EP3532661A1 - Method for producing carbon fibres from biosourced precursors and carbon fibres produced - Google Patents
Method for producing carbon fibres from biosourced precursors and carbon fibres producedInfo
- Publication number
- EP3532661A1 EP3532661A1 EP17794394.1A EP17794394A EP3532661A1 EP 3532661 A1 EP3532661 A1 EP 3532661A1 EP 17794394 A EP17794394 A EP 17794394A EP 3532661 A1 EP3532661 A1 EP 3532661A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lignin
- fiber
- fibers
- hydrocellulose
- precursor
- 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.)
- Withdrawn
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
- D01F9/17—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 from lignin
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
- C04B35/83—Carbon fibres in a carbon matrix
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- 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
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Definitions
- the invention relates to the field of carbon fibers, and more particularly to carbon fibers manufactured from biosourced precursors, for the manufacture of parts made of thermoplastic or thermosetting composite materials which can be used in particular in the field of aeronautics, automotive, wind, naval, building construction, sports.
- the invention relates to a method of manufacturing a highly carbonaceous fiber or a set of highly carbonaceous fibers and the fiber or set of fibers obtainable by such a manufacturing method.
- the carbon fiber market is booming. In recent years, the carbon fiber industry has grown steadily to meet the demands of different applications. The market is currently estimated at around 60 kt / y and is expected to grow to 150-200 kt / y by 2020-2025. This strong forecast growth is mainly related to the introduction of carbon fiber in composite materials used in the aerospace, energy, building, automotive and leisure sectors.
- Carbon fibers generally have excellent tensile properties, high thermal and chemical stability, good thermal and electrical conductivities, and excellent resistance to deformation. They can be used as reinforcements of composite materials which usually comprise a polymer resin (matrix). The composite materials thus reinforced exhibit excellent physical properties while maintaining an advantageous lightness. Lightening is one of the key measures in reducing C0 2 emissions for transport. The automotive and aerospace industry is in demand for compounds presenting, with equivalent performance, a greater lightness.
- PAN Polyacrylonitrile
- Polyacrylonitrile (PAN) is the most widely used precursor today for the manufacture of carbon fibers.
- PAN Polyacrylonitrile
- the production of carbon fibers from PAN includes the polymerization steps of PAN-based precursors, fiber spinning, thermal stabilization, carbonization and graphitization.
- the carbonization takes place under a nitrogen atmosphere at a temperature of 1000 to 1500 ° C.
- the carbon fibers obtained at the end of these steps consist of 90% carbon, about 8% nitrogen, 1% oxygen and less than 1% hydrogen.
- An additional step, designated by graphitization is sometimes performed. This step generally requires a temperature of 2500 to 3000 ° C.
- the last step is to obtain a material composed of 99% carbon, which makes it considerably more malleable, but also less resistant.
- These two stages of carbonization and graphitization require climbs at very high temperatures and are therefore energy-consuming.
- the blocking factors for a wider use of carbon fiber composite materials with the precursor of PAN fibers are their cost, which is partly related to the cost of oil and the management of the production line, particularly the rise in temperature, which is quite complex.
- Brai precursors have also been developed but, like acrylic precursors, they consume fossil resources and lead to energy consumption related to the high temperatures required during the carbonization and graphitization steps.
- the application WO2014064373 published May 1, 2014 filed by the Applicant describes a method of manufacturing, from a bio-resourced precursor, carbon fiber continuous doped with carbon nanotubes (CNTs).
- CNTs carbon nanotubes
- the presence of CNTs in the biosourced precursor makes it possible to increase the carbon yield of the precursor during carbonization, and also to increase the mechanical characteristics of the carbon fibers.
- the biosourced precursor may be cellulose transformed into fibers by dissolution and coagulation / spinning so as to form hydrocellulose (such as, for example, viscose, lyocell, rayon).
- hydrocellulose such as, for example, viscose, lyocell, rayon.
- CN1587457 describes a process for preparing a cellulosic precursor material for the manufacture of carbon fiber having improved properties and a lower cost of manufacture.
- the cellulosic preparation involves inserting the soot nanoparticles into the cellulosic solution.
- the object of the invention is to propose a process for manufacturing carbon fibers, said process being simple to implement, with a reduced number of steps, and making it possible to control costs, in particular by reducing expenditure. energy related to the steps of carbonization and graphitization.
- the invention further aims to provide a highly carbon fiber or a set of highly carbonaceous fibers, very mechanically stable with a higher carbon yield carbon fibers conventionally obtained from biosourced materials.
- the highly carbonaceous fibers according to the invention are light and have a density lower than conventional carbon fibers.
- the process can be carried out on organized and non-carbonized fiber assemblies such as Lyocell, viscose, rayon, for example, so as to form, rapidly and at low costs, sets of carbon fibers woven with know carbon fiber fabrics.
- the invention relates to a process for manufacturing a fiber or a set of highly carbonaceous fibers, mainly characterized in that it comprises the combination of a structured precursor comprising a fiber or a set of hydrocellulose fibers, and an unstructured precursor comprising lignin or a lignin derivative, in the form of a solution having a viscosity of less than 15,000 mPa.s and preferably less than 10 000 mPa.s at the temperature at which the combining step takes place, so as to obtain a fiber or a set of hydrocellulose fibers covered with said lignin, said method further comprising the following steps:
- This new manufacturing process from biosourced precursors, a highly carbonaceous carbon fiber or a set of highly carbonaceous carbon fibers has many advantages such as reducing the energy demand to manufacture materials. with equivalent properties, obtaining a higher carbon yield than observed with the methods of the prior art and the formation of fibers having a low density.
- the structured precursor comprises a twisted multi-filament, a non-twisted multi-filament, a set of non-woven fibers, or a set of woven fibers.
- the method according to the invention has the advantage of reducing the manufacturing costs of carbon fiber assemblies (for example woven).
- the unstructured precursor comprises between 1 and 50%, preferably between 5% and 15% by weight of lignin or a lignin derivative.
- the unstructured precursor is an aqueous solution, or an organic solution or a mixture of both.
- the unstructured precursor is a hydroalcoholic solution of lignin or lignin derivative.
- the structured precursor comprises at least one hydrocellulose fiber whose diameter is between 0.5 ⁇ and 300 ⁇ , preferably between 1 ⁇ and 50 ⁇ .
- the structured precursor and / or the unstructured precursor comprises carbon nanotubes, said carbon nanotubes being present at a concentration of between 0.0001% and 10% by weight, and preferably between 0.01% and 1% by weight; mass.
- the addition of carbon nanotubes (CNTs) to one or both of the precursors makes it possible to improve the carbon yield of the fiber obtained. Indeed, when such a substance is added to the lignin or lignin derivative, the lignin or lignin derivative act as a binder and cause an increase in the amount of CNT being effectively inserted into the resulting carbon fiber.
- the combination step includes impregnation. Impregnation has the advantage of being a method that can easily be implemented industrially. the combination and thermal and dimensional stabilization steps are repeated one or more times. This is particularly advantageous because it is possible to increase the carbon yield, to increase the diameter of the fibers obtained and / or to reduce their density.
- the manufacturing process further comprises, before the carbonization step, the following steps:
- the sizing and post-sizing drying steps are repeated one or more times. This is advantageous because it is possible to increase the amount of flame retardant associated with the fiber or to combine different treatments based on different substances.
- the manufacturing method according to the invention further comprises, after the carbonization step, a graphitization step.
- Graphitization makes it possible to increase the malleability of the carbon fiber or of the set of carbon fibers obtained by the process according to the invention.
- the manufacturing method according to the invention further comprises, after the carbonization step, a sizing step of bringing the fiber or set of highly carbonaceous fibers into contact with a solution comprising at least one organic component which can comprise at least one silane or silane derivative and / or at least one siloxane or siloxane derivative.
- This step makes it possible to improve the physicochemical properties of the fiber (for example a protection against abrasion and to improve the integrity of the fibers) and has the advantage, in the context of the invention, of being able to be carried out on a whole. fiber, that is to say for example on a carbon fiber fabric.
- the invention also relates to a fiber or a set of hydrocellulose fibers covered with a deposition of lignin or lignin derivative as an intermediate product obtained after the thermal and dimensional stabilization step of the manufacturing process according to the invention.
- the invention for which the ratio of the mass of fiber to the mass of lignin or lignin derivative is between 1/2 and 100/1.
- the deposition of lignin or lignin derivative of the fiber or set of hydrocellulose fibers covered with a lignin or lignin derivative deposit according to the invention may comprise between 0.50% and 50% by weight of flame retardant compound, preferably between 2% and 30% by weight with respect to lignin deposition).
- the invention further relates to a highly carbonaceous fiber or a highly carbon fiber fabric obtainable by the method according to the invention.
- this fiber or this set of fibers has, after the carbonization step, a density of between 0.20 and 1.95 g / cm 3 , preferably between 1.45 and 1.60 g / cm 3. .
- the invention further relates to the use of fibers or sets of highly carbonaceous fibers obtained according to the manufacturing method, for the manufacture of parts made of thermoplastic or thermosetting composite materials.
- the invention also relates to thermoplastic or thermosetting composite materials obtained with fibers or sets of fibers manufactured according to the manufacturing method of the invention.
- thermoplastic or thermosetting composite materials have the advantage of presenting, for an identical volume, a weight less than 5% by weight of conventional thermoplastic or thermosetting composite materials.
- FIG. 1 shows a diagram of an embodiment of the carbon fiber manufacturing method according to the invention. Steps framed by dots are optional.
- FIG. 2 represents an image obtained by scanning electron microscopy of a section of carbon fibers according to the invention.
- fiber or set of highly carbonaceous fibers a material composed of more than 80%, by mass, of carbon, preferably more than 90%, more preferably more than 95%, even more preferred more than 98% (materials considered materials of very high purity).
- hydrocellulose fiber cellulose fibers or cellulose derivatives, preferably continuous and regular diameter, obtained after dissolution of cellulose from lignocellulosic material.
- the hydrocellulose may, for example, be obtained after treatment with sodium hydroxide followed by dissolution with carbon disulphide. In this case, the hydrocellulose is more particularly called viscose.
- the hydrocellulose fiber can be obtained from lignocellulosic material dissolved in a solution comprising N-methylmorpholine N-oxide to form Lyocell.
- lignin a plant aromatic polymer whose composition varies with the plant species and generally formed from three phenylpropanoid monomers: p-coumaryl, coniferyl and sinapyl alcohols.
- lignin derivative a molecule having a lignin-type molecular structure and having substituents having been added during the lignin extraction process or later so as to modify its physicochemical properties.
- lignin modifications There are many processes for extracting lignin from lignocellulosic biomass and these can lead to lignin modifications.
- the Kraft process uses a strong base with sodium sulfide to separate lignin from cellulose fibers. This process can form thio-lignins. The sulphite process, resulting in the formation of lignosulfonates.
- lignin derivative a lignin having substituents that can be selected from: Thiol, Sulfonate, Alkyl, or Polyester.
- the lignins or lignin derivatives used in the context of the present invention generally have a molecular weight greater than 1000 g / mol, for example greater than 10000 g / mol.
- the invention relates to a method of manufacturing 1 a fiber or a set of highly carbonaceous fibers 2, comprising the combination 100 of a structured precursor comprising a fiber or a set of hydrocellulose fibers, and an unstructured precursor comprising lignin or a lignin derivative, in the form of a solution having a viscosity of less than 15,000 mPa.s at the temperature at which the reaction occurs. combination step 100.
- This combination step 100 makes it possible to obtain a fiber or a set of hydrocellulose fibers covered with said lignin or lignin derivative 20.
- the structured precursor 10 comprises a fiber or a set of hydrocellulose fibers.
- This fiber or this set of hydrocellulose fibers can take very different forms.
- One of the advantages of the invention is that the process can be implemented on hydrocellulose fibers having been previously shaped, for example in the form of a twisted multi-filament, a non-twisted multi-filament , a set of nonwoven fibers, or a set of woven fibers.
- the invention makes it possible to use directly hydrocellulose fibers having been previously organized, in the form of multi-filament or set of fibers.
- the method according to the invention then makes it possible, in particular by virtue of the lignin or lignin derivative deposition step on said hydrocellulose fibers, and after a carbonization and possibly graphitization step, to create multi-filaments or together fibers, such as a fabric, carbon fiber having a reduced density and advantageous mechanical properties for particular, the manufacture of composite materials for automotive or aeronautics.
- the structured precursor 10 comprises a twisted multi-filament, a non-twisted multi-filament, a set of non-woven fibers, or a set of woven fibers. Even more preferably, the structured precursor 10 is a twisted multi-filament, a non-twisted multi-filament, a set of non-woven fibers, or a set of woven fibers.
- the twisted multi-filaments that can be used according to the invention have for example a number of turns per meter between 5 and 2000 turns per meter, preferably between 10 and 1000 turns per meter,
- the structured precursor 10 according to the invention may comprise at least one hydrocellulose fiber whose diameter is between 0.5 ⁇ and 300 ⁇ , preferably between 1 ⁇ and 50 ⁇ .
- the structured precursor 10 according to the invention comprises at least one continuous hydrocellulose fiber having a regular diameter over its entire length, and in particular the absence of fibril. This improves the cohesion between the lignin deposition and the fiber.
- regular diameter it should be understood that the diameter varies from less than 20%, preferably less than 10% over the length of the fiber.
- This hydrocellulose fiber can be obtained by various known manufacturing processes. It may for example be obtained according to the manufacturing method described in application WO2014064373.
- the hydrocellulose fibers used may also be Lyocell or viscose fibers, the cellulose of which comes for example from wood or bamboo.
- hydrocellulose fiber production processes are based on the production of a cellulose preparation from dissolved cellulose, for example carbon disulfide, 4-methylmorpholine 4-oxide (N-methylmorpholine- N-oxide NMMO) or in an acid solution (for example: ortho-phosphoric acid or acid acetic acid), which is then used to form the continuous hydrocellulose fibers after immersion in a coagulation bath containing, for example, sulfuric acid.
- a coagulation bath containing, for example, sulfuric acid.
- the unstructured precursor 15 comprises lignin or a lignin derivative.
- Lignin represents 10 to 25% of the terrestrial biomass of lignocellulosic nature and it is currently little valorized by the industry. Thus, each year, several hundred tons of lignin or lignin derivatives are produced without any possible valorisation.
- Lignin is present mainly in vascular plants (or higher plants) and in some algae. It is a plant aromatic polymer whose composition varies with the plant species and generally formed from three phenylpropanoid monomers: the p-coumaryl, sinapyl and coniferyl alcohols as illustrated by the formulas below:
- the unstructured precursor comprises between 1 and 50% by weight of lignin or of a lignin derivative.
- the unstructured precursor comprises between 5% and 15% by weight of lignin or a lignin derivative.
- the deposition of lignin or lignin derivative is homogeneous while allowing an increase in the carbon yield of the carbon fiber obtained after the carbonization step 300.
- the unstructured precursor 15 is in the form of a solution having a viscosity of less than 15,000 mPa.s-1 and preferably less than 10,000 mPa.s- at the temperature at which takes place the combination step 100.
- a viscosity With such a viscosity, the deposition of lignin or lignin derivative is more homogeneous and allows to obtain a continuous carbon fiber having a regular diameter while allowing an increase in the carbon yield of the carbon fiber obtained after the carbonization step 300.
- regular diameter it is to be understood that, preferably, the carbon fiber has a diameter that does not vary by more than 20%, preferably by more than 10% over its length.
- the viscosity of the solution is measured at the temperature at which the combination step 100 takes place, for example by means of a free-flowing viscometer, or capillary viscosity or the brookfield method.
- the unstructured precursor used in the manufacturing process 1 is an aqueous solution, or an organic solution or a mixture of both.
- the use of unstructured precursor 15 in the form of a solution makes it possible to control the deposition and its thickness.
- the composition of the solution can be chosen according to the characteristics of the lignin or lignin derivative used.
- the unstructured precursor used in the manufacturing process 1 is a solution comprising water and an organic solvent such as an alcohol.
- the structured precursor 10 and / or the unstructured precursor 15 may comprise carbon nanotubes, said carbon nanotubes being present at a concentration of between 0.0001% and 10% by mass. Preferably, these carbon nanotubes are present at a concentration of between 0.01% and 1% by weight.
- the carbon nanotubes may be of the single wall, double wall or multiple wall type.
- the double-walled nanotubes can in particular be prepared as described by FLAHAUT et al in Chem. Corn. (2003), 1442.
- the multi-walled nanotubes may themselves be prepared as described in WO 03/02456.
- the nanotubes usually have an average diameter ranging from 0.1 to 100 nm, preferably from 0.4 to 50 nm and better still from 1 to 30 nm, indeed from 10 to 15 nm, and advantageously a length of 0.1. at 10 ⁇ . Their length / diameter ratio is preferably greater than 10 and most often greater than 100.
- the multiwall nanotubes may for example comprise from 5 to 15 sheets (or walls) and more preferably from 7 to 10 sheets.
- An example of crude carbon nanotubes is in particular commercially available from the company ARKEMA under the trade name Graphistrength® C100.
- these nanotubes can be purified and / or treated (for example oxidized) and / or milled and / or functionalized before being used in the process according to the invention.
- the purification of the crude or milled nanotubes can be carried out by washing with a sulfuric acid solution, so as to rid them of any residual mineral and metal impurities.
- the oxidation of the nanotubes is advantageously carried out by putting them in contact with a solution of sodium hypochlorite.
- the functionalization of the nanotubes can be carried out by grafting reactive units such as vinyl monomers on the surface of the nanotubes.
- the combination step 100 corresponds to the contacting of the structured precursor 10 with the unstructured precursor 15.
- This combination can be carried out by several alternative methods, generally at a temperature ranging from -10 ° C. at 80 ° C, preferably from 20 ° C to 60 ° C.
- a soaking, spraying or impregnation for example by padding
- the combination step 100 is an impregnation.
- the manufacturing method 1 according to the invention further comprises a step of thermal and dimensional stabilization 200 of the fiber or set of hydrocellulose fibers covered with said lignin 20 so as to obtain a fiber or a set of hydrocellulose fibers coated with a lignin deposit 30.
- the thermal and dimensional stabilization step 200 may comprise a drying allowing the evaporation of the solvent and / or a ventilation.
- the drying can be carried out via a rise in temperature, for example between 50 ° C. and 200 ° C.
- a rise in temperature for example between 50 ° C. and 200 ° C.
- a solid film of lignin or lignin derivative is formed on the surface of the fiber. This film may have varying thicknesses depending on the parameters used in the process such as viscosity of the solution or concentration of lignin or lignin derivative.
- the combination steps 100 and 200 thermal and dimensional stabilization can be repeated one or more times.
- the repetition of these steps makes it possible to increase the amount of lignin or lignin derivative deposited on the fiber or the set of hydrocellulose fibers.
- the manufacturing method 1 according to the invention further comprises a step of carbonization 300 of the fiber or of the set of hydrocellulose fibers covered with a lignin deposit 30 so as to obtain a fiber or a set of high carbon fiber 2.
- This carbonization step 300 can be carried out at a temperature of between 250 ° C. and 1000 ° C., preferably greater than 300 ° C. and preferably less than 600 ° C.
- the carbonization step 300 may for example last 2 to 60 minutes.
- This carbonization step may comprise a gradual rise in temperature.
- the carbonization takes place in the absence of oxygen and preferably under a nitrogen atmosphere. The presence of oxygen during carbonization should be limited preferably to 5 ppm.
- the inventors have shown that the method according to the invention allows, with equivalent mechanical properties, to use a lower temperature than the methods of the prior art. There is therefore a reduction in the amount of energy required to produce these carbon fibers, which is energy savings.
- This carbonization step can be carried out continuously and can be coupled to a drawing step of the carbon fiber so as to improve the mechanical properties of the carbon fiber obtained.
- the manufacturing method according to the invention may further comprise, before the carbonization step 300, the following steps:
- a sizing step 210 consisting of bringing into contact the fiber or the set of hydrocellulose fibers covered with a lignin deposit 30 with an aqueous solution comprising at least one flame retardant compound, said flame retardant compound being selectable from: potassium, sodium, phosphate, acetate, chloride, and urea, and
- drying step post sizing 220 a drying step post sizing 220.
- the sizing steps 210 and drying post sizing 220 can be repeated one or more times.
- the manufacturing method according to the invention may further comprise, after the carbonization step 300, a graphitization step 400.
- This graphitization step 400 may be carried out at a temperature of between 1000 ° C. and 2800 ° C. preferably greater than or equal to 1100 ° C and preferably less than 2000 ° C.
- the graphitization step 400 may for example last from 2 to 60 minutes, preferably from 2 to 20 minutes.
- This graphitization step 400 may comprise a gradual rise in temperature.
- the manufacturing method according to the invention may further comprise, after the carbonization step 300, a sizing step 500 of contacting the fiber or the set of highly carbonaceous fibers 2 with a solution of an organic component which may comprise at least one silane or silane derivative and / or at least one siloxane or siloxane derivative.
- This sizing 500 can also be performed after the graphitization step 400. It improves the integrity of the fiber and protects it from abrasion.
- the solution comprising at least one silane or silane derivative and / or at least one siloxane or siloxane derivative is preferably an aqueous solution, an organic solution or an aqueous emulsion.
- the invention relates to a fiber or a set of hydrocellulose fibers coated with a lignin deposit 30 as an intermediate product obtained after the thermal and dimensional stabilization step 200 of the manufacturing process according to the invention.
- This intermediate product has a ratio of the mass of fiber on the mass of lignin or lignin derivative between 1/2 and 100/1, preferably between 2/1 and 95/1.
- the lignin deposition of this intermediate product comprises between 0.50% and 50% by weight of flame retardant compound, preferably between 2% and 30% by weight.
- the invention relates to a fiber or set of highly carbonaceous fibers 2 obtainable by the method according to the invention.
- the fiber or the set of highly carbonaceous fibers 2 have, after the carbonization step 300, a density of between 0.20 and 1.95 g / cm 3 , preferably between 1.45 and 1.80 g / cm 3 .
- the invention relates to a fiber or a set of highly carbonaceous fibers 2 obtained from the combination of a structured precursor 10 and an unstructured precursor 15, said structured precursor 10 comprises a fiber or a set of the hydrocellulose fibers, said unstructured precursor comprises lignin or a lignin derivative and said fiber or set of fibers has, after the carbonization step 300, a density of between 0.20 and 1.95 g / cm 3 , preferably between 1.45 and 1.60 g / cm 3 .
- the fibers or set of highly carbonaceous fibers 2 obtainable by the process according to the invention have, after the carbonization step 300, a density of between 1.45 and 1.60. g / cm 3
- the invention relates to the use of fibers or highly carbon fiber assemblies that can be obtained via the manufacturing method according to the invention, for the manufacture of parts made of thermoplastic composite materials. or thermosetting.
- thermoplastic or thermosetting composite materials obtained from the fibers manufactured via the manufacturing method according to the invention.
- these thermoplastic or thermosetting composite materials have, for an identical volume, a weight less than 5% by weight of conventional thermoplastic or thermosetting composite materials.
- the following example illustrate the invention, but have no limiting character.
- the structured precursor used is based on hydrocellulose fibers (Rayon) marketed by the company Cordenka.
- the lignin was solubilized in an Ethanol / 60/40 water mixture at 60 ° C. After 2 hours of stirring, the solution was cooled to room temperature. The precipitated fraction was filtered. The final solution contained 10% by weight of lignin.
- the lignin impregnated fibers were continuously dried through ovens at 140 ° C for a residence time of about two minutes.
- Step 3 Sizing
- the fibers comprising a lignin deposit were sized in an aqueous base flame retardant formulation comprising 160 g / dm 3 of NH 3 Cl and 20 g / dm 3 of Urea.
- Step 4 drying post sizing
- the fibers covered with a lignin deposit after sizing were subjected to a drying step under the same conditions as step 2.
- the carbonization was carried out continuously in a nitrogen atmosphere at an average temperature of 350 ° C for an average duration of 16 minutes.
- the graphitization was carried out at an average temperature of 1100 ° C, under a nitrogen atmosphere, for an average duration of 16 minutes. Characteristics of carbon fibers obtained
- the lignin deposition on the hydrocellulose fiber was 6-7% by weight. Quantification of mass lignin deposition can be obtained by weighing the hydrocellulose fiber before step 1 and then after step 2 of drying.
- FIG. 2 shows an image obtained by scanning electron microscopy of a section of the carbon fibers obtained by the process according to the invention. This image shows that the carbon fibers are distinct without agglomerate creation and that the interface between the carbon fiber from the hydrocellulose fiber and the lignin after graphitization is not visible.
- These carbon fibers have a diameter of between 6 and 7 ⁇ which is larger than that of the hydrocellulose fibers used as structured precursor for the manufacture of these carbon fibers.
- Hydrocellulose fibers without lignin deposition, carbonized (reference) 22% Hydrocellulose fibers, with 7% lignin deposition, carbonized (according to the invention) 30% [0087]
- hydrocellulose fibers with lignin so as to form, before carbonization, hydrocellulose fibers coated with a lignin deposit makes it possible to go from 22% to 30% of carbon yield, ie an increase of more than 36%.
- carbon nanotubes in the unstructured precursor containing lignin makes it possible to further increase the carbon yield and to achieve carbon yields of 35%, ie an overall increase of nearly 60% of the carbon content. carbon yield.
- Fiber shrinkage / elongation set at 0% (no shrinkage, no stretching).
- These fibers have a higher elongation at break than conventional carbon fibers.
- the present invention comprises the use of a natural resource, cellulose, at the base of a structured precursor combined with another natural resource, lignin, as an unstructured precursor to obtain a carbon fiber or a lighter carbon fiber assembly, more efficient for the char yield and giving a lower cost carbonized material than precursors such as PAN fibers.
- the carbon fibers obtained by the process of the invention can advantageously be used as a replacement for conventional glass fiber or carbon fiber for the manufacture of parts made of thermoplastic or thermosetting composite materials which can be used in particular in the aerospace, automotive, wind, naval, building construction, sports.
- These fibers according to the invention have several advantages, in particular a reduction in the weight of the structures because the fibers according to the invention have a lower density than conventional glass fibers and carbon fibers.
Abstract
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PCT/FR2017/052952 WO2018078288A1 (en) | 2016-10-28 | 2017-10-26 | Method for producing carbon fibres from biosourced precursors and carbon fibres produced |
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EP (1) | EP3532661A1 (en) |
JP (1) | JP7062006B2 (en) |
KR (1) | KR20190070350A (en) |
CN (1) | CN109891011A (en) |
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GB2579864A (en) * | 2018-12-18 | 2020-07-08 | Univ Limerick | Improvements relating to thermoelectric materials |
GB201907004D0 (en) * | 2019-05-17 | 2019-07-03 | Univ Limerick | Improvements relating to carbon fibre processing |
KR102075114B1 (en) * | 2019-06-21 | 2020-02-07 | 국방과학연구소 | Carbon nanotube coating and heat treatment for manufacturing lyocell-based carbon fiber |
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JPS59144625A (en) * | 1982-12-25 | 1984-08-18 | Oji Paper Co Ltd | Production of carbon fiber sheet |
WO1999007926A2 (en) * | 1997-08-07 | 1999-02-18 | Achim Neumayr | Method for producing a cellulose fibre from hydrocellulose |
FR2826646B1 (en) | 2001-06-28 | 2004-05-21 | Toulouse Inst Nat Polytech | PROCESS FOR THE SELECTIVE MANUFACTURE OF ORDINATED CARBON NANOTUBES IN FLUIDIZED BED |
CN1255585C (en) | 2004-07-15 | 2006-05-10 | 东华大学 | Process for preparing precursor fiber of cellulose base carbon fiber |
DE602004006285T2 (en) * | 2004-12-07 | 2007-12-20 | Snecma Propulsion Solide | Process for producing carbon yarn or fiber sheets from a cellulosic material |
US20070087120A1 (en) * | 2005-10-18 | 2007-04-19 | Connors Donald F Jr | Fluid diffusion layers |
US7824651B2 (en) | 2007-05-08 | 2010-11-02 | Nanotek Instruments, Inc. | Method of producing exfoliated graphite, flexible graphite, and nano-scaled graphene platelets |
US20110285049A1 (en) | 2010-05-19 | 2011-11-24 | Baker Frederick S | Carbon nanotube (cnt)-enhanced precursor for carbon fiber production and method of making a cnt-enhanced continuous lignin fiber |
KR101264001B1 (en) | 2011-01-13 | 2013-05-13 | 경북대학교 산학협력단 | Precursor including lyocell/graphene nanocomposite and carbon-fiber by using the same and method of manufacturing the same |
KR101242377B1 (en) | 2011-10-05 | 2013-03-15 | 전남대학교산학협력단 | Preparation method of carbon-carbon composite fiber, and application to carbon heating element and carbon heater using the same |
TWI589741B (en) * | 2012-01-23 | 2017-07-01 | 茵芬提亞公司 | Method for stabilizing lignin fiber for further conversion to carbon fiber |
KR101230532B1 (en) | 2012-09-03 | 2013-02-06 | 국방과학연구소 | Carbon composite material |
FR2997097B1 (en) | 2012-10-22 | 2015-04-10 | Arkema France | PROCESS FOR PRODUCING CARBON FIBER, PRECURSOR MATERIAL USED BY THE PROCESS AND CARBON FIBER OBTAINED |
CN103774286B (en) * | 2014-01-08 | 2015-05-20 | 北京梦狐宇通竹纤维研究开发中心 | Preparation method of cellulose carbon nanofibre filter material |
US20160168363A1 (en) * | 2014-06-27 | 2016-06-16 | Api Intellectual Property Holdings, Llc | Nanocellulose-polymer composites, and processes for producing them |
US20160122515A1 (en) * | 2014-10-31 | 2016-05-05 | Api Intellectual Property Holdings, Llc | Automotive tires containing hydrophobic nanocellulose |
CN104593906B (en) * | 2015-02-15 | 2017-01-11 | 东华大学 | Preparation method of lignin-based carbon fiber |
FR3058167B1 (en) * | 2016-10-28 | 2019-11-22 | Arkema France | NEW PROCESS FOR MANUFACTURING HIGHLY CARBON MATERIALS AND HIGHLY CARBON MATERIAL OBTAINED |
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