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    • 专利摘要:
    The invention relates to a process for the preparation of a preimpregnated fibrous material, in particular in ribbon form, comprising a fibrous reinforcement and a thermoplastic polymer matrix comprising the following step: i) impregnating said fibrous material in the form of a wick single or several parallel strands of said melt polymer said melt polymer containing during said impregnation a neutral gas in the supercritical state, used as a processing aid by viscosity reduction in the molten state, preferably said gas being supercritical CO2.
    公开号:FR3017320A1
    申请号:FR1451140
    申请日:2014-02-13
    公开日:2015-08-14
    发明作者:Patrice Gaillard；Gilles Hochstetter；Thibaut Savart
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a process for the preparation of a preimpregnated fibrous material, a process for the preparation of a pre-impregnated fibrous material, a process for the preparation of a pre-impregnated fibrous material, and a process for the preparation of a pre-impregnated fibrous material. in particular in ribbon form, comprising a fibrous reinforcement and a thermoplastic polymer matrix.  [02] The invention also relates to a pre-impregnated material, in particular in the form of ribbon and more particularly wound on a reel.  [03] The invention also relates to the use of the method for the manufacture of calibrated ribbons suitable for the manufacture of three-dimensional (3D) composite parts by automatic robot deposition of said ribbons and the composite parts in 3D, resulting from the use of at least one prepreg fibrous material, in particular in the form of a ribbon.  [04] The manufacture of fibrous materials pre-impregnated with a thermoplastic polymer or a mixture of thermoplastic polymers in the molten route, also referred to as a thermoplastic resin, allows shaping of these pre-impregnated fibrous materials in the form of calibrated strips which can be used to manufacture composite materials.  The preimpregnated fibrous materials are used in the manufacture of structural parts to lighten them while maintaining mechanical strength comparable to that obtained for structural steel parts and / or by ensuring the evacuation of electrostatic charges and / or by providing thermal and / or chemical protection.  [5] In the present description, the term "band" is used to designate strips of fibrous material whose width is greater than or equal to 100 mm.  The term "ribbon" is used to designate ribbons of calibrated width and less than or equal to 100 mm.  [6] Such preimpregnated fibrous materials are particularly intended for the production of lightweight composite materials for the manufacture of mechanical parts having a three-dimensional structure and having properties of good mechanical strength, thermal and able to evacuate loads. Ref: 0402-ARK48 electrostatic, that is to say properties compatible with the manufacture of parts in particular in the fields of mechanics, aeronautics and nautical, automotive, energy, construction (buildings), health and medical, army and armaments, sports and recreation, and electronics.  Thus, the composite materials are used for the production of three-dimensional (3D) parts, the production of these composite materials can be done by a known process of strip removal assisted by a robot (AFP method (acronym Automatic Fiber Placement "for example).  [7] The composite materials obtained comprise the fibrous material, constituted by the reinforcing fibers, and a matrix constituted by the impregnating polymer.  The primary role of this matrix is to maintain the reinforcing fibers in a compact form and to give the desired shape to the final product.  Such a matrix serves inter alia to protect the reinforcing fibers against abrasion and an aggressive environment, to control the surface appearance and to disperse any fillers between the fibers.  The role of this matrix is important for the long-term behavior of the composite material, especially with regard to fatigue and creep [8]. In the present invention, the term "fibrous material" refers to an assembly of reinforcing fibers.  Before it is shaped, it is in the form of wicks.  After shaping, it comes in the form of strips or tablecloths, or braids, or pieces.  When the reinforcing fibers are continuous, their assembly constitutes a fabric.  When the fibers are short, their assembly constitutes a felt or a nonwoven.  [9] Fibers which may be included in the composition of the fibrous material are more particularly carbon fibers, glass fibers, basalt fibers, silicon carbide fibers (SICs), polymer-based fibers, fibers plants, or cellulosic fibers used alone or as a mixture.  [10] A good quality of the three-dimensional composite parts made from preimpregnated fibrous materials passes through a control on the one hand of the impregnation process of the reinforcing fibers by the thermoplastic polymer and on the other hand of the method of setting form of the fibrous material pre-impregnated as a semi-finished product.  Ref: 0402-ARK48 [11] Up to now, the manufacture of strips of preimpregnated fibrous materials reinforced by impregnation of thermoplastic polymer could be achieved by means of several processes chosen in particular according to the nature of the polymer, the type of composite material desired end and its scope.  Powder coating or extrusion technologies of molten polymer are used to impregnate thermosetting polymers such as epoxy resins for example as described in WO2012 / 066241A2.  These technologies are not generally applicable directly to the impregnation of thermoplastic polymers, in particular those with a high melting point, which have too high melt viscosity to obtain good quality products.  [12] Companies market strips of fibrous materials obtained by a method of impregnating unidirectional fibers by passing the fibers, continuously, in a melt of thermoplastic polymer containing an organic solvent such as benzophenone.  For example, US Pat. No. 4,541,884 to Imperial Chemical Industries can be referred to.  The presence of the organic solvent makes it possible in particular to adapt the viscosity of the molten mixture and to ensure a good coating of the fibers.  The fibers thus pre-impregnated are then shaped.  They may for example be cut into strips of different widths and then placed under a press, then heated to a temperature above the melting temperature of the polymer to ensure the cohesion of the material and in particular the adhesion of the polymer to the fibers.  This method of impregnation and shaping makes it possible to produce structural parts with high mechanical strength.  [013] One of the disadvantages of this technique lies in the heating temperature required to obtain these materials.  The melting temperature of the polymers depends in particular on their chemical nature.  It can be relatively high for poly (methyl methacrylate) (PMMA) polymers, or even very high for poly (phenylene sulfide) (PPS), poly (ether ether ketone) (PEEK) or poly ( ether ketone ketone) (PEKK) for example.  The heating temperature can therefore increase to temperatures higher than 250 ° C., and even higher than 350 ° C., temperatures which are much higher than the boiling point and the flash point of the solvent, which are respectively Ref: 0402- ARK48 305 ° C and 150 ° C for benzophenone.  In this case, there is a sudden departure of the solvent inducing a high porosity within the fibers and therefore causing the appearance of defects in the composite material.  The process is therefore difficult to reproduce and involves risks of explosion endangering the operators.  Finally, the use of organic solvents is to be avoided for environmental and health and safety reasons.  [14] Reference can also be made to the closest prior art of Honeywell International Inc., Document WO2008 / 061170 (D1).  This document describes a method for producing a unidirectionally oriented fiber structure.  The use of fibers of the same kind or of a fiber assembly is envisaged (page 12, lines 25 to 29).  However, this method consists of arranging the fibers unidirectionally and to coat or impregnate them by passing through a bath containing a viscous liquid.  This viscous liquid may be composed for example of a thermoplastic resin whose viscosity is the most important parameter (page 14, lines 6 to 9).  After soaking, three stages follow one another: spreading, uniformization and drying of the deposit in order to obtain the final product.  The fibers of the arrangement are thus glued to each other and form the desired structure.  To obtain a desired viscosity, solvents are used if necessary.  The disadvantages of this technique are similar to the drawbacks described with respect to the preceding technique, namely the use of a solvent to reduce the viscosity that leads during the melting of the polymer when the temperature is high, to a sudden departure of said solvent which induces a high porosity. within the fibers and which causes the appearance of defects in the composite material.  And finally, the use of organic solvents is to be avoided for environmental reasons and hygiene and safety of operators.  [15] Concerning the shaping of preimpregnated fibrous materials in the form of calibrated ribbons, suitable for the manufacture of three-dimensional composite parts by automatic dispensing by means of a robot, this is generally carried out in post-treatment.  [016] The quality of the pre-impregnated fibrous material tapes, and therefore the quality of the final composite material, depends not only on the homogeneity of the impregnation of the fibers, but also on the size and more particularly on the width and thickness. the thickness of the ribbons.  Regularity and control of these two dimensional parameters make it possible to improve the mechanical strength of the materials.  Ref: 0402-ARK48 [17] At present, whatever the process used to obtain tapes of fibrous materials, the manufacture of ribbons of small width, that is to say of width less than 100 mm, generally requires slitting (that is to say a cut) strips of width greater than 500 mm, also called tablecloths.  The ribbons thus dimensioned are then taken back to be deposited by a robot using a head.  [18] In addition, the web rolls not exceeding a length of the order of 1 km, the ribbons obtained after cutting are generally not long enough to manufacture some large size materials during removal by robot.  The ribbons must therefore be roped to obtain a longer length, creating extra thicknesses.  These extra thicknesses lead to the appearance of heterogeneities that are detrimental to obtaining good quality composite materials.  [19] Current techniques for impregnating fibrous materials and shaping such fibrous pre-impregnated materials in the form of calibrated ribbons thus have several disadvantages.  For example, it is difficult to homogeneously heat a molten mixture of thermoplastic polymers in a die and at the outlet of the die to the core of the material, which alters the quality of the impregnation.  In addition, the difference in temperature existing between the fibers and a molten mixture of polymers at the level of the impregnation die also alters the quality and homogeneity of the impregnation.  The use of organic solvents generally involves the appearance of defects in the material as well as environmental and safety risks.  The shaping, by high temperature post-treatment of the pre-impregnated fibrous material in the form of ribbons, remains difficult because it does not always allow a homogeneous distribution of the polymer within the fibers, which leads to obtaining a material of lower quality.  The splitting of webs for obtaining calibrated ribbons and the splicing of these ribbons induces an additional cost of manufacture.  Slitting also generates significant dust problems that pollute the ribbons of pre-impregnated fibrous materials used for robot removal and can cause malfunctions of robots and / or imperfections on the composites.  This potentially leads to robot repair costs, a shutdown of production and the scrapping of non-compliant products.  Finally, during the slitting step, a not insignificant amount of fibers is deteriorated, inducing a loss of properties, and in particular a reduction Ref: 0402-ARK48 of the mechanical strength and the conductivity, ribbons of fibrous material pre- impregnated.  [Technical problem] [020] The object of the invention is therefore to remedy at least one of the disadvantages of the prior art.  The invention aims in particular to provide a process for preparing a preimpregnated fibrous material, in particular in ribbon form, comprising a fibrous reinforcement and a thermoplastic polymer matrix in which the impregnation is carried out by melting the polymer without restriction on the choice of the thermoplastic polymer related to the melting temperature / viscosity of said polymer and obtaining a preimpregnated fibrous material having a homogeneous impregnation of the fibers and with a controlled porosity and dimensions and reproducible.  [BRIEF DESCRIPTION OF THE INVENTION] [021] For this purpose, the subject of the invention is a process for preparing a preimpregnated fibrous material, in particular in the form of a ribbon, comprising a fibrous reinforcement and a polymer matrix. thermoplastic mainly characterized in that it comprises the following step: i) impregnating said fibrous material in the form of a single wick or several parallel wicks by said polymer in the molten state said melt polymer containing at the time of said impregnation a neutral gas in the supercritical state, used as a processing aid by melt viscosity reduction, preferably said gas being supercritical CO2.  [022] Thus, by using a melt polymer viscosity reducing aid, by means of a neutral gas, which may be a mixture of neutral gases, in the supercritical state, melt impregnation of a fibrous material in the form of a single wick or several parallel wicks by said polymer can be implemented without restriction on the choice of the thermoplastic polymer and homogeneous impregnation around the fibers is ensured with control and reproducibility porosity and in particular for pre-impregnated "ready to use" a significant reduction in porosity until no porosity.  [023] Furthermore the method comprises in addition to step i) the following additional steps: Ref: 0402-ARK48 ii) shaping said wick or said parallel locks of said fibrous material impregnated according to step i), by calendering by at least one heating radiator, in the form of a single-directional single tape or multiple unidirectional parallel ribbons, with in the latter case said heating calender comprising multiple calendering grooves, preferably up to 200 calendering grooves, in accordance with the number of said ribbons and with a pressure and / or spacing between the rollers of said calender, controlled by a slave system.  [24] Thus, the method also makes it possible to obtain one or more ribbons of great length and of calibrated width and thickness and to form ribbons of calibrated dimensions without resorting to a slitting and splicing step.  [25] According to other optional features of the process: - said polymer is a thermoplastic polymer or a mixture of thermoplastic polymers; said thermoplastic polymer or thermoplastic polymer blend further comprises carbonaceous fillers, in particular carbon black or carbon nanofillers, preferably chosen from graphenes and / or carbon nanotubes and / or carbon nanofibrils or mixtures thereof ; the thermoplastic polymer or thermoplastic polymer blend further comprises liquid crystal polymers or cyclized poly (butylene terephthalate), or mixtures thereof, as an additive; said polymer, or mixture of thermoplastic polymers, is selected from amorphous polymers whose glass transition temperature is such that Te 80 ° C and / or from semi-crystalline polymers whose melting point T f is 150 ° C .; the thermoplastic polymer or mixture of thermoplastic polymers is selected from polyaryl ether ketones, in particular PEEK, or polyaryl ether ketone ketone, in particular PEKK or polyether-imides (PEI) aromatic or polyaryl sulfones, in particular polyphenylene sulfones (PPS), or polyarylsulphides, in particular polyphenylene sulfides, or from polyamides (PA), in particular aromatic polyamides optionally modified with urea units, or Ref: 0402-ARK48 polyacrylates, in particular polymethyl methacrylate (PMMA), or fluoropolymers, in particular polyvinylidene fluoride (PVDF); - It further comprises a step iii) winding said ribbon or said ribbons on one or more coils, the number of coils being identical to the number of ribbons, a coil being assigned to each ribbon; the impregnation step i) is completed by a step of covering said single wick or said parallel multiple wicks after impregnation with the molten polymer according to step i), with a molten polymer that may be identical to or different from said polymer, impregnation i), before said calendering step ii), preferably said molten polymer being identical to said impregnating polymer i), preferably said covering being effected by extrusion at right angles to said single wick or relative said multiple parallel strands; said fibrous material comprises continuous fibers selected from fibers of carbon, glass, silicon carbide, basalt, natural, in particular linen or hemp, sisal, silk, or cellulosic fibers, in particular viscose, or thermoplastic fibers with a Tg greater than the Tg of said polymer or said polymer mixture when it is amorphous or Tf greater than the Tf of said polymer or said polymer mixture when the latter is semi-crystalline, or a mixture of two or a plurality of said fibers, preferably carbon, glass or silicon carbide fibers or mixtures thereof, in particular carbon fibers; according to an exemplary embodiment, the volume ratio of said polymer or polymer mixture with respect to said fibrous material varies from 40 to 250%, preferably from 45 to 125% and more preferably from 45 to 80%; according to another exemplary embodiment, the volume ratio of said polymer or said polymer mixture with respect to said fibrous material varies from 0.2 to 15%, preferably from 0.2 to 10% and more preferably from 0.2 to 5%; the calendering step ii) is carried out by means of a plurality of heating calenders; - Advantageously, said (or said) calender (s) heater (s) of step ii) comprises an integrated induction heating system coupled to the presence of carbonaceous fillers in said thermoplastic polymer or mixture of thermoplastic polymers; Ref: 0402-ARK48 - advantageously, each heating calender is associated with a rapid heating device; advantageously, said impregnation step is carried out using an extrusion technique; said impregnation technique is the extrusion at right angle with respect to said single wick or with respect to said parallel multiple wicks; said neutral gas in the supercritical state is a supercritical neutral gas or a mixture of supercritical neutral gas; said neutral gas in the supercritical state is supercritical CO2 gas or a mixture of neutral gases in the supercritical state containing CO2 and a fluorinated gas or a mixture based on CO2 and nitrogen; said supercritical gas, preferably supercritical CO2, is injected at the level of the extrusion head; said supercritical gas, preferably supercritical CO2, is mixed with said molten impregnation polymer i) in a static mixer.  [026] The invention also relates to a pre-impregnated material, in particular in the form of ribbon more particularly wound on a reel, mainly characterized in that it is based on a pre-impregnated fibrous material such as obtained by the process defined above; advantageously, the pre-impregnated material is in the form of a ribbon having a width and a thickness suitable for robot removal in the manufacture of 3D parts, without the need for splitting, and preferably having a width of at least 5 mm and up to 100mm, preferably from 5 to 50mm and even more preferably from 5 to 10mm.  [027] The invention also relates to the use of the method as defined above, for the manufacture of calibrated ribbons suitable for the manufacture of composite parts in 3D by automatic robot deposition of said ribbons; the use of the preimpregnated fibrous material, in particular in the form of a ribbon, in the manufacture of 3D composite parts; the use of the preimpregnated fibrous material for the manufacture of said composite parts relates to the automobile, the civil or military aeronautics, the energy in particular wind and tidal, the energy storage devices, the Ref: 0402 -ARK48 thermal protection panels, solar panels, ballistics with parts for weapons or missiles, security, boating, sports and recreation, building and construction or electronics.  [28] The invention also relates to a three-dimensional (3D) composite part, resulting from the use of at least one pre-impregnated fibrous material, as defined above, in particular in the form of a ribbon.  Finally, the invention relates to a unit for implementing the process for preparing a preimpregnated fibrous material, in particular in the form of a ribbon, as defined above, said unit being mainly characterized in that it comprises: a) a device for continuously impregnating a wick or a plurality of parallel wicks of fibrous material comprising a molten polymer-fed impregnation die containing the neutral gas at the same time; supercritical state, b) a continuous calendering device of said wick or said parallel wicks, with shaping, in the form of a single ribbon or in the form of several unidirectional parallel ribbons, comprising: b1) at least one heating calender , in particular, a plurality of heating calandria in series, said calender having a calendering groove or a plurality of calendering grooves, and preferably in the latter case having up to 200 cala gorges. ndrage, b2) a controlled system for regulating the pressure and / or spacing between calendering rollers.  [Description of the drawings [030] Other features and advantages of the invention will appear on reading the description given by way of illustrative and nonlimiting example, with reference to the appended figures, which represent: FIG. a schematic side view of an implementation unit of the process for manufacturing a fibrous material pre-impregnated in the form of calibrated ribbons according to the invention, - Figure 2, a diagram in top view, of a unit for implementing the process for manufacturing a preimpregnated fibrous material in the form of calibrated ribbons according to the invention, Ref: 0402-ARK48 - FIG. 3, a sectional diagram of two constituent rolls of a calender as used in the unit of Figure 1 or 2.  Polymeric Matrix Thermoplastic, or thermoplastic polymer, is understood to mean a material that is generally solid at room temperature, that can be crystalline, semicrystalline or amorphous, and that softens during an increase in temperature. temperature, especially after passing its glass transition temperature (Tg) if amorphous and flows at a higher temperature and can observe a frank fusion at the passage of its so-called melting temperature (Tf) if crystalline or semi-crystalline, and which becomes solid again when the temperature falls below its melting temperature and below its glass transition temperature.  [032] Regarding the polymer of constitution of the impregnating matrix of the fibrous material of the present invention, this polymer is advantageously a thermoplastic polymer or a mixture of thermoplastic polymers.  The polymer or mixture of thermoplastic polymers is introduced into an impregnation die connected to a polymer extrusion system capable of extruding the thermoplastic polymer or thermoplastic polymer mixture in the molten state in the presence of the neutral gas in the supercritical state. , which can be a mixture of neutral gases in the supercritical state.  [33] Optionally, the thermoplastic polymer or thermoplastic polymer blend further comprises carbonaceous fillers, in particular carbon black or carbon nanofillers, preferably chosen from carbon nanofillers, in particular graphenes and / or nanotubes. of carbon and / or carbon nanofibrils or mixtures thereof.  These charges make it possible to conduct electricity and heat, and consequently make it possible to improve the lubrication of the polymer matrix when it is heated.  [34] According to another variant, the thermoplastic polymer or thermoplastic polymer blend may further comprise additives, such as liquid crystal polymers or cyclized poly (butylene terephthalate), or mixtures containing them, such as commercialized CBT100 resin Ref: 0402-ARK48 CYCLICS CORPORATION.  These additives make it possible in particular to fluidify the polymer matrix in the molten state, for better penetration into the core of the fibers.  Depending on the nature of the polymer or mixture of thermoplastic polymers used to make the impregnation matrix, in particular their melting temperature, one or other of these additives will be chosen.  [035] Advantageously, the thermoplastic polymer or thermoplastic polymer mixture is selected from amorphous polymers whose glass transition temperature is such that Te 80 ° C and / or from semi-crystalline polymers whose melting temperature T f is 150 ° C.  [036] More particularly, the thermoplastic polymers forming part of the impregnating matrix of the fibrous material may be chosen from: polymers and copolymers of the family of polyamides (PA), such as high-density polyamide, polyamide 6 (PA-6), polyamide 11 (PA-11), polyamide 12 (PA-12), polyamide 6. 6 (PA-6. 6), the polyamide 4. 6 (PA-4. 6), the polyamide 6. (PA-6. 10), the polyamide 6. 12 (PA-6. 12), aromatic polyamides optionally modified with urea units, in particular polyphthalamides and aramid, and block copolymers, in particular polyamide / polyether, polyureas, in particular aromatic polymers, polymers and copolymers of the family of acrylics such as polyacrylates, and more particularly polymethyl methacrylate (PMMA) or its derivatives, polymers and copolymers of the family of polyarylether ketones (PAEK) such as polyether ether ketone (PEEK), or polyarylether ketones ketones (PAEKK) such as polyetherketone ketone (PEKK) or their derivatives, aromatic polyetherimides (PEI), polyarylsulphides, in particular polyphenylene sulfides (PPS), polyarylsulphones, in particular polyphenylene sulfones (PPSU) - polyolefins, in particular polyethylene (PE); polylactic acid (PLA), polyvinyl alcohol (PVA), fluorinated polymers, in particular polyvinylidene fluoride (PVDF), or polytetrafluoroethylene (PTFE) or polychlorotrifluoroethylene (PCTFE), and their mixtures.  Ref: 0402-ARK48 [037] Preferably, the polymers constituting the matrix are chosen from thermoplastic polymers having a high melting temperature Tf, namely from 150 ° C. and higher, such as polyamides (PA) in particular aromatic polyamides optionally modified with urea units and their copolymers, polymethyl methacrylate (PPMA) and its copolymers, polyetherimides (PEI), polyphenylene sulphide (PPS), polyphenylene sulphone (PPSU) ), polyetherketoneketone (PEKK), polyetheretherketone (PEEK), fluorinated polymers such as polyvinylidene fluoride (PVDF).  [038] And more preferably, the thermoplastic polymer or mixture of thermoplastic polymers is selected from polyaryl ether ketones, in particular PEEK, or polyaryl ether ketone ketone, in particular PEKK or polyetherimides (PEI) aromatic or polyaryl sulfones, in particular polyphenylene sulfones (PPS), or polyarylsulfides, in particular polyphenylene sulfides, or from polyamides (PA), in particular aromatic polyamides optionally modified by urea units, or polyacrylates, in particular polymethyl methacrylate (PMMA), or fluoropolymers, in particular polyvinylidene fluoride (PVDF).  [39] For the fluoropolymers, it is preferred to use a homopolymer of vinylidene fluoride (VDF of formula CH2 = CF2) or copolymer of VDF comprising by weight at least 50% by weight of VDF and at least one other monomer copolymerizable with VDF .  The VDF content must be greater than 80% by weight, or even better 90% by weight, to ensure good mechanical strength to the structural part, especially when subjected to thermal stresses.
    [0002] The comonomer may be a fluorinated monomer chosen, for example, from vinyl fluoride. [40] For structural parts having to withstand high temperatures, in addition to the fluorinated polymers, PAEK (PolyArylEtherKetone) such as PEK polyether ketones, PEEK poly (ether ether ketone), polyethylene glycol are advantageously used according to the invention. (ether ketone ketone) PEKK, Poly (ether ketone ether ketone ketone) PEKEKK etc. Fibrous material: Ref: 0402-ARK48 [041] Concerning the fibers of constitution of the fibrous material, these are in particular fibers of mineral, organic or vegetable origin, such as carbon, glass, silicon carbide, basalt fibers, in particular flax or hemp, sisal, silk, or cellulosic, in particular viscose, or thermoplastic fibers with a Tg greater than the Tg of said polymer or said polymer mixture when it is amorphous or Tf greater than the Tf of said polymer or said polymer mixture when the latter is semi-crystalline, or a mixture of two or more of said fibers, preferably of carbon fibers, of glass or of silicon carbide or their mixture, in particular of carbon fibers. Among the fibers of mineral origin, it is possible to choose carbon fibers, glass fibers, basalt fibers, silica fibers, or silicon carbide fibers, for example. Among the fibers of organic origin, it is possible to choose fibers based on thermoplastic or thermosetting polymers, such as aromatic polyamide fibers, aramid fibers or polyolefin fibers, for example. Preferably, they are based on thermoplastic polymer and have a glass transition temperature Tg greater than the Tg of the polymer or thermoplastic polymer mixture of constitution of the impregnation matrix when the latter is amorphous, or a melting temperature Tf greater than the Tf of the polymer or thermoplastic polymer mixture of constitution of the impregnation matrix when it is semi-crystalline. Thus, there is no risk of fusion for the organic fibers constituting the fibrous material. Among the fibers of vegetable origin, it is possible to choose the natural fibers based on flax, hemp, silk, especially spider, sisal, and other cellulosic fibers, in particular viscose. These plant-based fibers can be used pure, treated or coated with a coating layer, in order to facilitate the adhesion and impregnation of the thermoplastic polymer matrix [43] The fibers constituting the fibrous material can be used alone or in mixtures. Thus, organic fibers may be blended with the mineral fibers to be impregnated with thermoplastic polymer and form the preimpregnated fibrous material. [44] The fibers are either single-stranded, multi-stranded or a mixture of both, and may have several grammages. They can also have several geometries. Thus, they may be in the form of short fibers, which then make up felt or non-woven fabrics which may be in the form of Ref: 0402-ARK48 strips, sheets, braids, locks or pieces, or in the form of continuous fibers, that make up 2D fabrics, fibers or wicks of unidirectional fibers (UD) or non-woven fibers. The fibers constituting the fibrous material may also be in the form of a mixture of these reinforcing fibers of different geometries. Preferably, the fibers are continuous. [45] Preferably, the fibrous material is constituted by continuous fibers of carbon, glass or silicon carbide or their mixture, in particular carbon fibers. It is used as a wick (s). [46] According to the volume ratio of polymer relative to the fibrous material, it is possible to produce so-called pre-impregnated materials "ready to use" or so-called "dry" prepreg materials. [47] In pre-impregnated materials known as "ready-to-use", the polymer or mixture of thermoplastic impregnating polymers is distributed uniformly and homogeneously around the fibers. In this type of material, the thermoplastic impregnating polymer must be distributed as homogeneously as possible within the fibers in order to obtain a minimum of porosities, ie voids between the fibers. Indeed, the presence of porosities in this type of material can act as points of concentration of stress, during a mechanical tensile stress for example, and which then form fracture initiation points of the pre fibrous material. -impregnated and weakened mechanically. A homogeneous distribution of the polymer or polymer mixture thus improves the mechanical strength and the homogeneity of the composite material formed from these preimpregnated fibrous materials. [48] Thus, in the case of so-called "ready-to-use" prepreg materials, the volume ratio of the thermoplastic polymer or mixture of polymers to fibrous material ranges from 40 to 250%, preferably 45 to 250% by weight. at 125%, and more preferably 45 to 80%. [49] So-called "dry" preimpregnated fibrous materials, in turn, comprise porosities between the fibers and a smaller amount of thermoplastic impregnating polymer that covers the surface fibers to hold them together. These "dry" prepreg materials are suitable for the manufacture of preforms for composite materials. These preforms can then be used to make the infusion of thermoplastic resin or thermosetting resin for example. The porosities make it possible in this case to facilitate the subsequent transport of the Ref: 0402-ARK48 infused polymer resin, within the preimpregnated fibrous material, in order to improve the final properties of the composite material and in particular its mechanical cohesion. In this case, the presence of the thermoplastic impregnating polymer on the so-called "dry" preimpregnated fibrous material makes it possible to make the infusion resin compatible. [50] Thus, in the case of so-called "dry" preimpregnated materials, the volume ratio of the polymer or of the polymer mixture with respect to the fibrous material advantageously varies from 0.2 to 15%, preferably from 0.2 to and 10% and more preferably 0.2 and 5%. In this case we speak of polymer web, low weight, deposited on the fibrous material to hold the fibers together. Impregnation step: [51] The process for preparing a pre-impregnated fibrous material, in particular in the form of a ribbon, according to the invention, is carried out by means of a device for continuous impregnation of a wick or of a plurality of parallel strands of fibrous material advantageously comprising a melt-polymer fed impregnation die containing the neutral gas in the supercritical state. [52] The method and the unit of implementation of this method are described below, with reference to FIGS. 1 and 2 which schematize, in a very simplified manner, the constituent elements of this unit 200. [53] Advantageously, the impregnation step of the fibrous material is performed by an extrusion technique. More particularly, an extrusion is made at the head of the square with respect to the single wick or with respect to multiple parallel locks. [054] Advantageously, the impregnation is carried out by passing one or more wicks F in a continuous impregnation device 40, this impregnation device 40 comprises an impregnation head 404, also designated 'impregnation. [055] For each wick to be impregnated is rolled by means of a device 10 reels 11 under the traction generated by cylinders (whose axes are shown). Preferably, the device 10 comprises a plurality of reels 11, each reel for unwinding a wick to impregnate. Thus, it is possible to impregnate several strands of fibers simultaneously. Each reel 11 is provided with a brake (not shown) so as to apply a tension on each fiber wick. In this case, an alignment module 20 allows to arrange the fiber locks parallel to each other. In this way the fiber locks can not be in contact with each other, which makes it possible to avoid mechanical degradation of the fibers in particular. [056] Optionally, the impregnation may be completed by a step of covering said single wick or said parallel multiple wicks after impregnation with the molten polymer, by a molten polymer which may be identical or different from said impregnating polymer, before the calendering step. Preferably, the molten polymer is identical to the impregnating polymer and preferably the covering is effected by extrusion at the head of the square with respect to the single wick or with respect to said multiple parallel strands. The use of a different polymer may allow, for example, to add properties to the composite material obtained or to improve its properties, compared to those provided with the impregnating polymer. The angle head is then supplied with thermoplastic polymer melted by an extruder, this assembly is symbolized by the arrow 41 in FIGS. 1 and 2. In fact, such a covering not only makes it possible to complete the step of impregnating the fibers. to obtain a final polymer volume content in the desired range, especially for obtaining fibrous materials known as "ready to use" good quality, but it also improves the performance of the composite material obtained. [057] Before passing through the impregnation head 404, the fiber lock or the parallel fiber locks pass into a heating device 30 whose temperature is controlled and variable, ranging from ambient temperature to 1000 ° C. . However, this temperature will be reduced for the organic polymers which would degrade completely towards 500 ° C and will have to remain within the limits of the temperature not to be exceeded for the impregnation. This heating temperature will not exceed 250 ° C in this case. This heating makes it possible to wear the fiber locks at a temperature which facilitates their impregnation without, however, minimizing the technical effect produced by the supercritical gas mixed with the molten polymer, namely a reduced viscosity. Indeed, this heating prior to impregnation thus prevents too rapid recrystallization of the polymer by contact with the locks. The heating device 30 may also make it possible to initiate the polymerization of a material previously deposited on the fiber locks or to degrade or even completely degrade the fiber size by thermal means. SUMMARY OF THE INVENTION The size corresponds to the small amount of polymer which generally covers the fiber locks to ensure the binder between these fibers within the lock but also a compatibility with the polymer matrix during a resin infusion process for example. This heating device 30 may, for example, be chosen from the following devices: a microwave or induction device, an IR or laser infrared device or other device allowing direct contact with the heat source such as a device to be used. flame. A microwave or induction device is very advantageous, in particular when it is coupled to the presence of carbon nanofillers in the polymer or polymer mixture since the carbon nanofillers amplify the heating effect and transmit it to the core of the material. [58] At the outlet of this heating device 30, the different strands of fibers pass through the impregnation head 404. This impregnation head is composed of an upper part 401 and a lower part 402 making it possible to adjust the pressure. opening of the die at the inlet of the fiber locks and at the outlet. The impregnating head 404 is connected to a worm-type polymer extrusion device 403, capable of extruding the polymer or polymer mixture in molten mode, the polymer therefore being at a high temperature and in the presence of a gas or supercritical gas mixture G. [59] Advantageously, the extrusion device of the polymer is composed of a single-screw extruder 403 having degassing zones (not shown). This extruder is preferably connected to a static mixer 405 itself connected to a gear pump (not shown) providing a constant polymer flow in the die. [60] In order to avoid a rise of supercritical gas in the feed hopper (not shown), the supercritical gas G is injected, preferably at a distance away from the feed hopper and the extrusion parameters are adapted. so that a sufficient quantity of viscous polymer is present between the inlet of the gas and the feed hopper and prevents a rise of the gas towards said hopper, preferably said gas being injected into a controlled zone of said static mixer under controlled depression . [61] At the outlet of the impregnation device or the pre-impregnated locks emerge to be driven to a calendering device. Ref: 0402-ARK48 Supercritical neutral gas [62] Supercritical neutral gas is a substance that is brought to a temperature and pressure above its temperature and critical pressure, a field in which no distinction can be made between gaseous and liquids. The properties of a supercritical neutral gas are intermediate between those of a gas and a liquid. We speak indifferently, gas or supercritical fluid. [63] In the present invention, the neutral gas in the supercritical state is a supercritical neutral gas or a mixture of supercritical neutral gases. [064] Advantageously, among the supercritical gases gases will be chosen such as carbon dioxide, ethane, propane, pentane, water, methanol, ethanol, nitrogen or mixtures based on of these supercritical gases. [65] More particularly, it is preferable to use supercritical carbon dioxide (designated CO2sc hereinafter), or supercritical gas mixtures containing CO2sc for fluidizing thermoplastic polymers to facilitate their impregnation or in the case of the manufacture of dry wicks. to make foaming. [66] Advantageously, the neutral gas in the supercritical state is supercritical CO2 gas or a mixture of neutral gases in the supercritical state containing the CO 2 and a fluorinated gas. According to another option the mixture is based on CO2 and nitrogen. [67] The supercritical gas G, preferably the supercritical CO2, is injected at the extrusion head 403. Preferably, the supercritical gas, preferably the supercritical CO2, is mixed with said molten impregnation polymer in the stage. i) of the method, in a static mixer 405, in particular under controlled depression in said mixer. Shaping step [68] As soon as it (their) out of the impregnating device 40 and, optionally, from the covering device 41, the wick (the parallel wicks) pre-impregnated with a molten polymer, are placed in the form of a single unidirectional ribbon or a plurality of parallel unidirectional ribbons B, by means of a continuous calender device comprising one or more heating calandres. Ref: 0402-ARK48 [69] With the prior art, hot calendering could not be envisaged for a shaping step but only for a finishing step because it did not allow heating at sufficient temperatures, in particular when the polymer, or mixture of thermoplastic polymers, of impregnation comprises polymers with a high melting temperature. [70] Advantageously, this hot calendering not only allows the impregnating polymer to be heated so that it penetrates, adheres and uniformly covers the fibers, but also to control the thickness and the width of the ribbon (s). fibrous material preimpregnated and in particular its porosity. [071] In order to be able to produce a plurality of unidirectional parallel ribbons, that is to say as many ribbons as pre-impregnated parallel rovings, by the impregnating device 40, possibly covered by the covering device 41, the calenders Heaters, referenced 60, 70, 80 in the diagram of Figure 1, advantageously comprise a plurality of calendering grooves, in accordance with the number of ribbons. This number of grooves can for example go up to 200. A SYST slave system also allows to regulate the pressure and / or spacing E between the rollers (601, 602); (701, 702) and (801, 802) calenders. FIG. 3 illustrates, by way of example, the detail of the calender 70. It can be seen in this FIG. 3 the rollers 701, 702 of the calender 70, the regulation of the pressure and / or the spacing E being made to control the thickness ep of the ribbons by an SYST servo system controlled by a computer program provided for this purpose. [072] The calendering device comprises at least one heating calender 60 Preferably, it comprises several heating calandres 60, 70, 80, connected in series. The fact of having several calender in series makes it possible to pack the porosities in the material and to reduce their rate. This plurality of calenders is therefore important when it is desired to produce so-called "ready-to-use" fibrous materials. On the other hand, to manufacture so-called "dry" fibrous materials it is possible to be satisfied with a lower number of calenders or even a single calender. [073] Advantageously each calender of the calendering device has an integrated induction heating system, for heating the polymer or mixture of thermoplastic polymers. Advantageously, when the polymer or mixture of polymers comprises carbon-containing fillers, such as carbon black or carbon nanofillers, preferably Ref: 0402-ARK48 chosen from carbon nanofillers, in particular graphenes and / or nanotubes of carbon. carbon and / or carbon nanofibrils or mixtures thereof, the induction heating effect is amplified by the presence of these charges which then lead the heat to the core of the material. [074] Advantageously, the heating calenders of the calendering device are coupled to a rapid heating device 50, 51, 52, which make it possible to heat the material not only at the surface but also at the core. The mechanical stress of the calenders coupled to these rapid heating devices makes it possible firstly to control the porosities and more particularly to minimize until the presence of porosities is eliminated and the polymer is homogeneously distributed, especially when the fibrous material Prepreg is a so-called "ready-to-use" material. These rapid heating devices are located before and / or after each calender, in order to quickly transmit thermal energy to the material. The rapid heating device may for example be chosen from the following devices: a microwave or induction device, an IR or laser infrared device or other device allowing direct contact with the heat source such as a flame device. A microwave or induction device is very advantageous, in particular when it is coupled to the presence of carbon nanofillers in the polymer or polymer mixture since the carbon nanofillers amplify the heating effect and transmit it to the core of the material. [75] According to an alternative embodiment, it is furthermore possible to combine several of these heating devices. [76] In the exemplary embodiment, each calender 60, 70, 80 of the calendering device is coupled to a rapid heater 50, 51, 52. [77] Optionally, a subsequent step is to wind the pre-impregnated and shaped ribbons. For this, the unit 200 for carrying out the method comprises a winding device 100 comprising as many bobbins 101 as ribbon, a bobbin 101 being assigned to each ribbon. A splitter 90 is generally provided to deflect the pre-impregnated ribbons to their respective coils 101, while avoiding that the ribbons touch to prevent any degradation. [78] Figure 3 shows schematically the detail of the grooves 73 of a calender, in the example, the calender 70 sectional view. The calender 70 comprises an upper Ref: 0402-ARK48 roller 701 and a lower roller 702. One of the rollers, for example the upper roller 701, comprises a crenellated portion 72, while the other roller, that is to say the lower roll 702 in the example comprises a grooved portion 76, the shape of the grooves being complementary to the shape of the protruding portions 72 of the upper roll. The distance E between the rollers 701, 75 and / or the pressure exerted by the two rollers against each other makes it possible to define the dimensions of the grooves 73, and in particular their thickness ep and the width I. Each groove 73 is provided to house a bit of fiber which is then pressed and heated between the rollers. The wicks then turn into parallel unidirectional ribbons whose dimensions, thickness and width are accurately calibrated by the grooves 73 of the calenders. Each calender advantageously comprises a plurality of grooves, the number of which can be up to 200, so as to produce as many ribbons as there are grooves and pre-impregnated locks. The calendering device further comprises the servo system SYST for simultaneously regulating the pressure and / or the spacing of the calendering rollers of all the calenders of the unit 200. [079] The ribbon (s) unidirectional (s) thus manufactured (s) present (s) a width and thickness suitable for robot removal in the manufacture of parts in three dimensions, without the need for slitting. The width of the ribbon (s) is advantageously between 5 and 100 mm, preferably between 5 and 50 mm, and even more preferably between 5 and 10 mm. The process for preparing a preimpregnated fibrous material which has just been described makes it possible to produce preimpregnated fibrous materials with high productivity while permitting homogeneous impregnation of the fibers and the control and reproducibility of the porosity, and thus the control and reproducibility of the performances of the final composite article in question. The homogeneous impregnation around the fibers and the absence of porosities are ensured by the impregnation stage by means of the polymer in the molten state containing a neutral gas or mixture of neutral gas in the supercritical state which assists the implemented by reducing the melt viscosity of said polymer and the use of a mechanically stressed shaping device (heating calendering), itself coupled to rapid heating devices which allow the material to be heated. on the surface but also at heart. The materials obtained are semi-finished products in the form of ribbons calibrated in thickness and width and which are used for the manufacture of structural parts Ref: 0402-ARK48 in three dimensions in the transport sectors such as automotive, civil aviation or military, nautical, or railway, renewable energies, sports and recreation, health and medical, weapons and missiles, security and electronics, by a process that may be assisted by the removal of a head robot for example, and known as the AFP method (from the acronym "Automatic Fiber Placement"). [80] This method therefore makes it possible to continuously produce ribbons of calibrated dimensions and of great length, so that it avoids slitting and splicing steps that are costly and detrimental to the quality of the composite parts manufactured later. The economics of eliminating the slitting step is about 30-40% of the total cost of producing a ribbon of preimpregnated fibrous material. [81] The combination of rapid heating devices with hot calenders facilitates the shaping of ribbons to the desired dimensions and allows to significantly increase the production rate of these ribbons compared to conventional shaping processes. Moreover, this combination makes it possible to densify the material by completely eliminating the porosities in so-called "ready-to-use" fibrous materials. [82] The rapid heaters also allow the use of many polymer grades, even the most viscous, which can cover all the desired strength ranges. [83] For the specific manufacture of so-called "dry" fibrous material ribbons, the step of impregnation with a melt polymer containing a supercritical neutral gas makes it possible to obtain a uniformly distributed weight of polymers, with a preferred level of deposited polymer of the order of 5 to 7 g / m and to obtain good penetration of the resins used to make, for example, infusion on preforms. Ref: 0402-ARK48
    权利要求:
    Claims (28)
    [0001]
    REVENDICATIONS1. Process for preparing a preimpregnated fibrous material, in particular in ribbon form, comprising a fibrous reinforcement and a thermoplastic polymer matrix, characterized in that it comprises the following step: i) impregnating said fibrous material in the form of a a single wick or several parallel wicks by said polymer in the molten state said melt polymer containing during said impregnation a neutral gas in the supercritical state, used as a processing aid agent by melt viscosity reduction, preferably said gas being supercritical CO2.
    [0002]
    2. Method according to claim 1, characterized in that said polymer is a thermoplastic polymer or a mixture of thermoplastic polymers. 15
    [0003]
    3. Method according to claim 2, characterized in that said thermoplastic polymer or thermoplastic polymer blend further comprises carbonaceous fillers, in particular carbon black or carbon nanofillers, preferably chosen from graphenes and / or nanotubes. of carbon and / or carbon nanofibrils or mixtures thereof.
    [0004]
    4. A process according to claims 2 or 3, characterized in that the thermoplastic polymer or thermoplastic polymer blend further comprises liquid crystal polymers or cyclized poly (butylene terephthalate), or mixtures thereof, as an additive.
    [0005]
    5. Method according to any one of claims 2 to 4, characterized in that said polymer, or mixture of thermoplastic polymers, is selected from amorphous polymers whose glass transition temperature is such that Te 80 ° C and / or among semi-crystalline polymers whose melting point T f is 150 ° C. Ref: 0402-ARK48-PRO 1082
    [0006]
    6. Method according to claim 5, characterized in that the thermoplastic polymer or mixture of thermoplastic polymers is selected from polyaryl ether ketones, in particular PEEK, or polyaryl ether ketone ketone, in particular PEKK or aromatic polyether-imides (PEI) or polyaryl sulfones, in particular polyphenylene sulfones (PPS), or polyarylsulfides, in particular polyphenylene sulfides, or from polyamides (PA), in particular aromatic polyamides optionally modified with urea units, or polyacrylates, in particular polymethyl methacrylate (PMMA) , or fluoropolymers, in particular polyvinylidene fluoride (PVDF).
    [0007]
    7. Method according to one of claims 1 to 6, characterized in that it comprises in addition to step i) the following additional steps: ii) shaping said wick or said parallel locks of said fibrous material impregnated according to step i), by calendering with at least one heating radiator, in the form of a single-directional single ribbon or unidirectional parallel multiple ribbons, with in the latter case said heating calender comprising multiple calendering grooves, preferably up to 200 grooves. calendering, in accordance with the number of said ribbons and with a pressure and / or spacing between the rollers of said calender regulated by a slave system.
    [0008]
    8. Method according to claim 7, characterized in that it further comprises a step iii) of winding said ribbon or said ribbons on one or more coils, the number of coils being identical to the number of ribbons, a coil being assigned to each ribbon.
    [0009]
    9. Method according to any one of claims 1 to 8, characterized in that said impregnation step i) is completed by a step of covering said single wick or said parallel multiple wicks after impregnation with the molten polymer according to the invention. step i), by a molten polymer which may be identical or different from said impregnating polymer i), Ref: 0402-ARK48-PRO 1082 before said calendering step ii), preferably said molten polymer being identical to said impregnating polymer i), preferably said covering being effected by extrusion at right angles to said single wick or with respect to said parallel multiple wicks.
    [0010]
    10. Method according to one of claims 1 to 9, characterized in that said fibrous material comprises continuous fibers selected from carbon fibers, glass, silicon carbide, basalt, natural in particular flax or hemp , of sisal, of silk, or cellulosic, in particular of viscose, or thermoplastic fibers of Tg greater than the Tg of said polymer or said polymer mixture when it is amorphous or of Tf greater than the Tf of said polymer or said mixture of polymers when the latter is semi-crystalline, or a mixture of two or more of said fibers, preferably carbon fibers, glass or silicon carbide or their mixture, in particular carbon fibers.
    [0011]
    11. Method according to one of claims 2 to 9, characterized in that the volume ratio of said polymer or polymer mixture with respect to said fibrous material ranges from 40 to 250%, preferably from 45 to 125% and more preferably from 45 to 125% by weight. at 80%.
    [0012]
    12. Method according to one of claims 2 to 9, characterized in that the volume ratio of said polymer or said polymer mixture relative to said fibrous material varies from 0.2 to 15%, preferably from 0.2 to 10%. % and more preferably 0.2 and 5%.
    [0013]
    13. The method of claim 7, characterized in that the calendering step ii) is performed by means of a plurality of heating calenders.
    [0014]
    14. The method of claim 7 or 13, characterized in that said (or said) calender (s) heater (s) of step ii) comprises an integrated induction heating system coupled to the presence of carbonaceous charges Ref: 0402-ARK48-PRO 1082in said thermoplastic polymer or thermoplastic polymer blend.
    [0015]
    15. The method of claim 13 or 14, characterized in that each heating calender is associated with a rapid heating device.
    [0016]
    16. Method according to any one of the preceding claims, characterized in that said impregnation step is performed using an extrusion technique.
    [0017]
    17. The method of claim 16, characterized in that said impregnation technique is the extrusion angle head with respect to said single wick or with respect to said parallel multiple wicks.
    [0018]
    18. Method according to one of claims 1 to 17, characterized in that said a neutral gas in the supercritical state is a supercritical neutral gas or a mixture of supercritical neutral gas.
    [0019]
    19. The process as claimed in claim 17, characterized in that said neutral gas in the supercritical state is supercritical CO2 gas or a mixture of neutral gases in the supercritical state containing CO2 and a fluorinated gas or a mixture based on CO2. and nitrogen.
    [0020]
    20. Method according to one of claims 1 to 19, characterized in that said supercritical gas, preferably supercritical CO2 is injected at the extrusion head.
    [0021]
    21. Method according to one of claims 1 to 19, characterized in that said supercritical gas, preferably supercritical CO2 is mixed with said molten impregnating polymer i) in a static mixer.
    [0022]
    22. Prepreg material, in particular in the form of ribbon more particularly wound on a reel, characterized in that it is based on a Ref: 0402-ARK48-PRO 1082 pre-impregnated fibrous material as obtained by a method as defined in one of claims 1 to 20.
    [0023]
    23. Prepreg material according to claim 22, characterized in that it is in the form of a ribbon having a width and a thickness suitable for robot removal in the manufacture of 3D parts, without the need for splitting, and preferably having a width of at least 5 mm and up to 100 mm, preferably from 5 to 50 mm and even more preferably from 5 to 10 mm.
    [0024]
    24. Use of the method as defined in one of claims 1 to 21, for the manufacture of calibrated ribbons suitable for the manufacture of 3D composite parts by automatic robot deposition of said ribbons.
    [0025]
    25. Use of the preimpregnated fibrous material, as defined in claim 22 or 23, in particular in ribbon form, in the manufacture of 3D composite parts.
    [0026]
    26. Use of the preimpregnated fibrous material according to claim 24 or 25, characterized in that said manufacture of said composite parts relates to automotive, civil or military aviation, energy in particular wind and tidal, storage devices energy, thermal protection panels, solar panels, ballistics with parts for weapons or missiles, security, boating, sports and recreation, building and construction or electronics.
    [0027]
    27. 3D composite part, characterized in that it results from the use of at least one preimpregnated fibrous material, as defined in claim 22 or 23, in particular in the form of tape.
    [0028]
    28. Unit for carrying out the process for preparing a preimpregnated fibrous material, in particular in the form of a ribbon, as defined in claims 1 to 21, said unit being mainly characterized in that it comprises: Ref. : 0402-ARK48-PRO 1082 '29 a) a device for continuously impregnating a wick or a plurality of parallel wicks of fibrous material comprising a molten polymer-fed impregnation die containing the gas neutral in the supercritical state, b) a device for continuously calendering said wick or said parallel wicks, with shaping, in the form of a single ribbon or in the form of several unidirectional parallel ribbons, comprising: minus one heating radiator, in particular several series heating radiators, said radiator having a calendering groove or several calendering grooves, and preferably in the latter case having up to 200 calendering grooves, b2) a controlled system for regulating the pressure and / or spacing between calendering rollers. Ref: 0402-ARK48-PRO 1082
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    同族专利:
    公开号 | 公开日
    EP3105027B1|2019-01-09|
    US20160346966A1|2016-12-01|
    WO2015121586A3|2015-10-08|
    FR3017320B1|2016-07-22|
    ES2710681T3|2019-04-26|
    WO2015121586A2|2015-08-20|
    CN106163755A|2016-11-23|
    CN106163755B|2019-12-10|
    EP3105027A2|2016-12-21|
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    EP1429582B1|2002-12-09|2013-01-16|Onkyo Corporation|Loudspeaker diaphragm and method for manufacturing the same|
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    法律状态:
    2016-01-08| PLFP| Fee payment|Year of fee payment: 3 |
    2017-01-12| PLFP| Fee payment|Year of fee payment: 4 |
    2018-01-11| PLFP| Fee payment|Year of fee payment: 5 |
    2020-01-13| PLFP| Fee payment|Year of fee payment: 7 |
    2021-01-12| PLFP| Fee payment|Year of fee payment: 8 |
    2022-01-18| PLFP| Fee payment|Year of fee payment: 9 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1451140A|FR3017320B1|2014-02-13|2014-02-13|PROCESS FOR THE PREPARATION OF A THERMOPLASTIC POLYMER PRE-IMPREGNATED FIBROUS MATERIAL USING A SUPERCRITICAL GAS|FR1451140A| FR3017320B1|2014-02-13|2014-02-13|PROCESS FOR THE PREPARATION OF A THERMOPLASTIC POLYMER PRE-IMPREGNATED FIBROUS MATERIAL USING A SUPERCRITICAL GAS|
    PCT/FR2015/050334| WO2015121586A2|2014-02-13|2015-02-11|Process for preparing a fibrous material pre-impregnated with thermoplastic polymer with the aid of a supercritical gas|
    ES15709244T| ES2710681T3|2014-02-13|2015-02-11|Method of preparing a preimpregnated fibrous material of thermoplastic polymer by means of a supercritical gas|
    US15/116,966| US20160346966A1|2014-02-13|2015-02-11|Method for preparing a fibrous material pre-impregnated with thermoplastic polymer with the aid of a supercritical gas|
    EP15709244.6A| EP3105027B1|2014-02-13|2015-02-11|Process for preparing a fibrous material pre-impregnated with thermoplastic polymer with the aid of a supercritical gas|
    CN201580019667.9A| CN106163755B|2014-02-13|2015-02-11|Method for preparing a fibrous material pre-impregnated with a thermoplastic polymer by means of a supercritical gas|
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