methacrylate molar mass equivalents according to DIN 55672-2:2016-03. Textile PAN with a number-average molecular weight of 50,000 to 120,000 g/mol polymethyl methacrylate molar mass equivalents has proven to be particularly advantageous.
  • the textile PAN used according to the invention is also characterized in that it has a Tonset Z measured in air of greater than 245°C, more preferably greater than 250°C and most preferably from 250 to 300°C.
  • the Tonset Z temperature is preferably up to 320°C, in particular up to 300°C.
  • the Tonset -Z temperature corresponds to T ei,r in DIN EN ISO 11357-5:2014-07 and represents the extrapolated initial temperature of the cyclization reaction of the PAN in air to the Ox-PAN.
  • the textile PAN used according to the invention has a T peak Z , measured in air, corresponding to T p,r in DIN EN ISO 11357-5:2014-7, from 260 to 360°C, in particular from 290 to 320°C.
  • T on-set Z and T peak Z are determined via DSC under air using the temperature sweep method, the heating rate used for the purpose of comparability is 10 K/min.
  • a TA-Instruments Q2000 differential scanning calorimeter with an autosampler unit was used for the measurements, and the "TZero" aluminum pans from TA-Instruments were used as measuring crucibles.
  • comonomers with a vinyl group such as are typically used in textile PAN, can be used as comonomers.
  • the use of a carboxylic acid-containing comonomer is not necessary because of the thermal properties that can be controlled by radiation.
  • Vinyl acetate, vinyl propionate, methyl acrylate, methyl methacrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, sodium methallyl sulfonate, sodium vinyl sulfonate, acrylamide, methacrylamide and vinyl acetamide are particularly suitable as comonomers.
  • the comonomers vinyl acetate and methyl acrylate are particularly preferred.
  • the comonomer content in the polymer is between 0 and 15% by weight, in particular between 0 and 7.5% by weight, in view of the productivity when spinning the polymer.
  • the textile PAN of the invention is converted into fiber form via solution spinning processes, in particular via wet, dry, or airgap spinning.
  • solution spinning processes in particular via wet, dry, or airgap spinning.
  • use is generally made here of industrial-scale spinning processes for polyacrylonitrile, which have been optimized over several decades in terms of productivity and economy.
  • the fibers used expediently have an individual filament diameter of 5 to 30 ⁇ m, in particular 8 to 18 ⁇ m and very particularly preferably 8 to 13 ⁇ m. It is also advantageous that the tensile strength of the fiber is between 25 and 80 cN/tex, in particular between 35 and 60 cN/tex.
  • the modulus of elasticity of the fibers is preferably from 500 to 2500 cN/tex, moduli of elasticity from 900 to 1500 cN/tex and in particular from 950 to 1250 cN/tex are particularly preferred.
  • the elongation of the textile PAN fibers is preferably from 5 to 25%, in particular from 8 to 16%.
  • the textile fibers are arranged in a multifilament, ie the fibers are arranged in a potentially endless fiber bundle consisting of several filaments.
  • the multifilament preferably consists of 1000 to 10,000,000 filaments, in particular 3000 to 300,000 filaments.
  • An essential feature of the invention is the ionizing irradiation of the fibers, preferably using an electron beam.
  • the resulting irradiated textile PAN fibers are referred to herein as E-PAN fibers.
  • Electron irradiation can be carried out under various atmospheric conditions. In the prior art, mostly air is used. However, it has surprisingly been shown that an inert gas atmosphere according to the invention, such as nitrogen, leads to better mechanical properties of the carbon fibers leads. In a preferred embodiment of the invention, the use of an inert gas atmosphere in the irradiation of the textile PAN fibers resulted in carbon fibers with 31% better tensile strength compared to the use of air. Various gases such as helium, neon, argon, krypton, xenon, nitrogen and carbon dioxide can be used as the inert gas. Nitrogen is particularly suitable according to the invention. The use of an inert gas during the irradiation also prevents the formation of ozone, which means that it does not have to be removed from the exhaust air.
  • the decisive parameter of electron irradiation for controlling the thermal properties of the E-PAN is the irradiation dose.
  • T onset-Z and T peak-Z are shifted towards lower temperatures in such a way that a higher radiation dose results in lower temperatures T onset-Z and T peak-Z .
  • These reduced T onset Z and T peak Z in the E-PAN compared to the non-irradiated textile PAN are called T onset Z E-PAN and T peak Z E-PAN in the following.
  • the distance between Tonset -Z E-PAN and T peak-Z E-PAN is preferably adjusted to about 40 to 110°C, in particular to 60 to 90°C.
  • the distance between Tonset -Z and T peak-Z is usually 10 to 60°C.
  • the distance between Tonset -E-PAN and T peak-ZE-PAN is thus greater than that between Tonset -Z and T peak-Z . This minimizes the risk of a textile PAN multifilament overheating in an uncontrolled manner or even burning off during exothermic oxidative thermal stabilization.
  • the irradiation dose can preferably be 10 to 10000 kGy, in particular 10 to 5000 kGy. Irradiation doses of from 70 to 1500 kGy, in particular from 300 to 1000 kGy, are particularly preferred.
  • acceleration voltage Another essential parameter of electron irradiation is the acceleration voltage. The higher this is, the deeper a fiber bundle is penetrated by the electron beam. However, radiation protection and the necessary financial outlay for plant construction are all the more complex. It was therefore an aim of the inventors to use the lowest possible acceleration voltage. High acceleration voltages of >1 MV, as used in the prior art, unnecessarily increase the required radiation protection precautions. At 900 kV, electron beam penetration depths of > 3 mm are already achieved in the multifilament, which corresponds to > 250 individual filaments lying one on top of the other.
  • acceleration voltages 100 to 900 kV, in particular 160 to 600 kV and particularly preferably 180 to 400 kV have proven particularly advantageous.
  • the current is another important parameter of the irradiation.
  • the radiation dose results from the current strength, acceleration voltage and time.
  • the current of irradiation with electron beams is preferably 0.1 to 100 mA, with the preferred range being 1 to 15 mA, particularly 2 to 10 mA.
  • the irradiation can be carried out discontinuously or continuously, with regard to a technical, cost-efficient process in which the shortest possible time should also elapse between irradiation and oxidative thermal stabilization, continuous irradiation appears to be more advantageous.
  • the process speed at which the fibers are continuously irradiated is preferably 0.5 to 100 m/min, in particular 5 to 50 m/min.
  • the fiber to be irradiated is subjected to a tensile force which prevents the fiber from shrinking.
  • This tensile force is preferably between 0.001 and 1 cN/filament, in particular between 0.03 and 0.3 cN/filament.
  • the irradiation of the fiber made of textile PAN is followed by the oxidative heat stabilization.
  • the E-PAN fibers can be stored for several weeks. It would therefore be conceivable to carry out continuous irradiation "online" immediately before the oxidative thermal stabilization or to carry out the irradiation continuously but then lay down or wind up the fibers and store them for any desired period of time. Experiments were therefore carried out in which E-PAN fibers were stabilized into Ox-PAN fibers one hour, one day, one week and 6 weeks after irradiation. The Ox-PAN fibers were then carbonized.
  • the fibers are oxidatively thermally stabilized immediately after irradiation. "Immediately” can also mean that stabilization and irradiation are connected by continuous thread guidance and their process speeds are coordinated with one another.
  • the atmosphere during stabilization should have an oxidizing character, so it is particularly advisable to use air.
  • the temperature is not constant during the oxidative thermal stabilization.
  • a continuously increasing temperature during the oxidative thermal stabilization with a defined start and end temperature and a defined stabilization time is advantageous.
  • this is accomplished through the use of a multi-heat zone stabilization oven.
  • the temperature profile over the entirety of the heating zones is characterized in principle by the fact that, starting with the second heating zone, each of the heating zones has a higher temperature than the previous one.
  • Tonset -Z E-PAN and T peak-Z E-PAN must first be determined by DSC under air according to DIN EN ISO 11357-5:2014-07 to find out , in which temperature range the cyclization reactions of the E-PAN occur, which are necessary for the oxidative thermal stabilization. Heating rates of 10 K/min should be used.
  • the starting temperature of the oxidative thermal stabilization should deviate from Tonset -Z E-PAN by a maximum of 30° C., in particular preferably a maximum of 20° C., preferably a maximum of 10° C.
  • the end temperature of the oxidative thermal stabilization should deviate from T Peak-Z E-PAN by a maximum of 30°C, preferably by a maximum of 20°C.
  • the density of the Ox-PAN fiber is at least 1.30 g/cm 3 .
  • the density of the Ox-PAN fiber is preferably in the range from 1.35 to 1.5 g/cm 3 , particularly preferably between 1.35 and 1.39 g/cm 3 . If the density of the resulting Ox-PAN fibers falls outside of this density range, either the temperature in the heating zones of the stabilization furnace or the process speed must be changed. Increasing the temperature in the heating zones or slowing down the process speed leads to a higher density of the Ox-PAN fiber. Decreasing the temperature or increasing the process speed leads to a lower density of the Ox-PAN fiber. This iterative parameter change is carried out until the Ox-PAN fiber reaches the corresponding density range.
  • the oxidative thermal stabilization lasts preferably 10 minutes to 4 hours, in particular 1 hour to 3 hours, particularly preferably 1 hour to 2 hours. However, it has also been shown that the range from 1.5 to 2.5 hours is advantageous.
  • the oxygen content of the Ox-PAN fiber is preferably 5 to 25% by weight, in particular 10 to 15% by weight and very particularly preferably from 11 to 13% by weight.
  • the fibers are preferably subjected to a tensile force during stabilization.
  • a high tensile force during stabilization usually leads to better mechanical properties of the resulting carbon fibers.
  • the magnitude of the tensile force also gives stretching or shrinkage of the fibers during stabilization. It has been shown that it is advantageous, especially at the beginning of the oxidative thermal stabilization, to select the tensile force in such a way that a stretching of 0 to 50%, preferably 0 to 10%, results.
  • the tensile forces that occur are preferably 0.03 to 1 cN per filament, in particular 0.05 to 0.5 cN per filament, with the range from 0.1 to 0.3 cN per filament being particularly preferred. Surprisingly, it was also found that an increase in the radiation dose is accompanied by an increase in the tensile forces for the same stretching.
  • the Ox-PAN fibers are preferably carbonized under an inert gas atmosphere.
  • inert gases are helium, neon, argon, krypton, xenon and nitrogen, with the use of nitrogen being preferred.
  • the final temperature during carbonization is decisive for the degree of carbonization and for the mechanical properties of the resulting carbon fibers.
  • the final temperature of the carbonization can be up to 1800°C.
  • the carbonization can be carried out continuously and discontinuously.
  • the Ox-PAN fiber is heated under an inert gas atmosphere from any desired temperature, usually room temperature, to the final carbonization temperature.
  • the heating rate during carbonization is preferably between 1 and 100 K/min, in particular between 5 and 20 K/min.
  • the Ox-PAN fiber should experience a tensile force in the fiber axis during batchwise carbonization.
  • the Ox-PAN fibers are guided through a carbonization furnace via godets, which in an advantageous embodiment has several heating zones.
  • the use of several carbonization furnaces is particularly preferred. When using two consecutive carbonization furnaces, these become LT (low temperature) and HT (high temperature) furnaces called.
  • the temperature in the LT furnace can be between 200 and 1000°C, preferably between 300 and 750°C. This temperature range should also be completely covered in the furnace over several heating zones.
  • the temperature can be between 800 and 1800°C, preferably between 1000 and 1400°C.
  • the fibers are subjected to a tensile force. This should result in an overall stretching of the fibers of -10 to +10%.
  • positive stretching of 0.1 to 15% is achieved in the LT oven and negative stretching or shrinkage of -0.1 to -15% in the HT oven.
  • the winding speed for continuous carbonization should be between 0.5 and 50 m/min and essentially depends on the size of the carbonization system.
  • the density of the resulting carbon fibers is preferably between 1.65 and 1.9 g/cm 3 , in particular between 1.7 and 1.8 g/cm 3 .
  • a higher density often goes hand in hand with an improvement in mechanical properties.
  • the irradiation of the multifilaments made of textile PAN leads to higher densities of the carbon fibers with a comparable density of the Ox-PAN fiber.
  • a graphitization can also be carried out after the carbonization.
  • an inert gas atmosphere is used here.
  • Helium, neon, argon, krypton and xenon can be used as inert gases.
  • the use of argon is preferred.
  • the graphitization is preferably carried out between 1800 and 3000°C. This is achieved using one or more graphitization furnaces, each of which is preferably equipped with multiple heating zones.
  • the starting temperature of graphitization can be between 1800 and 2200°C.
  • the final temperature can be between 2200 and 3000°C.
  • the graphitization is advantageously carried out continuously.
  • the multifilament should experience a tensile force. This is preferably between 0.01 and 0.5 cN per filament.
  • the stretching resulting therefrom is preferably between -5 and +5%, in particular between -2 and +2%.
  • the invention relates to a simple, inexpensive method for electron beam irradiation of multifilaments consisting of textile PAN and their use as precursors for the production of carbon fibers.
  • the irradiation of the textile PAN multifilaments should preferably be carried out under nitrogen. Surprisingly, this inert gas atmosphere leads to better mechanical properties of the resulting carbon fibers. In addition, it has proven to be advantageous to carry out the oxidative thermal stabilization immediately after the irradiation.
  • the irradiated multifilament can be converted into an Ox-PAN multifilament by means of a defined oxidative thermal stabilization which is advantageous with regard to the thermal properties of the precursor.
  • This can be converted into carbon fibers under an inert gas atmosphere.
  • the resulting carbon fibers have top values for maximum tensile strength (according to DIN EN ISO 5079:1995) of up to 3.1 ⁇ 0.6 GPa on average.
  • the modulus of elasticity is up to 212 ⁇ 9 GPa on average.
  • the core of the present invention relates to the process control during electron irradiation and the oxidative thermal stabilization.
  • a DSC measurement of the irradiated fiber was then used to determine its Tonset Z E-PAN at 204°C and a T Peak Z E-PAN at 282°C.
  • the multifilament was then stabilized in a stabilization oven with 4 heating chambers. Based on the determined Tonset -Z E-PAN, a temperature of 210°C in heating chamber 1 was selected. In the following heating chambers 2 to 4, 225°C, 245°C and 265°C were set. In heating chambers 1 and 2, the fiber was drawn 5% in each case.
  • the tensile force occurring was 426 cN in heating chamber 1, 527 cN in heating chamber 2, 428 cN in heating chamber 3 and 460 cN in heating chamber 4.
  • the density of the resulting Ox-PAN multifilament was 1.36 g/cm 3 .
  • the mechanical properties and the density of the Ox-PAN fibers can be seen in Table 1.
  • Comparative example 1 (Stabilization and carbonization of textile PAN 1, without irradiation)
  • the multifilament from Example 1 was continuously stabilized and carbonized without irradiation. Tonset -Z was determined to be 249°C and T peak-Z to be 299°C by means of DSC measurement.
  • the temperature in heating chamber 1 of the stabilization furnace was 240°C, in heating chambers 2 to 4 250, 265 and 275°C were set. Analogously to example 1, 5% was stretched in heating chambers 1 and 2 in each case.
  • the tensile force occurring was 171 cN in heating chamber 1, 203 cN in heating chamber 2, 255 cN in heating chamber 3, and 370 cN in heating chamber 4.
  • the density of the Ox-PAN multifilament was 1.39 g/cm 3 , the mechanical properties can be seen in Table 5.
  • the carbonization was also carried out analogously to Example 1.
  • the mechanical properties and density of the resulting carbon fibers can be seen in Table 5.
  • ⁇ u>Table 5 ⁇ /u> fiber Tensile strength [MPa] Modulus of elasticity [GPa] Strain [%] diameter [ ⁇ m] Density [g/ml] Ox-PAN 280 ⁇ 40 8.2 ⁇ 1.0 16.8 ⁇ 3.4 10.7 ⁇ 1.2 1.39 carbon fiber 2250 ⁇ 400 196 ⁇ 6 1.12 ⁇ 0.2 6.8 ⁇ 0.4 1.73
  • Comparative example 2 (irradiation in air, stabilization and carbonization analogous to KR 20160140268A)
  • the multifilament from example 1 was irradiated analogously to example 1, but under air instead of nitrogen, so that the irradiation dose and atmosphere correspond to those in KR 101755267 same. Thereafter, an approximately 15 cm long piece of the air-blasted fibers was fixed in graphite boats. The fibers were then oxidatively stabilized in air in a muffle furnace. The heating was from 200 to 240°C within 150 minutes and from 240 to 260°C within 90 minutes. The fibers were then carbonized at a heating rate of 5 K/min up to 1200° C. under nitrogen. The resulting mechanical properties can be seen in Table 6.
  • the tensile strength of these fibers roughly corresponds to the tensile strength of carbon fibers KR 20160140268A , the E modulus is about 50 GPa higher than that of carbon fibers KR 20160140268A .
  • ⁇ u>Table 6 ⁇ /u> dose Tensile strength [MPa] Modulus of elasticity [GPa] Strain [%] diameter [ ⁇ m] Density [g/ml] 1000kGy 1740 ⁇ 500 178 ⁇ 15 0.98 ⁇ 0.28 8.4 ⁇ 0.5 1.75
  • Example 2 (irradiation, stabilization and carbonization of textile PAN 2)
  • heating chambers 2 to 4 225°C, 245°C and 265°C were set.
  • the fiber was drawn 5% in each case.
  • the density of the resulting Ox-PAN multifilament was 1.36 g/cm 3 .
  • Subsequent carbonization was carried out continuously with the aid of an LT and an HT carbonization furnace in a nitrogen atmosphere.
  • the temperature profiles in LT and HT correspond to those in Example 1, the stretch in LT was +2% and in HT -3.5%.
  • the mechanical properties of the carbon fibers can be seen in Table 7.
  • Example 3 (irradiation, stabilization and carbonization of textile PAN 1 with different time intervals between irradiation and stabilization)
  • the multifilament was then tested in four experiments, each after a break of one hour, one day, one week and 6 weeks in one Stabilization oven stabilized with 4 heating chambers.
  • the stretching and temperatures in the stabilization oven correspond to those of example 1.
  • the tensile forces occurring in the stabilization oven can be seen in Table 8.
  • Example 10 shows the mechanical properties and the densities of the resulting carbon fibers. In the LT oven, the stretching was varied between 2 and 7% in the tests. ⁇ u>Table 10 ⁇ /u> Interval Irradiation Stabilization LT stretch [%] Tensile strength [GPa] Modulus of elasticity [GPa] Strain [%] Diameter [dtex] 1 hour 2 2.49 ⁇ 0.89 188 ⁇ 7 1.29 ⁇ 0.4 0.55 ⁇ 0.09 5 3.08 ⁇ 0.64 193 ⁇ 9 1.54 ⁇ 0.29 0.58 ⁇ 0.09 7 2.89 ⁇ 0.89 193 ⁇ 7 1.46 ⁇ 0.43 0.61 ⁇ 0.10 1d 2 2.52 ⁇ 0.66 192 ⁇ 9 1.29 ⁇ 0.31 0.61 ⁇ 0.19 5 2.85 ⁇ 0.60 196 ⁇ 9 1.42 ⁇ 0.29 0.66 ⁇ 0.18 7 2.60 ⁇ 0.62 195 ⁇ 9 1.30 ⁇ 0.29 0.53 ⁇ 0.08 1w 2 2.16 ⁇ 0.63 185 ⁇ 11 1.
  • Example 4 (irradiation, stabilization and carbonization of textile PAN 3)
  • a temperature of 210°C in heating chamber 1 was selected.
  • heating chambers 2 to 4 were 225°C, 245°C and 265°C set.
  • the fibers were each drawn 2%, in heating chambers 3 & 4 the drawing was -0.5%.
  • the density of the resulting Ox-PAN multifilament was 1.37 g/cm 3 .
  • Subsequent carbonization was carried out continuously with the aid of an LT and an HT carbonization furnace in a nitrogen atmosphere.
  • the temperature profiles in LT and HT correspond to those in Example 1, the stretch in LT was +5% and in HT -3.5%.
  • the mechanical properties of the carbon fibers can be seen in Table 11.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Fibers (AREA)

Claims (15)

  1. Procédé d'irradiation et de stabilisation par oxydation de fibres de polyacrylonitrile, PAN, pour fabriquer des fibres précurseurs de fibres de carbone, caractérisé en ce que
    (a) les fibres PAN sont à base d'un homopolymère ou d'un copolymère de PAN,
    dans lequel l'homopolymère ou le copolymère de PAN présente une température Tonset-z d'au moins 245 °C mesurée sous air (selon la norme DIN EN ISO 11357-5:2014-07), un poids moléculaire moyen de 20 000 à 250 000 g/mol d'équivalents en masse molaire de polyméthylméthacrylate (défini selon la norme DIN 55672-2:2016-03) ainsi qu'une teneur en comonomères inférieure ou égale à 15,0 % en poids,
    (2) les fibres PAN sont soumises à une irradiation ionisante avec des faisceaux d'électrons sous une atmosphère de gaz inerte avec une dose d'irradiation de 10 à 5000 kGy,
    (3) la température Tonset-z réduite est déterminée sous air par les fibres E-PAN obtenues par irradiation (Tonset-z E-PAN) (selon la norme DIN EN ISO 11357-5:2014-07), puis la thermostabilisation par oxydation est amorcée à une température de départ Tonset-z E-PAN de ±30 °C et la thermostabilisation par oxydation est effectuée à une température croissante jusqu'à une densité minimale des fibres PAN stabilisées par oxydation (Ox-PAN) de 1,30 g/cm3.
  2. Procédé selon la revendication 1, caractérisé en ce que le PAN présente un poids moléculaire moyen de 30 000 à 150 000 g/mol, en particulier de 50 000 à 120 000 g/mol.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la teneur en comonomère de PAN va de 0,0 à 12,0 % en poids, en particulier de 0,0 à 9,0 % en poids et de manière particulièrement préférée de 0,0 à 7,5 % en poids.
  4. Procédé selon au moins l'une quelconque des revendications précédentes, caractérisé en ce que le comonomère de PAN constitue un composé de vinyle, en particulier de l'acétate de vinyle, de vinylester d'acide propionique, d'acrylate de méthyle, de méthacrylate de méthyle, d'acrylate d'éthyle, d'acrylate de propyle, d'acrylate n-butyle, d'acrylate tert-butyle, de méthallylsulfonate de sodium, de vinylsulfonate de sodium, d'acrylamide, de méthacrylamide et/ou de vinylacétamide.
  5. Procédé selon au moins l'une quelconque des revendications précédentes, caractérisé en ce que la dose d'irradiation de l'irradiation ionisante va de 70 à 2500 kGy, en particulier de 300 à 1000 kGy.
  6. Procédé selon au moins l'une quelconque des revendications précédentes, caractérisé en ce que l'irradiation ionisante avec des faisceaux d'électrons est effectuée sous une atmosphère azotée.
  7. Procédé selon la revendication 6, caractérisé en ce que la tension d'accélération va, lors de l'irradiation ionisante avec des faisceaux d'électrons, de 100 à 900 kV, en particulier de 160 à 600 kV et de manière particulièrement préférée de 180 à 400 kV.
  8. Procédé selon la revendication 6 ou 7, caractérisé en ce que l'intensité du courant lors de l'irradiation ionisante avec des faisceaux d'électrons va de 0,1 à 100 mA, en particulier de 1 à 50 mA et de manière particulièrement préférée de 2 à 10 mA.
  9. Procédé selon au moins l'une quelconque des revendications 6 à 8, caractérisé en ce que le temps d'entreposage entre l'irradiation et la thermostabilisation par oxydation est inférieur à un jour, de préférence est inférieur à une heure.
  10. Procédé selon au moins l'une quelconque des revendications 6 à 9, caractérisé en ce que l'irradiation ionisante se déroule directement en amont de la thermostabilisation par oxydation lors du trajet de fil continu.
  11. Procédé selon au moins l'une quelconque des revendications précédentes, caractérisé en ce que la température de départ lors de la thermostabilisation par oxydation Tonset-z E-PAN est de ±20 °C, en particulier de ±10 °C.
  12. Procédé selon au moins l'une quelconque des revendications précédentes, caractérisé en ce que la température de fin de la thermostabilisation par oxydation TPeak-z E-Pan est de ±30 °C, en particulier de ±20 °C.
  13. Procédé selon au moins l'une quelconque des revendications précédentes, caractérisé en ce que la thermostabilisation par oxydation est effectuée jusqu'à une densité du PAN thermostabilisé par oxydation (Ox-PAN) de 1,30 à 1,5 g/cm3, en particulier de 1,35 à 1,39 g/cm3.
  14. Procédé selon au moins l'une quelconque des revendications précédentes, caractérisé en ce que la température Tonset-z va jusqu'à 320 °C, en particulier jusqu'à 300 °C.
  15. Utilisation des fibres Ox-PAN obtenues selon un procédé selon au moins l'une quelconque des revendications précédentes pour fabriquer des fibres de carbone par carbonisation, éventuellement avec une graphitisation consécutive.
EP20709517.5A 2019-03-01 2020-02-27 Procédé d'irradiation ionisante de fibres textiles en polyacrylonitrile et leur utilisation comme précurseur de la fibre de carbone Active EP3931381B1 (fr)

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DE102019105292.0A DE102019105292A1 (de) 2019-03-01 2019-03-01 Verfahren zur ionisierenden Bestrahlung von textilen Polyacrylnitrilfasern und deren Verwendung als Carbonfaserpräkursor
PCT/EP2020/055203 WO2020178149A1 (fr) 2019-03-01 2020-02-27 Procédé d'irradiation ionisante de fibres textiles en polyacrylonitrile et leur utilisation comme précurseur de la fibre de carbone

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