KR20190095293A - Method for producing fibrous material preimpregnated with thermoplastic polymer by spraying - Google Patents

Abstract

A method for producing a pre-impregnated fibrous material having continuous fibers and a thermoplastic polymer matrix, wherein the pre-impregnated fibrous material is made of unidirectional strips or a plurality of parallel unidirectional strips. The method includes impregnating the fibrous material in the form of strand 81a or several parallel strands with the thermoplastic polymer in powder form. The impregnation step is carried out by spraying the powder with the fibrous material, in the container 20, by means of drying, by one or more nozzle (s) or one or more spray gun (s), wherein the thermoplastic polymer in the fibrous material The amount of matrix is controlled by controlling the powder spray rate.

Description

Method for producing fibrous material preimpregnated with thermoplastic polymer by spraying

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

More particularly, the present invention provides for the production of pre-impregnated fibrous material of reduced and controlled porosity, especially in the core, to obtain ribbons of pre-impregnated fibrous material of corrected dimensions that can be used directly to produce three-dimensional composite parts. A process for producing a pre-impregnated fibrous material comprising an impregnation step for the invention.

In this description, the term “fibrous material” refers to an aggregate of reinforcing fibers. Before being molded, it is in the form of rovings. After molding, it becomes strips (or tape), or sheets. When the reinforcing fibers are continuous, the collection of fibers constitutes a fabric or nonwoven (NCF). When the fibers are short, the collection of fibers constitutes a felt or nonwoven material.

These pre-impregnated fibrous materials are especially for the production of lightweight composite materials for producing mechanical parts having good mechanical and thermal properties and three-dimensional structure. When the fibers are carbon fibers or the resin is loaded with suitable additives, these fibrous materials can dissipate static charges. Thus, they are particularly in the fields of appliances, civil or military aviation, ships, automobiles, oils and gases, especially offshore, stored gases, energy, health and medical, military and weapons, sports and recreation, and electronics. In their properties suitable for the manufacture of parts.

Such preimpregnated fibrous materials are also referred to as composite materials. They include a fibrous material composed of reinforcing fibers, and a matrix made of impregnated polymer. The main 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 controls the mechanical strength of the composite. This matrix also serves to protect the reinforcing fibers against abrasion and aggressive environments in order to monitor the surface appearance and disperse any fillers between the fibers. The role of this matrix is particularly important for the long-term behavior of composites against fatigue and creep.

The good quality of three-dimensional composite parts made from pre-impregnated fibrous materials passes in particular the monitoring of the process of impregnating reinforcing fibers with thermoplastic polymer.

In the present description, the term "strip" is used to designate strips of fibrous material having a width of at least 400 mm. The term "ribbon" is 400 mm or less and is used to designate ribbons of corrected width.

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

To date, the production of strips of fibrous materials reinforced by impregnation of thermoplastic polymers or thermosetting polymers, in particular, is carried out according to several processes depending on the nature of the polymer, the type of final desired composite material and its application range. It became. Powder impregnation or extrusion techniques in molten polymer crossheads are often used to impregnate reinforcing fibers with thermoset polymers, such as epoxy resins, for example, as described in patent WO2012 / 066241A2. Such techniques are generally not directly applicable to impregnation with thermoplastic polymers having a melt viscosity too high to obtain satisfactory impregnation and semifinished or good quality end products of fibers, in particular polymers with high glass transition temperature. .

Another known impregnation process is the continuous passage of the fibers through an aqueous dispersion of polymer powder or an aqueous dispersion of polymer particles or emulsion or an aqueous polymer suspension. For example, reference may be made to EP0324680. In this process, a dispersion of micrometer sized powders (approximately 20 μm) is used. After soaking in aqueous solution, the fibers are impregnated with polymer powder. The process then includes a drying step of passing the impregnated fibers through the first furnace to evaporate the absorbed water during soaking. Thereafter, a heat treatment step of passing the fibers impregnated and dried at a high temperature into the second heating zone is required to melt the polymer to attach, disperse and coat the fibers.

The main disadvantage of this method is sometimes incomplete deposition homogeneity. Another problem with this process is drying time and energy consumption, which have a strong impact on production costs. In addition, the particle sizes of the commonly used powders are fine (typically on a volume basis of 50 μm D50) and this also increases the final cost of the pre-impregnated ribbon or sheet.

Moreover, the drying step of this method induces porosity in the fibers impregnated preliminarily by moisture evaporation.

Thereafter, the preimpregnated fibrous material needs to be molded into ribbons, for example.

Companies market strips of fibrous materials 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. See, for example, US Pat. No. 4,541,884 to Imperial Chemical Industries. The presence of organic solvents makes it possible in particular to adapt the viscosity of the molten mixture and to ensure a good coating of the fibers. The preimpregnated fibers are then molded. The fibers are, for example, cut into strips of different widths and then placed under the press and then heated to a temperature above the melting temperature of the polymer to ensure material agglomeration, in particular adhesion of the polymer to the fibers. Can be. This impregnation and forming method facilitates the fabrication of structural parts with high mechanical strength.

One of the disadvantages of this technique is the heating temperature required to obtain these materials. The melting temperature of the polymers depends in particular on the chemistry of the polymers. It may be relatively high for poly (methyl methacrylate) (PMMA) polymers, or for example poly (phenylene sulfide) (PPS), poly (ether ether ketone) (PEEK) or poly (ether ketone ketone) It can even be very high for (PEKK). Thus, the heating temperature can rise to temperatures higher than 250 ° C. and even higher than 350 ° C., to temperatures higher than 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 departure of the solvent which induces high porosity in the fibers, causing defects in the composite material. Thus, the process is difficult to reproduce and entails an explosion hazard that puts the operator at risk. Finally, the use of organic solvents should be avoided for environmental, health and safety reasons.

Document EP0 406 067, as well as document EP0 406 067, filed under the common name of Atochem and French State, describe a technique for impregnating a fluidized bed of polymer powder. The fibers penetrate into a closed fluidization tank, where for EP 0 406 067 the fibers are selectively separated from each other via rollers or corrugated rolls, the fibers in contact with these rollers or cylinders and are electrostatically charged It is miraculously charged. This electrostatic polymer powder is attached to the surfaces of the fibers to allow the fibers to be impregnated.

International application WO 2016/062896 describes rovings powder coating by an electrostatic process at any voluntary load, by grounding the rovings and applying a potential difference between the tip of the gun or the powder coating nozzles and the rovings.

Document WO2008 / 135663 describes, in a third variant, the production of an impregnated fiber ribbon. In this document, the fiber ribbon is already preformed before the impregnation stage in the form of a fiber ribbon held together by restraint. In order to coat the ribbon with a polymer coating layer, this preformed ribbon is immersed in an enclosure that includes a fluid bed of fine polymer particles that are statically precharged and suspended in compressed air. This document does not enable the impregnation of one or more fiber spun yarns and the continuous molding of the prespun yarns in the form of one or more unidirectional parallel ribbons.

Document EP2586585 likewise describes the principle of impregnating fibers by passing the fibers through a fluid bed of polymer particles. However, it does not account for the continuous molding of one or more rough yarns so impregnated, in the form of one or more unidirectional parallel ribbons.

Patent application US 2002/0197397 describes a process for impregnating fibers with a mixture of polymer powders, said mixing being carried out directly in the fluidized bed without prior synthesis.

International patent application WO 2015/121583 describes a process for producing a pre-impregnated fibrous material by impregnation of the material and thermal calendering of the roving yarn in a fluidized bed.

Thermal calendaring can be performed downstream of the impregnation device and homogenize the polymer distribution and impregnation of the fibers. The porosity obtained is controlled and reproducible but not quantified.

Document EP0335186 describes the possibility of using a calender or press to compact a composite comprising pre-impregnated metal fibers, used for producing molded bodies for electromagnetic radiation protection. It does not disclose impregnating one or more fiber spun yarns and continuously forming them into one or more unidirectional parallel ribbons by thermal calendering.

Forming of pre-impregnated fibrous materials in the form of calibrated ribbons, suitable for producing three-dimensional composite parts by automatic removal with a robot, is generally carried out in postprocessing.

Thus, the document WO92 / 20521 describes the possibility of impregnating the roving of fibers by passing it through a fluidized bed of particles of thermoplastic powder. The fibers coated with the polymer particles are heated in an oven or heater so that the polymer completely penetrates and covers the fibers. The post-treatment of the obtained pre impregnated fibrous reinforcement can be carried out by passing through a set of polishing rollers which still makes it possible to improve the impregnation with the liquid matrix. One or more overlapped fibrous reinforcements may also be disposed between the two rollers to form a strip. This document impregnates one or more fiber spun yarns and does not allow for the continuous molding of pre-impregnated spun yarns in the form of one or more unidirectional parallel ribbons.

The quality of the ribbons of the pre-impregnated fibrous material, and thus the quality of the final composite material, depends not only on the impregnation homogeneity of the fibers and thus on the porosity control and reproduction of the pre-impregnated fibrous material, but also on the size, more particularly the width and thickness of the final ribbons. Depends. Balance and control of these two dimensional parameters improve the mechanical strength of the materials.

Currently, producing ribbons of small widths, meaning widths of less than 400 mm, regardless of the process used for impregnation of fibrous materials, do not allow slitting (meaning cutting) of more than 400 mm widths, commonly referred to as sheets. Require. These sized ribbons are then retrieved for deposition by the robot using the head.

Moreover, sheet rolls whose length does not exceed 1 km, ribbons obtained after cutting are generally not long enough to produce some large composite parts during removal by the robot. Thus, the ribbons must be flanked to obtain a longer length, creating additional thicknesses. These additional thicknesses create inhomogeneities that are detrimental to obtaining good quality composite materials that make up the composite parts.

In addition, these additional thicknesses require machine down time and robot restart and thus time and productivity losses.

Accordingly, current techniques for impregnating fibrous materials and forming such fibrous materials preimpregnated in the form of calibrated ribbons have several disadvantages. For example, it is difficult to homogeneously heat the molten mixture of thermoplastic polymers in the die and at the die outlet to the material core, which changes the impregnation quality. In addition, the existing temperature difference between the molten mixture of polymers and the fibers at the level of the impregnation die also alters the impregnation quality and homogeneity. Moreover, this impregnation melt mode does not make it possible to obtain high fiber levels or high production rates due to the high viscosity of the thermoplastic resins, especially when having the high glass transition temperatures required to obtain high performance composite materials. The use of organic solvents usually results in environmental, health and safety hazards, as well as material defects. Forming by hot post-treatment of the pre-impregnated fibrous material in the form of strips is still difficult because it does not always allow for homogeneous distribution of the polymer in the fibers, which has poorly controlled porosity Cause low quality materials. Slitting sheets and splicing such ribbons to obtain calibrated ribbons incurs additional manufacturing costs. Slitting can also cause significant dust problems that contaminate ribbons of pre-impregnated fibrous materials used for robot removal and can cause malfunctions of robots and / or defects of composites. This potentially leads to robot repair costs, production shutdowns and disposal of non-compliant products. Finally, during the slitting step, a significant amount of fibers deteriorate, causing a loss of properties of the ribbons of the pre-impregnated fibrous material, in particular a decrease in mechanical strength and conductivity.

Moreover, if impregnation does not always occur centrally and the above cited documents indicate complete impregnation, the porosity obtained appears to be too high, especially for the applications listed above.

Accordingly, the present invention aims to improve at least one of the disadvantages of the prior art. It is a main object of the present invention to propose a process for producing pre-impregnated fibrous material by impregnation technique combining the flow rate control of powder in the impregnation device and the diffusion control of the fibrous material at the level of the device, the final composite It is to obtain a pre-impregnated fibrous material that exhibits a reduced dependence on the performance of the part, controlled reproducible porosity, controlled dimensions and, in particular, homogeneous impregnation of the fibers in the core.

To this end, the subject matter of the present invention is a process for producing a pre-impregnated fibrous material comprising at least one thermoplastic polymer matrix and a fibrous material made of continuous fibers, which process, in particular in the core, is carried out by spinning or Impregnating the fibrous material in the form of several parallel rovings into at least one thermoplastic polymer matrix in powder form.

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

The invention further relates to the use of a ribbon as defined above in the manufacture of three-dimensional parts. The manufacture of the composite parts can be carried out in transport, in particular in motor vehicles, oil and gas, in particular offshore, gas storage, civil or military aviation, ships, railways; Renewable energy, in particular wind turbines, tidal turbines, energy storage devices, solar panels; Thermal protection panels; Sports and recreation, health and medical, weapons or missile parts and ballistics, security and electronics.

The invention also relates to a three-dimensional composite part, which is characterized by the use of at least one unidirectional ribbon of pre-impregnated fibrous material as defined above.

An object of the present invention is a process for producing a pre-impregnated fibrous material comprising a fibrous material made of continuous fibers and at least one thermoplastic polymer matrix, the pre-impregnated fibrous material being a single unidirectional ribbon or a plurality of The method consists of impregnating the fibrous material in the form of rovings or in the form of several parallel rovings, especially homogeneously in the core, by the at least one matrix of thermoplastic polymer in powder form. Wherein the impregnation step is carried out by spraying the fibrous material with the powder with one or more nozzles or one or more dry powder guns in the tank, wherein controlling the amount of the at least one thermoplastic polymer matrix in the fibrous material , Any static electricity at any voluntary charge Excluding the process, the fibrous material is implemented by controlling the flow rate of the powder by the nozzle (s) or the gun (s).

The inventors unexpectedly found that the flow control of the nozzle (or the nozzles) or the gun (or the guns) in the fibrous material is homogeneous with the thermoplastic polymer matrix, in particular at a well monitored resin ratio in the core. It was found that it can be impregnated.

The term “homogeneous” means that the impregnation is uniform and there is no width reduction of the ribbons or dry fibers at the surface of the pre-impregnated fibrous material.

Polymer matrix

Thermoplastic resins, or thermoplastic polymers, are generally solid at ambient temperature, may be semi-crystalline or amorphous, soften during temperature rise, in particular after passing the glass transition temperature (Tg), and flow at higher temperatures when amorphous Or a material that can provide pure fusion upon passing the melting temperature (Tf) when it is semicrystalline and becomes solid again during temperature reduction below the crystallization temperature (for semicrystalline) and below the glass transition temperature (for amorphous) It is understood that.

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

The polymer that constitutes the impregnation matrix of fibrous material is advantageously a thermoplastic polymer or a mixture of thermoplastic polymers. This polymer or mixture of thermoplastic polymers is ground in powder form for use in equipment such as tanks.

The tank type device can be open or closed.

Optionally, the thermoplastic polymer or thermoplastic polymer blend is preferably carbonaceous fillers, in particular selected from carbon nanofillers, in particular graphenes and / or carbon nanotubes and / or carbon nanofibrils or mixtures thereof Further comprising carbon black or carbon nanofillers. These charges facilitate the conduction of electricity and heat and consequently improve the lubrication of the polymer matrix when heated.

Optionally, the thermoplastic polymer is selected in particular from catalysts, antioxidants, heat stabilizers, UV stabilizers, light stabilizers, lubricants, fillers, plasticizers, flame retardants, nucleating agents, chain extenders and dyes or mixtures thereof. At least one additive.

According to another variant, the thermoplastic polymer or thermoplastic polymer blend may further comprise liquid crystal polymers or cyclized poly (butylene terephthalate), or mixtures containing them, such as CBT100 resin sold by CYCLICS CORPORATION. These compounds facilitate the fluidization of the polymer matrix, especially in the molten state for better penetration into the core of the fibers. Depending on the nature of the polymer used to make the impregnation matrix, or the mixture of thermoplastic polymers, in particular its melting temperature, one or the other of these compounds will be selected.

The thermoplastic polymer forming portion of the impregnated matrix of fibrous material can be selected from:

- Polymers and copolymers of a family of aliphatic, cycloaliphatic polyamides (PA) or semiaromatic PAs (also known as polyphthalamides (PPAs)),

- Polyureas, especially aromatics,

- Polymers and copolymers of the acrylic family, such as polyacrylates, more particularly polymethyl methacrylate (PMMA) or derivatives thereof,

- Polymers and noses of a family of polyarylether ketones (PAEK), such as poly (ether ether ketone) (PEEK), or polyarylether ketone ketones (PAEKK) or derivatives thereof, such as poly (ether ketone ketone) (PEKK) Polymers,

- Aromatic polyether-imide (PEI),

- Polyarylsulfides, in particular polyphenylene sulfides (PPS),

- Polyarylsulfones, in particular polyphenylenesulfone (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),

And mixtures thereof.

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

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

Advantageously, when the polymer is a mixture of two polymers P1 and P2, the weight ratio of polymers P1 and P2 is in the range of 1 to 99% to 99 to 1%.

Advantageously, the PEKK / PEI mixture is in the range of 90 to 10% by weight to 60 to 40% by weight, in particular 90 to 10% to 70 to 30% by weight.

Thermoplastic polymers are non-reactive final polymers that impregnate fibrous materials or reactive prepolymers that also impregnate fibrous materials, but after impregnation, depending on the end of the chain supported by the prepolymer, on its own or with other prepolymers, The extender may react during heating, especially in a heating calendar.

According to a first possibility, the prepolymer may comprise or consist of at least one reactive (polyamide) prepolymer that supports the same chain (ie to the same prepolymer), wherein the two terminal functional groups X 'and Y' Each is co-reactive with each other by condensation, more particularly X 'and Y' are amine and carboxy or carboxy and amine, respectively. According to a second possibility, the prepolymer may comprise or consist of at least two polyamide prepolymers which are mutually reactive and each support two identical terminal functional groups X 'or Y' (the same for the same prepolymer and two Different prepolymers), the functional group X 'of the prepolymer can only react with the functional group Y' of the other prepolymer, in particular by condensation, more particularly X 'and Y' are amine and carboxy or carboxy, respectively And amines.

According to a third possibility, the prepolymer is at -NH2, -CO2H and -OH, preferably NH2 and -CO2H, wherein n is 1 to 3, preferably 1 to 2, more preferably 1 or 2, more particularly 2 At least one prepolymer of said thermoplastic polyamide polymer, preferably less than 500, more preferably supporting at least one chain extender Y-A'-Y wherein the selected n terminal reactive functional groups X, A 'are a hydrocarbon divalent radical And may comprise or consist of a non-polymeric structure supporting two identical terminal reactive functional groups Y, reactive by polyaddition with at least one functional group X of said prepolymer a1), of molecular weight less than 400.

The number average molecular mass (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 may correspond to intrinsic viscosities of 0.8 or higher as determined by m-cresol according to ISO 307: 2007 but replace the solvent (use m-cresol instead of sulfuric acid and the temperature is 20 ° C.).

The reactive prepolymers according to the two options mentioned above have a number average molecular mass (Mn) in the range from 500 to 10,000, preferably from 1,000 to 6,000, in particular from 2,500 to 6,000.

Mn values are determined by calculation, in particular from terminal functional group ratios determined by potentiometric titration in solution and the functionality of the prepolymers. Mn masses can also be determined by size exclusion chromatography or by NMR.

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

The polyamides may be homopolyamides or copolyamides or mixtures thereof.

Advantageously, the polymers making up the matrix are in particular aliphatic polyamides, in particular PA11 and PA12, cycloaliphatic polyamides, and semiaromatic polyamides (polyphthalamides) optionally modified with urea units, and copolymers thereof Polyamide (PA), polymethyl methacrylate (PPMA) and copolymers thereof, polyetherimide (PEI), polyphenylene sulfide (PPS), polyphenylene sulfone (PPSU), polyetherketone ketone Fluorinated polymers such as (PEKK), polyetheretherketone (PEEK), polyvinylidene fluoride (PVDF).

For fluoropolymers, the homopolymer or VDF copolymer of vinylidene fluoride (VDF of formula CH ₂ = CF ₂ ) comprises at least 50% by weight of VDF and at least one other monomer copolymerizable with VDF. Particularly when subjected to thermal and chemical stresses, the VDF content should be greater than 80% by weight or more preferably 90% by weight to ensure good mechanical strength of the structural part. The comonomer may be a fluorinated monomer such as vinyl fluoride.

For structural parts that must withstand high temperatures, in addition to fluorinated polymers, PAEK (polyaryletherketone), such as polyether ketone (PEK), poly (ether ether ketone) (PEEK), poly (ether ketone ketone) ( PEKK), poly (ether ketone ether ketone ketone) (PEKEKK) or hot glass transition PAs Tg) are advantageously used according to the invention.

Advantageously, the thermoplastic polymer is a polymer having a glass transition temperature of Tg ≧ 80 ° C. or a semicrystalline polymer having a melting temperature of Tf ≧ 150 ° C.

Advantageously, the thermoplastic polymer is as follows:

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 mixtures thereof or copolyamides thereof;

Semiaromatic polyamides of formula X / YAr, as described in EP1505099, including semiaromatic polyamides optionally modified with urea units, in particular semiaromatic polyamides of formula A / XT, wherein A is from an amino acid The unit obtained from the unit obtained from the lactam and the formula (Ca diamine). (Cb dibasic acid), a represents the number of carbon atoms of the diamine and b represents the number of carbon atoms of the dibasic acid, a and b are 4 to 36, advantageously 9 to 18, the unit (Ca diamine) is selected from linear or branched aliphatic diamines, cycloaliphatic diamines and alkylaromatic diamines and the (Cb dibasic acids) unit is linear or branched Aliphatic dibasic acids, alicyclic dibasic acids and aromatic dibasic acids;

XT represents a unit obtained from the polycondensation of diamine and terephthalic acid at Cx, x represents the number of carbon atoms of diamine at Cx, x is 6 to 36, advantageously 9 to 18, in particular the formulas A / 6T, A As polyamides of / 9T, A / 10T or A / 11T, A is as defined above, in particular polyamide PA 6 / 6T, 66 / 6T, 6I / 6T, MPMDT / 6T, PA11 / 10T, 11 / 6T / 10T, MXDT / 10T or MPMDT / 10T, BACT / 10T, MXD6 and MXD10 and block copolymers, in particular polyamide / polyether (PEBA).

T is terephthalic acid, MXD is m-xylene diamine, MPMD is methylpentamethylene diamine, and BAC is bis (aminomethyl) cyclohexane.

Fibrous Material:

For the fibers of the composition of the fibrous material, they are especially fibers of mineral, organic or plant origin. Fibers of mineral origin can include, for example, carbon fibers, glass fibers, basalt fibers, silica fibers, or silicon carbide fibers. Fibers of organic origin can include thermoplastic or thermoset polymer based fibers such as, for example, semiaromatic polyamide fibers, aramid fibers or polyolefin fibers. Preferably, the fibers are based on an amorphous thermoplastic polymer and have a glass transition higher than the Tg of the polymer or thermoplastic polymer mixture of the composition of the impregnation matrix when amorphous, or higher than the Tf of the thermoplastic polymer or mixture of the composition of the impregnation matrix when semicrystalline. Has a temperature Tg. Advantageously, the fibers are based on a semi-crystalline thermoplastic polymer and melt higher than the Tg of the polymer or thermoplastic polymer mixture of the composition of the impregnation matrix when amorphous, or higher than the Tf of the thermoplastic polymer or mixture of the composition of the impregnation matrix when semicrystalline. It has a temperature Tf. Thus, there is no risk of fusing to the organic fibers that make up the fibrous material during impregnation with the thermoplastic matrix of the final composite. Fibers of plant origin may comprise flax, hemp, lignin, bamboo, silk, in particular spider, sisal-based natural fibers, other cellulose fibers, in particular viscose fibers. Such plant-based fibers may be used purely, treated or coated with a coating layer to facilitate attachment and impregnation of the thermoplastic polymer matrix.

The fibrous material may also be a fabric braided or woven with the fibers.

It may also correspond to fibers with retaining threads.

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

Organic fiber spinning yarns can have several weights. They can also have several geometries. The fibers may be in the form of short fibers that constitute felts or nonwovens, which may later be in the form of strips, sheets, or pieces, or of continuous fibers that make up 2D fabrics, strands or unidirectional (UD) or nonwoven fibers. It may be in the form. The fibers that make up the fibrous material may also be in the form of a mixture of these reinforcing fibers of other geometries. Preferably, the fibers are continuous.

Preferably, the fibrous material consists of continuous fibers of carbon, glass or silicon carbide or mixtures thereof, in particular carbon fibers. It is used in the form of slub or various scavengers.

In pre-impregnated materials, also known as "ready-to-use" materials, the mixture of polymers or thermoplastic impregnated polymers is distributed evenly and homogeneously around the fibers. In this type of material, the thermoplastic impregnated polymer should be distributed as homogeneously as possible in the fibers in order to obtain the minimum voids, i.e. the minimum voids between the fibers. Indeed, the presence of voids in this type of material can serve as stress concentration points, for example during the application of mechanical tensile stress, which later form breakpoints of pre-impregnated fibrous material and mechanically weaken it. Let's do it. Thus, homogeneous distribution of the polymer or polymer mixture improves the mechanical strength and homogeneity of the composite material formed from these preimpregnated fibrous materials.

Thus, in the case of "prepared for use" pre-impregnated materials, the level of fibers in the impregnated fibrous material is 45-65% by volume, preferably 50-60% by volume, in particular 54-60% by volume.

Impregnation rate measurement is performed by image analysis (especially the use of microscopes or cameras or digital cameras), by the cross section of the ribbon, by dividing the surface of the ribbon impregnated with polymer by the entire surface of the product (impregnated surface + porous surface). Can be implemented. In order to obtain a good quality image, it is desirable to coat the ribbon cut in the transverse direction in a standard polishing resin and to polish with a standard protocol that allows observation of the sample at least 6 magnifications of the microscope.

Advantageously, the porosity of the preimpregnated fibrous material is from 0% to 30%, in particular from 1% to 10%, in particular from 1% to 5%.

The porosity can be determined by electron microscopy or as a relative difference between the theoretical and experimental densities of the pre-impregnated fibrous material, corresponding to the closed porosity and as described in the Examples section of the present invention.

Impregnation Stage:

The sample implementation unit of the manufacturing process is impregnated including a tank (otherwise a tank with a tension device, which may be a compression roller (FIG. 4) in the case of the invention and a nozzle (s) or gun (s) (FIG. 3)). Except for being called a tank), it is described in international patent application WO 2015/121583 and shown in FIG. 1.

The impregnation step of the fibrous material is injection in a continuous impregnation machine, comprising a tank 20 having one or more nozzle (s) or gun or gun (s) for injecting polymer powder into the fibrous material at the roller inlet. By passing through one or more rovings.

The polymer (s) or polymer powder is injected into the tank using nozzle (s) or gun (s) at the level of the tensioning device, in particular the compression roller (input) on the fibrous material. The rovingspin (s) are circulated in this tank.

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

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

If the tank is closed, the tank then has a sealing system to prevent polymer powder from escaping from the tank.

Thus, this impregnation step is carried out dry, which means that the thermoplastic polymer matrix is in powder form and is injected into the air, but cannot be dispersed in a solvent or water.

Each impregnated spinning yarn is released from the reel 11 of the device 10 under the traction force generated by the cylinders (not shown). Preferably, the device 10 comprises several reels 11, each reel for loosening the rovings for impregnation. Thus, several fiber spinning yarns can be impregnated at the same time. Each reel 11 is provided with a brake (not shown) to apply tension to each fiber spinning yarn. In this case, the alignment module 12 can align the fiber spun yarns in parallel with each other. As such, the fiber spun yarns will not be in contact with each other, which helps to prevent mechanical degradation of the fibers by friction between the fibers.

Thereafter, the fiber spun yarn or the parallel fiber spun yarns move to the tank 20 equipped with the tensioning device 23 in the case of FIG. 1.

The compression roller may be stationary or rotary.

Thereafter, fiber spun yarn or parallel fiber spun yarns come from the tank after impregnation after controlling the flow rate of the powder by the nozzle (s) or the gun (s) on the fibrous material.

Accordingly, the inventors unexpectedly found that the fiber by the thermoplastic polymer matrix at a homogeneous resin ratio in which the control of the flow rate of the powder by the nozzle (or the nozzles) or the gun (or the guns) on the fibrous material was well controlled. It was found that it was possible to impregnate the material.

The inventors have also found that through the use of at least one tension device the impregnation has been improved compared to the processes of the prior art, in particular in the core.

Tension device refers to any system in which the rover has the ability to scroll in a tank. The tension device may have any shape from the moment the roving yarn scrolls.

Examples of tension devices are shown in detail in FIG. 3 without limiting the scope of the present invention.

This impregnation is carried out so that the polymer powder can penetrate the core of the fiber spun yarn and adhere to the fibers sufficiently to support the transport of the powder spun yarn out of the tank. The spinning yarn (s) pre-impregnated with powder is then preheated before calendering and directed to a heated calendering machine with the possibility of selective heating after calendering.

Optionally, this impregnation step can be completed by a spinning or pre-impregnated spinning yarns coating step, at the outlet of the impregnation tank 22 immediately by powder injection, just before the calendering molding step. For this purpose, the tank 20 can be connected to a coating device 30, which can comprise a cover crosshead, as described equally in patent EP0406067. The overlay polymer may be the same or different than the tank polymer powder. Preferably it has the same properties. Such coatings terminate the fiber impregnation stage, particularly at the end of the fiber impregnation stage, which achieves a final polymer volume fraction in the desired range and prevents the presence of excessively high fiber levels of preimpregnated rovings, which impedes tab welding during the manufacture of the composite part. Not only makes it possible to obtain "good quality fibrous materials" but also improves the performance of the obtained composite material.

As indicated above, the process of the present invention is carried out by a drying method, except for the electrostatic process at any charge.

The expression "optional charge" means that the potential difference between the fibrous material and the powder is applied. The charge is significantly controlled and amplified. The powder grains then impregnate the fibrous material by attracting the charged powder opposite the fiber. The powder can be electrically charged, negatively or positively, and reversely (positively or negatively) by different means (potential difference between two metal electrodes, mechanical friction in metal parts, etc.). .

The process of the invention may occur by the friction of the fibrous material on the implementing unit elements before or at the level of the tank but in any case does not exclude the presence of electrostatic charges which are any rods.

Advantageously, the tank comprises at least one tension device, wherein the spinning yarn (s) are in contact with some or the entire surface of the at least one tension device.

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

If the fibers are less than 45%, no reinforcement is necessary in terms of mechanical properties.

If it exceeds 65%, process limits are reached and mechanical properties are lost.

If the fibrous material, such as glass fibers, has a sizing, an optional desizing step may be performed before the fibrous material passes into the tank. The term “sizing” refers to surface treatments applied to (plastic sizing) reinforcing fibers at the end of the die (fabric size) and on the fabrics.

The “fabric” size applied to the filaments at the exit of the die consists of depositing a bonding agent to ensure cohesion of the filaments between the filaments, reduce wear and facilitate subsequent operations (weaving, draping, knitting) and electrostatic Prevents the formation of Hades.

The “plastic” or “finish” size applied to the fabrics consists of depositing a crosslinking agent and its role is to ensure a physico-chemical bond between the fibers and the resin and to protect the fiber from its environment.

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

Advantageously, the flow rate of the powder by the nozzle (s) or gun (s) is in the range of 10 g / min to 400 g / min, in particular 20 to 150 g / min.

This flow rate may be applied 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 fibrous material is essential for impregnation in the core, in particular of the fibrous material.

If less than 10 g / min, the airflow is not sufficient to carry the powder.

When it exceeds 400 g / min, the regime is turbulent.

Advantageously, the impregnation step is carried out with simultaneous diffusion of the rovings or the rovings between the inlet and the outlet of the tank.

The expression “inlet of the tank” corresponds to the vertical tangent of the edge of the tank comprising the nozzle (s) or gun (s) and a roller or rollers.

The expression “outlet of the tank” corresponds to the vertical tangent of the nozzle (s) or gun (s) and the other edge of the tank including the rollers or rollers.

Depending on the geometry of the tank, the distance between the inlet and the outlet of the tank corresponds to the diameter in the case of a cylinder, the width or the length in the case of a cube or in the case of a cube. Blooming consists of singing out as much as possible, and each component filament of the roving from other filaments surrounds it closely. It corresponds to the transverse spread of the rovings.

In other words, the transverse spreading or width of the rovings is increased between the tank inlet and the tank outlet to enable improved impregnation, especially in the core of fibrous material.

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

Advantageously, the tank comprises at least one tension device, wherein the spinning yarn (s) are in contact with some or the entire surface of the at least one tension device.

3 shows a tank 20 including a height adjustable tension device 82.

The rovingstack 81a corresponds to the pre-impregnation rovings, which partially or completely scrolls at the surface of the tension device 82 in contact with a part or the entire surface of the at least one tension device, and the system 82 is impregnated. This happens to be immersed in the tank. Thereafter, after controlling the powder flow rate at the roller inlet, the roving yarn exits the tank 81b.

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

Advantageously, the rough yarn 81a is in contact with or not in contact with the edge of the tank 83a.

Advantageously, the edges of the tank 83b are rollers, in particular cylindrical and rotary.

The rovings 81b may or may not be in contact with the edges or parallelepiped edges of the tank 83b, which may be rollers or stationary rollers, in particular cylindrical and rotating.

Advantageously, the rough yarn 81b is in contact with the edge of the tank 83b.

Advantageously, the edges of the tank 83b are rollers, in particular cylindrical and rotary.

Advantageously, the rovings 81a are in contact with the edge of the tank 83a and the edges of the tanks 83b are rollers, in particular cylindrical and rotational, and the rovings 81b are in contact with the edge of the tank 83b. The edges of the tank 83b are rollers, in particular cylindrical and rotary.

Advantageously, the tension device is perpendicular to the direction of the roving yarn or the roving yarns.

Advantageously, the diffusion of the rovingspin (s) is carried out at least in the at least one tension device.

Thus, the diffusion of rovings can be carried out at the edge or edges of the tank if there is contact between the rovings and the edges, mainly at the level of the tensioning device.

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

The convex shape is advantageous for diffusion while the concave shape is disadvantageous for diffusion but it is carried out regardless.

The expression "compression roller" means that a rolling roving yarn is partially or completely seated at the surface of the pressing roller, which means inducing diffusion of the roving yarn.

Advantageously, the at least one compression roller is cylindrical in shape and the diffusion ratio of the roving or the rovings between the inlet and the outlet of the tank is between 1% and 400%, preferably between 30% and 400%, preferably 30% to 150%, preferably 50% to 150%.

The diffusion depends on the fibrous material used. For example, diffusion of carbon fibrous materials is probably much more than diffusion of fibers.

Diffusion also depends on their agglomeration by the number of fibers or filaments, their average diameter and size in the spinning yarn.

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

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

Advantageously, the compression roller is cylindrical, grooveless and especially metallic.

When the tension device is at least one compression roller, according to a first variant, a single compression roller is provided in the tank and the impregnation is carried out at the spinning yarn (s) between the inlet of the compression roller and the perpendicular tangent to the compression roller. Is performed at an angle α ₁ .

The angle α ₁ formed by the roughing yarn (s) between the inlet of the compression roller and the normal tangent to the compression roller enables the formation of the area where the powder is to be concentrated, leading to a “wedge effect” which is Simultaneous diffusion of the rovings by the compression rollers enables the infiltration to a greater width of the rovings, thereby improving the infiltration as compared to the improved prior art techniques. Thus, the control and coupling of residence time allows for complete impregnation.

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

However, an angle (α ₁ ) of 0 to 5 ° is likely to create risks of mechanical stress, which will lead to breakage of the fibers and an angle (α ₁ ) of 85 ° to 89 ° is sufficient to create a “wedge effect”. Does not generate mechanical force

The angle α ₁ value 0 ° corresponds to the vertical fiber. It is obvious that the height of the cylindrical compression roller is adjustable to facilitate the vertical positioning of the fibers.

Penetration of the wall of the tank to enable drainage of rovings will not depart from the scope of the present invention.

Advantageously, the edge of the tank 83a is equipped with rollers, in particular cylindrical and rotational, followed by the rovings (s), leading to prediffusion.

Advantageously, there is one or more difficulties downstream of the tank where diffusion begins.

Advantageously, diffusion begins at one or more of the aforementioned tension devices and continues at the edge of tank 83a.

The diffusion after passing at the level of the compression roller or rollers is then maximum.

4 shows an embodiment of a single compression roller with a tank 20 that includes a powder 85 spray gun 84, but is not limited thereto, where a single cylindrical compression roller is present and the angle α _{1 is} shown. Shows.

Arrows on the fiber indicate the fiber scrolling direction.

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

Obviously, the "corner effect" caused by the angle α ₁ promotes impregnation on one side, but the diffusion of the roving yarn obtained through the compression roller also enables the impregnation on the other side of the roving yarn. In other words, the impregnation of the roving (at an angle (α ₁₎ formed by the roving (s) between the vertical tangent of the inlet and the compression roller (R ₁₎ of the at least one compression roller (R ₁₎ Diffusion is also possible with impregnation on the other side.

The angle α ₁ is as defined above.

According to a second variant, when the tension device is at least one compression roller, then two compression rollers R ₁ and R ₂ are in the tank and the impregnation is at the inlet of the compression roller R ₁ and the between the vertical tangent of the compression roller (R ₁₎ an angle (α ₁₎ in and / or the compression roller (R ₂₎ wherein the compression roller (R ₂₎ and the inlet of which is formed by the roving (s) between the vertical tangent of At an angle α ₂ formed by the spinning yarn (s), the compression roller R ₁ precedes the compression roller R ₂ and the spinning yarn or the rough yarns are rollers R ₂ . May pass up (FIGS. 5 and 6) or down (FIGS. 7 and 8).

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

Advantageously, the two compression rollers are identical, cylindrical, non-waveform and especially metal.

The diameters of the two compression rollers may also be the same or different and as defined above.

Advantageously, the diameters of the two compression rollers are the same.

The two compression rollers R ₁ and R ₂ can be at the same level with respect to each other and with respect to the bottom of the tank (FIGS. 6 and 7) or can be tilted with respect to each other and against the bottom of the tank, higher than the high or low of the compression roller (R ₁₎ compression roller (R ₂₎ to the bottom of the tank height (Figs. 5 and 8).

Advantageously, when the two rollers are at different heights and the roving yarn proceeds over the roller R2, then α ₂ is in the range of 0 to 90 °.

Advantageously, the impregnation is thus at an angle α ₁ formed by the rovings (s) between the inlet of the compression roller R ₁ and the vertical tangent of the compression rollers on one side of the rovings and / or rollers. (R ₂ ) the angle α ₂ formed by the spinning yarn (s) between the inlet of the compression roller R ₂ and the perpendicular tangent of the compression roller R ₂ on the opposite side of the spinning yarn obtained by passing over (R ₂ ) ) Is performed.

Advantageously, the rovingspun spreads at each angle α ₁ , α ₂ in this embodiment.

6 shows an embodiment with a tank 20 comprising a powder 85 spray gun 84 and two compression rollers R ₁ and R ₂ , where R ₁ precedes R ₂ and the two cylinders Mold compression rollers are provided side by side at the same level, showing the case where the one or more rough yarns emerge between the compression rollers R ₁ and R ₂ , but not limited thereto.

In this case, the angle α ₂ is zero and the one or more rovings move over the roller R ₂ .

Arrows on the fiber indicate the fiber scrolling direction.

In an alternative way, the rough yarn (s) exit after scrolling at the input between the compression rollers R ₁ and R ₂ and contacting some or all of the surface of the compression roller R ₂ .

Advantageously, the roving (s) is compressed after contact with a part or the whole of the surface of the compression roller (R ₂₎ under contact with a part or the whole of the surface and the roller (R ₂₎ of said compression roller (R ₁₎ roller (R ₂₎ coming out to the outside, the angle (α ₂₎ is formed by the roving (s) between the vertical tangent of the compression roller (R ₂₎ and the inlet of the compression roller (R _2). In this case, angle α ₂ = 90 °.

Advantageously, the impregnation is thus at an angle α ₁ formed by the roving yarn (s) between the entrance of the compression roller R ₁ and the vertical tangent of the compression roller on _one side of the roving yarn and on the same side but performed between the vertical tangent of the compression roller (R ₂₎ and the inlet of the compression roller (R ₂₎ at an angle (α ₂₎ formed by the roving (s), diffusion is also impregnated with the other side Makes it possible to let.

Advantageously, the rovingspun spreads at each angle α ₁ , α ₂ in this embodiment.

7 shows an example of an embodiment in which two compression rollers R ₁ and R ₂ are at the same level with respect to each other.

According to another embodiment of the second variant, when two compression rollers are present, then the distance between the two compression rollers R ₁ and R ₂ is then 0.15 mm to a length equivalent to the maximum dimension of the tank, preferably 10 mm to The height difference between 50 mm and two compression rollers R ₁ and R ₂ is the height corresponding to the maximum height of the tank minus the diameters of 0 to 2 compression rollers, and preferably the diameter of 0.15 mm to 2 compression rollers. It is the height corresponding to the maximum height of the tank minus the lift, and more preferably at a height difference of 10 mm to 300 mm, R ₂ is the upper compression roller.

FIG. 8 shows an embodiment with a tank 20 each comprising a powder 85 spray gun 84 and two compression rollers R ₁ and R ₂ , where R ₁ precedes R ₂ and at another level. Two cylindrical compression rollers are provided and show angles α ₁ , α ₂ , but are not limited thereto.

The flow rate of the powder by each gun in the fibrous material is the same or different, in particular the same.

Although the diameters of the compression rollers R ₁ and R ₂ are shown to be the same in FIGS. 5, 6, 7 and 8, the diameters of the respective cylindrical compression rollers can be different and the diameter of the compression roller R ₁ The diameter may be larger or smaller than the diameter of the compression roller R ₂ in the range as defined above.

Advantageously, the diameters of the two compression rollers are the same.

It is not within the scope of the present invention that the compression roller R ₁ is higher than the compression roller R ₂ .

According to a third variant, when two compression rollers are provided at different levels, then at least the third compression roller R ₃ is additionally provided vertically between the compression rollers R ₁ and R ₂ and (FIG. 9). Each compression roller comprises a powder 85 spray gun 84 and the flow rate of the powder by each gun with the fibrous material at the roller inlet is the same or different, especially the same.

Advantageously, the rough yarn (s) are in contact with some or all of the surface of the compression roller (R ₁ ), then some or all of the surface of the compression roller (R ₃ ) and of the compression roller (R ₂ ) Comes out after contact with some or all of the surface.

Advantageously, the impregnation is formed by the spinning yarn (s) between the inlet of the at least one compression roller R ₁ and a perpendicular tangent to the compression roller R ₁ on _one side of the spinning yarn (s). Not only the angle α ₁ but also the angle α ₃ formed by the vertical tangent of the roving yarn (s) and the compression roller R ₃ and on the other side the roving yarn (s) and the compression roller R ₂ Only at an angle α ₂ formed by the vertical tangent of.

Advantageously, when two compression rollers are provided at different levels and further provided with at least one third compression roller R ₃ , then the inlet of the at least one compression roller R ₂ and the compression roller R _The angle α ₂ formed by the roughing yarn (s) between the perpendicular tangents to ₂ ) is in the range of 180 ° to 45 °, in particular 120 ° to 60 °.

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

In Figure 9, R ₁ is of the two compression rollers, preceding the R ₂ (R ₁ and R ₂₎ and a represents an embodiment with a tank 20 containing a third compression roller (R ₃₎ an angle (α ₁ , α ₂ , α ₃ ), but is not limited thereto.

Although the diameters of the compression rollers R ₁ , R ₂ , R ₃ are shown to be the same 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 three rollers may have different diameters larger or smaller in the range as defined above.

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

Advantageously, in this third variant, the second diffusion control of the roughing yarn (s) is carried out at the level of the compression roller R ₃ , and the third diffusion control is performed at the compression roller R ₃ .

In this third variant, the flow rate is as defined above.

In this third variant, the rough yarn (s) are in contact with some or all of the surface of the compression roller R ₁ and then in contact with some or all of the surface of the compression roller R ₂ and the compression roller. It will still be within the scope of the present invention to come out after contact with some or all of the surface of (R ₃ ).

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

Advantageously, the volume diameter (D90) of the particles is 50 to 500 μm, advantageously 120 to 300 μm.

Advantageously, the volume diameter (D10) of the particles is 5 to 200 μm, advantageously 35 to 100 μm.

Advantageously, the volume diameter of the powder particles is in the ratio of D90 / D10 in the range of 1.5-50, advantageously 2-10.

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

The volume diameters (D10, D50, D90) of the particles are defined according to ISO 9276: 2014.

"D50" corresponds to the mean diameter divided by volume and refers to the particle size value obtained by dividing the irradiated particle population in exactly two parts.

"D90" corresponds to a value at 90% of the cumulative curve of the particle size distribution by volume.

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

According to another embodiment of the process according to the invention, there is a creel in front of the tank to control the tension of the roving yarn or roving yarns at the inlet of the tank.

Optionally, in the process according to the invention, one or more tension devices are found behind the tank.

Forming step

Upon leaving tank 20, the preimpregnated rovings (parallel rovings) optionally covered with molten polymer, via a continuous calendering device comprising one or more heating calenders, are provided with a single unidirectional ribbon or a plurality of parallel It is molded in the form of unidirectional ribbons.

Advantageously, the heating calendars of the calendering device are attached to rapid heating means capable of heating the material at the core as well as at the surface.

The spinning yarn diffused at the outlet of the tank 20 then contracts under the heating effect, which allows the insertion of molten polymer between the spinning yarns to reduce the porosity of the spinning yarn and in particular facilitate the impregnation in the core of the spinning yarn. Let's do it.

The mechanical stress of the calenders coupled to these rapid heating means enables the homogeneous distribution of the polymer and the removal of voids, especially when the fibrous material is a "ready to use" material.

Advantageously, this thermal calendering not only allows the impregnated polymer to be heated to infiltrate, adhere and cover the fibers uniformly, but also enables monitoring of the thickness and width of the ribbons of the pre-impregnated fibrous material.

The heating calendars 51, 52, 53 in the diagram of FIG. 1 are advantageously able to produce a plurality of one-way parallel ribbons, meaning pre-impregnated parallel rovings and the same number of ribbons passed through the tank. A plurality of calendaring grooves 73 according to the number of ribbons. The number of these grooves can be up to 200 for example. The controlled system SYST also enables the adjustment of the E spacing and / or pressure between the rollers 71, 75 of the calendar 70 to monitor the thickness ep of the ribbons. This calendar 70 is shown schematically in FIG. 2 described below.

The calendar device includes at least a heating calendar 51. Preferably, it comprises several heating calendars 51, 52, 53 connected in parallel and / or in series with respect to the running direction of the fiber rovings.

In particular, the process is characterized in that the continuous calendering step is carried out gradually at pressures between the rollers (in the direction of progress of the process) and / or at intervals between the rollers (in the direction of progress of the process).

Having several tandem calendars makes it possible to compact the material, reduce the porosity in the material and reduce their proportions. Thus, this plurality of calendars is important when intending to produce "ready to use" fibrous materials.

Having multiple parallel calendars increases the number of impregnated rovings.

Advantageously, each calendar of the calendering device comprises an induction or microwave integrated heating system, preferably by microwaves, for heating the mixture of polymers or thermoplastic polymers. Advantageously, the polymer or mixture of polymers is preferably selected from carbon nanofillers, in particular graphenes and / or carbon nanotubes and / or carbon nanofibrils or mixtures thereof. Likewise, when including carbon-containing fillers, the microwave or induction heating effect is amplified by the presence of these charges that later transfer heat to the core of the material.

Advantageously, each calender 51, 52, 53 of the instrument is located in front of and / or after each calender to quickly transfer thermal energy to the material and complete the impregnation of the fibers by the molten polymer. (41, 42, 43). The rapid heating device can be selected, for example, from the following devices: microwave devices or other devices in direct contact with heat sources such as induction, IR laser or infrared devices or devices of flame or hot gas. Microwaves or induction devices are particularly advantageous when coupled to the presence of carbon nanopillars in a polymer or polymer mixture as carbon nanofillers amplify the heating effect and deliver it to the core of the material.

According to an alternative embodiment, several of these heating appliances can also be combined.

The process may further comprise heating, prior to impregnation, the fiber spun yarns using microwave heating as preferred heating means, with respect to the heating system of the heating calendar.

Optionally, the subsequent step is to wind up one or more pre-impregnated and shaped ribbons. To that end, the unit 100 for implementing the process comprises a winding device 60 comprising coils 61 equal in number to ribbons, with a coil 61 assigned to each ribbon. Splitter 62 is generally provided to deflect pre-impregnated ribbons into their respective coils 61 while preventing the ribbons from contacting to prevent any degradation.

2 schematically shows a detailed cross-sectional view of the grooves 73 of the calendar 70. The calendar 70 includes an upper roller 71 and a lower roller 75. One of the rollers, for example the upper roller 71, comprises a crenellated part 72, and in the embodiment the other roller, which stands for the lower roller 75, comprises a grooved part 76; The shape of the grooves is complementary to the shape of the protruding portions 72 of the upper roller. The spacing E between the rollers 71, 75 and / or the pressure exerted by the two rollers relative to each other define the dimensions of the grooves 73, in particular their thickness ep and width l. Makes it possible to do Each groove 73 is provided to receive fiber rovings, which are then pressed between the rollers and heated. Thereafter, the roving yarns turn into parallel one-way ribbons and its thickness and width are corrected by the grooves 73 of the calendars. Each calendar advantageously includes a plurality of grooves to produce an equal number of ribbons with grooves and pre-impregnated rovings, the number of which may be up to 200. The calendering device further comprises a central instrument, represented by SYST in FIG. 1, controlled by a computer program provided for this purpose, capable of simultaneously adjusting the pressure and / or spacing of the calendering rollers of all unit 100 calendars. Include.

The unidirectional ribbon (s) thus produced have a width (l) and a thickness (ep) that are adapted for robot removal in manufacturing three-dimensional parts, without having to be split at the right width. The width of the ribbon (s) is advantageously between 5 and 400 mm, preferably between 5 and 50 mm, even more preferably between 5 and 15 mm.

Thus, the process just described for producing pre-impregnated fibrous material enables the production of high productivity pre-impregnated fibrous materials, while in particular enabling homogeneous impregnation of the fibers, porosity and reproducibility control, It allows for the control and reproduction of the results of the final composite product. Homogeneous impregnation and absence of voids around the fibers is achieved by the impregnation step in the tank by controlling the flow rate of the powder by the gun (s) on the fibrous material, and the simultaneous development of the spinning yarn in the compression roller or the compression rollers. It is guaranteed by the "corner effect" in conjunction with. The materials obtained are semi-finished products in the form of ribbons with thickness and width correction, with low porosity.

The process thus enables the production of calibrated ribbons of pre-impregnated fibrous material adapted to produce three-dimensional composite parts by automatic removal of the ribbons using a robot.

Advantageously, the thermoplastic polymer of the ribbon obtained by the process according to the invention is selected from amorphous polymers having a glass transition temperature of Tg ≧ 80 ° C. and / or semicrystalline polymers having a melting temperature Tf of ≧ 150 ° C.

Advantageously, the thermoplastic polymer is as follows:

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 mixtures thereof or copolyamides thereof, in particular 1010/11, 1010/12 Aliphatic polyamides selected from the like and the like;

Semi-aromatic polyamides of formula X / YAr, as described in EP1505099, optionally comprising aromatic polyamides, in particular polyphthalamides, in particular semi-aromatic polyamides of formula A / XT, optionally modified with urea units, here Where A is selected from units obtained from amino acids, units obtained from lactams and units having the formula (Ca diamine). (Cb dibasic acid), a represents the number of carbon atoms of the diamine and b is the carbon atom of the dibasic acid A and b are 4 to 36, advantageously 9 to 18, respectively;

XT represents the unit obtained from the polycondensation of diamine and terephthalic acid at Cx, x represents the number of carbon atoms of the diamine at Cx, x is from 6 to 36, advantageously from 9 to 18,

In particular polyamides of the formulas A / 6T, A / 9T, A / 10T or A / 11T, wherein A is as defined above, in particular polyamide PA 6 / 6T, 66 / 6T, 6I / 6T, PA11 / 10T, 11 / 6T / 10T, MXDT / 10T or MPMDT / 10T, BACT / 10T aramid, and block copolymers, in particular polyamide / polyether (PEBA).

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

Advantageously, the thermoplastic polymer of the ribbon obtained by the process according to the invention is in particular PA 11, PA 12, PA 11/1010, PA 12/1010, PA 11 / 10T, PA 11 / 6T / 10T, PA MXDT / 10T, The semi-aromatic polyamide selected from PA MPMDT / 10T and PA BACT / 10T, and the fibrous material of the ribbon obtained by the process according to the invention is made of carbon fiber.

Advantageously, polyamide selected from PA 11, PA 12, PA 11/1010, PA 12/1010, PA 11 / 10T, PA 11 / 6T / 10T, PA MXDT / 10T, PA MPMDT / 10T and PA BACT / 10T The ribbon of thermoplastic polymer is used for civil or military aviation or for automobiles.

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

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

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

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

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

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

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

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

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

Advantageously, the manufacture of the composite parts can be achieved by transportation, in particular motor vehicles, oil and gas, in particular offshore, gas storage, civil or military aviation, ships, railways; Renewable energy, in particular wind turbines, tidal turbines, energy storage devices, solar panels; Thermal protection panels; Sports and recreation, health and medical, weapons or missile parts and ballistics, security and electronics.

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

Advantageous Embodiments of the Process of the Invention

Advantageously, the fibrous material is selected from carbon fibers and glass fibers.

Advantageously, the thermoplastic polymers used to impregnate the carbon fibers are polyamides, in particular aliphatic polyamides or semiaromatic polyamides such as PA 11, PA 12, PA 11/1010 or PA 12/1010, in particular polyamides, PA 11 / 10T, PA 11 / 6T / 10T, PA MXDT / 10T or PA MPMDT / 10T, or PA BACT / 10T, PEKK and PEI or mixtures thereof.

Advantageously, the thermoplastic polymers used to impregnate the carbon fibers are polyamides, in particular aliphatic polyamides or semiaromatic polyamides such as PA 11, PA 12, PA 11/1010 or PA 12/1010, in particular polyamides, PA 11 / 10T, PA 11 / 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 or glass fibers, is 45 to 65% by volume, preferably 50 to 60% by volume, in particular 54 to 60% by volume.

Table 1 below categorizes advantageous embodiments according to the process of the invention carried out in one or more grooveless cylindrical compression rollers and in a tank for carbon fiber or glass fiber rovings:

In embodiments that include PEKK or PEI, PEKK can be combined with PEI and PEI can be combined with PEKK in the proportions defined above.

Advantageously, in the compositions of Table 1 defined above where two compression rollers are present in the tank, roller R ₂ is above roller R ₁ with respect to the bottom of the tank, in particular H ₂ -H ₁ is 1 cm. To 30 cm, preferably 1 to 10 cm, in particular 1 cm to 3 cm, in particular about 2 cm and the angle α ₂ in the range 0 to 90 °, in particular 25 to 45 °, in particular 25 to 35 ° And the slub moves over R ₂ .

These embodiments correspond to FIG. 5.

Advantageously, in the compositions of Table 1 defined above where two compression rollers are present in the tank, roller R ₂ is above roller R ₁ with respect to the bottom of the tank, in particular H ₂ -H ₁ is 1 cm. ˜30 cm, in particular about 2 cm and the angle α ₂ is 90-180 °, in particular 115-135 °, in particular 115-125 °, and the rovings move below R ₂ .

1 shows a diagram of an implementation unit of a process for producing a preimpregnated fibrous material according to the invention.
FIG. 2 shows a cross-sectional view of the two rollers that make up a calendar as used in the unit of FIG. 1.
3 shows details of the height adjustable tension device 82 and the tank 20. The edge of the tank inlet is provided with a rotating roller 83a through which the roving yarn 81a advances, and the edge of the tank outlet is equipped with a rotating roller 83b through which the roving yarn 81b advances.
4 shows a single compression roller embodiment with a tank 20 including a powder 85 spray gun 84 where a single cylindrical compression roller is present and showing an angle α ₁ .
Arrows on the fiber indicate the fiber scrolling direction.
FIG. 5 shows an embodiment with two compression rollers R ₁ and R ₂ , with R ₁ preceded by R ₂ and a tank 20 each comprising a powder 85 spray gun 84. shows, without limitation, two cylindrical compression rollers (R ₂ from R ₁ a height H ₂ above the height H ₁₎ an angle (α _1, α ₂₎ to different height and for the bottom of the tank to the city.
Arrows on the fiber spun yarn indicate the direction of the spun scrolling direction.
FIG. 6 shows a sample embodiment with a tank 20 comprising a powder 85 spray gun 84, wherein the two compression rollers R ₁ and R ₂ are cylindrical and side by side at the same level with each other. And angle α ₁ , and angle α ₂ = 0 ° and the roving yarn passes between the two rollers.
FIG. 7 shows a sample embodiment with a tank 20 each comprising a powder 85 spray gun 84, wherein the two compression rollers R ₁ and R ₂ are cylindrical and at the same level as each other. Side by side and with angle α ₁ , and angle α ₂ = 90 ° and the rovings proceed below R ₂ .
8 shows a sample embodiment with a tank 20 each containing a powder 85 spray gun 84, with two cylindrical compression rollers R ₁ and R ₂ being at different levels and R ₁ precedes R ₂ , shows angles α ₁ , α ₂ and the roughing yarn passes under roller R ₂ .
Figure 9 is each powder 85, the spray gun to 84, R ₁ is two compression rollers, preceding the R ₂ comprises a (R ₁ and R ₂₎ and the powder (85) comprises a spray gun (84) An embodiment with a compression roller R ₃ and a tank 20 is shown and the angles α ₁ , α ₂ , α ₃ are shown.
10 shows a photograph taken with a scanning electron microscope of a carbon fiber rovings ¼ "Toray carbon fiber cross section impregnated with PA 11 / 6T / 10T with D50 = 100 μm according to the process described in WO 2015/121583 (calender After ring).
The process according to WO 2015/121583 shows a lack of homogeneity in the various regions of the preimpregnated rovings indicated by white arrows.
FIG. 11 shows a photograph taken with a scanning electron microscope cross section of ¼ "carbon fiber rovings (Toray 12K T700S MOE fibers) impregnated with polyamide PA powder MPMDT / 10T of D50 = 115 μm in accordance with the process of the present invention ( As described in Example 2, after calendaring).
12 shows the impregnation of flax fibers with molten PA11 as a comparative example with the process of the present invention (Example 2).
FIG. 13 shows the impregnation of MPMDT / 10T (D50 = 115 μm) Toray T700 S 24K 60E carbon fiber obtained by melting as a process and comparative example of the present invention (Example 2).

The following examples illustrate the scope of the invention in a non-limiting manner.

Example 1 (comparative)

12K carbon fiber rovings were impregnated with PA 11 / 6T / 10T as described in WO 2015/121583.

D50 = 100 μm

Results:

The results show a lack of homogeneity in the various regions of the preimpregnated rovings provided in FIG. 10 and indicated by white arrows.

Example 2: General Procedure for Impregnating Fibrous Materials with Polyamide Powder in a Tank with a Single Roller

The following procedure was performed:

- Cylindrical compression roller, 25 mm diameter in tank (L = 500 mm, l = 500 mm, H = 600 mm).

- Flow rate 25 to 30 g / min

-Angle of 25 ° (α ₁ )

- Toray, approximately 100% diffusion (ie multiplied by 2) for 12K T700S M0E 1/4 "carbon fiber carbon spinning

- D 50 = 115 μm for powder of MPMDT / 10T. (D10 = 49 μm, D90 = 207 μm)

- Edge of the tank with a fixed roller.

A fibrous material (¼ "carbon fiber spun yarn) preimpregnated with polyamide (MPMDT / 10T) was prepared according to this procedure and is shown in FIG.

This shows the effect of the dry powder impregnation process and the control of the powder flow rate in the tank with the compression roller.

Example 3: Determination of the Relative Difference Between Theoretical Density and Experimental Density and Porosity Ratio (General Method)

a) required data includes:

- Density of thermoplastic matrix

- Density of fibers

- Weight of Stiffener:

(단일 로잉으로부터) 예를 들어 ¼ 인치 테이프에 대한 선형 밀도 (g/m)

Linear density (g / m), for example on a ¼ inch tape (from a single row)

예를 들어 보다 넓은 테이프 또는 패브릭에 대한 단위 면적당 질량 (g/㎡).

Eg mass per unit area (g / m 2) for a wider tape or fabric.

b) measurement to be taken:

The number of samples should be at least 30 to represent the material from which the results were investigated.

Measures to be taken include:

- Size of collected samples:

(선형 밀도가 공지되어 있다면) 길이.

Length (if linear density is known).

(단위 면적당 중량이 공지되어 있다면) 길이 및 폭.

Length and width (if weight per unit area is known).

- Experimental Density of Collected Samples:

공기와 물에서 중량 측정.

Weigh in air and water.

- Fiber content determination is determined according to ISO 1172: 1999 or by thermogravimetric analysis (TGA), for example as determined in B. Benzler, Applikationslabor, Mettler Toledo, Giesen, UserCom 1/2001.

The determination of the carbon fiber content can be determined according to ISO 14127: 2008.

Determination of Theoretical Fiber Mass Ratio:

a) Determination of Theoretical Fiber Mass Ratio:

From here,

m _l linear density of the tape,

Length of L sample, and

Me _air The mass of the sample measured in air.

The change in fiber mass ratio should be directly related to the matrix level change without taking into account the change in the amount of fibers in the reinforcement.

b) Determination of theoretical density:

Where d _m and d _f are the densities of the matrix and the fibers, respectively.

If the samples do not have porosity, the theoretical density calculated in this way is the accessible density.

c) Evaluation of Porosity:

Therefore, porosity is a relative difference between theoretical density and experimental density.

Claims (29)

A method for producing a pre-impregnated fibrous material comprising a fibrous material made of continuous fibers and at least one thermoplastic polymer matrix,
The pre-impregnated fibrous material is made of a single one-way ribbon or a plurality of one-way parallel ribbons and the method is roving or several parallel rovings by the at least one matrix of thermoplastic polymer in powder form. Impregnating the fibrous material in the form of yarns, in particular homogeneously in the core, the impregnating step of impregnating the fibrous material with one or more nozzles or one or more dry powder guns in tank 20. Controlled by spraying, controlling the amount of the at least one thermoplastic polymer matrix in the fibrous material excludes any electrostatic process at any voluntary charge, and the nozzle (s) in the fibrous material Or by controlling the flow rate of the powder by the gun (s), A method for producing a non-impregnated fibrous material. The method of claim 1,
The tank 20 includes at least one tension device 82, wherein the rovings 81a or the rovings are in contact with some or the entire surface of the minus one tensioning device 82. Powder injection is carried out at the inlet of the tension machine (82). The method according to claim 1 or 2,
The fiber content of the preimpregnated fibrous material is 45 to 65% by volume, preferably 50 to 60% by volume, in particular 54 to 60% by volume. The method according to any one of claims 1 to 3,
Pre-impregnated, characterized in that the flow rate of the powder by the nozzle (s) or the gun (s) in the fibrous material consists of 10 g / min to 400 g / min, in particular 20 to 150 g / min A method for producing fibrous material. The method according to any one of claims 1 to 4,
Wherein the impregnation step is carried out by simultaneous diffusion of the rovings (81a) or the rovings between the inlet and the outlet of the tank (20). The method of claim 5,
Wherein said diffusion of said spinning yarn (81a) or said spinning yarns is carried out at least in said at least one tension device (82). The method according to claim 2 or 6,
Wherein said at least one tension device (82) is a convex, concave or cylindrical compression roller. The method of claim 7, wherein
At least one compression roller is cylindrical in shape and the diffusion ratio of the rovings 81a or the rovings between the inlet and the outlet of the tank 20 is 1% to 400%, preferably 30% to 400%, A method for producing pre-impregnated fibrous material, characterized in that it preferably consists of 30% to 150%, preferably 50% to 150%. The method of claim 8,
A single compression roller is present in the tank 20 and the impregnation is carried out at an angle α ₁ formed by the roving yarn 81a or the roving yarns between the inlet of the compression roller and the vertical tangent of the compression roller. A method for producing a preimpregnated fibrous material, characterized in that. The method of claim 9,
The angle α ₁ is in the range of 0 to 89 °, preferably 5 ° to 85 °, preferably 5 ° to 45 °, preferably 5 ° to 30 °. Method for preparing the same. The method of claim 8,
2, the two compression rollers (R _1, R ₂₎ is the roving between the vertical tangent of the compression roller (R ₁₎ is present in the tank 20 and the inlet of the impregnation the compression roller (R ₁₎ ( to 81a) or the roving (81a) or said Cao Fang between the vertical tangent of the compression roller (R ₂₎ and the entrance angle (α ₁₎ and / or the compression roller (R ₂₎ formed by said Cao Fang yarns yarns Is carried out at an angle α ₂ , by which the compression roller R ₁ precedes the compression roller R ₂ (in the advancing direction of the method) and the roving yarn 81a or the roving yarn is formed of the roller ( R ₂ ) A process for producing a pre-impregnated fibrous material, characterized in that it can proceed up or down. The method of claim 11,
The two compression rollers R ₁ , R ₂ are 0.15 mm apart from the length corresponding to the maximum dimension of the tank 20, preferably 10 mm to 50 mm apart and the two compression rollers R ₁ , The height difference between R ₂ ) corresponds to the maximum height of the tank 20 minus the diameters of the two compression rollers, preferably 0.15 mm to the tank minus the diameters of the two compression rollers ( 20) in the range of heights corresponding to the maximum height, more preferably at a height difference of 10 mm to 300 mm, R ₂ being an upper compression roller, for producing a pre-impregnated fibrous material Way. The method according to any one of claims 1 to 12,
The method comprises at least one heating calender 51 in the form of a single one-way ribbon or a plurality of one-way parallel ribbons, depending on the number of ribbons and the pressure and / or spacing between the rollers of the calendar controlled by the closed loop system. , 52, 53, by calendering to form the spinning yarns 81a or the parallel spinning yarns of the impregnated fibrous material, when in the form of the plurality of unidirectional parallel ribbons Wherein, the heating calender comprises a plurality of calendering grooves (73), preferably up to 200 calendering grooves. The method of claim 13,
The calendering step is performed using a plurality of heated calenders 51, 52, 53 connected in parallel and / or in series with respect to the direction of motion of the fiber spun yarns 81a. Method for Making a Sex Material. The method according to claim 13 or 14,
The heated calender (s) comprises an induction integrated heating system by microwaves or preferably microwaves, coupled to the presence of carbonaceous charges in the thermoplastic polymer or mixture of thermoplastic polymers. Method for Making a Sex Material. The method according to any one of claims 13 to 15,
The heating calender (s) are carbonaceous in the quick make-up heating devices 41, 42, 43, in particular the polymer or the polymer mixture, located in front of and / or behind the (each) shells 51, 52, 53. Preparation of pre-impregnated fibrous material, characterized by a microwave or induction heating device, or an infrared device, coupled to the presence of fillers, or coupled to laser heating or in direct contact with another heat source such as a flame or hot gas How to. The method according to any one of claims 1 to 16,
The impregnation step (s) is completed by the coating of the single roving yarn 81a or the plurality of parallel roving yarns after the impregnation with powder, the coating step being the same as the polymer in powder form in the tank 20. The molten thermoplastic polymer, which may be different or different, is carried out before the calendering step, the molten polymer preferably having the same properties as the polymer in the form of a tank 20 powder, preferably the coating comprises A process for producing a pre-impregnated fibrous material, characterized in that it is carried out by spinning (81a) or extrusion at right angles to the plurality of parallel rovings. The method according to any one of claims 1 to 17,
The thermoplastic polymer is preferably carbonaceous fillers, in particular carbon black or carbon nanofiller, selected from carbon nanofillers, in particular graphenes and / or carbon nanotubes and / or carbon nanofibrils or mixtures thereof. Further comprising them. The method of claim 1, wherein
Wherein said thermoplastic polymer further comprises liquid crystal polymers or cyclized poly (butylene terephthalate), or mixtures containing them as additives. The method of claim 1, wherein
The at least one thermoplastic polymer is: polyaryl ether ketone (PAEK), in particular poly (ether ether ketone) (PEEK); Polyaryl ether ketone ketones (PAEKK), in particular poly (ether ketone ketones) (PEKK); Aromatic polyetherimides (PEI); Polyaryl sulfones, in particular polyphenylene sulfones (PPSU); Polyarylsulfides, in particular polyphenylene sulfides (PPS); Polyamides (PA), in particular aromatic polyamides optionally modified by urea units; PEBAs, polyacrylates, in particular polymethyl methacrylate (PMMA); Polyolefins, in particular polypropylene, polylactic acid (PLA), polyvinyl alcohol (PVA), and fluorinated polymers, in particular polyvinylidene fluoride (PVDF) or polytetrafluoroethylene (PTFE) or polychlorotrifluoro Ethylene (PCTFE) and mixtures thereof, especially preferably 90 to 10% to 60 to 40% by weight, in particular 90 to 10% to 70 to 30% by weight of a mixture of PEKK and PEI To pre-impregnated fibrous material. The method of claim 20,
Wherein said at least one thermoplastic polymer is a polymer having a glass transition temperature of Tg ≧ 80 ° C. or a semi-crystalline polymer having a melting temperature Tf of ≧ 150 ° C. 2. The method of claim 1, wherein
The fibrous material is carbon fibers, glass, silicon carbide, basalt with a glass transition temperature Tg greater than the Tg of the polymer or polymer mixture when amorphous, or greater than Tf of the polymer or polymer mixture when amorphous , Silica, natural fibers, in particular flax or hemp, lignin, bamboo, sisal, silk, or cellulose, in particular viscose, or amorphous thermoplastic fibers, or amorphous or greater than or equal to the Tg of the polymer mixture A continuous selected from semicrystalline thermoplastic fibers having a melting temperature Tf higher than Tf of the polymer or of the polymer mixture, or of a mixture of two or more of the fibers, preferably of carbon fibers, glass or silicon carbide, especially of carbon fibers Producing a pre-impregnated fibrous material, characterized in that it comprises fibers Method for groups. As a unidirectional ribbon of pre-impregnated fibrous material, in particular a ribbon wound on a reel,
The ribbon according to one of the preceding claims, characterized in that it is obtained by a method as defined in accordance with one of the preceding claims. The method of claim 23, wherein
The ribbon has a width (l) and a thickness (ep), preferably at least 5 mm and a maximum of 400 mm, preferably adapted for robot removal when producing three-dimensional parts without requiring slitting. Ribbon having a width l, preferably 5 to 50 mm, even more preferably 5 to 15 mm. The method of claim 23 or 24,
Thermoplastic polymers are in particular aliphatic polyamides such as PA 11, PA 12, 11/1010 or 12/1010 or PA 11 / 10T, PA 11 / 6T / 10T, PA MXDT / 10T, PA MPMDT / 10T and PA BACT / A unidirectional ribbon, characterized in that the polyamide is selected from semiaromatic polyamides selected from 10T. Use of a method as defined in any of claims 1 to 22 for producing calibrated ribbons suitable for producing three-dimensional composite parts by automatic removal of the ribbons using a robot. Use of a ribbon of pre-impregnated fibrous material as defined in claim 23 or 24 when producing three-dimensional composite parts. The method of claim 27,
Said manufacture of the composite parts can be carried out in transport, in particular in motor vehicles, oil and gas, in particular offshore, gas storage, civil aviation or military, ships, railways; Renewable energy, in particular wind turbines, tidal turbines, energy storage devices, solar panels; Thermal protection panels; Use of a ribbon of pre-impregnated fibrous material, characterized in the fields of sports and recreation, health and medical, weapons or missile parts and ballistics, security and electronics. As a three-dimensional composite part,
The part is characterized in that it results from the use of at least one unidirectional ribbon of pre-impregnated fibrous material as defined in claim 23 or 24.

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