JP2020501951A - Method for producing fibrous material pre-impregnated with thermoplastic polymer by injection - Google Patents

Abstract

The present invention is a method of producing a pre-impregnated fiber material comprising a fiber material made of continuous fibers and at least one thermoplastic polymer matrix, wherein the pre-impregnated fiber material comprises a single unidirectional ribbon or a plurality of one-way ribbons. Being made with directional parallel ribbons, and wherein the method comprises the homogenization of the fibrous material in the form of a roving or several parallel rovings, in particular in the core, with the at least one matrix of thermoplastic polymer in powder form Characterized in that the impregnating step is performed by spraying the fiber material with the powder using one or more nozzles or one or more dry spray guns in a tank. Controlling the proportion of said at least one thermoplastic polymer matrix in said fibrous material, excluding any electrostatic steps in any charging; It is performed by controlling the flow rate of the powder by the nozzle or the gun relative to the fibrous material, a manufacturing method.

Description

  The present invention relates to a method for producing a fibrous material preimpregnated with a thermoplastic polymer.

  More particularly, the present invention relates to a method for producing a pre-impregnated fibrous material, comprising a reduced and controlled porosity for obtaining a pre-impregnated fibrous material ribbon, which can be used directly for the production of three-dimensional composite parts. The method comprises an impregnation step for the preparation of a pre-impregnated fibrous material of standardized dimensions, especially in its core, having

  As used herein, the term "fibrous material" refers to an aggregate of reinforcing fibers. Before being formed, the fibrous material is in the form of rovings. After molding, the fibrous material becomes a strip (or tape) or sheet. If the reinforcing fibers are continuous, their aggregation constitutes a fabric or non-woven (NCF). If the fibers are short, their aggregation constitutes a felt or non-woven material.

  Such pre-impregnated fibrous materials are intended in particular for the production of lightweight composites for producing mechanical parts having a three-dimensional structure and good mechanical and thermal properties. If the fibers are carbon or the resin is loaded with suitable additives, these fiber materials can release an electrostatic charge. Thus, they are especially suitable for components in the fields of mechanics, civil or military aviation, and voyages, automobiles, oil and gas, especially marine, stored gas, energy, health and medical, military and military, sports and recreation, and electronics. It has properties compatible with the manufacture of

  Such pre-impregnated fiber materials are also called composites. They include a fibrous material composed of reinforcing fibers and a matrix composed of an impregnated polymer. The primary role of this matrix is to keep the reinforcing fibers in a compact form and to give the final product the desired shape. This matrix also ensures charge transfer between the fibers and thus regulates the mechanical strength of the composite. Such matrices also help protect the reinforcing fibers from abrasion and aggressive environments and distribute any charge between the fibers to control the appearance of the surface. The role of this matrix is important for the long-term behavior of the composite, especially with regard to fatigue and creep.

  Good three-dimensional composite parts made from pre-impregnated fiber materials are achieved, inter alia, by controlling the method of impregnating the reinforcing fibers with the thermoplastic polymer.

  As used herein, the term “strip” is used to refer to a strip of fiber material that is 400 mm or more in width. The term "ribbon" is used to refer to a ribbon having a standardized width of 400 mm or less.

  The term "roving" is also used to refer to a fibrous material.

  Heretofore, the production of strips of fibrous material reinforced by impregnation of thermoplastic or thermoset polymers has depended on several properties, especially depending on the nature of the polymer, the type of composite material ultimately desired and the scope of its application. Made according to the method. As described in, for example, WO 2012/066241 A2, powder impregnation or extrusion techniques on a molten polymer crosshead are often used to impregnate reinforcing fibers with a thermosetting polymer such as an epoxy resin. These techniques are generally not directly applicable to thermoplastic polymers, especially those having a high glass transition temperature and having a melt viscosity that is too high to obtain sufficient impregnation of the fibers and semifinished or good finished products.

  Another known impregnation method is the continuous passage of fibers in an aqueous dispersion of polymer powder or an aqueous dispersion of polymer particles or an emulsion or aqueous polymer suspension. For example, EP0324680 can be referred to. In this method, a dispersion of micrometer-sized powder (about 20 μm) is used. After soaking in the aqueous solution, the fibers are impregnated with the polymer powder. The method then comprises a drying step consisting of passing the impregnated fibers through a first oven to evaporate the water absorbed during the immersion. A heat treatment step of passing the impregnated and dried fibers through a second heating zone at an elevated temperature is then required to melt the polymer to adhere, disperse and coat the polymer on the fiber.

  A major disadvantage of this method is the sometimes incomplete sediment uniformity. Another problem with this method is the drying time and energy consumption, which strongly affects the manufacturing costs. Furthermore, the particle size of commonly used powders is fine (typically 20 μm D50 by volume), which also increases the final cost of the pre-impregnated ribbon or sheet.

  Further, the drying step of the method induces porosity in the pre-impregnated fibers by evaporating the water.

  The pre-impregnated fiber material then needs to be formed into, for example, a ribbon.

  Strips of fibrous material obtained by a method of impregnating unidirectional fibers by continuously passing the fibers through a thermoplastic polymer melt containing an organic solvent such as benzophenone are commercially available. For example, reference may be made to US Pat. No. 4,541,884 to Imperial Chemical Industries. The presence of the organic solvent makes it possible, in particular, to adapt the viscosity of the melt mixture and ensure a good coating of the fibers. The fibers thus pre-impregnated are then shaped. They are, for example, cut into strips of different widths, then placed under a press, and then heated to a temperature above the melting temperature of the polymer to ensure cohesion of the material, especially the adhesion of the polymer to the fibers. Good. This impregnation and molding method facilitates the production of structural parts having high mechanical strength.

  One of the drawbacks of this technique is the heating temperature required to obtain these materials. The melting temperatures of the polymers depend in particular on their chemistry. The melting temperature is, for example, relatively high for poly (methyl methacrylate) (PMMA) polymers or poly (phenylene sulfide) (PPS), poly (ether ether ketone) (PEEK) or poly (ether ketone ketone) (PEKK). Can be much higher. Thus, the heating temperature may rise to above 250 ° C., even above 350 ° C., above the boiling point and flash point of the solvent, which are 305 ° C. and 150 ° C. for benzophenone, respectively. In this case, there is a sudden withdrawal of the solvent, which induces high porosity in the fiber and thus causes the appearance of defects in the composite. Therefore, this method is difficult to reproduce and involves an explosion hazard that puts the worker at risk. Finally, the use of organic solvents should be avoided for environmental and health and safety reasons.

  Documents EP0406067 filed under the joint name of Atochem and France, and document EP0201367, describe techniques for impregnating fluidized beds of polymer powders. With respect to EP0406067, the fibers are optionally separated from one another by rollers or grooved rolls, and the fibers are electrostatically charged by friction in contact with these rollers or cylinders. This static charge allows the polymer powder to adhere to the surface of the fibers and thereby impregnate them.

  WO 2016/062896 describes an electrostatic method for powder coating rovings by arbitrary charging by grounding the rovings and applying a potential difference between the tip or nozzle of the powder coating gun and the rovings. Explain.

  Document WO 2008/135661 describes, in a third variant, the production of an impregnated fiber ribbon. In this document, the fiber ribbon is already preformed in the form of a fiber ribbon supported together by restraints before the impregnation step. The ribbon thus preformed is pre-charged with static electricity and immersed in a container containing a fluidized bed of polymer microparticles suspended in compressed air to coat the ribbon with a polymer coating layer. Such documents do not facilitate the impregnation of one or more fiber rovings and the continuous forming of pre-impregnated rovings in the form of one or more unidirectional parallel ribbons.

  Document EP2586585 also describes the principle of impregnating fibers by passing the fibers through a fluidized bed of polymer particles. However, it does not describe continuously forming one or more rovings so impregnated in the form of one or more unidirectional parallel ribbons.

  US Patent Application Publication No. 2002/0197397 describes a method of impregnating fibers with a mixture of polymer powders, said mixing being performed directly in a fluidized bed without prior compounding.

  WO 2015/121583 describes a method for producing a pre-impregnated fibrous material by impregnating a fluidized bed with the material and heating calendering the roving.

  Hot calendering takes place downstream of the impregnation device and makes it possible to homogenize the polymer distribution and the impregnation of the fibers. The resulting porosity is controlled and reproducible but not quantified.

  Document EP 0 335 186 describes the possibility of using a calender or a press for consolidating composites containing pre-impregnated metal fibers, which are used for the production of shaped bodies for protection against electromagnetic radiation. This document does not disclose impregnating one or more fiber rovings and continuously forming them into one or more unidirectional parallel ribbons by hot calendering.

  The shaping of the pre-impregnated fibrous material in the form of a standardized ribbon suitable for the production of three-dimensional composite parts by automatic unloading with a robot generally takes place in a post-treatment.

  Thus, WO 92/20521 describes the possibility of impregnating a roving of fibers by passing a particle of thermoplastic powder through a fluidized bed. The fiber thus coated with the polymer particles is heated in a furnace or heater so that the polymer penetrates well and coats the fiber. Post-treatment of the resulting pre-impregnated fiber reinforcement can be performed by passing it through a set of abrasive rollers, allowing for improved impregnation with the matrix still liquid. Also, one or more stacked fiber reinforcements can be placed between the two rollers to form a strip. Such documents do not allow to impregnate one or more fiber rovings and to continuously form pre-impregnated rovings in the form of one or more unidirectional parallel ribbons.

  The quality of the ribbon of pre-impregnated fibrous material, and thus the quality of the final composite, depends not only on the uniformity of impregnation of the fiber and thus on the control and reproducibility of the porosity of the pre-impregnated fibrous material, but also on the final ribbon size, It also depends on the width and thickness. The uniformity and control of these two-dimensional parameters improves the mechanical strength of the material.

  Currently, regardless of the process used to impregnate the fibrous material, the production of narrow, i.e., less than 400 mm wide ribbons generally requires slitting (i.e., cutting) over 400 mm width, also referred to as sheets. . The ribbon so dimensioned is then returned for deposition by a robot using the head.

  Further, the length of the sheet roll does not exceed 1 km, and the ribbon obtained after cutting is generally not long enough to produce some large composite parts during robotic removal. Therefore, the ribbon must be adjacent to obtain a longer length, resulting in extra thickness. These extra thicknesses, which lead to a non-uniform appearance, lead to the appearance of non-uniformities which are detrimental to obtaining a good quality composite material constituting the composite part.

  Furthermore, these extra thicknesses require downtime and restarting of the robot, thus incurring a loss of time and productivity.

  Accordingly, current techniques for impregnating fiber materials and forming such fiber materials pre-impregnated in the form of standardized ribbons have several disadvantages. For example, it is difficult to uniformly heat a molten mixture of thermoplastic polymer in a die and at the die exit to a core of material, which changes the impregnation quality. Furthermore, existing temperature differences between the fiber and the molten mixture of polymer at the level of the impregnation die also change the quality and homogeneity of the impregnation. Furthermore, in this impregnating melt mode, it is possible to obtain high fiber levels or high production rates due to the high viscosity of the thermoplastic, especially if it has the high glass transition temperature required to obtain high performance composites. Not possible. The use of organic solvents usually involves the appearance of defects in the material and generally environmental, health and safety risks. Forming the pre-impregnated fibrous material in the form of a strip by high temperature post-treatment is still difficult because it does not necessarily facilitate uniform distribution of the polymer within the fiber, thereby lowering the porosity and poorly controlling the porosity. Quality material is brought. Slitting the sheets to obtain standardized ribbons and joining these ribbons results in additional manufacturing costs. Slitting can also create serious dust problems that contaminate ribbons of pre-impregnated fibrous material used for robotic removal, and can cause robot malfunction and / or composite imperfections. This potentially leads to robot repair costs, production downtime and disposal of nonconforming products. Finally, during the slitting process, a considerable amount of the fibers degrade, causing a loss of the properties of the ribbon of pre-impregnated fiber material, in particular a reduction in the mechanical strength and conductivity.

  Furthermore, the impregnation is not always carried out centrally, and if the cited references indicate exhaustive impregnation, the resulting porosity will be too high, especially for the above-mentioned applications.

International Publication No. 2012/066241 EP-A-0324680 U.S. Pat. No. 4,541,884 European Patent No. 0 406 067 European Patent No. 0201367 WO 2016/062896 International Publication No. 2008/135661 European Patent No. 2,586,585 US Patent Application Publication No. 2002/0197397 WO 2015/121583 European Patent Publication No. 0335186 International Publication No. 92/20521

  Accordingly, the present invention aims to remedy at least one of the disadvantages of the prior art. The main object of the present invention is to provide a method for producing a pre-impregnated fibrous material by impregnation technology which combines the control of the flow rate of the powder in the impregnating device and the control of the spreading of the fibrous material at the level of the device. Pre-impregnated fibrous material with reduced and controlled and reproducible porosity, which controls the uniform impregnation and size of the fibers, especially in the core, where the performance of the final composite part depends The purpose is to obtain.

  In this regard, the subject of the present invention is a process for the production of a pre-impregnated fibrous material comprising a fibrous material made of continuous fibers and at least one thermoplastic polymer matrix, wherein said pre-impregnated fibrous material is in the form of a roving or several parallel rovings. A method comprising the step of impregnating at least one thermoplastic polymer matrix in the form of a powder, especially in a core of a fibrous material.

  The invention also relates to a unidirectional ribbon of pre-impregnated fibrous material, in particular a ribbon wound on a reel, characterized in that it is obtained by a method as defined above.

  The invention further relates to the use of a ribbon as defined above in the manufacture of a three-dimensional part. The production of the composite parts is carried out in the transport sector, in particular for automobiles, oil and gas, especially for marine, gas storage, civil or military aviation, navigation, railways; renewable energy, especially for wind turbines, tidal turbines, energy storage devices Related to sports and recreation, health and medical, ballistics using weapons or missile parts, security and electronics.

  The invention also relates to a three-dimensional composite part, characterized in that it results from the use of at least one unidirectional ribbon of pre-impregnated fibrous material as defined above.

  It is an object of the present invention to provide a method for producing a pre-impregnated fiber material comprising a fiber material made of continuous fibers and at least one thermoplastic polymer matrix, wherein said pre-impregnated fiber material comprises a single unidirectional ribbon or a plurality of fibers. Made in a unidirectional parallel ribbon, wherein the method comprises homogeneously impregnating the fibrous material in the form of a roving or several parallel rovings, in particular in a core, with said at least one matrix of thermoplastic polymer in powder form And wherein the impregnating step is performed by spraying the powder on the fibrous material using one or more nozzles or one or more dry spray guns in a vessel, wherein the fibrous material contains Controlling the amount of the at least one thermoplastic polymer matrix includes controlling the flow rate of the powder through the nozzle or the gun with respect to the fibrous material. It is carried out by excluding the electrostatic process at any charge, a manufacturing method.

  The inventors unexpectedly found that by controlling the flow rate of the nozzle (or the plurality of nozzles) or the gun (or the plurality of guns) on the fibrous material, the thermoplastic polymer matrix It has been found that uniform impregnation of the material, especially in the core, with a well monitored resin ratio is possible.

  The term "homogeneous" means that the impregnation is uniform and that the width of the ribbon or dry fiber does not decrease at the surface of the pre-impregnated fiber material.

A polymer matrix thermoplastic, or thermoplastic polymer, is generally a solid, which may be semi-crystalline or amorphous at ambient temperature, and especially during temperature rise after its glass transition temperature (Tg). In the case of amorphous, it can flow at a higher temperature, and in the case of semi-crystalline, it can show pure melting when its melting temperature (Tf) has passed, and it has a temperature lower than the crystallization temperature (semi-crystalline). Is understood to mean a material that becomes solid again during a drop below its glass transition temperature (if amorphous).

  Tg and Tf are determined by differential scanning calorimetry (DSC) according to the 11357-2: 2013 and 11357-3: 2013 standards, respectively.

  The polymer making up the impregnated matrix of the fibrous material is advantageously a thermoplastic polymer or a mixture of thermoplastic polymers. This polymer or mixture of thermoplastic polymers is ground into a powder form for use in devices such as baths.

  The device in the form of a bath may be open or closed.

  Optionally, the thermoplastic polymer or thermoplastic polymer blend is a carbonaceous filler, especially carbon black or carbon nanofiller, preferably carbon nanofiller, especially graphene and / or carbon nanotubes and / or carbon nanofibrils or It further includes those selected from mixtures thereof. These charges promote the conduction of electricity and heat and consequently improve the lubricity of the polymer matrix when heated.

  Optionally, said thermoplastic polymer comprises, inter alia, a catalyst, an antioxidant, a heat stabilizer, a UV stabilizer, a light stabilizer, a lubricant, a filler, a plasticizer, a flame retardant, a nucleating agent, a chain extender and It contains at least one additive selected from dyes or mixtures thereof.

  According to another variation, the thermoplastic polymer or thermoplastic polymer blend may further comprise a mixture of a liquid crystal polymer or a cyclized poly (butylene terephthalate), or a CBT100 resin marketed by CYCLICS CORPORATION. These compounds promote the fluidization of the polymer matrix, especially in the molten state, for better penetration of the fibers into the core. Depending on the nature of the polymer used to make the impregnated matrix, or of the mixture of thermoplastic polymers, in particular its melting temperature, any of these compounds will be chosen.

The thermoplastic polymer forming part of the impregnated matrix of the fibrous material can be selected from:
-Polymers and copolymers of the family of aliphatic, cycloaliphatic polyamides (PA) or semi-aromatic PAs (also known as polyphthalamides (PPA));
-Polyureas, especially aromatic,
-Polymers and copolymers of the acrylic family, such as polyacrylates, more particularly polymethyl methacrylate (PMMA) or derivatives thereof,
-Polymers and copolymers of the family of the polyaryletherketones (PAEK), such as polyetheretherketone (PEEK), or the polyaryletherketoneketones (PAEKK), such as polyetherketoneketone (PEKK), or derivatives thereof;
-Aromatic polyetherimide (PEI),
Polyaryl sulfides, in particular polyphenylene sulfide (PPS),
Polyaryl sulfones, in particular polyphenylene sulfone (PPSU),
Polyolefins, in particular polypropylene (PP),
-Polylactic acid (PLA),
-Polyvinyl alcohol (PVA),
Fluorinated polymers, in particular polyvinylidene fluoride (PVDF), or polytetrafluoroethylene (PTFE) or polychlorotrifluoroethylene (PCTFE),
As well as mixtures thereof.

  Advantageously, when said thermoplastic polymer is a mixture, it is added to the vessel in the form of a "dry blend" or a powder previously obtained by the compound, or added directly to the vessel in the form of a "dry blend" Is done.

  Advantageously, it is added to the vessel in the form of a powder previously obtained by "dry blending" or directly to the vessel in the form of "dry blending", the mixture being a mixture of PEKK and PEI.

  Advantageously, when said polymer is a mixture of two polymers P1 and P2, the proportion by weight of polymers P1 and P2 is in the range from 1-99% to 99-1%.

  Advantageously, the PEKK / PEI mixture ranges from 90 to 10% to 60 to 40%, especially from 90 to 10% to 70 to 30% by weight.

  The thermoplastic polymer is the non-reactive final polymer impregnating the fibrous material, or also carried by the reactive prepolymer after impregnation but also after impregnation or using a chain extender, especially during heating in a heated calender. It may be a reactive prepolymer that can react by itself or with another prepolymer, depending on the end of the chain.

  According to a first possibility, the prepolymer may comprise or consist of at least one reactive (polyamide) prepolymer supported on the same chain (ie on the same prepolymer). The two terminal functional groups X 'and Y' functional groups each co-react by condensation, more specifically X 'and Y' are amine and carboxy or carboxy and amine, respectively. According to a second possibility, said prepolymers are reciprocal, each having two identical terminal functional groups X ′ or Y ′ (identical for the same prepolymer and different between the two prepolymers) May comprise or consist of at least two polyamide prepolymers having the formula, wherein said functional group X 'of the prepolymer can only react with said functional group Y' of another prepolymer, in particular by condensation. More specifically, X ′ and Y ′ are amine and carboxy, or carboxy and amine, respectively.

  According to a third possibility, the prepolymer is of the thermoplastic polyamide polymer having n terminal reactive functional groups X selected from -NH2, -CO2H and -OH, preferably NH2 and -CO2H. It may comprise or consist of at least one prepolymer, n is 1-3, preferably 1-2, more preferably 1 or 2, more preferably 2, and at least one of the non-polymeric structures The kind of chain extenders YA′-Y (A ′ is a hydrocarbon biradical) is preferably combined with at least one functional group X of said prepolymer a1) having a molecular weight of less than 500, more preferably less than 400. It has two identical terminal reactive functional groups Y, which react by polyaddition.

  The number average molecular weight Mn of the final polymer of the thermoplastic matrix is preferably in the range of 10,000 to 40,000, preferably 12,000 to 30,000. These Mn values are measured in m-cresol according to ISO 307: 2007, but can correspond to an intrinsic viscosity of 0.8 or more by changing the solvent. (Use m-cresol instead of sulfuric acid and the temperature is 20 ° C).

  Said reactive prepolymers according to the above two options have a number average molecular weight Mn in the range from 500 to 10,000, preferably from 1,000 to 6,000, especially from 2,500 to 6,000.

  The Mn value is determined in particular by calculation from the proportion of terminal functional groups determined by potentiometric titration in solution and the functionality of the prepolymer. Further, the Mn mass can be measured by size exclusion chromatography or NMR.

  The nomenclature used to define polyamides is described in ISO 1874-1: 2011 "Plastics-Polyamide (PA) Materials for Molding and Extrusion-Part 1: Names", especially on page 3 (Tables 1 and 2), It is also well known to those skilled in the art.

  The polyamide may be a homopolyamide, a copolyamide or a mixture thereof.

  Advantageously, the polymers constituting the matrix are polyamides (PA), in particular aliphatic polyamides, especially PA11 and PA12, cycloaliphatic polyamides, and semiaromatic polyamides optionally modified with urea units (polyphthalamides). ) And its copolymers, polymethyl methacrylate (PPMA) and its copolymers, polyetherimide (PEI), polyphenylene sulfide (PPS), polyphenylene sulfone (PPSU), polyether ketone ketone (PEKK), polyether ether ketone (PEEK), It is selected from fluorinated polymers such as polyvinylidene fluoride (PVDF).

For the fluoropolymer, it is a homopolymer of vinylidene fluoride (VDF of the formula CH ₂ ＣＦCF ₂ ) or a VDF copolymer comprising at least 50% by weight of VDF and at least one other monomer copolymerizable with VDF. In order to guarantee good mechanical strength of the structural parts, especially when subjected to thermal and chemical stresses, the VDF content must be above 80% by weight, even better 90% %Must. The comonomer may be a fluorinated monomer, for example, vinyl fluoride.

  Structural parts that must withstand high temperatures include, in addition to fluorinated polymers, PAEK (polyaryletherketone), such as polyetherketone PEK, poly (etheretherketone) PEEK, poly (etherketoneketone) PEKK, poly ( Ether ketone (ether ketone ketone) PEKEKK or high temperature glass transition PA Tg are advantageously used according to the invention.

  Advantageously, said thermoplastic polymer is a polymer whose glass transition temperature is Tg ≧ 80 ° C. or a semicrystalline polymer whose melting point is Tf ≧ 150 ° C.

Advantageously, the thermoplastic polymer is
-Polyamide 6 (PA-6), polyamide 11 (PA-11), polyamide 12 (PA-12), polyamide 66 (PA-66), polyamide 46 (PA-46), polyamide 610 (PA-610), polyamide 612 (PA-612), polyamide 1010 (PA-1010), polyamide 1012 (PA-1012), or a mixture thereof or an aliphatic polyamide selected from a copolyamide thereof;
A semi-aromatic polyamide optionally modified with urea units, such as a semi-aromatic polyamide of formula X / YAr, as described in EP 1505099, comprising a semi-aromatic polyamide of formula A / XT, In the formula, A is a unit obtained from an amino acid, a unit obtained from a lactam, and a formula (Ca diamine). Selected from units having (Cb diacid), a represents the number of carbon atoms of the diamine, b represents the number of carbon atoms of the diacid, and a and b are each between 4 and 36, advantageously The unit (Ca diamine) is selected from linear or branched aliphatic diamines, alicyclic diamines, and alkyl aromatic diamines, and the (Cb diacid) unit is a linear Or selected from branched diacids, cycloaliphatic diacids and aromatic diacids;
XT refers to units obtained from the polycondensation of diamine and terephthalic acid in Cx, x represents the number of carbon atoms of the diamine in Cx, and x is between 6 and 36, preferably between 9 and 18 And in particular polyamides of the formula A / 6T, A / 9T, A / 10T or A / 11T, where A is as defined above, in particular polyamides PA6 / 6T, 66 / 6T, 6I / 6T, MPMDT / 6T, PA 11 / 10T, 11 / 6T / 10T, MXDT / 10T or MPMDT / 10T, BACT / 10T, MXD6 and MXD10, and block copolymers, especially polyamide / polyether (PEBA).

  T is terephthalic acid, MXD is m-xylylenediamine, MPMD is methylpentamethylenediamine, and BAC is bis (aminomethyl) cyclohexane.

Textile material:
With respect to the constituent fibers of the fibrous material, the constituent fibers are, in particular, fibers of inorganic, organic or plant origin. Fibers of inorganic origin can include, for example, carbon fibers, glass fibers, basalt fibers, silica fibers, or silicon carbide fibers. Fibers of organic origin may include, for example, thermoplastic or thermoset polymer based fibers such as semi-aromatic polyamide fibers, aramid fibers or polyolefin fibers. Preferably, they are based on an amorphous thermoplastic polymer, which is higher than the glass transition temperature Tg of the polymer or thermoplastic polymer mixture of the composition of the impregnated matrix if the impregnated matrix is amorphous, or if the impregnated matrix composition is less than half. If crystalline, it has a higher Tg than the Tf of the thermoplastic polymer or mixture in the impregnated matrix configuration. Advantageously, they are based on a semi-crystalline thermoplastic polymer and are higher than the Tg of the polymer or thermoplastic polymer mixture of the composition of the impregnated matrix if the impregnated matrix is amorphous, or the impregnated matrix composition is semi-crystalline. Has a Tf higher than the melting point Tf of the thermoplastic polymer or mixture of the impregnated matrix composition. Thus, there is no risk of the organic fibers making up the fibrous material fusing during the impregnation of the thermoplastic matrix of the final composite. Fibers of plant origin may include flax, hemp, lignin, bamboo, silk, especially spider silk, sisal, and other cellulosic fibers, especially natural fibers based on viscose fibers. These plant-based fibers can be used in a pure state, treated with a coating layer, or coated to facilitate adhesion and impregnation of the thermoplastic polymer matrix.

  The fibrous material may also be knitted or woven with fibers.

  The fibrous material may also correspond to a fiber having a retaining yarn.

  These constituent fibers can be used alone or in combination. Thus, the organic fibers can be mixed with the inorganic fibers and impregnated with the thermoplastic polymer to form a pre-impregnated fiber material.

  Organic fiber rovings can have some weight. They can also have several shapes. The fibers may be in the form of staple fibers, which in turn comprise a felt or non-woven which may be in the form of strips, sheets or pieces, or may be in the form of continuous fibers, which is a 2D fabric , Twist yarns or unidirectional (UD) or non-woven fibers. The fibers that make up the fibrous material may be in the form of a mixture of these reinforcing fibers of different shapes. Preferably, the fibers are continuous.

  Preferably, the fibrous material consists of continuous fibers of carbon, glass or silicon carbide or mixtures thereof, especially carbon fibers. It is used in the form of roving or some roving.

  In pre-impregnated materials, also known as "ready-to-use" materials, the polymer or mixture of thermoplastic impregnated polymers is uniformly and homogeneously distributed around the fibers. In this type of material, the thermoplastic impregnated polymer must be distributed as homogeneously as possible in the fibers in order to obtain the least amount of porosity, ie the least amount of voids between the fibers. In fact, the presence of porosity in this type of material can act as a focal point, for example, when subjected to stress during mechanical tensile stress, which then acts as a point of destruction for the pre-impregnated fiber material. Form a starting point to mechanically weaken the fiber material. Thus, a homogeneous distribution of the polymer or polymer mixture improves the mechanical strength and homogeneity of the composite formed from these pre-impregnated fibrous materials.

  Thus, for a "ready-to-use" pre-impregnated material, the level of fibers in said impregnated fiber material is 45-65% by volume, preferably 50-60% by volume, especially 54-60% by volume.

  The measurement of the impregnation rate is carried out by image analysis (especially using a microscope or a camera or a digital camera), the cross section of the ribbon, the surface of the ribbon impregnated with the polymer by the total surface area of the product (impregnated surface area + porous surface area). Can be done by dividing by To obtain a good quality image, the transversely cut ribbon can be coated with a standard abrasive resin and polished using a standard protocol that allows the sample to be viewed at least 6 times the microscope magnification. preferable.

  Advantageously, the porosity of the pre-impregnated fiber material is between 0% and 30%, in particular between 1% and 10%, in particular between 1% and 5%.

  Porosity corresponds to independent porosity and is measured by electron microscopy or as a relative difference between the theoretical and experimental densities of the pre-impregnated fiber material as described in the Examples section of the present invention. can do.

Impregnation stage:
A mounting unit as an example of a manufacturing method is described in WO-A-2015 / 121583 and is a tank (also called an impregnation tank, in the case of the present invention, a compression roller (FIG. 4)). 1 except for a tensioning device and a bath with a nozzle or gun (FIG. 3).

  The step of impregnating the fibrous material comprises one step in a continuous impregnation device by injection comprising a tank (20) having one or more nozzles or one or more guns for injecting the polymer powder onto the fibrous material at the roller entrance. This is performed by passing the above roving.

  The polymer or polymer powder is injected into the vessel using a nozzle or gun at the level of a tensioning device, especially a compression roller (entrance) on the fibrous material. The roving circulates in this tank.

  The tank may have any shape, in particular a cylindrical or parallelepiped shape, in particular a cuboid or cuboid shape, advantageously a cuboid shape.

  The tank may be an open or closed tank. Advantageously, the vessel is open.

  If the vessel is closed, the vessel is equipped with a sealing system to prevent polymer powder from coming out of the vessel.

  Thus, this impregnation step is performed dry, that is, the thermoplastic polymer matrix is in powder form and is injected into the air but cannot be dispersed in solvents or water.

  Each roving to be impregnated is unwound from the reel (11) device (10) under traction generated by a cylinder (not shown). Preferably, the device 10 comprises a number of reels 11, each for unwinding a roving for impregnation. Therefore, it is possible to impregnate several fiber rovings simultaneously. Each reel (11) is provided with a brake (not shown) for applying tension to each fiber roving. In this case, the alignment module (12) allows the fiber rovings to be arranged parallel to one another. In this way, the fiber rovings do not touch each other, which helps to prevent mechanical degradation of the fibers due to friction between them.

  The fiber rovings or parallel fiber rovings are then moved into a trough (20) with a tensioning device, in the case of FIG. 1, a compression roller (23).

  The compression roller may be fixed or rotary.

  A fiber roving or parallel fiber roving then emerges from the bath after impregnation, after controlling the flow rate of the powder by the nozzle or the gun on the fiber material.

  Thus, the inventors unexpectedly found that by controlling the flow rate of the powder through the nozzle (or the plurality of nozzles) or the gun (or the plurality of guns) on the fibrous material, It has been found that the polymer matrix allows for uniform impregnation of the fiber material with a well controlled and homogeneous resin ratio.

  We have also found that by using at least one tensioning device, the impregnation is improved compared to prior art methods, in particular that the impregnation is a core impregnation.

  A tensioning device refers to any system in which a roving has the ability to scroll within a bath. The tension device can take any shape from the moment the roving can scroll.

  Without limiting the scope of the invention, an example of a tension device is detailed in FIG.

  This impregnation is performed to allow the polymer powder to penetrate the core of the fiber roving and adhere to the fiber sufficiently to support the removal of the powder-containing roving from the vat. The roving preimpregnated with the powder is then directed to a heated calendering device that can be preheated prior to calendering and optionally heated after calendering.

  Optionally, this impregnation step can be completed by powder injection just at the outlet of the impregnation bath (20) and by a roving or pre-impregnation roving coating step just before the calendering molding step. For this purpose, the tank airlock (20) can be connected to a coating device (30), which may also be provided with a cover crosshead, as also described in EP0406067. The overlay polymer may be the same or different from the bath polymer powder. Preferably, the overlay polymer is of the same nature. Such coatings provide a final polymer volume fraction within the desired range and avoid the presence on the surface of pre-impregnated rovings of excessively high fiber levels that would interfere with tap welding during the manufacture of composite parts. To facilitate the completion of the fiber impregnation step, not only to obtain a good "ready-to-use" quality fiber material, but also to improve the performance of the resulting composite material.

  The method of the present invention as described above is performed by a dry method except for an electrostatic step in any charging.

  The expression "at any charge" means that a potential difference is applied between the fiber material and the powder. Charging is significantly controlled and amplified. The powder particles then impregnate the fibrous material by attracting the charged powder to the opposite side of the fiber. The powder can be negatively or positively charged by different means (potential difference between two metal electrodes, mechanical friction of metal parts, etc.) and the fiber can be charged reversely (positively or negatively).

  The method of the present invention, which may be manifested by the friction of the fibrous material on the mounting unit elements in front of or at the level of the bath, does not in any case eliminate the presence of an unintended load, electrostatic charge.

  Advantageously, the bath comprises at least one tension device, said roving being in contact with part or all of the surface of said at least one tension device.

  Advantageously, the level of fibers in the impregnated fiber material is between 45 and 65% by volume, preferably between 50 and 60% by volume, in particular between 54 and 60% by volume.

  For fibers less than 45%, reinforcement is not necessary from a mechanical property standpoint.

  Above 65%, process limits are reached and mechanical properties are lost.

  If the fiber material, such as glass fiber, has sizing, an optional desizing step can be performed before the fiber material enters the bath. The term "sizing" refers to the surface treatment applied to the reinforcing fibers at the end of the die (fabric size) and the fabric (plastic sizing).

  The "textile" size applied to the filaments at the exit of the die ensures the bonding of the filaments between them, reduces wear and facilitates subsequent operations (weaving, draping, knitting), and builds up static charge Consisting of adhesion of a binder to prevent

  The "plastic" or "finish" size applied to the fabric consists of the attachment of a crosslinker, the role of the crosslinker ensures a physicochemical bond between the fiber and the resin and protects the fiber from its environment That is.

  Advantageously, the level of fibers in said impregnated fibrous material is in the range from 50 to 60% by volume, in particular from 54 to 60% by volume.

  Advantageously, the flow rate of the powder by the one or more nozzles or the one or more guns is in the range from 10 g / min to 400 g / min, in particular from 20 to 150 g / min.

  This flow rate applies to each gun or nozzle and may be the same or different for each gun or nozzle.

  The flow rate of the powder on the fiber material, especially the impregnation of said fiber material, is essential for the core.

  Below 10 g / min, the air flow is not enough to carry the powder.

  Above 400 g / min, the state becomes turbulent.

  Advantageously, the impregnation step is carried out with the roving or the several rovings extending simultaneously between the inlet and the outlet of the vessel.

  The expression "inlet of the tank" corresponds to the vertical tangent of the edge of the tank with one or more rollers having one or more nozzles or guns.

  The expression “outlet of the vat” corresponds to the vertical tangent of the other edge of the vat with one or more rollers having one or more nozzles or guns.

  Depending on the geometry of the tank, the distance between the inlet and the outlet of the tank corresponds to the diameter for a cylinder, the side for a cube, or the width or length for a cuboid. I do. The unrolling consists in selecting each constituent filament of the roving as much as possible from the other filaments which surround it closely. This corresponds to the lateral extension of the roving.

  In other words, the lateral extension or width of the roving is increased between the tank inlet and the tank outlet, thus facilitating improved impregnation, especially at the core of the fibrous material.

  The tank may be open or closed, in particular the tank is open.

  Advantageously, the bath comprises at least one tension device, said roving being in contact with part or all of the surface of said at least one tension device.

  FIG. 3 illustrates a trough (20) with a height-adjustable tensioning device (82).

  The roving (81a) is in contact with a part or the entire surface of said at least one tensioning device, and thus corresponds to a pre-impregnated roving scrolling partially or completely on the surface of the tensioning device (82); The system (82) is immersed in a bath where the impregnation takes place. The roving then leaves the tank (81b) after controlling the powder flow at the roller entrance.

  The roving (81a) may or may not contact the edge (83a) of the tank, which may be a rotating or stationary roller or the edge of a parallelepiped.

  Advantageously, said roving (81a) is in contact with or not in contact with the edge (83a) of the tank.

  Advantageously, the edge (83b) of the tank is a roller, in particular a cylindrical, rotating type.

  Said roving (81b) may or may not be in contact with a roller, in particular a cylindrical rotary or fixed roller, or an edge (83b) of a tank, which may be an edge of a parallelepiped. Is also good.

  Advantageously, said roving (81b) is in contact with the edge (83b) of the tank.

  Advantageously, the edge (83b) of the tank is a roller, in particular a cylindrical, rotating type.

  Advantageously, said roving (81a) is in contact with the edge (83a) of the tank, the edge (83b) of the tank being a particularly cylindrical and rotary roller, said roving (81b) comprising And the edge (83b) of the tank is a roller, in particular cylindrical and rotatable.

  Advantageously, said tensioning device is perpendicular to the direction of said roving.

  Advantageously, the spreading of the roving takes place at least with the at least one tensioning device.

  Thus, the spreading of the roving is mainly at the level of the tensioning device, but can also take place at the edge of the vat if there is contact between the roving and said edge.

  In another embodiment, the at least one tensioning device is a convex, concave or cylindrical compression roller.

  The convex configuration is advantageous for spreading, while the concave configuration is disadvantageous for spreading, but is performed independently.

  The expression "compression roller" means that the rolling roving is partially or completely located on the surface of the compression roller, which results in the spreading of the roving.

  Advantageously, the at least one compression roller is cylindrical in shape and the spreading percentage of the roving between the inlet and the outlet of the vat is between 1% and 400%, preferably between 30% and 400%. , Preferably between 30% and 150%, preferably between 50% and 150%.

  Spreading depends on the fiber material used. For example, the spread of carbon fiber material is much greater than the spread of flax fiber.

  Spreading also depends on the number of fibers or filaments in the roving, their average diameter, and their bonding by size.

  The diameter of the at least one compression roller ranges from 3 mm to 500 mm, preferably from 10 mm to 100 mm, in particular from 20 mm to 60 mm.

  If it is less than 3 mm, the fiber deformation caused by the compression roller is too large.

  Advantageously, the compression roller is cylindrical and grooveless and is in particular made of metal.

If the tensioning device is at least one compression roller, according to a first variant, a single compression roller is present in the bath and the impregnation is carried out by means of the roving, perpendicular to the entrance of the compression roller and to the compression roller. It takes place at an angle alpha ₁ which is formed between the tangent line.

The angle α ₁ formed by the roving between the entrance of the compression roller and the vertical tangent of the compression roller provides a “wedge effect” by allowing the formation of a region where powder concentrates, and The simultaneous spreading of the rovings by C.I. allowed the impregnation over a wider width of the rovings, thus improving the impregnation compared to the improved prior art techniques. Therefore, in combination with the control of the residence time, thorough impregnation becomes easy.

Advantageously, the angle alpha ₁ is 0 to 89 °, preferably 5 ° to 85 °, preferably 5 ° to 45 °, preferably in the range of 5 ° to 30 °.

However, an angle α _{1 of} 0-5 ° can create a risk of mechanical stress, which leads to fiber breakage, and an angle α ₁ of 85 ° -89 ° creates a “wedge effect”. Do not generate enough mechanical force to cause

A value of the angle α ₁ of 0 ° corresponds to a vertical fiber. Obviously, the height of the cylindrical compression roller is adjustable, thus facilitating the vertical positioning of the fibers.

  It is not outside the scope of the present invention if the walls of the vessel were perforated to allow the roving to exit.

  Advantageously, the rim (83a) of the tank is provided with rollers, in particular cylindrical and rotary, on which the roving runs, so that it will pre-extend.

  Advantageously, there is one or more problems downstream of the tank where spreading is initiated.

  Advantageously, the spreading is initiated at said one or more of said tensioning devices and continues at the end (83a) of the vat.

  Thus, spreading is maximized after passing through the level of one or more compression rollers.

FIG. 4 illustrates an embodiment for, but not limited to, a single compaction roller, wherein the reservoir (20) includes a powder (85) spray gun (84) and a single cylindrical compaction roller is present. And the angle α ₁ is shown.

  Arrows on the fibers indicate the scroll direction of the fibers.

  Advantageously, the level of the powder in the tank is located at least at an intermediate height of the compression roller.

Obviously, the "corner effect" provided by the angle α ₁ promotes impregnation on one side, but the spreading of the roving obtained through a compression roller also allows impregnation on the other side of the roving . In other words, the impregnation is at an angle alpha ₁ which is formed between said at least one compression roller R ₁ of the inlet and vertical tangent of said compression roller R ₁ by the roving, on one surface of the roving Although possible, spreading also allows impregnation of other surfaces.

The angle α ₁ is as defined above.

According to a second variant, if the tensioning device is at least one compression roller, there are two compression rollers R ₁ and R ₂ in the tank and the impregnation is performed by the roving at the entrance of the compression roller R ₁ . At an angle α ₁ formed between the pressure roller R _{1 and} a vertical tangent to the compression roller R ₁ and / or between the inlet of the compression roller R _{2 and} the vertical tangent to the compression roller R ₂ by the roving. place in that the angle alpha _2, the compression roller R _1, said prior to compression roller R _2, the rovings pass over the rollers R ₂ (FIGS. 5 and 6) or lower (FIGS. 7 and 8) be able to.

  Advantageously, the two compression rollers are of the same or different shapes and are selected from convex, concave or cylindrical shapes.

  Advantageously, the two compression rollers are identical and cylindrical, not grooved, and in particular are metal.

  The diameters of the two compression rollers can be the same or different, as defined above.

  Advantageously, the diameter of the two compression rollers is the same.

The two compression rollers R ₁ and R ₂ may be at the same level relative to each other and to the bottom of the vat (FIGS. 6 and 7) or may be inclined relative to each other and to the bottom of the vat. well, the height of the compression roll R ₁ is higher than that of the compression roller R ₂ to the bottom of the tank, or lower (FIGS. 5 and 8).

Advantageously, located on the two rollers have different heights, if roving runs over roller R2, alpha ₂ is in the range of 0 to 90 °.

Thus, advantageously, the impregnation is on one surface of the roving at an angle α ₁ formed by the roving between the entrance of the compression roller R ₁ and a vertical tangent to the compression roller, and on the opposite side of the roving, the line at an angle alpha ₂ which is formed _(obtained by passing on the roller R ₂₎ between the vertical tangent and the inlet of said compression roller R ₂ with respect to said compression roller R ₂ by the roving Will be

Advantageously, the roving in this embodiment is subjected to spreading at each angle α ₁ and α ₂ .

6, but are not limited to, two compression rollers _{R 1} and _R 2 _{(R 1} precedes _{R 2)} have, with the bath (20) with a powder (85) spray gun (84) has been described embodiments, two cylindrical compression rollers aligned horizontally at the same level are present, the one or more rovings shown may appear between the compression roller R ₁ and R ₂ I have.

In this case, the angle alpha ₂ is equal to 0, the one or more roving passes through the rollers R _2.

  Arrows on the fibers indicate the scroll direction of the fibers.

In an alternative method, the rovings scroll input between the compression roller R ₁ and R _2, appearing after coming into contact with part or all of the compression roller R ₂ of surface.

Advantageously, the roving is in contact with part or all of the compression roller R ₁ of the surface, compaction roller under the roller R ₂ after contact with part or all of the compression roller R ₂ surface appear on the outside of R _2, the angle alpha ₂ is formed by the roving between the compression roller R ₂ inlet with vertical tangent of the compression roller R _2. In this case, the angle α ₂ = 90 °.

Thus, advantageously, the impregnation is on one surface of the roving at an angle α ₁ formed by the roving between the entrance of the compression roller R ₁ and a vertical tangent to the compression roller, and on the same side of the roving, but it carried out at an angle alpha ₂ which is formed between the vertical tangent to the inlet of said compression roller R ₂ compression roller R ₂ by the roving, spreader also the impregnation of other surfaces enable.

Advantageously, the roving in this embodiment is subjected to spreading at each angle α ₁ and α ₂ .

FIG. 7 shows an example of an embodiment having _two compression rollers R ₁ and R ₂ at the same level as each other.

According to another embodiment of the second variant, if two compression rollers are present, the distance between the two compression rollers R ₁ and R ₂ are 0 in length corresponding to the maximum dimension of the vessel .15 mm, preferably 10 mm to 50 mm, and the height difference between the _two compression rollers R ₁ and R ₂ corresponds to the maximum height of the bath subtracted from the diameter of 0 to 2 compression rollers. Height, preferably a height difference between 0.15 mm and the maximum height of the bath subtracted from the diameter of the two compression rollers, more preferably a height difference between 10 mm and 300 mm, R ₂ Is an upper compression roller.

FIG. 8 shows an implementation with two compression rollers R ₁ and R ₂ (R ₁ precedes R ₂ ) each having, but not limited to, a tank (20) with a powder (85) spray gun (84). The configuration is described, where there are two cylindrical compression rollers at different levels and angles α ₁ and α ₂ are shown.

  The flow rate of the powder by each gun on the fiber material is the same or different, especially the same.

Although the diameters of the compression rollers R ₁ and R ₂ are shown as identical in FIGS. 5, 6, 7 and 8, the diameter of each cylindrical compression roller may be different and the diameter of the compression roller R ₁ is it may be greater than the diameter of the compression roller R ₂ in the above-mentioned range, or may be smaller.

  Advantageously, the diameter of the two compression rollers is the same.

When compression rollers R ₁ is higher than the compression roller R ₂ is not outside the scope of the invention.

According to the third modification, if two compression rollers is present on different levels, further there is at least a third compression roller R _3, and is disposed vertically between the compression roller R ₁ and R ₂ (FIG. 9). Each compression roller is provided with a powder (85) spray gun (84), and the flow rate of the powder onto the fiber material at the roller entrance by each gun is the same or different, especially the same.

Advantageously, the roving is in contact with part or all of the compression roller R ₁ surface, then in contact with part or all of a surface of said compression roller R _3, a portion of said compaction roller R ₂ surface Or appear after contact with all.

Advantageously, the impregnation is on one surface of the roving, at an angle alpha ₁ which is formed between the vertical tangent to the inlet and compression roller R ₁ of said at least one compression roller R ₁ by the roving, and at an angle alpha ₃ formed by a vertical tangent to the rovings and compression roller R _3, and the other surface is performed only at an angle alpha ₂ which is formed by a vertical tangent to the rovings and compression roller R _2.

Advantageously, present at a level of two compression rollers are different, if at least one of the third compression roller R ₃ of additionally present, the compression roller at least one inlet of the compression roller R ₂ and by the roving R ₂ angle alpha ₂ which is formed between the vertical tangent to the, 180 ° ~45 °, in particular from 120 ° to 60.

Advantageously, the angle alpha ₃ is 0 ° to 180 °, preferably in the range of 45 ° to 135 °.

FIG. 9 illustrates an embodiment having, but not limited to, a tank (20) with two compression rollers R ₁ and R ₂ (R ₁ precedes R ₂ ) and a third compression roller R _3. And angles α ₁ , α ₂ and α ₃ are shown.

Although the diameters of the compression rollers R ₁ , R ₂ , and R ₃ are shown as identical in FIG. 9, the diameter of each cylindrical compression roller may be different, or the two compression rollers may have the same diameter. And the third may have a larger or smaller different diameter in the range as defined above.

  Advantageously, the diameters of the three compression rollers are identical.

Advantageously, in this third modification, the second spreading control roving is done at the level of the compaction roller R _3, third spreading control is performed by the compression roller R _3.

  The flow rate in the third modification is as defined above.

In this third variant, the roving is in contact with part or all of the compression roller R ₁ surface, then in contact with part or all of the compression roller R ₂ of the surface, of said compression roller R ₃ Appearing after contacting some or all of the surface is still within the scope of the present invention.

  Advantageously, the spray speed in the tank is in the range from 10 g / min to 400 g / min, in particular from 20 to 150 g / min.

  Advantageously, the volume diameter D90 of the particles is between 50 and 500 μm, preferably between 120 and 300 μm.

  Advantageously, the volume diameter D10 of the particles is between 5 and 200 μm, advantageously between 35 and 100 μm.

  Advantageously, the volume diameter of the powder particles is within the D90 / D10 ratio in the range from 1.5 to 50, preferably from 2 to 10.

  Advantageously, the average volume diameter of the thermoplastic polymer powder particles is between 30 and 300 μm, in particular between 50 and 200 μm, more particularly between 70 and 200 μm.

  The volume diameter of the particles (D10, D50 and D90) is specified according to ISO 9276: 2014.

  "D50" corresponds to the average diameter by volume, meaning the value of the particle size that divides the examined particle population into exactly two parts.

  “D90” corresponds to the value at 90% of the cumulative curve of the volume particle size distribution.

  "D10" corresponds to a size of 10% of the particle volume.

  According to another embodiment of the method according to the invention, there is a creel in front of the tank for controlling the tension of said roving or rovings at the inlet of the tank.

  Optionally, in the method according to the invention there is one or more tension devices after the tank.

Upon exiting the forming step bath (20), a pre-impregnated roving, optionally coated with molten polymer (parallel roving), is provided by a continuous calender device comprising one or more heated calenders, with a single unidirectional ribbon. Alternatively, it is formed in the form of a plurality of parallel unidirectional ribbons.

  Advantageously, the heating calendar of the calendar device is associated with a rapid heating means which allows the material to be heated not only on the surface but also on the core.

  The expanded roving at the outlet of the tank (20) then shrinks under the influence of heating, which reduces the porosity of the roving by facilitating the insertion of the molten polymer between the roving fibers, in particular the roving of the roving. Facilitates impregnation in the core.

  The mechanical stress of the calendar associated with these rapid heating means allows the elimination of the presence of porosity and a homogeneous distribution of the polymer, especially when the fibrous material is a "ready-to-use" material.

  Advantageously, this hot calendering not only allows the impregnated polymer to be heated to uniformly infiltrate, adhere, and coat the fibers, but also monitors the thickness and width of the ribbon of pre-impregnated fiber material. Enable.

  (51), (52), (53) in the schematic diagram of FIG. 1 in order to be able to produce a number of unidirectional parallel ribbons passing through the tank, ie as many as the pre-impregnated parallel rovings. The calender, denoted by, advantageously comprises a plurality of calendering grooves (73), depending on the number of ribbons. The number of grooves may be, for example, up to 200. The controlled system SYST also allows adjustment of the pressure and / or E spacing between the rollers (71), (75) of the calendar (70) to monitor the ribbon thickness ep. Such a calendar (70) is schematically illustrated in FIG. 2, described below.

  The calendar device comprises at least a heating calendar (51). Preferably, the calender device comprises several heating calendars (51), (52), (53) connected in parallel and / or in series with the direction of travel of the fiber roving.

In particular, the method is characterized in that the continuous calendering step is performed progressively with increasing pressure between the rollers (in the direction of the process) and / or decreasing distance between the rollers (in the direction of the process). I do. )
Having several continuous calendars makes it possible to consolidate the materials and to reduce their porosity and their proportions. This plurality of calendars is therefore important when it is intended to produce a "ready-to-use" fiber material.

  Having several parallel calendars increases the number of pre-impregnated rovings.

  Advantageously, each calender of the calendering device comprises a preferably microwave-induced or microwave integrated heating system for heating the polymer or the mixture of thermoplastic polymers. Advantageously, the polymer or polymer mixture is selected from carbon-containing fillers, such as carbon black or carbon nanofillers, preferably carbon nanofillers, especially graphene and / or carbon nanotubes and / or carbon nanofibrils or mixtures thereof. When included, the effects of microwaves or induction heating are amplified by the presence of these charges, which then transfer heat to the core of the material.

  Advantageously, each of the calendars (51), (52), (53) of the device transfers heat energy to the material quickly and before and / or before each calendar to complete the impregnation of the fiber with the molten polymer. It is tied to a rapid heating device (41), (42), (43) arranged later. The rapid heating device can be selected, for example, from the following devices: microwave devices or induction, IR laser or infrared devices, or other devices for direct contact with a heat source such as a flame or hot gas. Microwave or inductive devices are very advantageous, especially when combined with the presence of carbon nanofillers in polymers or polymer mixtures, since carbon nanofillers amplify the heating effect and transfer it to the core of the material .

  According to alternative embodiments, it is also possible to combine some of these heating devices.

  The method may further comprise, prior to said impregnation, heating the fiber rovings with microwave heating in a preferred heating means, similar to the heating system of the heating calendar.

  Optionally, a subsequent step is one or more pre-impregnation and winding of the formed ribbon. To that effect, the unit (100) for carrying out the method comprises a winding device (60) comprising as many coils (61) as ribbons, the coils (61) being assigned to each ribbon. A divider (62) is generally provided to deflect the pre-impregnated ribbon into its respective coil (61) while preventing the ribbon from contacting to prevent any degradation.

  FIG. 2 schematically shows details of a groove (73) in a cross-sectional view of the calendar (70). The calendar (70) includes an upper roller (71) and a lower roller (75). One roller, for example the upper roller (71), has a notched portion (72), the other roller (in this example, lower roller (75)) has a groove portion (76), and the shape of the groove is , Complementary to the shape of the protrusion (72) of the upper roller. The spacing E between the rollers (71), (75) and / or the pressure applied to each other by the two rollers makes it possible to define the dimensions of the grooves 73, in particular their thickness ep and their width l. Each groove (73) is provided for receiving a fiber roving, which is then pressed and heated between rollers. The roving then becomes a parallel one-way ribbon whose thickness and width have been standardized by the calendar grooves (73). Each calendar advantageously comprises a plurality of grooves, the number of which can be up to 200 in order to produce as many ribbons as grooves and pre-impregnated rovings. The calendaring device further comprises a central device, indicated by SYST in FIG. 1, controlled by a computer program provided for this purpose, which comprises the pressure and / or spacing of the calendar rollers of all the unit 100 calendars. Enables simultaneous adjustment.

  The one-way ribbon produced in this way has a width l and a thickness ep suitable for robotic removal in the production of three-dimensional parts without having to be split at the correct width. The width of the ribbon is advantageously between 5 and 400 mm, preferably between 5 and 50 mm, even more preferably between 5 and 15 mm.

  In this way, the above-described method for producing a pre-impregnated fiber material allows for the production of a highly productive pre-impregnated fiber material, while homogeneously impregnating the fibers and controlling porosity and reproducibility. And thus control and reproducibility of the expected final composite product results. The uniform impregnation around the fibers and the lack of porosity can be attributed to the "wedge effect" by controlling the flow rate of the powder with the gun on the fiber material and in conjunction with the simultaneous deployment of rovings on one or more compression rollers. Is ensured by the impregnation step in the tank. The resulting material is a semi-finished product in the form of a ribbon with standardized thickness and width and low porosity.

  Thus, the method allows for the production of a standardized ribbon of pre-impregnated fiber material adapted for the production of three-dimensional composite parts by automatically removing said ribbon using a robot.

  Advantageously, the thermoplastic polymer of the ribbon obtained by the process according to the invention is obtained from an amorphous polymer whose glass transition temperature Tg is ≧ 80 ° C. and / or a semi-crystalline polymer whose melting point Tf is ≧ 150 ° C. Selected from polymers.

Advantageously, the thermoplastic polymer is
-Polyamide 6 (PA-6), polyamide 11 (PA-11), polyamide 12 (PA-12), polyamide 66 (PA-66), polyamide 46 (PA-46), polyamide 610 (PA-610), polyamide 612 (PA-612), polyamide 1010 (PA-1010), polyamide 1012 (PA-1012), mixtures thereof and copolyamides thereof, particularly aliphatic polyamides selected from 1010/11, 1010/12, and the like.
Aromatic polyamides optionally modified with urea units, in particular polyphthalamides, in particular polyphthalamides, in particular semi-aromatics of the formula X / YAr, as described in EP 1505099, including semi-aromatic polyamides of the formula A / XT A polyamide, wherein A is a unit derived from an amino acid, a unit derived from a lactam, and a compound represented by the formula (Ca diamine). Selected from units having (Cb diacid), a represents the number of carbon atoms of the diamine, b represents the number of carbon atoms of the diacid, and a and b are each between 4 and 36, advantageously Between 9 and 18;
XT refers to units obtained from the polycondensation of diamine and terephthalic acid in Cx, x represents the number of carbon atoms of the diamine in Cx, and x is between 6 and 36, preferably between 9 and 18 Between
In particular polyamides of the formula A / 6T, A / 9T, A / 10T or A / 11T (A is as defined above), especially polyamides PA6 / 6T, 66 / 6T, 6I / 6T, PA11 / 10T , 11 / 6T / 10T, MXDT / 10T or MPMDT / 10T, BACT / 10T aramid, and block copolymers, especially polyamide / polyether (PEBA).

  Advantageously, the fiber material of the ribbon obtained by the method according to the invention is made of carbon fibers.

  Advantageously, the thermoplastic polymers of the ribbons obtained by the process according to the invention are in particular PA11, PA12, PA11 / 1010, PA12 / 1010, PA11 / 10T, PA11 / 6T / 10T, PA MXDT / 10T, PA MPMDT / 10T. And PA BACT / 10T, and the fiber material of the ribbon obtained by the method according to the invention is made of carbon fibers.

  Advantageously, the thermoplastic polymer is a polyamide selected from PA11, PA12, PA11 / 1010, PA12 / 1010, PA11 / 10T, PA11 / 6T / 10T, PA MXDT / 10T, PA MPMDT / 10T and PA BACT / 10T. Some such ribbons are used in civil or military aviation or automobiles.

  Advantageously, the thermoplastic polymer of the ribbon obtained by the method according to the invention is PEKK.

  Advantageously, the fiber material of the ribbon obtained by the method according to the invention is made of carbon fibers.

  Advantageously, the thermoplastic polymer of the ribbon obtained by the method according to the invention is PEKK, and the fiber material of the ribbon obtained by the method according to the invention is made of carbon fibers.

  Advantageously, the thermoplastic polymer of the ribbon obtained by the method according to the invention is PEI.

  Advantageously, the fiber material of the ribbon obtained by the method according to the invention is made of carbon fibers.

  Advantageously, the thermoplastic polymer of the ribbon obtained by the method according to the invention is PEI, and the fibrous material of the ribbon obtained by the method according to the invention is made of carbon fibers.

  Advantageously, the thermoplastic polymer of the ribbon obtained by the process according to the invention is preferably a mixture of PEKK and PEI of 90 to 10% to 60 to 40%, in particular 90 to 10% to 70 to 30% by weight. is there. Advantageously, the fiber material of the ribbon obtained by the method according to the invention is made of carbon fibers.

  Advantageously, the thermoplastic polymer of the ribbon obtained by the method according to the invention is a mixture of PEKK and PEI, and the fiber material of the ribbon obtained by the method according to the invention is made of carbon fibers.

  According to another aspect, the invention relates to the use of a ribbon of pre-impregnated fiber material as defined above in the manufacture of a three-dimensional composite part.

  Advantageously, said production of said composite part is carried out in the transport sector, in particular in automobiles, oil and gas, in particular in marine, gas storage, civil or military aviation, in navigation, in rail; in renewable energies, in particular in wind turbines, tidal turbines Related to sports and recreation, health and medical, ballistics using weapons or missile components, security and electronics.

  According to yet another aspect, the invention relates to a three-dimensional composite part, characterized in that it results from the use of at least one unidirectional ribbon of pre-impregnated fibrous material as defined above.

Advantageous embodiments of the method according to the invention Advantageously, the fibrous material is selected from carbon fibers and glass fibers.

  Advantageously, the thermoplastic polymer used to impregnate the carbon fibers is a polyamide, especially an aliphatic polyamide such as PA11, PA12, PA11 / 1010 or PA12 / 1010, or a semi-aromatic polyamide, especially a polyamide, PA11 / 10T, PA11 / 6T / 10T, PA MXDT / 10T or PA MPMDT / 10T, or PA BACT / 10T, PEKK and PEI or mixtures thereof.

  Advantageously, the thermoplastic polymer used to impregnate the carbon fibers is a polyamide, especially an aliphatic polyamide such as PA11, PA12, PA11 / 1010 or PA12 / 1010, or a semi-aromatic polyamide, especially a polyamide, PA11 / 10T, PA11 / 6T / 10T, PA MXDT / 10T or PA MPMDT / 10T, or PA BACT / 10T, PEKK and PEI or mixtures thereof.

  Advantageously, the level of fibers in the fibrous material consisting of impregnated carbon fibers or glass fibers is between 45 and 65% by volume, preferably between 50 and 60% by volume, in particular between 54 and 60% by volume.

  In embodiments comprising PEKK or PEI, PEKK may be combined with PEI, and PEI may be combined with PEKK in the proportions defined above.

Advantageously, in the above compositions of Table I which are two compression rollers are present in the tank, the roller R ₂ is above the roller R ₁ to the bottom of the tank, in particular, H ₂ -H ₁ is From 1 cm to 30 cm, preferably from 1 to 10 cm, in particular from 1 cm to 3 cm, in particular about 2 cm, the angle α ₂ is from 0 to 90 °, especially from 25 to 45 ° C, especially from 25 to 35 °, roving travels over the _{R 2.}

  These embodiments correspond to FIG.

Advantageously, in the composition of Table I in which the two compression rollers are present in the tank, the roller R ₂ is above the roller R ₁ to the bottom of the tank, in particular H ₂ -H _1, 1 cm In the range of ３０30 cm, in particular about 2 cm, the angle α ₂ is 90-180 ° C., especially 115-135 °, especially 115-125 °, and the roving runs under R ₂ .

FIG. 3 is a view of a mounting unit of the method for producing a pre-impregnated fiber material according to the present invention. FIG. 2 is a sectional view of two rollers constituting a calendar as used in the unit of FIG. 1. The vat (20) having a height adjustable tensioning device (82) is described in detail. A rotating roller 83a on which the roving 81a travels is provided at the edge of the tank entrance, and a rotating roller 83b on which the roving 81b travels is provided at the edge of the tank outlet. FIG. 3 illustrates an embodiment of a single compression roller having a tank (20) with a powder (85) spray gun (84), where there is a single cylindrical compression roller and an angle α ₁ is shown. I have. Arrows on the fibers indicate the scroll direction of the fibers. But not limited to, illustrates an embodiment having a respective powder (85) spray gun (84) of the two having a bath (20) comprising a compression roller _{R 1} and _R 2 _{(R 1} precedes _{R 2)} , and the two cylindrical compression roller is located different heights relative to the bottom of the tank (R ₂ height H ₂ is on the R ₁ of the height H _1), the angle alpha ₁ and alpha ₂ It is shown. The arrow on the fiber roving indicates the scrolling direction of the roving. FIG. 7 shows an exemplary embodiment having a tank (20) with a powder (85) spray gun (84), wherein two compression rollers R ₁ and R ₂ are cylindrical with side by side at the same level as one another. And the angles α ₁ and α ₂ = 0 ° are shown, and the roving passes between the two rollers. FIG. 3 shows an exemplary embodiment having a tank (20) with a powder (85) spray gun (84) each, wherein two compression rollers R ₁ and R ₂ are cylindrical with side-by-side at the same level as one another. And angles α ₁ and α ₂ = 90 ° are shown, and the roving passes below R ₂ . FIG. 3 illustrates an exemplary embodiment having a tank (20) with a powder (85) spray gun (84) each, with two different levels of two cylindrical compression rollers R ₁ and R ₂ (R ₁ is R ₂₎ . Preceding), the angles α ₁ and α ₂ are indicated, and the roving passes under the roller R2. Each powder (85) two compression rollers comprising a spray gun (84) _{R 1} and _R 2 _{(R 1} precedes _{R 2),} and having a compression roller _{R 3} containing powder (85) spray gun (84) FIG. 4 shows an embodiment with a bath (20), wherein angles α ₁ , α ₂ and α ₃ are shown. Scanning electron of cross section of carbon fiber roving 1/4 inch Toray carbon fiber, 12K T700S MOE impregnated with PA11 / 6T / 10T polyamide powder of D50 = 100 μm according to the method described in WO2015 / 121583 (after calendering). It is a photograph taken under a microscope. The method according to WO2015 / 121583 shows a lack of homogeneity in some areas of the pre-impregnated roving, indicated by white arrows. Of 1/4 inch "carbon fiber roving" (Toray 12K T700S MOE fiber) impregnated with polyamide PA powder MPMDT / 10T of D50 = 115 μm according to the method of the present invention (after calendering as described in Example 2). 3 is a photograph of a cross section taken by a scanning electron microscope. It is a figure which shows the impregnation of the flax fiber with the molten PA11 as a comparative example with the method (Example 2) of this invention. It is a figure which shows the impregnation of the MPMDT / 10T (D50 = 115 micrometers) Toray T700S24K60E carbon fiber obtained by fusion as a comparative example with the method (Example 2) of this invention.

  The following examples illustrate, without limitation, the scope of the present invention.

[Example 1 (Comparative Example)]
12K carbon fiber rovings were impregnated with PA11 / 6T / 10T as described in WO2015 / 121583.

  D50 = 100 μM.

result:
The results are shown in FIG. 10, which shows a lack of homogeneity in some areas of the pre-impregnated roving, indicated by white arrows.

[Example 2]
General Procedure for Impregnating Fiber Material with Polyamide Powder in a Vessel with a Single Roller The following procedure was performed.

A cylindrical compression roller (L = 500 mm, l = 500 mm, H = 600 mm) in the tank, diameter 25 mm.
Flow rate 25-30 g / min; angle α _{1 of} 25 °.
-Toray 12K T700S MOE 1/4 inch carbon fiber roving about 100% spread (ie twice the width).
D50 = 115 μm (D10 = 49 μm, D90 = 207 μm) for MPMDT / 10T powder.
-The edge of the bath with fixed rollers.

  Following this procedure, a fiber material (（inch carbon fiber roving) pre-impregnated with polyamide (MPMDT / 10T) was prepared and is shown in FIG.

  This demonstrates the effectiveness of the dry powder impregnation method in a vessel with compression rollers and the control of powder flow.

[Example 3]
Porosity measurement, relative difference between theoretical and experimental densities (general method)
a) The required data includes:
The density of the thermoplastic matrix.
The fiber density;
The weight of the reinforcement;
For example, the linear density (g / m) for a 1/4 inch tape (from one row).
For example, mass per unit area (g / m ² ) in the case of wide tape or cloth

b) The number of samples must be at least 30 for the measurements to be taken to be representative of the investigated material.

The measurements to be made include:
The size of the sample collected:
Length (if the linear density is known).
Length and width (if the weight per unit area is known).
The experimental density of the collected samples:
Weight measurement in air and water.
The measurement of the fiber content is carried out according to ISO 1172: 1999 or Measured by thermogravimetric analysis (TGA) as measured by Benzler, Applicationslab, Mettler Toledo, Giesen, UserCom 1/201.

  The carbon fiber content can be measured according to ISO 14127: 2008.

Measurement of theoretical fiber mass ratio:
a) Measurement of theoretical fiber mass ratio:

式中、
ｍ_ｌは、テープの線密度であり、
Ｌは、試料の長さであり、
Ｍｅ_ａｉｒは、空気中で測定された試料の質量である。

Where:
_ml is the linear density of the tape,
L is the length of the sample,
Me _air is the mass of the sample measured in air.

  It is believed that variations in fiber mass ratio are directly related to variations in matrix levels, without taking into account variations in the amount of fibers in the reinforcement.

  b) Measurement of theoretical density:

式中、ｄ_ｍ及びｄ_ｆは、マトリックス及び繊維のそれぞれの密度である。

Wherein, d _m and d _f are the respective densities of the matrix and fiber.

  The theoretical density calculated in this way is the attainable density when there are no pores in the sample.

c) Evaluation of porosity:
Thus, porosity is the relative difference between theoretical and experimental densities.

Claims (29)

  A method for producing a pre-impregnated fiber material comprising a fiber material made of continuous fibers and at least one thermoplastic polymer matrix, wherein the pre-impregnated fiber material is a single unidirectional ribbon or a plurality of unidirectional parallel ribbons. The method produced comprises the step of homogeneously impregnating the fibrous material in the form of a roving (81a) or several parallel rovings, in particular with a core, with the at least one matrix of thermoplastic polymer in powder form. The impregnating step is performed by spraying the powder on the fibrous material using one or more nozzles or one or more dry spray guns in a tank (20); Controlling the amount of the at least one thermoplastic polymer matrix may include controlling a flow rate of the powder by the nozzle or the gun relative to the fibrous material. Done by Gosuru, excluding electrostatic process at any charging method.   The vat (20) comprises at least one tensioning device (82), wherein the roving (81a) or some of the rovings are in contact with some or all of the surface of the minus one tensioning device (82). The method according to claim 1, characterized in that the injection of the powder takes place at the entrance of the tensioning device (82).   Method according to claim 1 or 2, characterized in that the fiber level in the pre-impregnated fiber material is between 45 and 65% by volume, preferably between 50 and 60% by volume, in particular between 54 and 60%.   The flow rate of the powder by the nozzle or the gun with respect to the fiber material is 10 g / min to 400 g / min, particularly 20 to 150 g / min. the method of.   5. The method according to claim 1, wherein the impregnating step is performed while simultaneously spreading the roving (81 a) or the several rovings between an inlet and an outlet of the tank (20). 6. The method according to one of the preceding claims.   Method according to claim 5, characterized in that the spreading of the roving (81a) or of the several rovings is performed with at least the at least one tensioning device (82).   Method according to claim 2 or 6, characterized in that the at least one tensioning device (82) is a convex, concave or cylindrical compression roller.   The at least one compression roller is cylindrical and the spreading percentage of the roving (81a) or some of the rovings between the inlet and the outlet of the tank (20) is between 1% and 400%, preferably Method according to claim 7, characterized in that it is between 30% and 400%, preferably between 30% and 150%, preferably between 50% and 150%. A single compression roller is present in the vat (20), and the impregnation is formed by the roving (81a) or some of the rovings between the inlet of the compression roller and a vertical tangent to the compression roller. 9. The method according to claim 8, wherein the method is performed at an angle α ₁ . Method according to claim 9, characterized in that the angle? ₁ ranges from 0 to 89, preferably from 5 to 85, preferably from 5 to 45, preferably from 5 to 30. . In the tank (20) there are two compression rollers R ₁ and R ₂ and the impregnation is caused by the roving (81a) or some of the rovings perpendicular to the inlet of the compression roller R ₁ and to the compression roller. at an angle alpha ₁ which is formed between the tangent line, and / or, between the vertical tangent to said compression roller R ₂ and the inlet of said compression roller R ₂ by the roving (81a) or the number of roving performed at an angle alpha ₂ which is formed on the compression roller R ₁ (traveling in the direction of the process), prior to said compression roller R _2, the rovings (81a) or the roving, the rollers R ₂ 9. The method according to claim 8, wherein the vehicle can travel up or down. The two compression rollers R ₁ and R ₂ are separated by a length corresponding to the maximum dimension of the vessel (20) by 0.15 mm, preferably 10 mm to 50 mm, and the two compression rollers R ₁ and R ₂ The height difference between 0 and the height corresponding to the maximum height of the tank (20) subtracted from the diameter of the two compression rollers, preferably 0.15 mm to the diameter of the two compression rollers A height difference corresponding to the maximum height of the tank (20), more preferably a height difference between 10 mm and 300 mm, wherein R ₂ is an upper compression roller, The method according to claim 11.   The roving (81a) or the parallel rovings of the impregnated fiber material is calendered using at least one heated calendar (51, 52, 53) to a single unidirectional ribbon or a plurality of unidirectional parallels. Further comprising the step of shaping in the form of a ribbon, in the latter case the heating calender comprises a plurality of calender grooves (73), preferably up to 200 calender grooves, depending on the number of the ribbons, the roller of the calender 13. The method according to any one of the preceding claims, wherein the pressure and / or interval between them is controlled by a closed loop system.   The said calendering step is performed using a plurality of heating calenders (51, 52, 53) connected in parallel and / or series with respect to the moving direction of the fiber roving (81a). Item 14. The method according to Item 13.   The heating calendar, characterized in that it comprises an integrated microwave or induction heating system, preferably by microwave, associated with the presence of a carbonaceous charge in the thermoplastic polymer or a mixture of thermoplastic polymers. Item 15. The method according to Item 13 or 14.   The heating calendar is a rapid auxiliary heating device (41, 42, 43) arranged before and / or after the (each) shell (51, 52, 53), in particular carbonaceous material in the polymer or in the polymer mixture; Claims characterized in that it is combined with a microwave or induction heating device associated with the presence of a filler, or with an infrared device, or with laser heating or with direct contact with another heat source such as a flame or a hot gas. Item 16. The method according to any one of Items 13 to 15.   The impregnating step is completed by coating the single roving (81a) or the plurality of parallel rovings after impregnating the powder, wherein the coating step is performed in a bath (20) before the calendering step. Is carried out using a molten thermoplastic polymer which may be the same as or different from the polymer in the form of a powder, wherein the molten polymer is preferably of the same nature as the polymer in the form of a tank (20) powder 17. The method according to any of the preceding claims, characterized in that the coating is preferably performed by extruding at right angles to the single roving (81a) or to the plurality of parallel rovings. Method.   The thermoplastic polymer is selected from carbonaceous fillers, especially carbon black or carbon nanofillers, preferably carbon nanofillers, especially graphene and / or carbon nanotubes and / or carbon nanofibrils or mixtures thereof. The method according to any one of claims 1 to 17, further comprising:   The method according to any one of claims 1 to 18, wherein the thermoplastic polymer further comprises a liquid crystal polymer or a cyclized poly (butylene terephthalate), or a mixture containing them as an additive.   The at least one thermoplastic polymer is polyaryletherketone (PAEK), especially poly (etheretherketone) (PEEK); polyaryletherketoneketone (PAEKK), especially poly (etherketoneketone) (PEKK); Aromatic polyether imides (PEI); polyaryl sulfones, especially polyphenylene sulfone (PPSU); polyaryl sulfides, especially polyphenylene sulfide (PPS); polyamides (PA), especially aromatic polyamides optionally modified with urea units; PEBA, polyacrylates, especially polymethyl methacrylate (PMMA); polyolefins, especially polypropylene, polylactic acid (PLA), polyvinyl alcohol (PVA), and fluorinated polymers, especially polyvinylidene fluoride PVDF) or polytetrafluoroethylene (PTFE) or polychlorotrifluoroethylene (PCTFE); and mixtures thereof, particularly preferably 90 to 10% to 60 to 40%, especially 90 to 10% to 70 to 70% by weight. 20. The method according to claim 1, wherein the method is selected from a mixture of 30% PEKK and PEI.   21. The method according to claim 20, wherein the at least one thermoplastic polymer is a polymer having a glass transition temperature Tg of ≥80C or a semi-crystalline polymer having a melting point Tf of ≥150C. Method.   The fiber material is carbon fiber, glass, silicon carbide, basalt, silica, natural fiber, especially flax or hemp, lignin, bamboo, sisal, silk, or cellulose, especially viscose, or the polymer or the polymer mixture is amorphous. An amorphous material having a Tg higher than the glass transition temperature Tg of the polymer or the polymer mixture when it is crystalline, and a Tg higher than the Tf of the polymer or the polymer mixture when the polymer or the polymer mixture is semi-crystalline. A thermoplastic thermoplastic fiber, or a polymer having a melting point Tf higher than the Tg of the polymer or the polymer mixture when the polymer or the polymer mixture is amorphous, and the polymer when the polymer or the polymer mixture is semi-crystalline. Or from the Tf of the polymer mixture Comprising a semi-crystalline thermoplastic fiber having a high Tf, or a mixture of two or more of said fibers, preferably a carbon fiber, a mixture of glass or silicon carbide, especially a continuous fiber selected from carbon fibers, A method according to any one of the preceding claims.   23. Unidirectional ribbon of pre-impregnated fibrous material, characterized in that it is obtained by the method according to any one of claims 1 to 22, in particular a ribbon wound on a reel.   Width (l) and thickness (ep) suitable for robotic removal in the manufacture of three-dimensional parts that do not require slits, preferably at least 5 mm up to 400 mm, preferably 5-50 mm, even more preferably 5-15 mm. 24. The ribbon according to claim 23, having a width (l).   The thermoplastic polymer is in particular an aliphatic polyamide, for example a polyamide selected from PA11, PA12, 11/1010 or 12/1010, or PA11 / 10T, PA11 / 6T / 10T, PA MXDT / 10T, PA MPMDT / 10T, 25. The ribbon according to claim 23, wherein the ribbon is a semi-aromatic polyamide selected from PA BACT / 10T.   23. Use of the method according to any of the preceding claims for the production of a standardized ribbon suitable for the production of three-dimensional composite parts by automatic removal of said ribbon using a robot.   Use of a ribbon of pre-impregnated fibrous material according to claim 23 or 24 in the manufacture of a three-dimensional composite part.   The production of the composite part is carried out in the transport sector, in particular in automobiles, oil and gas, in particular in marine, gas storage, civil aviation or military, navigation, railways; renewable energies, in particular wind turbines, tidal turbines, energy storage devices 28. The use according to claim 27, characterized in that it relates to sports and recreation, health and medicine, ballistics using weapons or missile parts, security and electronics.   A three-dimensional composite part obtained from the use of at least one unidirectional ribbon of the pre-impregnated fiber material according to claim 23 or 24.

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