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    • 专利摘要:
    The present invention relates to a reinforcing material comprising at least one fibrous reinforcement associated on at least one of its faces with a porous layer, the porous layer or layers representing at most 10% of the total mass of the reinforcing material, preferably 0 , 5 to 10% of the total mass of the reinforcing material, and preferably 2 to 6% of the total mass of the reinforcing material, characterized in that the porous layer contains a partially crosslinked thermoplastic polymer. The subject of the invention is also a precursor material for such a reinforcing material, as well as their method of preparation and the methods of manufacturing a preform or a composite part from such material.
    公开号:FR3073774A1
    申请号:FR1761056
    申请日:2017-11-22
    公开日:2019-05-24
    发明作者:Andrea Viard；Thibaut Benethuiliere
    申请人:Hexcel Fabrics SA；
    IPC主号:
    专利说明:

    The present invention relates to the technical field of reinforcement materials, suitable for the constitution of composite parts. More specifically, the invention relates to reinforcing materials, suitable for producing composite parts in association with an injected or infused resin, comprising a porous layer of a partially crosslinked thermoplastic polymer, as well as associated methods and uses.
    The manufacture of parts or composite articles, that is to say comprising, on the one hand, one or more fibrous reinforcements, in particular of the unidirectional fibrous sheet type and, on the other hand, a matrix (which is, the more often, mainly of the thermosetting type and can indure one or more thermoplastics) can, for example, be carried out by a process known as direct or LCM (from the English "Liquid Composite Molding"). A direct process is defined by the fact that one or more fibrous reinforcements are implemented in the dry state (that is to say without the final matrix), the resin or matrix, being implemented separately, by example, by injection into the mold containing your fibrous reinforcements (RTM process, from the English "Resin Transfer Molding"), by infusion through the thickness of the fibrous reinforcements (LRI process, from the English "Liquid Resin Infusion" or RFI process, from the English "Resin Film Infusion"), or alternatively by manual coating / impregnation with a roller or a brush, on each of the unitary layers of fibrous reinforcements, applied successively to the form.
    For your RTM, LRI or RFI processes, it is generally first of all necessary to manufacture a fibrous preform or stack of the shape of the desired finished article, then to impregnate this preform or stack of a resin intended to constitute the matrix. The resin is injected or infused by differential pressure in temperature, then once all the necessary quantity of resin is contained in the preform, the assembly is brought to a higher temperature to carry out the polymerization / crosslinking cycle and thus entail its hardening.
    The composite parts used in the automotive, aeronautical or naval industry are in particular subject to very strict requirements, in particular in terms of mechanical properties. To save fuel and facilitate the maintenance of parts, the aeronautical industry has replaced many metallic materials with composite materials that are lighter.
    The resin which is subsequently associated, in particular by injection or infusion, with the fibrous reinforcements, during the production of the part, can be a thermosetting resin, for example of the epoxy type. To allow correct flow through a preform consisting of a stack of different layers of fibrous reinforcements, this resin is, most often, very fluid, for example with a viscosity of the order of 50 to 200 mPa.s ., or even lower, at the infusion / injection temperature. The major drawback of this type of resin is their brittleness, after polymerization / crosslinking, which results in low resistance to the impact of the composite parts produced.
    In order to solve this problem, it has been proposed in the documents of the prior art to associate the layers of fibrous reinforcements with porous polymeric thermoplastic layers, and in particular with a nonwoven (also called veil) of thermoplastic fibers. Such solutions are described in particular in patent applications or patents EP 1125728, US 6,828,016, WO 00/58083, WO 2007/015706, WO 2006/121961, US 6,503,856, US 2008/7435693, WO 2010/046609, WO 2010 / 061114 and EP 2,547,816, US 2008/0289743, US 2007/8361262, US 2011/9371604, WO 2011/048340. The addition of this porous thermoplastic layer, in particular of the nonwoven type, makes it possible to improve the mechanical properties of the composite parts obtained, in the compression after impact test (CAI), a test commonly used to characterize the resistance of structures to 'impact.
    However, these solutions have certain drawbacks. First of all, thermoplastic polymeric porous layers used have more often a high melting temperature, in particular higher than 150 ° C., which makes the manufacturing process of these reinforcing materials expensive.
    In addition, the polymeric thermoplastic material constituting the porous layer can interact with the thermosetting resin which will then be injected or infused. This is all the more true as the melting point of the thermoplastic material is low. The consequences are that it can modify the local stoichiometry of the thermosetting resin and that it can spread in your fibrous reinforcements during the impregnation of the latter by the thermosetting resin, which we want to avoid.
    To solve this problem, it has been proposed in the prior art, by the applicant, an epoxy powder such as that used for the fabric developed under the reference Hexcel Primetex 43098 S 1020 S E01 1F, instead of a porous layer thermoplastic polymer. Such a thermosetting layer obtained by depositing an epoxy powder having a softening temperature of the order of 100 ° C., allows composite parts to be produced more quickly and less costly, and in particular at a lower temperature, since '' low temperature preforming can be performed. However, such a technique poses practical problems due to the use of powder and above all does not make it possible to obtain properties in terms of satisfactory mechanical strength.
    The object of the present invention is therefore to provide new reinforcing materials for the production of composite parts in association with an injected or infused resin, which make it possible to retain your beneficial effects on your mechanical performance observed in the case of the use of materials. reinforcement comprising a porous thermoplastic layer. In this context, the present invention relates to a reinforcing material comprising at least one fibrous reinforcement associated on at least one of its faces with a porous polymeric layer, the polymeric porous layer (s) present representing at most 10% of the total mass of the material. reinforcement, preferably from 0.5 to 10% of the total mass of the reinforcement material, and preferably from 2 to 6% of the total mass of the reinforcement material. In the context of the invention, said at least one porous polymeric layer comprises, or even consists of, a partially crosslinked thermoplastic polymer. Such reinforcements, in which the mass of the polymeric part represents at most 10% of the total mass of the reinforcing material, are conventionally called dry reinforcement materials, in contrast in particular to prepregs, which comprise a larger part of polymer and do not do not require the addition of an external resin when making composite parts and are therefore subject to all other problems. In the context of the invention, due to the partially crosslinked nature of the porous layer present in the reinforcing material, the latter will be only partially soluble, or even completely insoluble, in the thermosetting resin, thermoplastic or the mixture of resins thermosetting and thermoplastic which will be injected or hot infused into the reinforcement material.
    In particular, it can be considered that the thermoplastic part of the partially crosslinked thermoplastic polymer making up the porous layer will allow the use of a low temperature during the manufacture and use of the reinforcing material, and therefore a gain in cost and time of production of the composite part, while the thermosetting part will oppose the complete dissolution of the porous layer in the thermosetting resin, thermoplastic or the mixture of thermosetting and thermoplastic resins which will then be injected or infused. Since the thermoplastic part of the partially crosslinked thermoplastic polymer constitutes only part of the porous layer, even if this part melts in particular in a range going from 80 to 130 ° C., this will not make the porous layer completely soluble in thermosetting, thermoplastic resin or mixture of thermosetting and thermoplastic resins injected or infused, since the crosslinked part will not melt. The presence of this thermoplastic part also has the advantage of making it possible to manufacture the reinforcing material associating porous layer (s) and fibrous reinforcement (s) at a temperature compatible with automated manufacturing processes, in particular for placing fibers. and hot forming of preforms deposited flat.
    Another advantage is that the melting temperature of the porous layer, which in fact corresponds to the melting temperature of its thermoplastic part, will be able to be less than 150 ° C., thus making it possible to carry out all the stages of the manufacturing process prior to the injection of the resin necessary in the end for the production of the piece (of the preparation of the dry material, through its removal and its preforming) at a temperature below 150 ° C, or even less.
    The object of the present invention is therefore to combine the beneficial effects of the use of a porous thermoplastic layer on the impact resistance performance, while having the possibility of carrying out all the stages of the manufacturing process prior to infusion or injection of the resin at temperatures below 150 ° C, or even 140 ° C, which may even be in some cases in the range from 80 to 130 ° C.
    The invention also relates to methods for preparing reinforcing materials in accordance with the invention. In particular, such a method will include the following successive steps:
    al) having a fibrous reinforcement, a2) having at least one porous polymeric layer comprising or consisting of a partially crosslinked thermoplastic polymer, a3) proceeding to the association of the fibrous reinforcement and the at least one porous layer polymer comprising or consisting of a partially crosslinked thermoplastic polymer.
    Such a process can also start from a precursor material comprising a fibrous reinforcement associated on at least one of its faces with a porous polymeric layer comprising or consisting of a thermoplastic polymer carrying crosslinkable functions and which allows, after crosslinking at least part of the crosslinkable functions present on the thermoplastic polymer, to lead to a reinforcing material according to the invention. Such a precursor material also forms an integral part of the invention.
    Finally, the present invention relates to the use of a reinforcing material according to the invention, for the production of a preform or of a composite part, in combination with a thermosetting thermoplastic resin or a mixture of thermosetting and thermoplastic resins, as well as a process for manufacturing a preform or a composite part from at least one reinforcing material according to the invention, in which a thermosetting, thermoplastic resin or a mixture of thermosetting and thermoplastic resins is injected or infused within said reinforcing material or a stack of several reinforcing materials according to the invention.
    Definitions.
    By “porous layer” is meant a permeable layer allowing a liquid such as a resin to pass through which would be injected or infused through the material during the formation of a preform or of a composite part. In particular, the opening factor of such a layer determined according to the method described in application WO 2011/086266, belongs to the range going from 30 to 99%, preferably to the range going from 40 to 70%. By way of example of a porous layer, mention may be made of porous films, your grids produced by interlacing wires, the layers obtained by powder deposition, fabrics and nonwovens. However, in the context of the invention, whatever the embodiment described, it will be preferable to use a porous layer in the form of a nonwoven, also called a veil. The porous layer is called polymeric because it is composed of a polymer or mixture of polymers and contains a partially crosslinked thermoplastic polymer. In the present description, the porous polymeric layer may more simply be called “porous layer”, for the sake of simplicity. In particular, the porous layer may consist only of a partially crosslinked thermoplastic polymer or of a mixture of a partially crosslinked thermoplastic polymer and a thermoplastic polymer. In this second case, the partially crosslinked thermoplastic polymer / thermoplastic polymer mixture will preferably contain at least 10% by mass of partially crosslinked thermoplastic polymer, preferably at least 70% by mass of partially crosslinked thermoplastic polymer, relative to the mass of the mixture of partially crosslinked thermoplastic polymer / thermoplastic polymer. In the case of a partially crosslinked thermoplastic polymer / thermoplastic polymer mixture, it will be possible to use a high degree of crosslinking in the partially crosslinked thermoplastic polymer, in particular from 50 to 90%, combined with the presence of the thermoplastic polymer, which preferably, will have a melting temperature in the range of 80 to 130 ° C. Conversely, it will, in particular, be possible to use a low degree of crosslinking in the partially crosslinked thermoplastic polymer, in particular from 30 to 70%, combined with the presence of the thermoplastic polymer, which may then have a melting temperature. higher, in particular greater than 150 ° C, or even greater than 180 ° C, for example in the range from 180 to 400 ° C. Such a melting temperature can be determined according to standard ISO 113573. By way of example of a thermoplastic polymer, mention may be made of polyamides, polyesters, polyamide-imides, polyethersulfones, polyimides, polyetherketones, polymethyl methacrylates, aromatic polyethers, etc. In the context of the invention, the polymeric material constituting the porous layer is preferably a partially crosslinked thermoplastic polymer and not a mixture with a thermoplastic polymer.
    The polymer used in the context of the invention is said to be “partially crosslinked” because it has a thermoplastic part corresponding to linear or branched chains and a crosslinked part forming a three-dimensional network. The crosslinked part is obtained by crosslinking of a thermoplastic polymer carrying crosslinkable functions. Said crosslinkable functions are distributed over the thermoplastic polymer, before the crosslinking step. In particular, the thermoplastic polymer carrying crosslinkable functions may be in the form of a branched polymer carrying a crosslinkable function at the end of the branching chain.
    Any type of crosslinkable functions may be suitable: crosslinkable functions under the action of heat, under the action of UV, gamma or beta radiation, or those requiring the presence of a catalyst of the peroxide type which will then be used mixed with the partially crosslinkable thermoplastic polymer.
    For practical reasons, partially crosslinked thermoplastic polymers obtained by crosslinking crosslinkable functions under the action of heat or radiation, and not requiring a chemical catalyst, will be preferred. Preferably, it will be chosen to use crosslinkable functions under the action of UV, gamma or beta radiation, which allow better control of the crosslinking. Crosslinking can be carried out under an inert atmosphere or in ambient air. By way of example of functions which can be crosslinked under the action of UV, gamma or beta radiation, mention may be made of your unsaturated functions.
    Advantageously, the partially crosslinked thermoplastic polymer belongs to the family of copolyamides, and in particular caprolactams and / or lauryllactams.
    Partially crosslinkable thermoplastic polymers comprising such unsaturated functions which are crosslinkable under the action of UV, gamma or beta radiation, are in particular described in application EP 1591468 and are, in particular, marketed by the company ARKEMA under the reference Platamid® HX2632 .
    By way of a polymer which is suitable in the context of the invention, mention may be made of your partially crosslinked thermoplastic polymers obtained by crosslinking a branched copolyamide with unsaturated ends consisting of:
    at least one unit originating from a multifunctional monomer (A) chosen from diethylene triamine, pentaerythritol, mellitic acid and 2,2-dimethylolpropionic acid,
    - at least sequences resulting from condensation in the presence of at least one unsaturated monoacid used as chain limiter,
    - or at least two alpha, omega-aminocarboxylic acids not having the same number of carbon atoms,
    - or at least two lactams which do not have the same number of carbon atoms,
    - or at least one lactam, at least one dicarboxylic acid and at least one diamine,
    - either a lactam and / or an alpha, omega-aminocarboxylic acid not having the same order of carbon atoms,
    - either a diamine and a dicarboxylic acid,
    - or at least one diamine, at least one dicarboxylic acid and at least one alpha, omega-aminocarboxylic acid, the proportion of (A) being less than 9% by mass of the whole of (A) and other monomers previously mentioned.
    In particular, the sequences of the branched copolyamide with unsaturated ends comprise at least caprolactam and lauryllactam or else comprise at least caprolactam, hexamethylene diamine and adipic acid.
    The unsaturated monoacid of the branched copolyamide with unsaturated ends is, in particular, crotonic acid or undecylenic acid.
    By way of example of thermoplastic polymers crosslinked under the action of heat and not requiring a catalyst, mention may be made of those obtained by crosslinking copolyamides comprising isocyanate and epoxy functions.
    Such polymers are notably described in your patents EP 1808468 and US 9205630 and are, for example, marketed by the company Evonik under the reference Vestamelt Hylink (X1333). The polymer composing the porous layer comprises a thermoplastic part and a crosslinked part. The thermoplastic part preferably represents from 30 to 90% by mass, and preferably from 30 to 70% by mass of the mass of the polymer. Thus, there remains a significant portion of non-crosslinked porous layer, necessary for the production of the preform.
    The mass part represented by the thermoplastic part of a partially crosslinked thermoplastic polymer can be determined, by dissolving the thermoplastic part in a solvent where it is soluble (for example by immersion for 3 days at room temperature (23 ° C)), and by measuring the difference in mass before and after solubilization (the residue obtained after solubilization is, for example, filtered and dried at 50 ° C for 4 hours), as described in the examples.
    Advantageously, the thermoplastic part of the partially crosslinked polymer has a melting temperature belonging to the range from 80 to 130 ° C, preferably to the range from 80 to 120 ° C. The melting temperature of the partially crosslinked polymer which corresponds to the melting temperature of its thermoplastic part can be determined by DSC: from the English Differential Scanning Analysis, according to standard ISO 11357-3. With such melting temperatures, it is possible to produce the material according to the invention, carry out your operations of depositing and producing a preform, for the production of a composite part, at temperatures below 130 ° C., which is particularly advantageous from an industrial point of view.
    The polymer making up the porous layer may be an amorphous polymer, but will preferably be a semi-crystalline polymer. Semi-crystalline polymers having a glass transition temperature lower than their melting temperature, their softening can be obtained more easily, which allows you to associate them more easily by bonding to the fibrous reinforcement or promotes the deposition and / or preforming of the material. reinforcement according to the invention, thereafter. In addition, semi-crystalline polymers in particular have an organized molecular structure in which the chains are aligned which gives them superior mechanical properties than amorphous polymers for which the molecular structure is not organized.
    By “fibrous reinforcement associated on at least one of its faces with a porous layer”, it is meant that the fibrous reinforcement is linked to at least one porous layer which is affixed on one of the faces of the latter. Such a connection will in particular be carried out by bonding, in particular produced by virtue of the hot tackiness of the porous layer, due to its thermoplastic part. It is also possible, in particular in the case of a stack comprising several fibrous reinforcements and several porous layers, that this connection is supplemented or replaced by a mechanical connection of the sewing, knitting type, or by any other physical means (needling ... ).
    The reinforcing materials according to the invention can be qualified as “dry” because they are intended to be associated with a binder, in particular with a thermosetting resin, for the manufacture of a composite part. Also, the mass of partially crosslinked thermoplastic polymer making up the porous layer or layers of the reinforcing material according to the invention does not represent more than 10% of the total mass of the reinforcing material according to the invention, and preferably represent 0, 5 to 10%, and preferably 2 to 6% of the total mass of the reinforcing material according to the invention.
    By “nonwoven”, which can also be called “veil”, is conventionally meant a set of continuous or short fibers arranged randomly. These nonwovens or veils may, for example, be produced by the dry ("Drylaid"), wet ("Wetlaid"), melt ("Spunlaid"), by extrusion ("Spunbond"), extrusion processes. blowing ("Meltblown"), or by solvent spinning ("electrospinning", "Flashspining", "Forcespinning"), well known to those skilled in the art. In particular, the fibers constituting the nonwoven can have an average diameter in the range from 0.5 to 70 μm, and preferably from 0.5 to 20 μm. The nonwovens can be made of short fibers or, preferably, continuous fibers. In the case of a nonwoven of short fibers, your fibers may have, for example, a length of between 1 and 100 mm. Nonwovens provide random and preferably isotropic coverage.
    Advantageously, you or the nonwovens present in the reinforcement materials according to the invention has (have) a surface mass comprised in the range going from 0.2 and 20 g / m 2 . The thickness of a nonwoven in the reinforcement materials according to the invention may vary depending on the mode of association with the fibrous reinforcement. Preferably, each of the nonwovens present in the reinforcing materials according to the invention has a thickness of 0.5 to 50 microns after association with the fibrous reinforcement, preferably from 3 to 35 microns, when the association is made by application of heat and pressure to use the hot tackiness of the nonwoven. When the association is made by mechanical means, of the sewing, knitting or needling type, the thickness of the nonwoven may be greater than 50 microns, in particular in the range from 50 to 200 microns. The characteristics of these nonwovens can be determined according to the methods described in application WO 2010/046609.
    By “fibrous reinforcement” is meant a layer of reinforcing fibers, which may be in the form of a fabric or a unidirectional sheet of reinforcing fibers in particular. The reinforcing fibers are glass, carbon, aramid, ceramic fibers, carbon fibers being particularly preferred.
    Conventionally, in this field, by "ply or unidirectional layer of reinforcing fibers" means a ply consisting exclusively or almost exclusively of reinforcing fibers deposited in the same direction, so as to extend substantially parallel your to each other. In particular, according to a particular embodiment of the invention, the unidirectional sheet has no weft thread interlacing your reinforcing fibers, or even sewing which would aim to give cohesion to the unidirectional sheet before its association with another layer, and in particular with a porous polymeric layer. This makes it possible in particular to avoid any undulation within the unidirectional sheet. A unidirectional layer of reinforcing fibers may consist of a single thread, although it will most often consist of several aligned threads arranged side by side. The wires are arranged so as to provide total or almost total coverage over the entire surface of the sheet. In this case, in each of the layers making up the intermediate material, your threads are preferably arranged edge to edge, minimizing or even avoiding any lack of material ("gap" in English) or overlap ("overlap" in English) .
    In the unidirectional sheet, the reinforcing thread or threads are preferably not associated with a polymeric binder and therefore qualified as dry, that is to say that they are neither impregnated, coated, nor associated with a any polymeric binder before their association with the porous polymeric layers. Reinforcement fibers are, however, more often characterized by a standard mass sizing rate which can represent at most 2% of their mass. This is particularly suitable for producing composite parts by resin diffusion, according to direct methods well known to those skilled in the art.
    The fibers constituting the fibrous reinforcements used in the context of the invention are preferably continuous. The fibrous reinforcements generally consist of several threads.
    In particular, a carbon thread consists of a set of filaments and generally comprises from 1,000 to 80,000 filaments, advantageously from 12,000 to 24,000 filaments. Particularly preferably, in the context of the invention, carbon threads of 1 to 24 K, for example, of 3K, 6K, 12K or 24K, and preferably of 12 and 24K, are used. For example, your carbon threads present in the fibrous reinforcements used in the context of the invention have a titer of 60 to 3800 Tex, and preferably from 400 to 900 Tex. A fibrous reinforcement can be produced with any type of carbon thread, for example, High Resistance (HR) threads whose tensile modulus is between 220 and 241GPa and whose tensile breaking stress is between 3450 and 4830MPa, Intermediate Module (IM) wires whose tensile modulus is between 290 and 297GPa and whose tensile breaking stress is between 3450 and 6200MPa and High Modulus (HM) wires whose tensile modulus is between 345 and 448GPa and whose tensile breaking stress is between 3450 and 5520Pa (according to "ASM Handbook", ISBN 0-87170-703-9, ASM International 2001).
    MâiàiaiLdejOnforts ^
    The invention can be adapted for different types of reinforcing materials: simple reinforcing materials comprising a single fibrous reinforcement intended to be stacked on top of each other, or else more complex reinforcing materials comprising several fibrous reinforcements in the form of 'a stack, which can be used alone or also in the form of stack.
    In particular, by way of example of simple reinforcing materials, mention may be made of those consisting of a unidirectional sheet of reinforcing fibers corresponding to the fibrous reinforcement, associated on at least one of its faces with a porous layer as provided in the part of the invention. In order to have a symmetrical material, the fibrous reinforcement, and in particular the unidirectional sheet of reinforcing fibers, is associated on each of its faces with a porous layer as provided for in the context of the invention and the porous layers present on each of the faces of the unidirectional ply of reinforcing fibers are preferably identical. In the context of the invention, the porous layer has a hot tacky character and the association of the fibrous reinforcement and the porous layer will advantageously be achieved thanks to the hot sticky nature of the porous layer. This tackiness results from the thermoplastic part of the partially crosslinked polymer making up the porous layer.
    As an example of more complex reinforcing materials, mention may be made of those consisting of a stack of layers of unidirectional reinforcing fibers oriented in different directions, with at least one porous layer as provided for in the context of the invention. interposed between two unidirectional layers of reinforcing fibers and / or on the surface of the stack. According to a first variant, such a material may consist of a stack corresponding to a sequence (CM / R) n , with CM which denotes a porous polymeric layer comprising or consisting of a partially crosslinked thermoplastic polymer as provided in the frame of the invention and R a fibrous reinforcement and n denoting an integer, with preferably all your layers CM which have an identical grammage, or even which are identical.
    According to a second variant, such a material may consist of a stack corresponding to a sequence (CM / R) n / CM, with CM which denotes a porous polymeric layer comprising or consisting of a partially crosslinked thermoplastic polymer as provided in te framework of the invention and R a fibrous reinforcement and n denoting an integer, preferably with the outer porous polymeric layers comprising or consisting of a partially crosslinked thermoplastic polymer having a grammage equal to the half-grammage of each of the inner porous layers polymeric Comprising or consisting of a partially crosslinked thermoplastic polymer.
    In particular, in such stacks, the fibrous reinforcements R are unidirectional sheets of reinforcing fibers, preferably of identical grammage.
    Such materials are qualified by NCF (from the English “Non-crimp fabric”). Conventionally in this field of NCF, the association of unidirectional layers of reinforcing fibers together and with at least one porous layer is produced by sewing or knitting. Of course, provision may be made to replace or even complete this association by sewing or knitting, by an adhesion produced by virtue of the hot tackiness of the porous layer, or by any other means of the physical bonding type (needling, etc.). ).
    In particular, in the case of NCFs, the reinforcing material according to the invention is composed of unidirectional sheets extending in different orientations chosen from the angles 0 °, 30 °, 45 °, 60 °, 90 °, 120 ° , 135 °. All the tablecloths can have different orientations or only some of them. By way of example, the reinforcement material according to the invention can be produced according to the following stacks: 0 ° / 90 °, 90 ° / 0 °, 457 135 °, 135/45 °, 9070 790 °, 0790 ° / 0 ° , 1357457135 °,
    45 ° / 135 ° / 45 °, 0 ° / 45 ° / 90 °, 9074570 °, 4570790 °, 9070745 °,
    07135790 °, 90713570 °, 13570790 °, 90707135 °, 45 ° / 0 ° / 135 °,
    13570745 °, 45713570 °, 07135745 °, 45 ° / 135 ° / 90 °, 907135745 °, 13574570 °, 07457135 °, 135745790 °, 907457135 °, 60707120 °, 120 ° / 0 ° / 60 °, 30 ° / 0 ° / 150 °, 15070730 °, 13570 ° / 45790 °, 90745707135 °, 45713570790 °, 90707135 ° / 45 o , 07457135790 °, 907135745790 °, 90 ° / 13570 ° / 45 °, 45707135790 °, the 0 ° corresponding to the direction advancement of the machine for producing the reinforcing material according to the invention. In the case of a combination by sewing or knitting, the general direction of the sewing or knitting yarns will also generally correspond to 0 °. The realization of such multiaxlaux is known and implements conventional techniques for example described in the work "Textile Structural Composites, Composite Materials Sériés Volume 3" by Tsu Wei Chou & Franck.K.Ko, ISBN 0-444-42992- 1, Elsevier Science Publishers BV, 1989, Chapter 5, paragraph 3.3 or in patent FR2761380 which describes a process and a device for producing multiaxial fibrous webs. In particular, your unidirectional tablecloths can be created before or deposited online, when the multiaxial is created. The connection by sewing or knitting between your different unidirectional sheets can be carried out according to sewing or knitting stitches, extending on parallel lines between them. In particular, your sewing or knitting stitches are spaced, within the same line in a step, preferably identical, from 1 to 20 mm, preferably from 2 to 12 mm. Likewise, two consecutive sewing or knitting lines are, for example, spaced from one another by 2 to 50 mm, preferably by 5 to 15 mm. Preferably, all of your consecutive lines of sewing in a series of lines parallel to each other will be spaced by the same distance. By way of example of material constituting the sewing thread which is particularly suitable in the context of the invention, mention may be made of polyesters (PET), polypropylenes (PP), polyethylenes (PE), phenylene polysulphides (PPS) , polyethylene naphthalates (PEN), your liquid crystal polymers (LCP), your polyketones, polyamides, your crosslinkable thermoplastics, carbon, glass, basalt, silica, and their mixture. Polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polylactic acid and their copolymers are examples of polyesters which can be used. The yarn will, for example, have a titer in the range from 5 to 150 dTex, in particular less than 30 dTex, for example determined according to determined according to standard EN ISO 2060. For more details on your constructions usable in your type materials NCF, reference may be made to documents EP 2547816 or WO 2010/067003 in particular
    Material d ^ jOnfQrt £ r ^^
    The invention also relates to a precursor material comprising a fibrous reinforcement associated on at least one of its faces with a porous polymeric layer comprising or consisting of a thermoplastic polymer carrying crosslinkable functions and which allows, after crosslinking at least part of the crosslinkable functions present on the thermoplastic polymer, to lead to a reinforcing material according to the invention. This precursor material differs from the material according to the invention, only in that the polymer is not yet partially crosslinked. The crosslinked functions are therefore in crosslinkable and noncrosslinked form. For the rest, the other characteristics are identical in all respects to that of the reinforcement material according to the invention described above. Figure 1 illustrates the transformation of such a precursor reinforcing material comprising a fibrous reinforcement associated on one of its faces with a porous crosslinkable thermoplastic layer, in a reinforcing material according to the invention, following the partial crosslinking of the layer porous.
    Procré £ de jréB ^ aWMl jdiy! ^^
    Nnyention
    In the context of the invention, the crosslinking of the porous layer or layers can be carried out before or after it is deposited on a fibrous reinforcement, or even associated with said fibrous reinforcement.
    In particular, according to a first variant, a reinforcing material according to the invention can be prepared, by implementing the following successive steps:
    al) having a fibrous reinforcement, a2) having at least one porous polymeric layer comprising or consisting of a partially crosslinked thermoplastic polymer, a3) proceeding to the association of the fibrous reinforcement and the at least one porous layer polymer comprising or consisting of a partially crosslinked thermoplastic polymer.
    In particular, step a3) can be obtained by applying the at least one porous layer to the fibrous reinforcement, said application being accompanied or followed by heating of the partially crosslinked thermoplastic polymer causing it to soften or melt, then followed cooling.
    According to a second variant, a reinforcement material according to the invention can be prepared, by implementing the following successive steps: bl) having a precursor material according to the invention, comprising a fibrous reinforcement associated on at least one of its facing a porous polymeric layer comprising or consisting of a thermoplastic polymer carrying crosslinkable functions, b2) crosslinking at least part of the crosslinkable functions present on the thermoplastic polymer.
    In this case, the method may include the following successive steps, upstream of step b1): c1) having a fibrous reinforcement, c2) having at least one porous polymeric layer comprising or consisting of a thermoplastic polymer carrier of crosslinkable functions, c3) proceed to the association of the fibrous reinforcement and the at least one porous polymeric layer comprising or consisting of a thermoplastic polymer carrying crosslinkable functions.
    In particular, step c3) is obtained by application of the at least one porous layer on the fibrous reinforcement, said application being accompanied or followed by heating of the thermoplastic polymer carrying crosslinkable functions resulting in its softening or melting, but not causing the crosslinking of the crosslinkable functions, then followed by cooling.
    Preferably, whatever the variant chosen, the crosslinkable functions can be crosslinked by irradiation, in particular under the action of UV, gamma or beta radiation, or even by heating.
    Crosslinking can also be carried out by adding a catalyst of the peroxide type then present within the porous layer. This can be introduced by deposition, in particular by spraying onto the porous layer.
    The crosslinking mode chosen will of course be chosen as a function of the polymer used and of the crosslinkable functions present.
    Crosslinking can be carried out under an inert atmosphere or in ambient air. Most often, in the case of UV, gamma or beta crosslinking, the crosslinking is carried out at a temperature belonging to the range from 20 to 50 ° C.
    The crosslinking conditions will be adapted by a person skilled in the art, as a function of the crosslinkable thermoplastic polymer used, and in particular as a function of the crosslinkable functions present on said polymer. In particular, in the case of gamma or beta radiation, doses in the range from 25 to 300kGy and preferably from 50 to 200 kGy (kiloGray) will be adapted, with preferably application of an acceleration voltage of 80 to 300 kV (kiloelectronVolt) in the case of beta radiation.
    By adjusting the crosslinking rate, in particular obtained by modulating the parameters of the radiation used, it is possible to control the degree of insolubility of the partially crosslinked porous layer obtained.
    As previously exposed, the crosslinking can be carried out on a porous polymeric layer comprising or consisting of a thermoplastic polymer carrying crosslinkable functions, before its association with a fibrous reinforcement as after this association. However, depending on the crosslinking technique used, and in particular in the case of crosslinking by irradiation which is more easily controllable, the technique chosen may depend on the number of porous layers and their accessibility.
    When the crosslinking step is carried out on a material which is a precursor of a reinforcing material according to the invention, said precursor material comprising a fibrous reinforcement associated on at least one of its faces with a porous polymeric layer comprising or consisting of a polymer thermoplastic carrying crosslinkable functions, this can be carried out as the last step of an automated process, in particular by scrolling the product obtained under beta radiation (also called "e-beam" in English). In the case where crosslinking is activated under gamma radiation, it is even conceivable to carry out the irradiation on rollers or pallets of precursor material.
    Also, in the case of simple materials comprising a single fibrous reinforcement, the first or the second variant may be implemented, although the second variant is preferred. Depending on the crosslinking technique used (irradiation under beta radiation), it may be necessary to perform irradiation on both sides of the material, your reinforcing fibers acting as a screen against radiation.
    In the case of more complex materials comprising at least one porous layer between two fibrous reinforcements, and in particular, in the case of NCFs, the first variant will preferably be used, in particular in cases where crosslinking is carried out under irradiation with beta radiation.
    Of course, whatever the preparation process used, the porous layer and the reinforcing material will be chosen, so that in the end, the polymer porous layer (s) representing at most 10% of the total mass of the reinforcing material, preferably from 0.5 to 10% of the total mass of the reinforcing material, and preferably from 2 to 6% of the total mass of the reinforcing material obtained.
    UtiljsatimLA ^ rQ "Mjrtillsaiit un mataiLjde ^ reinforcement ^ composite donation
    The reinforcing materials of the invention comprising a fibrous reinforcement associated on at least one of its faces with a porous polymeric layer comprising or consisting of a thermoplastic polymer carrying crosslinkable functions are perfectly suitable, for the production of a preform or of '' a composite part, in combination with a thermosetting resin, thermoplastic or a mixture of thermosetting and thermoplastic resins.
    Conventionally, in a process for manufacturing a preform or a composite part from at least one reinforcing material according to the invention, a thermosetting, thermoplastic resin or a mixture of thermosetting and thermoplastic resins is injected or infused within said reinforcing material or a stack of several reinforcing materials.
    In the context of the invention, due to the presence of a thermoplastic part in the porous layer present in the reinforcing material, prior to the infusion or injection of the resin, a deposit or a shaping using the hot tackiness of said at least one porous layer present in the reinforcing material can be implemented. Advantageously, the methods for manufacturing a preform or a composite part include a step of depositing or shaping a material according to the invention, in which the porous layer is heated to a temperature which results in at least partial melting of the porous layer (s) defined in the context of the invention, and in particular at a temperature belonging to the range from 80 to 130 ° C, preferably to the range from 80 to 120 ° C.
    The steps used for the manufacture of the composite part are entirely conventional for those skilled in the art. It is possible to produce a planar preform, or even a preform according to a desired three-dimensional shape. In particular, the deposition of a reinforcing material according to the invention can be carried out continuously with the application of a pressure perpendicular to the deposition surface in order to apply it thereon. Such methods known under the abbreviations AFP (from the English Automated Fiber Placement) or ATL (from the English Automated Tape Lay-up) are for example described in the documents WO 2014/076433 A1 or WO 2014/191667. Different strips of material according to the invention can be deposited one next to the other along parallel or non-parallel deposition paths, depending on the preform to be produced, so as to form a succession of folds deposited on each other. Concomitantly with the deposition, the thermoplastic material of the porous layer is activated, that is to say softened, so as to use the hot tackiness of the material. When a fold is fully deposited, the orientation is modified in order to deposit the next fold according to a different deposition trajectory to the previous fold. Each strip is deposited parallel or not (depending on the geometry of the part to be produced) to the preceding strip, with or without inter-strip space and with bonding over the entire surface. This removal process is, more particularly, suitable for widths of reinforcing material of between 3 and 300 mm, with, preferably, little variation in width (<0.25 mm). In the case where the reinforcing material has a wider width, it can be deposited by any other suitable means.
    In particular, the manufacture of the composite part uses, as final steps, a step of diffusion, by infusion or injection, of a thermosetting, thermoplastic resin or of a mixture of thermosetting and thermoplastic resins within the material. reinforcement or a stack of reinforcement materials according to the invention, followed by a step of consolidating the desired part by a polymerization / crosslinking step according to a defined cycle in temperature and under pressure, and by a step d 'cooling. According to a particular embodiment, also adapted to all of your implementation variants described in relation to the invention, your diffusion, consolidation and cooling steps are implemented in an open or closed mold.
    In particular, a resin diffused within the stack may be of a thermoplastic or preferably thermosetting nature, or made up of a mixture of thermosetting and thermoplastic resins. By way of example of a thermoplastic resin, mention may be made of polyamides, polyesters, polyamide-imides, polyethersulfones, polyimides, polyetherketones, polymethyl methacrylates, aromatic polyethers, etc. The thermosetting resins which can be used are, in particular, chosen from epoxides, unsaturated polyesters, vinylesters, phenolic resins, polyimides, bismaleimides, your phenolformaldehyde, urea-formaldehyde resins, your 1,3,5-triazine-2,4,6-triamines, benzoxazines, your cyanate esters, and their mixtures. Such a resin may also include one or more hardening agents, well known to those skilled in the art for use with the selected thermosetting polymers. In particular, the invention will be implemented with a thermosetting resin, and in particular an epoxy resin.
    The invention will preferably use an infusion under reduced pressure, in particular under a pressure below atmospheric pressure, in particular less than 1 bar and, preferably, between 0.1 and 1 bar, of the thermosetting resin for producing of the composite part. The infusion will preferably be carried out in an open mold, for example by infusion under a vacuum cover.
    The composite part is obtained in the end after a heat treatment step. In particular, the composite part is generally obtained by a conventional consolidation cycle of the polymers considered, by performing a heat treatment, recommended by the suppliers of these polymers, and known to those skilled in the art. This consolidation step of the desired part is carried out by polymerization / crosslinking according to a defined temperature and pressure cycle, followed by cooling. In the case of thermosetting resin, there is most often a step of gelling the resin before it hardens. The pressure applied during the treatment cycle is low in the case of infusion under reduced pressure and higher in the case of injection into an RTM mold.
    The examples below, with reference to the appended Figures, illustrate the invention, but are in no way limiting.
    Figure 1 very schematically shows the partial crosslinking of the porous layer of a precursor reinforcement material presented in section and comprising a fibrous reinforcement associated on one of its faces with a crosslinkable thermoplastic porous layer, leading to a reinforcement material according to l invention, then comprising fibrous reinforcement associated with a partially crosslinked thermoplastic porous layer.
    Figure 2 shows schematically the process used in your exemptions for the manufacture of reinforcement materials, called "veiled DUs".
    FIG. 3 shows the crosslinking rate obtained for an HX2632 veil and a veiled UD material produced with such a veil, as a function of the beta irradiation dose applied.
    Figures 4 to 6 show images obtained under optical microscopy, when different webs and resin are placed between two glass slides, and subjected or not to heating.
    Figures 7 and 8 show DMA curves obtained on different resin / fleece test pieces according to standard EN 6032 (1Hz, 1 ° C / min, Amplitude 15 pm).
    Figure 9 presents the curve of behavior in fusion of the HX2632 veil after irradiation under a beta radiation of lOOkGy by DSC, according to standard ISO 11357-3.
    Figure 10 schematically illustrates a method of depositing a reinforcing material.
    Figure 11 schematically illustrates the peel test used in the examples.
    Figure 12 schematically illustrates a preforming process for making a non-planar preform.
    Figure 13 shows where the diameter measurement mentioned in Table 5 is carried out.
    Figure 14 shows the image obtained under electron microscopy, of Hylink powder and RTM6 resin placed between two glass slides, after heating to 180 ° C.
    Figure 15 shows the DMA curves obtained on different resin / veil or resin / powder test pieces according to standard EN 6032 (1Hz, 1 ° C / min, Amplitude 15 pm).
    MaténayM / Prsdujteutilses
    The porous layers according to the invention were produced with:
    1) Or a veil of fibers made of a Platamid® HX2632 polymer marketed by the company Arkema (copolyamide having unsaturated terminal unsaturations making it possible to obtain a three-dimensional network under UV, gamma or beta treatment) which has a melting temperature of 117 ° C - this veil (hereinafter called HX2632 veil) is obtained by meltblown ("meltblown" in English) and has a surface mass of 4 g / m 2 and a thickness of
    100 µm before lamination on the fibrous reinforcement. The diameter of the fibers which constitute it is 15 μm. The opening factor of such a layer, determined according to the method described in application WO 2011/086266, is 50 +/- 10%.
    2) Or by deposition of a thermoplastic copolyamide powder crosslinkable in temperature due to the presence of epoxy and isocyanate functions, allowing the creation of a three-dimensional T network, Vestamelt Hylink (X1333) marketed by Evonik which has a melting temperature 123 ° C. Crosslinking can be initiated at a temperature of 150 ° C.
    The porous layers used for comparison were produced with:
    1) Either a 1R8D04 thermoplastic veil sold by the company Protechnic (66, rue des Fabriques, 68702 - CERNAY Cedex France) which has a melting temperature of 160 ° C - this veil (hereinafter referred to as 1R8D04 veil) is obtained by fusion -blowing (“meltblown” in English) and has a surface mass of 4 g / m 2 and a thickness of 100 μm before lamination on the fibrous reinforcement. The diameter of the fibers which constitute it is 15 μm. The opening factor of such a layer, determined according to the method described in application WO 2011/086266, is 50 +/- 10%.
    2) Or by depositing a layer of epoxy powder used in the Hexcel Primetex 43098 S 1020 S E01 1F fabric. The average diameter of the powder is 51 μm (D50, median value), its glass transition is in the range from 54 to 65 ° C.
    The fibrous reinforcements used in all your cases are unidirectional carbon fibers marketed by the applicant under the reference IMA 12K. The properties of these 12K fibers are summarized in Table 1 below:
    Table 1
    Hexcel IMA 12K tensile force (MPa) 6.067 voltage module (GPa) 297 final elongation at break (%) 1.8 density (g / cm 3 ) 1.79 weight / length (g / m) 0.445 filament diameter(Pm) 5.1
    The thermosetting resins used for the production of composite parts are the RTM6 and RTM230ST epoxy resins sold by the company Hexcel Composite, Dagneux France.
    Mesuresjréalisées
    DSC: from English Differential Scanning Analysis. The analyzes were carried out on a Q2000 device from TA Instruments, Guyancourt, France.
    DMA: from English Dynamic Mechanical Analysis. The analyzes were carried out on a Q800 device from TA Instruments, Guyancourt, France.
    Analysis with a hot microscope: The analyzes were carried out on an Axio M2m Microscope Imager from Zeiss, Marly-le-Roi, France, equipped with a heating device from Linkam Scientific Instruments, Tadworth, UK.
    Rheology: The viscosity analyzes were carried out on a HAAKE Mars rheometer from Thermofisher Scientific, Courtaboeuf, France.
    ContreçoIlag ^ jdjesj £ Qiies r ^ dit UD veiled
    The veil is laminated directly on each side of the unidirectional sheets based on carbon fibers thanks to a machine (Figure 2) specifically dedicated to this effect just after the formation of the sheet with the desired grammage. The carbon wires 1 are unwound from carbon reels 3 fixed on a creel 4, pass through a comb 5, are driven in the axis of the machine using a guide roller 6 and a comb 7, a guide bar Sa. The carbon wires are preheated using a heating bar 9 and are then spread out using the spreading bar 8b and the heating bar 10 to ground. desired carbon surface area of the unidirectional sheet 17. The web rolls 13a and 13b are unwound without tension and transported using continuous belts 15a and 15b fixed between your free rotating rollers 14a, 14b, 14c, 14d and the bars heated 12a, 12b. The sails 2a and 2b are preheated in the areas 11a and 11b before being in contact with your carbon wires 1 and laminated on either side of two heated bars 12a and 12b whose air gap is controlled. A grille 16, which can be cooled, then applies pressure to the unidirectional sheet with a veil on each side 17. A deflection roller 18 makes it possible to redirect the product 17 to the traction system comprising a trio of call 19 then d winding 20 controlled by a motor to form a roller made up of the intermediate product claimed 17.
    The test conditions for the manufacture of the unidirectional layers of carbon combined with a veil on each side (called “veiled DU”) are indicated in Table 2 below.
    Table 2: Process parameters for the implementation of the unidirectional layers associated with a veil on each side
    Sail Measured surface mass of unidirectional (g / m 2 ) Line speed (m / min) T bar (° C)(9) T bar(° C)(10) T sail preheating(° C)(lia & 11b) T bars(° C)(12a &12b) sailHX2632 210 2.4 60 65 85 100 sail1R8D04 210 2.4 200 200 160 180
    A. E5SAI> REALIZED „WITH WUSATIOl ^ OF SAILS.
    I. Inf! U £ n £ e_d £ j ^ rj3dj ££ ^^ fibtfinye
    The HX2632 veil is treated with different beta radiations (COMET equipment, Flamatt, Switzerland, acceleration voltage of 150 kiloelectronVolt-kV and irradiation doses of 50 and 100 kiloGray - kGy).
    The irradiation is carried out before association of the veil with the unidirectional. As the thermoplastic copolyamides are soluble in formic acid, the crosslinked portion is determined as follows: the veils or the veiled DU obtained at the end of these irradiations are immersed in formic acid for 3 days at room temperature (23 ° C), then the residue obtained is filtered and dried at 50 ° C for 4 h. FIG. 3 shows the change in the% mass that this residue represents (therefore corresponding to the crosslinked part), relative to the total mass of the veil obtained after crosslinking. The results obtained are the same whether the irradiation is carried out on the veil alone or on a veil / unidirectional association.
    It appears that the crosslinked portion varies from 30 to 60% and varies, depending on the irradiation conditions used.
    Π. InflyensgjieJarétiçulaü ^^
    B "
    The HX2632 veil, before irradiation, and RTM6 epoxy resin applied to the veil are placed between two glass slides, the whole being itself placed under an optical microscope. The whole is then subjected to a temperature rise of 2 ° C / min to a temperature of 180 ° C, corresponding to the final temperature tors of the infusion or injection of the resin tors of the realization of 'a composite part. This is therefore the critical cycle for keeping the veil at temperature, since no pre-crosslinking step of the resin is used.
    Figure 4 shows the image obtained at 23 ° C (left) and 180 ° C therefore post-crosslinking of the resin (right). It therefore appears that the veil dissolves in the resin when it is not partially crosslinked.
    Figure 5 presents the image obtained at 180 ° C when the veil used is the HX2632 veil subjected to an irradiation of 100 kGy of beta rays, with the use of two thermosetting resins: RTM6 (on the left), and RTM230ST (on the right) . It therefore appears that the crosslinking obtained makes the veil insoluble in these two resins.
    Figure 6 shows, for its part, the evolution of this insolubility as a function of the crosslinking rate: 50 kGy treatment of beta rays (35 +/- 5 by mass of crosslinked part) (left), treatment with 100 kGy of beta rays (57 +/- 5 by mass of crosslinked part) (right). The crosslinking rates are obtained by performing the arithmetic mean on six measurements and the standard deviation is defined as the quadratic mean of the deviations from the
    J-Z (x, y h.
    medium ( 1 ). The increase in the crosslinked part therefore makes it possible to also increase and control the insoluble part of the veil.
    It appears from the photographs presented that the presence of the crosslinked part of the porous layer makes it possible to keep the integrity of the veil in the liquid resin and seems to reduce the molecular mobility of the thermoplastic part.
    ΙΠ- Influence of crosslinking studied by DMA
    These results can be correlated to the DMA curves (obtained according to standard EN 6032) on the RTM6 / sail samples. These samples were prepared by impregnating the veil held vertically in a metal mold. Once the impregnation with RTM6 resin had been carried out, the samples were prepolymerized at 120 ° C. for 45 minutes, followed by a 2 hour post-curing at 180 ° C. As can be seen in Figure 7 (Analysis DMA, 1Hz, l ° C / min - Amplitude 15 pm), the radiation dose applied to the veil has a great influence on the thermomechanical properties symbolized by the DMA results: by increasing the crosslinking rate, it is possible to maintain the thermomechanical performance of the material up to the glass transition of the epoxy-amine network of the RTM6 resin, and the thermoplastic contribution is negligible (Dose of 100kGy in Beta electron beam). On the other hand, without crosslinking, the thermoplastic transition is clearly visible at around 80 ° C and results in a decrease in thermomechanical properties. This confirms the results obtained in optical microscopy and shows that by irradiating the veil, it is possible to control the interactions between the veil and the epoxy resin.
    This is the whole point of the invention, since it appears that once treated under lOOkGy of Beta radiation, the HX2632 web does not impact the thermomechanical properties of the thermosetting resin, despite its low melting point.
    Furthermore, Figure 8 obtained with the HX2632 veil subjected to an electron beam irradiation (Beta radiation) of 100 kGy shows that these observations are confirmed regardless of the resin used: RTM6 or RTM230ST.
    IV. EtudefiarDSÇ
    The last step to fully understand the behavior of the veil after irradiation was to check that it was still capable of melting after irradiation. Also, it has been verified in the case of the most crosslinked sails (crosslinked portion representing 57% by mass, obtained after irradiation under electron beam of 100 kGy and 35% by mass, obtained after irradiation under electron beam of 50 kGy), that the crosslinked part present in the veil did not prevent the subsequent fusion of the veil.
    Indeed, the fact that the veil retains a hot tackiness is necessary for its subsequent connection to the unidirectional, and during shaping, in particular for the production of preform.
    The behavior in fusion of the veil after irradiation was observed by DSC, according to standard ISO 11357-3. The curves obtained and presented
    Figure 9 show that the beta electron beam irradiation leads to a slight difference in terms of the melting point of the haze, but which occurs anyway around 100 0 C. This low melting point is very advantageous, in in terms of time and cost, and will make it possible to lower the temperature which will be used, during the subsequent forming step for the production of the preform, which is generally carried out, in the prior art, at temperatures above 150 ° C.
    V. EÈl! Èls_jréalisés_j5 ^^
    Einygnîisn
    1) Crosslinking on a veiled DU
    Measurements of the crosslinking level were carried out on the veiled UD with a HX2632 veil laminated on each side of the unidirectional, according to the conditions in Table 2. The voltage applied for the electron beam irradiation was 150 kV and the applied dose was 100 kGy. As carbon fiber does not react to irradiation but can act as a barrier to radiation due to its density, the influence of the treatment on one or both sides of the material has been evaluated. The veiled UD material irradiated by electron beam (beta radiation) was immersed in formic acid for 3 days, then filtered and dried to assess the rate of crosslinking, as previously described.
    The results are summarized in Table 3 below and compared with the level of crosslinking obtained by irradiating the veil only. It appears that the results obtained are similar on the two materials, confirming that the treatment can be carried out at two different stages of the process: on the veil only, upstream of its association with the unidirectional or on the veiled DU. However for the latter, the treatment must be done on both sides of the material because of the density of the reinforcing fibers, depending on the crosslinking mode used (irradiation under an electron beam). In the case of gamma irradiation, treatment on one side is sufficient.
    Table 3 giving the% of crosslinked mass share obtained on the total mass of the porous layer considered
    UD veiled Sail lOOkGy beamof electrons (one side) 22 +/- 6 59 +/- 5 lOOkGy beamof electrons (on both sides) 57 +/- 5
    2) Installation and preforming
    2.1) Installation
    The deposition of the veiled DU is carried out continuously with the application of a pressure perpendicular to the depositing surface in order to apply it thereon. Such methods known under the abbreviations AFP (from the English Automated Fiber Placement) or ATL (from the English Automated Tape Lay-up) are for example described in the documents WO 2014/076433 A1 or WO 2014/191667 and illustrated in Figure 10. Different strips of intermediate material are deposited one next to the other along parallel deposition paths, so as to form folds 200i, 200 2 ... The device 300 activates the thermoplastic material (veil, powder ...), that is to say to use the hot tackiness of the material, and is integral with the depositing member 400. This is moved to deposit the different strips of material which are cut at the end of the trajectory. When a fold is fully deposited, the orientation is modified in order to deposit the next fold according to a different deposition trajectory to the previous fold. Each strip is deposited parallel to the previous strip, without inter-strip space and with a bonding over the entire surface.
    Such a process could be successfully applied with your materials according to the invention. In particular, the following conditions were used:
    - Veiled UD reinforcement materials used: unidirectional laminated on each of its faces with a HX2632 sheet, then subjected to Beta radiation of 50kGy or to Beta radiation of 100kGy, on each of its faces.
    - Power and speed of removal carried out with a FANUC M16ÎB machine, sold by the company FANUC (Japan) Table 4:
    Depositing power (Watts) Removal speed(Mm / s) Sail HX2632 830 430 Sail 1R8D04 1000 370
    - Orientation and number of folds: [(45/0/90/135/0) 12.
    In the case of activation of a thermosetting material of the epoxy powder type used in the prior art, the main advantage is the activation temperature of the material which is of the order of 100 ° C. On the other hand, this type of material generally causes fouling of the depositing member 400. This is why thermoplastic materials, for example in the form of a veil (such as those mentioned in WO 2010/046609), are generally preferred, but those used in the prior art are activated at temperatures above 150 ° C.
    The veiled UD reinforcement material of the invention proposes to respond to the problem of activation of the material at temperatures below 150 ° C., even if it has a partially crosslinked thermoplastic material. In particular, the UD material veiled with a HX2632 web crosslinked on each of the faces of the carbon web can be deposited at temperatures between 80 and 130 ° C, more particularly between 100 and 120 ° C, allowing to reduce from 20 to 40% the power required for the removal of the material compared to a conventional thermoplastic fleece and to accelerate the removal speed, especially during the many phases of acceleration of the removal means (energy savings). The crosslinking rate of the thermoplastic web does not influence these results, the residual thermoplastic part making it possible to ensure the thermoliant nature of the material, regardless of the quantity. More particularly, the same deposit parameters can be used with a thermoplastic percentage of between 30 and 70% by mass after crosslinking of the HX2632 web. These results confirm that the present invention makes it possible to carry out your removal operations in a particularly advantageous manner on the industrial level.
    The quality of the removal of the material was evaluated by means of an unstandardized peel test which is used for comparison. The peel assembly is shown in Figure il. To do this, two strips of veiled UD material are associated in parallel with each other using the power and speed of removal specified above. The duo thus formed is peeled in traction at an arbitrary speed of 50 mm / min over a distance of 200 mm (preforming distance mentioned in Figure 11), in order to measure the force generated by the peeling. The quality of the removal is thus evaluated by measuring the average of the peel force generated over 200 mm. The results presented in Table 5 thus compare the quality of the deposition between a UD reinforcement material veiled with a 1R8D04 thermoplastic veil laminated on each of its faces and with a HX2632 veil treated with 50 or 100 kGy of Beta radiation also against glued on each of its faces. The three sails have a grammage of 4 g / m 2 . It thus clearly appears that despite the irradiation treatment undergone by the HX2632 fleece, this in no way affects its tackiness and it is thus possible to obtain deposition qualities equivalent to those obtained with a pure thermoplastic fleece.
    Table 5 giving the peeling force generated over 200mm between two strips of UD intermediate material veiled according to the veil used
    1R8D04 HX2632 50kGy Beta HX2632 lOOkGy Beta Average peeling force over 200mm (N) 0.13 +/-0.03 0.12 +/- 0.02 0.14 +/- 0.04
    2.2) Preforming
    The multiaxial planar preform obtained in paragraph 2.1 can subsequently be preformed by again using the heat-bonding nature of the thermoplastic material present on the unidirectional reinforcing material. To do this, the flat preform is positioned on the preforming tool at room temperature and a silicone vacuum cover covers the assembly which is then heated in an oven to a temperature enabling the thermo-adhesive nature of the thermoplastic material to be activated 5 or thermosetting. Reduced pressure is then applied to allow the flat preform to be preformed into the desired three-dimensional shape, then the assembly is always cooled under vacuum before recovering the preform. The entire process is described in FIG. 12. In (i), a two-dimensional preform positioned on the tool is shown, with the application of the vacuum cover, heating leads in (ii) to activation of the fusible character, in (iii), there is application of the vacuum, preforming step, followed by cooling with active vacuum in (iv) leading, at the end of (v) and (vi) to the ready preform .
    While the reinforcement materials using webs such as those described in patent WO 2010/046609 must be preformed at temperatures above 150 ° C., the materials as described in the invention can be preformed at temperatures below 130 ° C, preferably less than 120 ° C. This again shows a real industrial interest in carrying out the entire process at temperatures below 130 ° C.
    In order to assess the quality of the preform obtained, a diameter measurement is made on it. In the same way as to evaluate the quality of the removal, three veiled UD materials are compared: laminating with 1R8D04 sails, HX2632 sails subjected to Beta 25 radiation of 50kGy and HX2632 sails subjected to Beta radiation of 100kGy .
    The preforms such as that presented in FIG. 12 were previously obtained by stacking 10 unidirectional plies [(45/0/90/135/0)] 2 with a surface mass of 210 g / m 2 . The preforming cycles as well as the radius measurements performed on the preforms obtained are presented in Table 6. Figure 13 describes the location of the diameter measurement on the preform.
    Table 6
    1R8D04 HX2632 50kGyBeta HX2632 lOOkGyBeta Preforming step 30min170 ° C 30min 120 ° C 30min 120 ° C Measured diameter (mm) 20.0 21.3 22.0 Theoretical diameter (mm) 20
    The results clearly underline the advantage of the invention, since it makes it possible at the same time to reduce the preforming temperatures significantly, without however altering the quality of the preform obtained. In the example presented, a diameter of 22mm for 20mm theoretical is considered perfectly acceptable.
    3) Panel processing
    A preform of 340 mm x 340 mm consisting of the stacking sequence adapted to the grammage of carbon is placed in an injection mold 10 under press. A frame of known thickness surrounding the preform makes it possible to obtain the volume ratio of TVF fibers desired.
    Four reinforcing materials are compared, two according to the invention described above and two others used in the prior art (Table 7).
    Table 7
    Material 1 comparison Comparative material 2 Material 3 according to the invention Material 4 according to the invention Reinforcement fiber Hexcel IMA 12K Porous layer Epoxy powder used in Hexcel Primetex fabric43098 S 1020 S E01 1F Sail1R8D04 SailHX263250kGy Beta SailHX2632lOOkGyBeta Areal mass of the reinforcement fibers of the veiled DU (g / m 2 ) 210
    The epoxy resin marketed by Hexcel under the reference HexFIow
    RTM6 is injected at 80 ° C at 2 bars through the preform which is maintained at 140 ° C in the press. The pressure applied by the press is 5.5 bars. When the preform is filled and the resin leaves the mold, the outlet pipe is closed and the polymerization cycle begins (3 ° C / min up to 180 ° C followed by a post-baking of 2 hours at 180 ° C and from cooling to
    5 ° C / min).
    Test pieces are then cut to the dimensions suitable for carrying out compression tests after impact (CAI), shear in the plane (IPS), compression on a perforated plate (OHC) as well as initiation and propagation of cracks (GIc and GIIc) summarized in Table 8.
    Table 8
    IPS CAI Glc / GIIC CMB Orientation of the folds of the preform [45/135] 2s [45/0/135/90] 3s [0J16 [45/0/135 / 90J3S Test machine Instron 5582 Zwick Z300 Instron2519 Zwick Z300 EN standard 6031 6038 6033/6034 6036
    The results obtained for all of these tests are listed in Tables 9 to 11. In the case of the GIc and GIIc tests, obtaining a value greater than 700 J / m 2 is considered to be very satisfactory and is 5 whatever the material.
    Table 9 - IPS
    IPS (dry, 23 ° C) Material 1 comparison Comparative material 2 Material 3 according to the invention Material 4 according to the invention Stress (MPa) 66 102 101 100 Module (MPa) 4.4 4.4 4.5 4.6
    Table 10 - CAI
    CAI normalized to60% TFV (dry,23 ° C) Material 1 comparison Comparative material 2 Material 3 according to the invention Material 4 according to the invention 30J (MPa) 126 259 262 255 70J (MPa)192 217 211
    Table 11 - OHC
    Compression Material 1 comparison Comparative material 2 Material 3 according to the invention Material 4 according to the invention OHC (MPa) 257 285 295 295
    The mechanical results presented show that, in addition to the previously detailed process problems to which the materials of the invention respond, these also make it possible to obtain composite parts with optimal properties, in particular in terms of impact resistance (CAI). , mechanical properties showing sensitivity to holes such as hole compression (OHC), in-plane shear (1RS) or even crack resistance (priming and propagation GIc, GIIc).
    It is in particular possible to obtain a compressive rupture stress after impact greater than 250 MPa under an impact of 30J.
    It can thus be seen that on the one hand, although the epoxy powder makes it possible to solve the problem of carrying out all of the steps of the process for producing the dry preform at temperatures between 80 and 130 ° C., it does not allow for as much to obtain composite parts with optimal mechanical properties. On the other hand, the conventional polyamide fleece conversely allows optimal mechanical properties to be obtained but does not solve the problem of the low temperature process.
    The present invention therefore makes it possible to combine both a process for producing the dry preform at temperatures below 130 ° C. and optimal mechanical properties on composite parts.
    B. ESSAOEAUSEÎAV ^^
    POWDER
    Firstly, the Hylink binder was crosslinked for 30 minutes at 180 ° C. in an oven. The measurement of the mass of the crosslinked part, as well as the hot optical microscopy were carried out, as in part AI and II, in order to verify the behavior of the polymer. The contents of crosslinked share were measured by immersion in formic acid for 3 days at room temperature, then filtration and drying at 50 ° C. for 4 h. The results obtained are as follows:
    - initial crosslinked part: 7% +/- 3%, based on the total mass of polymer
    - crosslinked portion after 30 minutes at 180 ° C: 60% +/- 9%, based on the total mass of polymer.
    Figure 14 shows the image obtained under an optical microscope at 180 ° C therefore post-crosslinking of the RTM6 resin present. The photograph presented highlights the capacity of the polymer to partially crosslink under the increase in temperature, allowing it to remain insoluble in the RTM6 resin, in the same way as in the case of the HX2632 veil subjected to irradiation.
    Again, these results can be correlated to the DMA curves on the RTM6 / Hylink binder samples (according to EN 6032). The samples were pre-polymerized at 120 ° C for 45 minutes, followed by a 2 hour post-cure at 180 ° C. As shown in the results presented in Figure 15, the crosslinking treatment at temperature applied to the Hylink binder has a great influence on the DMA results: by increasing the crosslinking rate, it is possible to maintain the thermomechanical performance of the material in the same way as for the HX2632 fleece. Consequently, the thermoplastic contribution is negligible, which confirms the microscopy observations.
    权利要求:
    Claims (34)
    [1" id="c-fr-0001]
    1 - Reinforcement material comprising at least one fibrous reinforcement associated on at least one of its faces with a porous polymeric layer, the porous polymeric layer or layers representing at most 10% of the total mass of the reinforcement material, preferably 0, 5 to 10% of the total mass of the reinforcing material, and preferably 2 to 6% of the total mass of the reinforcing material, characterized in that the porous polymeric layer (s) has ( s) contains a partially crosslinked thermoplastic polymer.
    [2" id="c-fr-0002]
    2 - Reinforcement material according to claim 1, characterized in that the partially crosslinked thermoplastic polymer comprising the porous layer comprises a thermoplastic part and a crosslinked part and the thermoplastic part represents from 30 to 90% by mass, preferably from 30 to 70 % by mass of the mass of the polymer.
    [3" id="c-fr-0003]
    3 - Reinforcement material according to claim 1 or 2, characterized in that the partially crosslinked thermoplastic polymer comprising the porous layer comprises a thermoplastic part and a crosslinked part and the thermoplastic part has a melting temperature below 150 ° C, or even at 140 ° C and preferably belonging to the range going from 80 to 130 ° C, and preferably to the range going from 80 to 120 ° C.
    [4" id="c-fr-0004]
    4 - Reinforcement material according to any one of claims 1 to 3, characterized in that the partially crosslinked thermoplastic polymer making up the porous layer is a semi-crystalline polymer.
    [5" id="c-fr-0005]
    5 - Reinforcement material according to any one of claims 1 to 4, characterized in that the partially crosslinked thermoplastic polymer is obtained by crosslinking of crosslinkable functions under the action of heat or radiation, and does not require chemical catalyst.
    [6" id="c-fr-0006]
    6 - Reinforcement material according to claim 5, characterized in that the crosslinkable functions are chosen from your unsaturated functions.
    [7" id="c-fr-0007]
    7 - Reinforcement material according to any one of claims 1 to 6, characterized in that the partially crosslinked thermoplastic polymer belongs to the family of copolyamides.
    [8" id="c-fr-0008]
    8 - Reinforcement material according to any one of claims 1 to 7, 5 characterized in that the partially crosslinked thermoplastic polymer is obtained by crosslinking of a branched copolyamide with unsaturated ends consisting of:
    - at least one unit originating from a multifunctional monomer (A) chosen from diethylene triamine, pentaerythritol, mellitic acid
    10 and 2,2-dimethylolpropionic acid,
    - at least sequences resulting from condensation in the presence of at least one unsaturated monoacid used as chain limiter,
    - or at least two alpha, omega-aminocarboxylic acids having no
    15 not the same number of carbon atoms,
    - or at least two lactams which do not have the same number of carbon atoms,
    - or at least one lactam, at least one dicarboxylic acid and at least one diamine,
    20 - either a lactam and / or an alpha, omega-aminocarboxylic acid not having the same order of carbon atoms,
    - either a diamine and a dicarboxylic acid,
    - or at least one diamine, at least one dicarboxylic acid and at least one alpha, omega-aminocarboxylic acid,
    The proportion of (A) being less than 9% by mass of the whole of (A) and of the other monomers previously mentioned.
    [9" id="c-fr-0009]
    9 - Reinforcement material according to claim 8, characterized in that the sequences of the copolyamide connected to unsaturated ends comprise at least caprolactam and lauryllactam.
    30
    [10" id="c-fr-0010]
    10 - Reinforcement material according to claim 8, characterized in that the sequences of copolyamide connected to unsaturated ends comprise at least caprolactam, hexamethylene diamine and adipic acid.
    [11" id="c-fr-0011]
    11 - Reinforcement material according to any one of claims 8 to 10, characterized in that the unsaturated monoacid of the copolyamide connected to unsaturated ends is crotonic acid or undecylenic acid.
    [12" id="c-fr-0012]
    12 - Reinforcement material according to any one of claims 1 to 5, characterized in that the partially crosslinked thermoplastic polymer is obtained by crosslinking of a copolyamide comprising isocyanate and epoxy functions.
    [13" id="c-fr-0013]
    13 - Reinforcement material according to any one of claims 1 to 12, characterized in that the fibrous reinforcement is a unidirectional sheet of reinforcing fibers, a fabric of reinforcing fibers or a stack of unidirectional sheets linked together by sewing or any other physical means (needling ...).
    [14" id="c-fr-0014]
    14 - Reinforcement material according to any one of claims 1 to
    13 characterized in that the fibrous reinforcement consists of carbon fibers.
    [15" id="c-fr-0015]
    15 - Reinforcement material according to any one of claims 1 to
    14 characterized in that it consists of a unidirectional sheet of reinforcing fibers corresponding to the fibrous reinforcement, associated on at least one of its faces with a porous layer.
    [16" id="c-fr-0016]
    16 - Reinforcement material according to claim 15 characterized in that it consists of a unidirectional sheet of reinforcing fibers corresponding to the fibrous reinforcement, associated on each of its faces with a porous layer and the porous layers present on each of the faces of the unidirectional ply of reinforcing fibers are identical.
    [17" id="c-fr-0017]
    17 - Reinforcement material according to any one of claims 1 to 16 characterized in that the porous layer has a hot tackiness and the association of the fibrous reinforcement and the porous layer has been achieved thanks to the hot tackiness of the porous layer.
    [18" id="c-fr-0018]
    18 - Reinforcement material according to any one of claims 1 to 14, characterized in that it consists of a stack of layers of unidirectional reinforcing fibers oriented in different directions, with at least one porous layer interposed between two unidirectional layers of reinforcing fibers and / or on the surface of the stack.
    [19" id="c-fr-0019]
    19 - Reinforcement material according to claim 18 characterized in that it consists of a stack corresponding to a sequence (CM / R) n , with CM which denotes a porous polymeric layer comprising or consisting of a partially crosslinked thermoplastic polymer and R a fibrous reinforcement and n denoting an integer, preferably with all of your layers CM which have an identical grammage.
    [20" id="c-fr-0020]
    20 - Reinforcement material according to claim 18 characterized in that it consists of a stack corresponding to a sequence (CM / R) n / CM, with CM which denotes a porous polymeric layer comprising or consisting of a partially thermoplastic polymer crosslinked and R a fibrous reinforcement and n denoting an integer, preferably with the external porous polymeric layers comprising or consisting of a partially crosslinked thermoplastic polymer having a grammage equal to the half-grammage of each of the internal porous polymeric layers comprising or consisting of '' a partially crosslinked thermoplastic polymer.
    [21" id="c-fr-0021]
    21 - Reinforcement material according to claim 19 or 20 characterized in that the fibrous reinforcements R are unidirectional sheets of reinforcing fibers, preferably of identical grammage.
    [22" id="c-fr-0022]
    22 - Reinforcement material according to one of claims 18 to 21, characterized in that the association of unidirectional layers of reinforcing fibers together and with the at least one porous layer is produced by sewing, knitting or needling.
    [23" id="c-fr-0023]
    23 - Reinforcement material according to any one of claims 1 to 22, characterized in that the porous layer or layers present (s) is (are) a porous film, a grid, a powder deposit, a fabric or, preferably a nonwoven or veil.
    [24" id="c-fr-0024]
    24 - precursor material of a reinforcing material according to any one of claims 1 to 23, characterized in that it comprises a fibrous reinforcement associated on at least one of its faces with a porous polymeric layer comprising or consisting of a thermoplastic polymer carrying crosslinkable functions.
    [25" id="c-fr-0025]
    25 - Process for preparing a reinforcing material according to any one of claims 1 to 23, characterized in that it comprises the following successive steps:
    al) having a fibrous reinforcement, a2) having at least one porous polymeric layer comprising or consisting of a partially crosslinked thermoplastic polymer, a3) proceeding to the association of the fibrous reinforcement and the at least one porous layer polymer comprising or consisting of a partially crosslinked thermoplastic polymer.
    [26" id="c-fr-0026]
    26 - Preparation process according to claim 25 characterized in that the combination of step a3) is obtained by application of the at least one porous layer on the fibrous reinforcement, said application being accompanied or followed by heating of the partially crosslinked thermoplastic polymer causing it to soften or melt, then followed by cooling.
    [27" id="c-fr-0027]
    27 - Process for preparing a reinforcing material according to any one of claims 1 to 23, characterized in that it comprises the following successive steps:
    bl) having a precursor material according to claim 24, comprising a fibrous reinforcement associated on at least one of its faces with a porous polymeric layer comprising or consisting of a thermoplastic polymer carrying crosslinkable functions, b2) crosslinking d '' at least part of the crosslinkable functions present on the thermoplastic polymer.
    [28" id="c-fr-0028]
    28 - Preparation process according to claim 27, characterized in that the crosslinking of step b2) is carried out under the action of heat, or preferably under the action of UV, gamma or beta radiation.
    [29" id="c-fr-0029]
    29 - Preparation process according to claim 27 or 28, characterized in that it comprises the following successive steps, upstream of step b1):
    cl) having a fibrous reinforcement, c2) having at least one porous polymeric layer comprising or consisting of a thermoplastic polymer carrying crosslinkable functions, c3) proceeding to the association of the fibrous reinforcement and the at least one porous polymeric layer comprising or consisting of a thermoplastic polymer carrying crosslinkable functions.
    [30" id="c-fr-0030]
    30 - Preparation process according to claim 29, characterized in that the combination of step c3) is obtained by application of the at least one porous layer on the fibrous reinforcement, said application being accompanied or followed by heating thermoplastic polymer carrying crosslinkable functions resulting in its softening or melting, but not causing crosslinking of the crosslinkable functions, then followed by cooling.
    [31" id="c-fr-0031]
    31 - Process for manufacturing a preform or a composite part from at least one reinforcing material according to any one of claims 1 to 23, characterized in that a thermosetting resin, thermoplastic or a mixture of thermosetting and thermoplastic resins is injected or infused into said reinforcing material or a stack of several reinforcing materials according to any one of claims 1 to 23.
    [32" id="c-fr-0032]
    32 - A method of manufacturing a preform or a composite part according to claim 31, characterized in that it comprises, prior to infusion or injection of the resin, a deposit or shaping using the hot tackiness of said at least one porous layer present in the reinforcing material.
    [33" id="c-fr-0033]
    33 - Use of a reinforcing material according to any one of claims 1 to 23, for the production of a preform or a composite part, in combination with a thermosetting resin, thermoplastic or a mixture of thermosetting and thermoplastic resins .
    [34" id="c-fr-0034]
    34 - Manufacturing process according to claim 31 or 32 or use according to claim 33, characterized in that a thermosetting resin, and in particular an epoxy resin, is injected or infused.
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    同族专利:
    公开号 | 公开日
    US20200353717A1|2020-11-12|
    ES2897536T3|2022-03-01|
    EP3713759B1|2021-08-11|
    CN111386191A|2020-07-07|
    FR3073774B1|2019-11-15|
    AU2018372375A1|2020-05-14|
    JP2021504513A|2021-02-15|
    WO2019102136A1|2019-05-31|
    EP3713759A1|2020-09-30|
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    法律状态:
    2018-10-11| PLFP| Fee payment|Year of fee payment: 2 |
    2019-05-24| PLSC| Publication of the preliminary search report|Effective date: 20190524 |
    2019-10-14| PLFP| Fee payment|Year of fee payment: 3 |
    2020-10-13| PLFP| Fee payment|Year of fee payment: 4 |
    2021-11-09| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1761056A|FR3073774B1|2017-11-22|2017-11-22|REINFORCING MATERIAL COMPRISING A POROUS LAYER OF A PARTIALLY RETICULATED THERMOPLASTIC POLYMER AND RELATED METHODS|
    FR1761056|2017-11-22|FR1761056A| FR3073774B1|2017-11-22|2017-11-22|REINFORCING MATERIAL COMPRISING A POROUS LAYER OF A PARTIALLY RETICULATED THERMOPLASTIC POLYMER AND RELATED METHODS|
    PCT/FR2018/052925| WO2019102136A1|2017-11-22|2018-11-20|Reinforcement material comprising a porous layer made of partially cross-linked thermoplastic polymer and associated methods|
    CN201880075179.3A| CN111386191A|2017-11-22|2018-11-20|Reinforcing material comprising a porous layer made of a partially cross-linked thermoplastic polymer and related method|
    ES18816199T| ES2897536T3|2017-11-22|2018-11-20|Reinforcing material comprising a porous layer of a partially cross-linked thermoplastic polymer and associated methods|
    JP2020528160A| JP2021504513A|2017-11-22|2018-11-20|Reinforcing materials and related methods containing a porous layer made of a partially crosslinked thermoplastic polymer|
    AU2018372375A| AU2018372375A1|2017-11-22|2018-11-20|Reinforcement material comprising a porous layer made of partially cross-linked thermoplastic polymer and associated methods|
    US16/762,104| US20200353717A1|2017-11-22|2018-11-20|Reinforcement material comprising a porous layer made of partially cross-linked thermoplastic polymer and associated methods|
    EP18816199.6A| EP3713759B1|2017-11-22|2018-11-20|Reinforcement material comprising a porous layer made of partially cross-linked thermoplastic polymer and associated methods|
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