EP3481629A1 - Composite sheet made from fabric and polyetherimide with controlled porosity - Google Patents

Composite sheet made from fabric and polyetherimide with controlled porosity

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Publication number
EP3481629A1
EP3481629A1 EP17735144.2A EP17735144A EP3481629A1 EP 3481629 A1 EP3481629 A1 EP 3481629A1 EP 17735144 A EP17735144 A EP 17735144A EP 3481629 A1 EP3481629 A1 EP 3481629A1
Authority
EP
European Patent Office
Prior art keywords
pei
sheet
fabric
mol
bar
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP17735144.2A
Other languages
German (de)
French (fr)
Inventor
Eric Forest
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Porcher Industries SA
Original Assignee
Porcher Industries SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Porcher Industries SA filed Critical Porcher Industries SA
Publication of EP3481629A1 publication Critical patent/EP3481629A1/en
Pending legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/10—Fibres of continuous length
    • B32B2305/18—Fabrics, textiles
    • B32B2305/188—Woven fabrics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/718—Weight, e.g. weight per square meter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/02—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/12—Pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2607/00—Walls, panels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a composite sheet of controlled porosity comprising a textile structure and polyetherimide (PEI), used in particular to serve as skin with controlled porosity in an in situ foaming process of thermoplastic materials. It also relates to a process for producing such sheets and their use in the manufacture of foamed sandwich panels.
  • PEI polyetherimide
  • the in situ foaming process is based on the use of skins ("facings” or “skins” in English) and a layer or film of thermoplastic polymeric material placed in the presence of a foaming agent, making it possible to produce a sandwich with foamed heart.
  • the in situ process makes it possible to achieve, in a single step, adhesion between the skins and the foam that forms, especially when the skins comprise a compatible polymer material of the same nature or identical to the polymer material of the foam, allowing to obtain various adhesion mechanisms such as mechanical interlocking, self-adhesion through bonds between the polymer chains, adsorption (interatomic or intermolecular forces).
  • a typical example is the sandwich comprising a polyetherimide-based foam and composite skins of glass fabric and thermoplastic polymer, which may also be PEI.
  • the method comprises stacking the two or more PEI-impregnated glass cloth sheets, optionally with an impregnating solvent, and one or more plies of PEI film in the presence of a foaming agent (typical acetone), a precompacting, a heating with gradual opening allowing the foaming and the expansion of the foam.
  • a foaming agent typically acetone
  • the foaming solvent is in large quantity, typically about 20% by weight of the core, and one of the difficulties is to control its evacuation.
  • Acetone may in particular have a tendency to soften the skins, to generate surface defects as well as a poor tension of these skins on the surface of the sandwich, and to limit the adhesion between the foam and the skins, with harmful consequences on the skin. mechanical performance.
  • the invention aims to provide a composite sheet mono or multilayer textile structure / PEl of controlled porosity allowing in particular to solve these problems.
  • Another object of the invention is to provide such a sheet which can be used in particular for serving as a skin in an in-situ foaming process for PEI-based thermoplastic materials, allowing an optimal evacuation of gases during the course of the process. foaming process, especially acetone, to obtain skin without surface defects and with good tension.
  • Another object of the invention is to provide a method for obtaining such a composite sheet.
  • a composite sheet comprising at least one textile structure and a polyetherimide (PEI), the latter impregnating and densifying (consolidating) the textile structure, the composite sheet having a certain porosity to acetone.
  • PEI polyetherimide
  • the composite sheet preferably has an acetone porosity of between about 3% and about 8% by weight of acetone absorption (greater than 99% pure), preferably between about 4% and about 5%, such as measured by the acetone method, consisting in measuring 40x40 mm of said composite sheet, dried for 2 h at 70 ° C, weighing the initial mass of the test piece, then placing the test piece in the acetone overlay for 24 hours, recover the specimen, wipe it and weigh it, compare with the initial mass and deduce the intake of acetone en masse.
  • a composite sheet comprising at least one textile structure and a polyetherimide (PEI), the latter impregnating and densifying (consolidating) the textile structure, of the type prepared by a process comprising the having one fold of fabric or a plurality of superposed folds of fabric, impregnating it with PEI by dusting, or depositing a film of PEI on one or both sides of the fabric or stack, subjecting the stacking to a softening, then cooling and consolidation, using a continuous or semi-continuous molding.
  • PEI polyetherimide
  • This continuous or semi-continuous molding may be carried out with heating at a temperature of between about 300 and about 500 ° C, in particular between about 360 and about 400 ° C, for a period between about 30 seconds and about 3 minutes. More detailed process data is given below for each of the modes, continuous and semi-continuous.
  • the two preceding are combined, the composite sheet produced by continuous or semi-continuous molding according to the second embodiment having the acetone porosity of the first.
  • the following additional features apply to each of these three embodiments.
  • the mass ratio of PEI relative to the total weight of the sheet may especially be between about 20 and about 50%, preferably between about 23 and about 43%, more preferably between about 30 and about 36%, for example about 33% .
  • This mass ratio should be as regular as possible to have a homogeneous sheet and a porosity evenly distributed throughout the sheet.
  • the mass ratio of PEI has a regularity of + 1-5%, preferably of +/- 3%, better of + 1-2%, or even less, by mass of resin on / in the whole sheet.
  • the regularity can be measured according to standard EN2331, calcination method (NF EN 2331 May 1 993, Aerospace series - Textile glass fiber prepregs - Test method for the determination of resin and fiber contents and the mass per unit area fibers).
  • the composite sheet comprises at least one textile structure and a polyetherimide (PEI), the latter impregnating and densifying (consolidating) the textile structure, the mass ratio of PEI relative to the total weight of the sheet is included between about 20 and about 50%, preferably between about 23 and about 43%, more preferably between about 30 and about 36%, for example about 33%, the weight ratio of PEI having a regularity of +/- 5%, preferably +/- 3%, better +/- 2%, or even less, by mass of resin on the whole of the sheet, and the sheet having a porosity of between about 3% and about 8% by weight of acetone absorption, preferably between about 4% and about 5% as measured by the acetone method.
  • PEI polyetherimide
  • the textile or fabric structure may in particular be formed of glass, carbon, basalt and blends, for example glass / carbon.
  • the mass surface area of the glass fabric may in particular be between about 50 and about 600 g / m 2 , preferably between about 100 and about 400 g / m 2 .
  • the glass threads may in particular have a title of 10 to 300 tex, and the carbon son may in particular have a title of 60 to 800 tex.
  • the sheet may comprise in particular from 1 to 4 plies of textile structure
  • the sheet may especially have a thickness less than or equal to about 3 mm, especially 2 mm.
  • PEI polystyrene resin
  • the monomer has a molecular weight of 592.61 g / mol.
  • PEI of grade defined by the number-average molar mass (Mn), of between about 15,000 and about 50,000 g / mol, preferably between about 18,000 and about 30,000 g / mol. mol; for example, about 28,000 g / mol.
  • the measurement method for determining the PEI grades is, in the usual way, gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • About 25 mg of sample are weighed exactly.
  • 10 ml of HFiP eluent are added.
  • the dissolution is carried out at ambient temperature for 24 hours.
  • the method preferentially uses 3 columns for more precision.
  • the molar masses are calculated conventionally by PMMA calibration (in English "under PMMA narrow calibration”).
  • the following eluent can be used: HFiP (hexafluoroisopropanol) - 0.1 M KTFA (potassium trifluoroacetate).
  • HFiP hexafluoroisopropanol
  • KTFA potassium trifluoroacetate
  • the fabric, in particular glass, used during the impregnation with the PEI may be ecru, that is to say, a sized fabric (it includes the sizing in the term sizing) It may also be a fabric desensitized (including desizing), especially by a heat treatment (for example at about 400 ° C in an oven for about 72 hours).
  • the ecru or desensitized fabric can be treated by what is called a finishing or
  • the twill may be mentioned, especially for the flat appearance of the textile structure, and the satin, in particular for better drapability.
  • Three different weaves and contextures were tested with Ec9 68tex glass: 8H satin of 305 g / m 2 23x21 yarn / cm; satin 4H of 220 g / m 2 19.5x12 yarn / cm; and twill 2/2 270 g / m 2 22/16 threads / cm.
  • the different grammages make it possible to obtain different thicknesses and therefore different mechanical performances for composite plates of 1 or more plies.
  • the impregnation of the textile structure by the PEI can in particular have been obtained by depositing the PEI on both sides of the textile structure by dusting or under the form of films.
  • the present invention also relates to a method of manufacturing a composite sheet according to the invention, while one can also define the composite sheet by its method of obtaining.
  • the PEI is deposited on one or both sides of the textile structure, and this can be advantageously achieved by powdering the PEI.
  • Conventional dusting methods such as gravitational dusting and electrostatic powdering, can be used. Once the dusting is done, the assembly is pressed or calendered at a temperature above the softening temperature of the PEI.
  • PEI films which can be deposited on one or both sides of the textile structure and the assembly is carried out. typically by pressing or calendering at a temperature above the softening temperature of the PEI.
  • the softening temperature or Tg may be in particular of the order of 205 to 220 ° C for the PEI depending on the grades. However, in order to obtain adequate viscosities, in particular less than or equal to 1000 Pa.s, preferably to 600 Pa.s in the melt, it is preferable to heat between about 300 and about 500 ° C., in particular between about 360 and about 400 ° C. .
  • the consolidation of a textile coated with polymer powder or laminated with a film is carried out statically in press without shear or in dynamics (with a running speed ⁇ 20m / min) under a negligible shear due to the wide air gap.
  • the viscosity values are therefore given here at the indicated melt temperature, under almost zero shear, namely in particular between 10 -2 and 1 second -1 .
  • the measurement can be carried out using a plane-plane Couette viscometer (the polymer being placed between two planes).
  • PEI resins having an apparent viscosity of between 600 and 1500, in particular between 800 and 1200 Pa.s at 360 ° C., as measured under virtually zero shear, namely in particular between 10 -2 and 1, are used.
  • the measurement can be carried out using a planar plane Couette viscometer.
  • the deposition conditions of the invention make it possible to obtain the mass ratio of PEI with respect to the total weight of the sheet of between approximately 20 and approximately 50%, preferably between approximately 23 and approximately 43%, better still between approximately 30% and about 36%, for example about 33%, the mass ratio of PEI having a regularity of +/- 5%, preferably +/- 3%, better +/- 2%, better still +/- 1% or even less, in mass of resin on the whole of the sheet.
  • the consolidation is done under conditions of adequate viscosity.
  • This viscosity may in particular be less than or equal to 1000 Pa.s in the melt, preferably less than or equal to 600 Pa.s (almost nil shear measurement conditions, see above).
  • the temperature may especially be between about 300 and about 500 ° C, especially between about 360 and about 400 ° C, especially depending on the grade of PEI used, to obtain this viscosity.
  • rapid molding or consolidation methods namely continuous molding (consolidation) or molding (consolidation). semi-continuously.
  • the duration of treatment at elevated temperature may in particular be limited to a duration of between about 30 seconds and about 3 minutes.
  • two consolidation technologies can be used. These two technologies are not static, but are continuous or semi-continuous, integrating a certain rate of passage under pressure and a high temperature.
  • Consolidation according to a continuous technology in which a pressure of between about 20 and about 100 bar may be applied, preferably between about 40 and about 80 bar, a temperature of between about 300 and about 500 ° C., in particular between about 360 and about 400 ° C. ° C, for a throughput rate of about 0.1 to about 5, preferably about 1 to about 2 m / min, for a high temperature treatment time of from about 30 seconds to about 3 minutes.
  • Continuous technology of the isobaric type This technology combines the effect of temperature and pressure between two continuous metal strips that face each other.
  • a temperature and a pressure of up to 100 bar (according to the invention it is set between about 20 and about 100 bar, preferably between about 50 and about 80 bar) by means of heating (for example by a heated oil) up to 500 ° C (according to the invention the temperature may be between about 300 and about 500 ° C, in particular between about 360 and about 400 ° C).
  • the press has a hot zone, then a cold zone at the exit to facilitate demolding. Rates are in the range of about 0.1 to about 5, preferably about 1 to about 2 m / min, for a high temperature treatment time of about 30 seconds to about 3 minutes.
  • Consolidation according to a semi-continuous technology in which a pressure of between about 5 and about 50 bar, preferably between about 10 and about 25 bar, a temperature between about 300 and about 500 ° C, in particular between about 360 and about 400 ° C, for a throughput rate of about 0.1 to about 5, preferably about 0.4 to about 1.2 m / min, for a high temperature treatment time of between about 30s and about 3 min.
  • Semi-continuous technology is based on the principle of a single-plate compression press composed of hot and cold zones. The material to be consolidated is placed between 2 metal strips that pass between the plates of the compression press.
  • the press opens a few millimeters (5 or 10) and the strips + the material is pulled down (by a clamp) a few centimeters (5 to 15), the press of closes for from 5 to 20 seconds. And so on. Both technologies require more or less thick metal strips treated with a suitable release agent.
  • the leaves can at the end of production be evaluated with the following tests:
  • Routine tests based on the information contained in this application make it possible to produce sheets having the porosity according to the invention. It can be specified that the process aims to contain the consolidation within the limits to obtain the porosity according to the invention. For a given PEI (of a certain grade, having a given application temperature), it is therefore necessary to choose the correct heating temperature, so that the PEI is at a viscosity of less than or equal to 1000 Pa.s, preferably at 600 Pa.s. Then, applying the heat treatment time to consolidate to the desired level for obtaining porosity.
  • the composite sheet according to the invention may be defined as being obtained or capable of being obtained by a process comprising having a fold of textile structure or several superposed folds of textile structure, preferably having undergone a finishing, impregnating it with PEI on one or both sides of the textile structure or the stack, by softening (attaining a viscosity preferably less than or equal to 1000 Pa.s, in particular 600 Pa.s), then cooling the PEI (powdering or filming techniques, preferably), and consolidation, in particular by continuous or semi-continuous process, with heating to reach a viscosity of preferably less than or equal to 1000 Pa.s, in particular 600 Pa. s, for about 30s to about 3min. Pressures and temperatures were indicated above.
  • the composite sheet is obtained or obtainable by a method comprising having a fold of textile structure or several superposed folds of textile structure, having undergone finishing with a silane (for example aminosilane or epoxysilane), to impregnate it with PEI by powdering or to deposit a PEI film on one or both sides of the textile structure or of the stack, by softening at a viscosity of less than or equal to 1000 Pa. .s, in particular to 600 Pa.s, then cooling of the PEI, and consolidation, in particular by continuous or semi-continuous process, with heating for about 30s to about 3min at a viscosity of less than or equal to 1000 Pa.s, especially 600 Pa.s.
  • a silane for example aminosilane or epoxysilane
  • the composite sheets thus produced can be used as skins in an in-situ foaming process of thermoplastic materials, allowing an optimal evacuation of the gases during the foaming process, in particular acetone, making it possible to obtain skins without surface defects and with a good tense.
  • the level of porosity according to the invention makes it possible to fulfill the objectives of the invention and in particular to ensure a good surface tension, which is not possible with more or perfectly consolidated composite sheets, that is, that is, having a porosity lower than the scope of the invention.
  • Impregnation of the PEI film or films it is possible to use one or more films which are superimposed) with a foaming agent, especially acetone; this will be called the heart;
  • the assembly is placed between the platens of the press, preferably preheated, at a temperature above the glass transition temperature and taking into account the amount of foaming agent, it is typically between about 155 and about 210 ° C; a pressure is applied on the whole, it is typical to press around 40 bars; the whole is heated to the appropriate temperature for foaming, then it opens gradually press to develop the foam; then follows the cooling step.
  • the method of measuring porosity by taking acetone can be further detailed as follows. It is derived from EN2378: fiber reinforced plastics - Determination of water absorption by immersion.
  • test tube Place the test tube for 1 hour in a desiccator to allow it to cool
  • This example is based on the use of a glass fabric made of glass fiber E of 68tex title with an average diameter of 9 ⁇ .
  • This fabric has an 8H satin weave with an average thread count of 22.9 threads / cm in warp and 21.1 threads / cm in weft in order to obtain an average grammage after treatment close to 309 g / m 2 .
  • this fabric is treated with a silane finish bath at 0.1% by weight to reach 303 g / m 2 .
  • This treated fabric is impregnated with commercial PEI powder MW 55,000 g / mol (with GPC method calibrated with PMMA, MW 46842 g / mol, Mn 21 344 g / mol) by means of gravitational powder coating technology. 75 g / m 2 per side.
  • the PEI powder is fixed on the glass cloth by softening and then cooling the polymer.
  • the grammages and fiber content of the prepreg obtained were measured at 3 points according to EN2337 standard by calcination.
  • the prepreg described above is consolidated via isobaric continuous compression technology on an installation having heating zones of a length of about 2.2 m.
  • the consolidation conditions are as follows:
  • Consolidated monoplates have the following properties:
  • This example is based on the use of a glass fabric made of glass fiber E of 68tex title with an average diameter of 9 ⁇ .
  • This fabric has 2/2 twill weave with an average thread count of 22.9 threads / cm in warp and 16 threads / cm in weft to obtain an average basis weight after treatment close to 285 g / m 2 .
  • this fabric is treated with a silane-based finish bath at 0.1% by weight to reach 277 g / m 2 .
  • This treated fabric is impregnated with the same MW 55,000 g / mol PEI powder as in Example 1, by means of gravitational powder coating technology. 68 g / m 2 per side.
  • the PEI powder is fixed on the glass fabric by softening and cooling the polymer.
  • the grammages and fiber content of the prepreg obtained were measured at 3 points according to EN2337 standard by calcination.
  • the prepreg described above is consolidated via a semi-continuous compression technology, comprising a heating zone with a length of about 0.6 m.
  • the consolidation conditions are as follows:
  • Acetone uptake rate 4.9% by weight
  • Chain direction traction module 21, 4 GPa
  • This example is based on the use of a glass fiberglass fabric
  • This fabric has an 8H satin weave with an average thread count of 22.9 threads / cm in warp and 21.1 threads / cm in weft in order to obtain an average grammage after treatment close to 309 g / m 2 .
  • this fabric is treated with a silane finish bath at 0.1% by weight to reach 303 g / m 2 .
  • This treated fabric is impregnated with PEI MW 55,000 g / mol powder (as in the previous examples) by means of a gravitational dusting technology at a rate of 75 g / m 2 per side.
  • the PEI powder is fixed on the glass cloth by softening and then cooling the polymer.
  • the grammages and fiber content of the prepreg obtained were measured at 3 points according to EN2337 standard by calcination.
  • the prepreg described above is consolidated via sequential compression technology, on an installation comprising 3 presses of which 2 heated to 360 ° C and one to 80 ° C.
  • the consolidated 2-ply plates have the following properties:
  • Example 4 The composite sheets of Examples 1 to 3 were used to produce foamed sandwich panels, according to a standard method comprising the impregnation of PEI film with acetone (the core), the formation of the sandwich by placing the heart between two composite sheets according to the invention, placing the assembly between the two plates of a press, heating at a temperature above the glass transition temperature between about 155 and about 210 ° C while applying pressure is applied on the whole, obtaining the foaming and the progressive opening of the press to develop the foam, then cooling.
  • a standard method comprising the impregnation of PEI film with acetone (the core), the formation of the sandwich by placing the heart between two composite sheets according to the invention, placing the assembly between the two plates of a press, heating at a temperature above the glass transition temperature between about 155 and about 210 ° C while applying pressure is applied on the whole, obtaining the foaming and the progressive opening of the press to develop the foam, then cooling.
  • the composite sheets of Examples 1 and 2 made it possible to obtain sandwich panels with good adhesion between the foam core and the composite covering sheets. In contrast to the composite sheets of Examples 1 and 2, the composite sheets of Example 3 failed to obtain a good surface appearance.
  • the continuous or semi-continuous molding process according to Examples 1 and 2 proves to be more efficient for producing high performance composite sheets for the foamed sandwich application.
  • a characteristic of the composite sheets produced by these processes that emerges different between these two groups of molding process (Examples 1 and 2 versus 3) is, from the same grade of PEI, obtaining different acetone porosities. the processes of Examples 1 and 2 leading to higher acetone porosity.

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Abstract

A composite sheet comprising at least a textile structure and a polyetherimide (PEI), the latter impregnating and densifying the textile structure, the sheet having a porosity of between approximately 3% and approximately 8% by mass of acetone sorption, and preferably between approximately 4% and approximately 5%, as measured by the acetone uptake method. The manufacturing method comprises continuous or semi-continuous moulding. This sheet can be used as a skin of a foamed structure made from PEI.

Description

Feuille composite à base de tissu et de polyétherimide à porosité contrôlée  Composite sheet of fabric and polyetherimide with controlled porosity
La présente invention concerne une feuille composite de porosité contrôlée comprenant une structure textile et du polyétherimide (PEI), utilisable notamment pour servir de peau à porosité contrôlée dans un procédé de moussage in situ de matériaux thermoplastiques. Elle a aussi pour objet un procédé de production de telles feuilles et leur utilisation dans la fabrication de panneaux sandwich à cœur moussé. The present invention relates to a composite sheet of controlled porosity comprising a textile structure and polyetherimide (PEI), used in particular to serve as skin with controlled porosity in an in situ foaming process of thermoplastic materials. It also relates to a process for producing such sheets and their use in the manufacture of foamed sandwich panels.
Le procédé de moussage in situ est basé sur l'utilisation de peaux (« facings » ou « skins » en anglais) et d'une couche ou film de matériau polymérique thermoplastique mis en présence d'un agent de moussage, permettant de produire un sandwich à cœur moussé. Le procédé in situ permet de réaliser, en une seule étape, l'adhésion entre les peaux et la mousse qui se forme, notamment lorsque les peaux comportent un matériau polymère compatible, de même nature ou identique au matériau polymère de la mousse, permettant d'obtenir divers mécanismes d'adhésion tels que des interactions mécaniques (« mechanical interlocking »), de l'auto-adhésion par des liaisons entre les chaînes de polymère, de l'adsorption (forces interatomiques ou intermoléculaires).  The in situ foaming process is based on the use of skins ("facings" or "skins" in English) and a layer or film of thermoplastic polymeric material placed in the presence of a foaming agent, making it possible to produce a sandwich with foamed heart. The in situ process makes it possible to achieve, in a single step, adhesion between the skins and the foam that forms, especially when the skins comprise a compatible polymer material of the same nature or identical to the polymer material of the foam, allowing to obtain various adhesion mechanisms such as mechanical interlocking, self-adhesion through bonds between the polymer chains, adsorption (interatomic or intermolecular forces).
Un exemple typique est le sandwich comportant une mousse à base de polyétherimide et des peaux en composite de tissus de verre et de polymère thermoplastique, qui peut aussi être du PEI. Le procédé comprend l'empilement des deux ou plus feuilles de tissu de verre imprégnées de PEI, éventuellement avec présence d'un solvant d'imprégnation, et d'un ou plusieurs plis de film de PEI en présence d'un agent de moussage (typiquement de l'acétone), un précompactage, un chauffage avec ouverture progressive permettant le moussage et l'expansion de la mousse. Le solvant de moussage est en quantité importante, typiquement environ 20% en poids du cœur, et l'une des difficultés est de maîtriser son évacuation. L'acétone peut notamment avoir tendance à ramollir les peaux, à générer des défauts de surface ainsi qu'un mauvais tendu de ces peaux à la surface du sandwich, et limiter l'adhésion entre la mousse et les peaux, avec des conséquences néfastes sur les performances mécaniques.  A typical example is the sandwich comprising a polyetherimide-based foam and composite skins of glass fabric and thermoplastic polymer, which may also be PEI. The method comprises stacking the two or more PEI-impregnated glass cloth sheets, optionally with an impregnating solvent, and one or more plies of PEI film in the presence of a foaming agent ( typically acetone), a precompacting, a heating with gradual opening allowing the foaming and the expansion of the foam. The foaming solvent is in large quantity, typically about 20% by weight of the core, and one of the difficulties is to control its evacuation. Acetone may in particular have a tendency to soften the skins, to generate surface defects as well as a poor tension of these skins on the surface of the sandwich, and to limit the adhesion between the foam and the skins, with harmful consequences on the skin. mechanical performance.
L'invention a pour objectif de fournir une feuille composite mono ou multicouches structure textile/PEl de porosité contrôlée permettant notamment de résoudre ces problèmes.  The invention aims to provide a composite sheet mono or multilayer textile structure / PEl of controlled porosity allowing in particular to solve these problems.
Un autre objectif de l'invention est de proposer une telle feuille utilisable notamment pour servir de peau dans un procédé de moussage in situ de matériaux thermoplastiques à base de PEI, permettant une évacuation optimale des gaz au cours du procédé de moussage, notamment l'acétone, permettant d'obtenir des peaux sans défaut de surface et avec un bon tendu. Another object of the invention is to provide such a sheet which can be used in particular for serving as a skin in an in-situ foaming process for PEI-based thermoplastic materials, allowing an optimal evacuation of gases during the course of the process. foaming process, especially acetone, to obtain skin without surface defects and with good tension.
Un autre objectif de l'invention est de proposer un procédé permettant d'obtenir une telle feuille composite.  Another object of the invention is to provide a method for obtaining such a composite sheet.
Ces objectifs sont notamment obtenus, selon un premier mode de réalisation, par une feuille composite comprenant au moins une structure textile et un polyétherimide (PEI), ce dernier imprégnant et densifiant (consolidant) la structure textile, la feuille composite ayant une certaine porosité à l'acétone. La feuille composite a de préférence une porosité à l'acétone comprise entre environ 3% et environ 8% en masse d'absorption d'acétone (pure à plus de 99%), de préférence entre environ 4% et environ 5%, telle que mesurée par la méthode à la prise d'acétone consistant, sur une éprouvette de 40x40 mm de ladite feuille composite, séchée pendant 2 h à 70°C, à peser la masse initiale de l'éprouvette, placer ensuite l'éprouvette dans de l'acétone à recouvrement pendant 24 h, récupérer l'éprouvette, l'essuyer et la peser, comparer à la masse initiale et en déduire la prise d'acétone en masse.  These objectives are obtained in particular, according to a first embodiment, by a composite sheet comprising at least one textile structure and a polyetherimide (PEI), the latter impregnating and densifying (consolidating) the textile structure, the composite sheet having a certain porosity to acetone. The composite sheet preferably has an acetone porosity of between about 3% and about 8% by weight of acetone absorption (greater than 99% pure), preferably between about 4% and about 5%, such as measured by the acetone method, consisting in measuring 40x40 mm of said composite sheet, dried for 2 h at 70 ° C, weighing the initial mass of the test piece, then placing the test piece in the acetone overlay for 24 hours, recover the specimen, wipe it and weigh it, compare with the initial mass and deduce the intake of acetone en masse.
Ces objectifs sont également obtenus, selon un deuxième mode de réalisation, par une feuille composite comprenant au moins une structure textile et un polyétherimide (PEI), ce dernier imprégnant et densifiant (consolidant) la structure textile, du type préparée par un procédé comprenant le fait de disposer d'un pli de tissu ou de plusieurs plis superposés de tissu, de l'imprégner de PEI par poudrage ou dépose d'un film de PEI sur une ou deux faces du tissu ou de l'empilement, en soumettant l'empilement à un ramollissement, puis refroidissement et consolidation, en utilisant un moulage en continu ou en semi-continu. Ce moulage en continu ou en semi-continu peut être réalisé avec chauffage à une température comprise entre environ 300 et environ 500°C, notamment entre environ 360 et environ 400°C, pendant une durée comprise entre environ 30s et environ 3 min. Des données de procédé plus détaillées sont données plus loin, pour chacun des modes, continu et semi-continu.  These objectives are also obtained, according to a second embodiment, from a composite sheet comprising at least one textile structure and a polyetherimide (PEI), the latter impregnating and densifying (consolidating) the textile structure, of the type prepared by a process comprising the having one fold of fabric or a plurality of superposed folds of fabric, impregnating it with PEI by dusting, or depositing a film of PEI on one or both sides of the fabric or stack, subjecting the stacking to a softening, then cooling and consolidation, using a continuous or semi-continuous molding. This continuous or semi-continuous molding may be carried out with heating at a temperature of between about 300 and about 500 ° C, in particular between about 360 and about 400 ° C, for a period between about 30 seconds and about 3 minutes. More detailed process data is given below for each of the modes, continuous and semi-continuous.
Dans un troisième mode de réalisation, les deux précédents sont combinés, la feuille composite produite par moulage continu ou semi-continu selon le deuxième mode ayant la porosité à l'acétone du premier. En outre, les caractéristiques additionnelles qui suivent s'appliquent à chacun de ces trois modes de réalisation.  In a third embodiment, the two preceding are combined, the composite sheet produced by continuous or semi-continuous molding according to the second embodiment having the acetone porosity of the first. In addition, the following additional features apply to each of these three embodiments.
Le taux massique de PEI par rapport au poids total de la feuille peut notamment être compris entre environ 20 et environ 50%, de préférence entre environ 23 et environ 43%, mieux encore entre environ 30 et environ 36%, par exemple environ 33%. Ce taux massique doit être aussi régulier que possible pour avoir une feuille homogène et une porosité également répartie dans l'ensemble de la feuille. Ainsi, selon une caractéristique de l'invention, le taux massique de PEI ont une régularité de +1-5%, de préférence de +/-3%, mieux de +1-2%, voire moins, en masse de résine sur/dans l'ensemble de la feuille. La régularité peut être mesurée suivant la norme EN2331 , méthode par calcination (NF EN 2331 Mai 1 993, Série aérospatiale - Préimprégnés de fibres de verre textile - Méthode d'essai pour la détermination des teneurs en résine et fibres et de la masse surfacique des fibres). The mass ratio of PEI relative to the total weight of the sheet may especially be between about 20 and about 50%, preferably between about 23 and about 43%, more preferably between about 30 and about 36%, for example about 33% . This mass ratio should be as regular as possible to have a homogeneous sheet and a porosity evenly distributed throughout the sheet. Thus, according to one characteristic of the invention, the mass ratio of PEI has a regularity of + 1-5%, preferably of +/- 3%, better of + 1-2%, or even less, by mass of resin on / in the whole sheet. The regularity can be measured according to standard EN2331, calcination method (NF EN 2331 May 1 993, Aerospace series - Textile glass fiber prepregs - Test method for the determination of resin and fiber contents and the mass per unit area fibers).
Dans un mode de réalisation préféré, la feuille composite comprend au moins une structure textile et un polyétherimide (PEI), ce dernier imprégnant et densifiant (consolidant) la structure textile, le taux massique de PEI par rapport au poids total de la feuille est compris entre environ 20 et environ 50%, de préférence entre environ 23 et environ 43%, mieux encore entre environ 30 et environ 36%, par exemple environ 33%, le taux massique de PEI ayant une régularité de +/-5%, de préférence de +/-3%, mieux de +/-2%, voire moins, en masse de résine sur l'ensemble de la feuille, et la feuille ayant une porosité comprise entre environ 3% et environ 8% en masse d'absorption d'acétone, de préférence entre environ 4% et environ 5%, telle que mesurée par la méthode à la prise d'acétone.  In a preferred embodiment, the composite sheet comprises at least one textile structure and a polyetherimide (PEI), the latter impregnating and densifying (consolidating) the textile structure, the mass ratio of PEI relative to the total weight of the sheet is included between about 20 and about 50%, preferably between about 23 and about 43%, more preferably between about 30 and about 36%, for example about 33%, the weight ratio of PEI having a regularity of +/- 5%, preferably +/- 3%, better +/- 2%, or even less, by mass of resin on the whole of the sheet, and the sheet having a porosity of between about 3% and about 8% by weight of acetone absorption, preferably between about 4% and about 5% as measured by the acetone method.
La structure textile ou tissu peut être notamment formée de fils de verre, de carbone, de basalte, et mélanges, par exemple verre/carbone.  The textile or fabric structure may in particular be formed of glass, carbon, basalt and blends, for example glass / carbon.
La surface massique du tissu de verre peut être notamment comprise entre environ 50 et environ 600 g/m2, de préférence entre environ 100 et environ 400 g/m2. The mass surface area of the glass fabric may in particular be between about 50 and about 600 g / m 2 , preferably between about 100 and about 400 g / m 2 .
Les fils de verre peuvent notamment avoir un titre de 1 0 à 300 tex, et les fils de carbone peuvent notamment avoir un titre de 60 à 800 tex.  The glass threads may in particular have a title of 10 to 300 tex, and the carbon son may in particular have a title of 60 to 800 tex.
La feuille peut comprendre notamment de 1 à 4 plis de structure textile  The sheet may comprise in particular from 1 to 4 plies of textile structure
La feuille peut notamment avoir une épaisseur inférieure ou égale à environ 3 mm, notamment à 2 mm.  The sheet may especially have a thickness less than or equal to about 3 mm, especially 2 mm.
Il existe plusieurs grades pour le PEI correspondant à des longueurs de chaîne macromoléculaire différentes et donc des viscosités différentes. Plus les chaînes sont longues, plus les résines thermoplastiques présentent des viscosités élevées. Le PEI est formé des unités monomères suivantes : There are several grades for PEI corresponding to different lengths of macromolecular chain and therefore different viscosities. The longer the chains, the more the thermoplastic resins have high viscosities. The PEI is formed of the following monomeric units:
Le monomère a une masse moléculaire de 592,61 g/mol. Selon la présente invention, on pourra utiliser notamment un PEI de grade, défini par la masse molaire en masse (MW), compris entre environ 20 000 et environ 100 000 g/mol, de préférence entre environ 30 000 et environ 100 000 g/mol , notamment entre environ 30 000 et environ 60 000 g/mol ; par exemple environ 47 000 ou 55 000 g/mol. The monomer has a molecular weight of 592.61 g / mol. According to the present invention, it is possible to use in particular a PEI of a grade, defined by the mass-weight mass (MW), of between about 20,000 and about 100,000 g / mol, preferably between about 30,000 and about 100,000 g / mol. mol, especially between about 30,000 and about 60,000 g / mol; for example, about 47,000 or 55,000 g / mol.
Selon la présente invention, on pourra utiliser notamment un PEI de grade, défini par la masse molaire en nombre (Mn), compris entre environ 15 000 et environ 50 000 g/mol, de préférence entre environ 18 000 et environ 30 000 g/mol ; par exemple environ 28 000 g/mol.  According to the present invention, it will be possible to use in particular a PEI of grade, defined by the number-average molar mass (Mn), of between about 15,000 and about 50,000 g / mol, preferably between about 18,000 and about 30,000 g / mol. mol; for example, about 28,000 g / mol.
La méthode de mesure permettant de déterminer les grades du PEI est, de manière usuelle, la chromatographie par perméation de gel (GPC). A titre d'exemple, on peut mentionner la GPC calibrée au PMMA, et notamment la suivante. 25 mg environ d'échantillon sont pesés exactement. 10 ml d'éluant HFiP sont rajoutés. La dissolution est réalisée à température ambiante pendant 24 heures. La méthode utilise préférentiellement 3 colonnes pour davantage de précision. Les masses molaires sont calculées classiquement par calibration au PMMA (en anglais « under PMMA narrow calibration »). On peut employer l'éluant suivant : HFiP (hexafluoroisopropanol) - 0,1 M KTFA (trifluoroacétate de potassium). On peut apporter les précision suivantes :  The measurement method for determining the PEI grades is, in the usual way, gel permeation chromatography (GPC). By way of example, mention may be made of GPC calibrated with PMMA, and in particular the following. About 25 mg of sample are weighed exactly. 10 ml of HFiP eluent are added. The dissolution is carried out at ambient temperature for 24 hours. The method preferentially uses 3 columns for more precision. The molar masses are calculated conventionally by PMMA calibration (in English "under PMMA narrow calibration"). The following eluent can be used: HFiP (hexafluoroisopropanol) - 0.1 M KTFA (potassium trifluoroacetate). The following can be made:
Débit : 1 ml/min Flow rate: 1 ml / min
T °C analyse : 40°C T ° C analysis: 40 ° C
Concentration : concentration exacte injectée, aux environs de 2,7 g/l  Concentration: exact concentration injected at around 2.7 g / l
Volume injection : 100 μΙ Injection volume: 100 μΙ
Colonnes : 3 colonnes : 10 μιτι, 1000 À, 8,0 mm x 100 mm ; 10 μιτι, 1000 À, 8,0 mm x 300 mm ; 10 μιτι, 100 À, 8,0 mm x 300 mm Columns: 3 columns: 10 μιτι, 1000 Å, 8.0 mm x 100 mm; 10 μιτι, 1000 Å, 8.0 mm x 300 mm; 10 μιτι, 100 Å, 8.0 mm x 300 mm
Détection(s) : RI (indice de réfraction) Detection (s): RI (refractive index)
Calibration : étalons étroits de PMMA (polyméthylméthacrylate). Le tissu, notamment de verre, employé lors de l'imprégnation avec le PEI peut être écru c'est-à-dire un tissu ensimé (on inclut l'encollage dans le terme ensimage) Il peut aussi s'agir d'un tissu désensimé (on inclut le désencollage), notamment par un traitement thermique (par exemple à environ 400°C dans un four pendant environ 72h). Calibration: narrow standards of PMMA (polymethyl methacrylate). The fabric, in particular glass, used during the impregnation with the PEI may be ecru, that is to say, a sized fabric (it includes the sizing in the term sizing) It may also be a fabric desensitized (including desizing), especially by a heat treatment (for example at about 400 ° C in an oven for about 72 hours).
Le tissu écru ou désensimé peut être traité par ce qu'on appelle un finissage ou The ecru or desensitized fabric can be treated by what is called a finishing or
«finish », dont on a trouvé qu'il améliorait la compatibilité et l'adhésion tissu-polymère, ce qui se traduit par une amélioration substantielle des performances mécaniques en traction et en flexion. Les produits suivants sont bien appropriés : les aminosilanes (par exemple AMEO d'Evonik), les epoxysilanes (par exemple Silquest® A-1871 de Monentive Performance Materials). Le tissu et donc la feuille composite selon l'invention peuvent donc comprendre l'un de ces produits. La mise en œuvre peut être réalisée par bain ou aspersion, par exemple. "Finish", which has been found to improve compatibility and tissue-polymer adhesion, resulting in substantial improvement in mechanical tensile and flexural performance. The following products are very suitable: aminosilanes (for example AMEO from Evonik), epoxysilanes (for example Silquest® A-1871 from Monentive Performance Materials). The fabric and therefore the composite sheet according to the invention may therefore comprise one of these products. The implementation can be carried out by bath or spraying, for example.
En ce qui concerne l'armure de la structure textile, il n'y a pas de limitations. On peut citer en particulier le sergé, notamment pour l'aspect plat de la structure textile, et le satin, notamment pour une meilleure drapabilité. Trois armures et contextures différentes ont été testés avec du verre Ec9 68tex : satin de 8H de 305 g/m2 23x21 fils/cm ; satin de 4H de 220 g/m2 19.5x12 fils/cm ; et sergé 2/2 270 g/m2 22/16 fils/cm. Les différents grammages permettent d'obtenir des épaisseurs et donc performances mécaniques différentes pour des plaques composites de 1 ou plusieurs plis. As for the armor of the textile structure, there are no limitations. In particular, the twill may be mentioned, especially for the flat appearance of the textile structure, and the satin, in particular for better drapability. Three different weaves and contextures were tested with Ec9 68tex glass: 8H satin of 305 g / m 2 23x21 yarn / cm; satin 4H of 220 g / m 2 19.5x12 yarn / cm; and twill 2/2 270 g / m 2 22/16 threads / cm. The different grammages make it possible to obtain different thicknesses and therefore different mechanical performances for composite plates of 1 or more plies.
Comme cela va être davantage détaillé par la suite, dans la feuille selon l'invention, l'imprégnation de la structure textile par le PEI peut notamment avoir été obtenue en déposant le PEI sur les deux faces de la structure textile par poudrage ou sous la forme de films.  As will be further detailed later, in the sheet according to the invention, the impregnation of the textile structure by the PEI can in particular have been obtained by depositing the PEI on both sides of the textile structure by dusting or under the form of films.
La présente invention a aussi pour objet un procédé de fabrication d'une feuille composite selon l'invention, tandis que l'on peut aussi définir la feuille composite par son procédé d'obtention.  The present invention also relates to a method of manufacturing a composite sheet according to the invention, while one can also define the composite sheet by its method of obtaining.
Dans un mode de réalisation, le PEI est déposé sur l'une ou les deux faces de la structure textile, et ceci peut être avantageusement réalisé par poudrage du PEI. On peut utiliser les méthodes classiques de poudrage, telles que le poudrage gravitationnel et le poudrage électrostatique. Une fois le poudrage effectué, l'ensemble est pressé ou calandré à une température supérieure à la température de ramollissement du PEI.  In one embodiment, the PEI is deposited on one or both sides of the textile structure, and this can be advantageously achieved by powdering the PEI. Conventional dusting methods, such as gravitational dusting and electrostatic powdering, can be used. Once the dusting is done, the assembly is pressed or calendered at a temperature above the softening temperature of the PEI.
Dans un autre mode de réalisation, on peut utiliser des films de PEI, que l'on peut déposer sur l'une ou les deux faces de la structure textile et l'assemblage se fait classiquement par pressage ou calandrage à une température supérieure à la température de ramollissement du PEI. In another embodiment, it is possible to use PEI films, which can be deposited on one or both sides of the textile structure and the assembly is carried out. typically by pressing or calendering at a temperature above the softening temperature of the PEI.
La température de ramollissement ou Tg peut être notamment de l'ordre de 205 à 220°C pour le PEI selon les grades. Toutefois pour obtenir des viscosités adéquates, notamment inférieures ou égales à 1000 Pa.s, de préférence à 600 Pa.s au fondu, il est préférable de chauffer entre environ 300 et environ 500°C, notamment entre environ 360 et environ 400°C. Traditionnellement, la consolidation d'un textile revêtu de poudre polymère ou contrecollé avec un film, est réalisée statiquement sous presse sans cisaillement ou en dynamique (avec une vitesse de défilement <20m/min) sous un cisaillement négligeable dû à l'entrefer large. Les valeurs de viscosité sont donc données ici à la température au fondu indiquée, sous un cisaillement quasiment nul, à savoir notamment compris entre 10"2 et 1 seconde"1. La mesure peut être effectuée en utilisant un viscosimètre de Couette plan-plan (le polymère étant placé entre deux plans). The softening temperature or Tg may be in particular of the order of 205 to 220 ° C for the PEI depending on the grades. However, in order to obtain adequate viscosities, in particular less than or equal to 1000 Pa.s, preferably to 600 Pa.s in the melt, it is preferable to heat between about 300 and about 500 ° C., in particular between about 360 and about 400 ° C. . Traditionally, the consolidation of a textile coated with polymer powder or laminated with a film, is carried out statically in press without shear or in dynamics (with a running speed <20m / min) under a negligible shear due to the wide air gap. The viscosity values are therefore given here at the indicated melt temperature, under almost zero shear, namely in particular between 10 -2 and 1 second -1 . The measurement can be carried out using a plane-plane Couette viscometer (the polymer being placed between two planes).
De préférence, on utilise des résines PEI ayant une viscosité apparente comprise entre 600 et 1500, notamment entre 800 et 1200 Pa.s à 360 °C, telle que mesurée sous un cisaillement quasiment nul, à savoir notamment compris entre 10"2 et 1 seconde"1. La mesure peut être effectuée en utilisant un viscosimètre de Couette plan-plan. Preferably, PEI resins having an apparent viscosity of between 600 and 1500, in particular between 800 and 1200 Pa.s at 360 ° C., as measured under virtually zero shear, namely in particular between 10 -2 and 1, are used. second "1 . The measurement can be carried out using a planar plane Couette viscometer.
Les conditions de dépôt de l'invention permettent d'obtenir le taux massique de PEI par rapport au poids total de la feuille compris entre environ 20 et environ 50%, de préférence entre environ 23 et environ 43%, mieux encore entre environ 30 et environ 36%, par exemple environ 33%, le taux massique de PEI ayant une régularité de +/-5%, de préférence de +/-3%, mieux de +/-2%, mieux encore de +/-1 %, voire moins, en masse de résine sur l'ensemble de la feuille.  The deposition conditions of the invention make it possible to obtain the mass ratio of PEI with respect to the total weight of the sheet of between approximately 20 and approximately 50%, preferably between approximately 23 and approximately 43%, better still between approximately 30% and about 36%, for example about 33%, the mass ratio of PEI having a regularity of +/- 5%, preferably +/- 3%, better +/- 2%, better still +/- 1% or even less, in mass of resin on the whole of the sheet.
Une fois la structure textile imprégnée de PEI de manière régulière, on procède à la consolidation ou densification, dans des conditions permettant d'obtenir le niveau de porosité régulier conforme à l'invention.  Once the textile structure is impregnated with PEI in a regular manner, consolidation or densification is carried out under conditions that make it possible to obtain the level of regular porosity according to the invention.
La consolidation est faite dans des conditions de viscosité adéquate. Cette viscosité peut notamment être inférieure ou égale à 1000 Pa.s au fondu, de préférence inférieure ou égale à 600 Pa.s (conditions de mesure à cisaillement quasiment nul, voir ci- dessus) La température peut notamment être comprise entre environ 300 et environ 500°C, notamment entre environ 360 et environ 400°C, notamment selon le grade du PEI utilisé, pour obtenir cette viscosité. Pour éviter une dégradation du PEI à ces températures, on préfère alors utiliser des méthodes de moulage ou consolidation rapides, à savoir le moulage (consolidation) en continu ou le moulage (consolidation) en semi-continu. La durée de traitement à température élevée peut notamment être limitée à une durée comprise entre environ 30s et environ 3 min. The consolidation is done under conditions of adequate viscosity. This viscosity may in particular be less than or equal to 1000 Pa.s in the melt, preferably less than or equal to 600 Pa.s (almost nil shear measurement conditions, see above). The temperature may especially be between about 300 and about 500 ° C, especially between about 360 and about 400 ° C, especially depending on the grade of PEI used, to obtain this viscosity. To avoid degradation of the PEI at these temperatures, it is then preferred to use rapid molding or consolidation methods, namely continuous molding (consolidation) or molding (consolidation). semi-continuously. The duration of treatment at elevated temperature may in particular be limited to a duration of between about 30 seconds and about 3 minutes.
Deux technologies de consolidation peuvent notamment être employées. Ces deux technologies en sont pas statiques, mais sont continues ou semi-continues, intégrant une certaine vitesse de passage sous pression et une température élevée.  In particular, two consolidation technologies can be used. These two technologies are not static, but are continuous or semi-continuous, integrating a certain rate of passage under pressure and a high temperature.
La consolidation selon une technologie continue, dans laquelle on peut appliquer une pression entre environ 20 et environ 100 bars, de préférence entre environ 40 et environ 80 bars, une température entre environ 300 et environ 500 °C, notamment entre environ 360 et environ 400 °C, pour une vitesse de passage d'environ 0,1 à environ 5, de préférence d'environ 1 à environ 2 m/min, pour une durée de traitement à température élevée comprise entre environ 30s et environ 3 min.  Consolidation according to a continuous technology, in which a pressure of between about 20 and about 100 bar may be applied, preferably between about 40 and about 80 bar, a temperature of between about 300 and about 500 ° C., in particular between about 360 and about 400 ° C. ° C, for a throughput rate of about 0.1 to about 5, preferably about 1 to about 2 m / min, for a high temperature treatment time of from about 30 seconds to about 3 minutes.
La technologie continue de type isobare. Cette technologie combine l'effet de la température, de la pression entre deux bandes métalliques continues qui tournent en vis- à-vis. Sur les 2 bandes sont appliquées une température et une pression pouvant atteindre 100 bars (selon l'invention elle est réglée entre environ 20 et environ 100 bars, de préférence entre environ 50 et environ 80 bars) par l'intermédiaire d'un chauffage (par exemple par une huile chauffée) jusqu'à 500°C (selon l'invention la température peut être comprise entre environ 300 et environ 500 °C, notamment entre environ 360 et environ 400 °C). La presse dispose d'une zone chaude, puis d'une zone froide en sortie pour faciliter le démoulage. Les vitesses sont de l'ordre d'environ 0,1 à environ 5, de préférence d'environ 1 à environ 2 m/min, pour une durée de traitement à température élevée comprise entre environ 30s et environ 3 min.  Continuous technology of the isobaric type. This technology combines the effect of temperature and pressure between two continuous metal strips that face each other. On the two strips are applied a temperature and a pressure of up to 100 bar (according to the invention it is set between about 20 and about 100 bar, preferably between about 50 and about 80 bar) by means of heating ( for example by a heated oil) up to 500 ° C (according to the invention the temperature may be between about 300 and about 500 ° C, in particular between about 360 and about 400 ° C). The press has a hot zone, then a cold zone at the exit to facilitate demolding. Rates are in the range of about 0.1 to about 5, preferably about 1 to about 2 m / min, for a high temperature treatment time of about 30 seconds to about 3 minutes.
D'autres technologies de moulage en continu de type isochore utilisant des valeurs similaires peuvent être utilisées.  Other isochoric continuous molding technologies using similar values can be used.
La consolidation selon une technologie semi-continue, dans laquelle on peut appliquer une pression entre environ 5 et environ 50 bars, de préférence entre environ 10 et environ 25 bars, une température entre environ 300 et environ 500 °C, notamment entre environ 360 et environ 400 °C, pour une vitesse de passage d'environ 0,1 à environ 5, de préférence d'environ 0,4 à environ 1 ,2 m/min, pour une durée de traitement à température élevée comprise entre environ 30s et environ 3 min. La technologie semi- continue repose sur le principe d'une presse de compression mono-plateau composée de zones chaudes et froides. Le matériau à consolider est placé entre 2 feuillards métalliques qui passent entre les plateaux de la presse de compression. Toutes les 5 à 20 secondes la presse s'entrouvre de quelques millimètres (5 ou 10) et les feuillards + le matériau est tiré en aval (par une pince) de quelques centimètres (5 à 15), la presse de referme pour de 5 à 20 secondes. Et ainsi de suite. Les 2 technologies nécessitent des bandes métalliques plus ou moins épaisses et traités avec un démoulant adéquat. Consolidation according to a semi-continuous technology, in which a pressure of between about 5 and about 50 bar, preferably between about 10 and about 25 bar, a temperature between about 300 and about 500 ° C, in particular between about 360 and about 400 ° C, for a throughput rate of about 0.1 to about 5, preferably about 0.4 to about 1.2 m / min, for a high temperature treatment time of between about 30s and about 3 min. Semi-continuous technology is based on the principle of a single-plate compression press composed of hot and cold zones. The material to be consolidated is placed between 2 metal strips that pass between the plates of the compression press. Every 5 to 20 seconds the press opens a few millimeters (5 or 10) and the strips + the material is pulled down (by a clamp) a few centimeters (5 to 15), the press of closes for from 5 to 20 seconds. And so on. Both technologies require more or less thick metal strips treated with a suitable release agent.
Les feuilles peuvent en fin de production être évaluées avec les tests suivants: The leaves can at the end of production be evaluated with the following tests:
- Grammage - Weight
- Epaisseur - Thickness
- Taux de fibres par calcination  - Fiber content by calcination
- Densité par pesée dans l'air et dans l'eau  - Density by weighing in air and water
- Porosité par absorption d'acétone après un bain de 24h (voir mode opératoire) Porosity by absorption of acetone after a bath of 24 hours (see procedure)
- Module et contrainte de traction dans le sens chaîne et trame. - Module and tensile stress in the warp and weft direction.
Des essais de routine basés sur les informations contenues dans cette demande permettent de produire des feuilles ayant la porosité selon l'invention. Il peut être précisé que le procédé vise à contenir la consolidation dans les limites permettant d'obtenir la porosité conforme à l'invention. Il convient donc de choisir, pour un PEI donné (d'un certain grade, ayant une température de mise en œuvre donnée) la bonne température de chauffe, pour que le PEI soit à une viscosité inférieure ou égale à 1000 Pa.s, de préférence à 600 Pa.s. Ensuite, on applique la durée de traitement thermique permettant de consolider au niveau souhaité pour l'obtention de la porosité.  Routine tests based on the information contained in this application make it possible to produce sheets having the porosity according to the invention. It can be specified that the process aims to contain the consolidation within the limits to obtain the porosity according to the invention. For a given PEI (of a certain grade, having a given application temperature), it is therefore necessary to choose the correct heating temperature, so that the PEI is at a viscosity of less than or equal to 1000 Pa.s, preferably at 600 Pa.s. Then, applying the heat treatment time to consolidate to the desired level for obtaining porosity.
Ainsi, la feuille composite selon l'invention peut être définie comme étant obtenue ou susceptible d'être obtenue par un procédé comprenant le fait de disposer d'un pli de structure textile ou de plusieurs plis superposés de structure textile, de préférence ayant subi un finissage, de l'imprégner de PEI sur une ou deux faces de la structure textile ou de l'empilement, par ramollissement (atteinte d'une viscosité de préférence inférieure ou égale à 1000 Pa.s, notamment à 600 Pa.s), puis refroidissement du PEI (techniques de poudrage ou de film, de préférence), et consolidation, notamment par procédé continu ou semi-continu, avec chauffage pour atteindre une viscosité de préférence inférieure ou égale à 1000 Pa.s, notamment à 600 Pa.s, pendant d'environ 30s à environ 3min. Pressions et températures ont été indiquée supra.  Thus, the composite sheet according to the invention may be defined as being obtained or capable of being obtained by a process comprising having a fold of textile structure or several superposed folds of textile structure, preferably having undergone a finishing, impregnating it with PEI on one or both sides of the textile structure or the stack, by softening (attaining a viscosity preferably less than or equal to 1000 Pa.s, in particular 600 Pa.s), then cooling the PEI (powdering or filming techniques, preferably), and consolidation, in particular by continuous or semi-continuous process, with heating to reach a viscosity of preferably less than or equal to 1000 Pa.s, in particular 600 Pa. s, for about 30s to about 3min. Pressures and temperatures were indicated above.
Dans un mode de réalisation plus précis, la feuille composite est obtenue ou susceptible d'être obtenue par un procédé comprenant le fait de disposer d'un pli de structure textile ou de plusieurs plis superposés de structure textile, ayant subi un finissage avec un silane (par exemple aminosilane ou époxysilane), de l'imprégner de PEI par poudrage ou dépose d'un film de PEI sur une ou deux faces de la structure textile ou de l'empilement, par ramollissement à une viscosité inférieure ou égale à 1000 Pa.s, notamment à 600 Pa.s, puis refroidissement du PEI, et consolidation, notamment par procédé continu ou semi-continu, avec chauffage pendant environ 30s à environ 3min à une viscosité de inférieure ou égale à 1000 Pa.s, notamment à 600 Pa.s. In a more specific embodiment, the composite sheet is obtained or obtainable by a method comprising having a fold of textile structure or several superposed folds of textile structure, having undergone finishing with a silane (for example aminosilane or epoxysilane), to impregnate it with PEI by powdering or to deposit a PEI film on one or both sides of the textile structure or of the stack, by softening at a viscosity of less than or equal to 1000 Pa. .s, in particular to 600 Pa.s, then cooling of the PEI, and consolidation, in particular by continuous or semi-continuous process, with heating for about 30s to about 3min at a viscosity of less than or equal to 1000 Pa.s, especially 600 Pa.s.
Les feuilles composites ainsi produites peuvent être employées comme peaux dans un procédé de moussage in situ de matériaux thermoplastiques, permettant une évacuation optimale des gaz au cours du procédé de moussage, notamment l'acétone, permettant d'obtenir des peaux sans défaut de surface et avec un bon tendu. De manière surprenante, le niveau de porosité selon l'invention permet de remplir les objectifs de l'invention et notamment d'assurer un bon tendu de surface, ce que ne permettent pas des feuilles composites plus ou parfaitement consolidées, c'est-à-dire ayant une porosité inférieure au domaine de l'invention.  The composite sheets thus produced can be used as skins in an in-situ foaming process of thermoplastic materials, allowing an optimal evacuation of the gases during the foaming process, in particular acetone, making it possible to obtain skins without surface defects and with a good tense. Surprisingly, the level of porosity according to the invention makes it possible to fulfill the objectives of the invention and in particular to ensure a good surface tension, which is not possible with more or perfectly consolidated composite sheets, that is, that is, having a porosity lower than the scope of the invention.
On rappellera que le procédé standard de fabrication d'un sandwich mousse PEI entre deux feuilles de composite PEI, utilisable ici, comprend (The Development of In-Situ Foamed Sandwich Pabels, Proefschrift, 1997, Université Technique de Delft, par Pieter- Willem Christiaan PROVO KLUIT, Delft University Press, Mekelweg 4, 2628 CD Delft, Pays-Bas):  It will be recalled that the standard method for manufacturing a PEI foam sandwich between two sheets of PEI composite, usable here, comprises (The Development of In-Situ Foamed Sandwich Pabels, Proefschrift, 1997, Technical University of Delft, by Pieter Willem Christiaan PROVO KLUIT, Delft University Press, Mekelweg 4, 2628 Delft CD, The Netherlands):
Imprégnation du ou des films de PEI (on peut en effet utiliser un ou plusieurs films que l'on superpose) avec un agent de moussage, notamment de l'acétone ; on appellera ceci le cœur ;  Impregnation of the PEI film or films (it is possible to use one or more films which are superimposed) with a foaming agent, especially acetone; this will be called the heart;
Constituer le sandwich en plaçant le cœur entre deux feuilles composites selon l'invention ;  Constituting the sandwich by placing the heart between two composite sheets according to the invention;
Placer l'ensemble entre les deux plateaux d'une presse, généralement préchauffée ;  Place the assembly between the two plates of a press, generally preheated;
Optionnellement pré-compacter l'ensemble entre ces deux plateaux, à une température un peu inférieure à la température de transition vitreuse de l'ensemble PEI/agent de moussage, maintien de ces conditions pendant un temps donné, puis refroidissement à température ambiante et enfin retrait de la pression ; ceci permet d'améliorer la liaison entre les peaux et le cœur et la distribution homogène de l'agent de moussage ;  Optionally pre-compact the assembly between these two trays at a temperature slightly lower than the glass transition temperature of the PEI / foaming agent, maintaining these conditions for a given time, then cooling to room temperature and finally withdrawal of pressure; this makes it possible to improve the bond between the skins and the core and the homogeneous distribution of the foaming agent;
Procéder au moussage ; l'ensemble est placé entre les plateaux de la presse, de préférence préchauffée, à une température supérieure à la température de transition vitreuse et tenant compte de la quantité d'agent moussant, elle est typiquement comprise entre environ 155 et environ 210°C ; une pression est appliquée sur l'ensemble, il est typique de presser aux environs de 40 bars ; on chauffe l'ensemble à la température adéquate pour le moussage, puis on ouvre progressivement la presse pour développer la mousse ; suit ensuite l'étape de refroidissement. Proceed to foaming; the assembly is placed between the platens of the press, preferably preheated, at a temperature above the glass transition temperature and taking into account the amount of foaming agent, it is typically between about 155 and about 210 ° C; a pressure is applied on the whole, it is typical to press around 40 bars; the whole is heated to the appropriate temperature for foaming, then it opens gradually press to develop the foam; then follows the cooling step.
La méthode de mesure de la porosité par la prise d'acétone peut être davantage détaillée comme suit. Elle est dérivée de la norme EN2378 : plastiques renforcés de fibres - Détermination de l'absorption d'eau par immersion.  The method of measuring porosity by taking acetone can be further detailed as follows. It is derived from EN2378: fiber reinforced plastics - Determination of water absorption by immersion.
Appareillage  Equipment
- Bêcher en verre de dimensions appropriées au nombre d'éprouvettes  - Glass beaker of appropriate dimensions to the number of test pieces
Enceinte thermo-régulée  Thermo-regulated enclosure
- Balance de précision à 0.1 mg  - Precision balance at 0.1 mg
Mode opératoire  Operating mode
- Découpe des éprouvettes de 40 x 40 mm sans bavures ni trous (de préférence au minimum 5 par référence)  - Cutting test pieces 40 x 40 mm without burrs or holes (preferably at least 5 by reference)
- Placer l'éprouvette à l'étuve pendant 2h à 70°C pour la sécher  - Place the test piece in an oven for 2 hours at 70 ° C to dry
- Placer l'éprouvette 1 h en dessiccateur pour la laisser refroidir  - Place the test tube for 1 hour in a desiccator to allow it to cool
- Peser la masse initiale de l'éprouvette MO  - Weigh the initial mass of the MO specimen
Remplir les bêcher avec au minimum 4ml / cm2 de surface d'éprouvette Fill the beakers with at least 4ml / cm 2 of specimen surface
- Placer les éprouvettes dans le bêcher sans quelles se touchent ou qu'elles touchent les parois  - Place the specimens in the beaker without touching them or touching the walls
Refermer le bêcher pour 24h  Close the beaker for 24h
- Après 24h sortir l'éprouvette du bain d'acétone (pure à plus de 99%)  - After 24h leave the test tube acetone bath (more than 99% pure)
- Essuyer l'éprouvette avec du papier non pelucheux  - Wipe the test tube with lint-free paper
Peser immédiatement et noter la masse M  Weigh immediately and note the mass M
Remplir le tableau de suivi et calculer la moyenne M - MO de l'ensemble des éprouvettes, et déterminer la porosité en %.  Complete the monitoring chart and calculate the average M - MO of all test pieces, and determine the porosity in%.
L'invention va être maintenant décrite plus en détail à l'aide de modes de réalisation pris à titre d'exemples non limitatifs.  The invention will now be described in more detail using embodiments taken as non-limiting examples.
Exemple 1 :  Example 1
Cet exemple est basé sur l'utilisation d'un tissu de verre constitué de fibre de verre E de titre 68tex avec un diamètre moyen de 9μηι.  This example is based on the use of a glass fabric made of glass fiber E of 68tex title with an average diameter of 9μηι.
Ce tissu présente une armure de satin 8H avec une contexture moyenne de 22,9 fils/cm en chaîne et 21 , 1 fils/cm en trame afin d'obtenir un grammage moyen après traitement proche de 309 g/m2. This fabric has an 8H satin weave with an average thread count of 22.9 threads / cm in warp and 21.1 threads / cm in weft in order to obtain an average grammage after treatment close to 309 g / m 2 .
Après désensimage, ce tissu est traité avec un bain de finish à base de silane à hauteur de 0, 1 % en masse pour atteindre 303 g/m2. Ce tissu traité est imprégné de poudre commerciale PEI MW 55 000 g/mol (avec la méthode GPC calibrée au PMMA, MW 46842 g/mol, Mn 21 344 g/mol) par l'intermédiaire d'une technologie de poudrage gravitationnelle à raison de 75 g/m2 par face. La poudre PEI est fixée sur le tissu de verre par ramollissement, puis refroidissement du polymère. After desizing, this fabric is treated with a silane finish bath at 0.1% by weight to reach 303 g / m 2 . This treated fabric is impregnated with commercial PEI powder MW 55,000 g / mol (with GPC method calibrated with PMMA, MW 46842 g / mol, Mn 21 344 g / mol) by means of gravitational powder coating technology. 75 g / m 2 per side. The PEI powder is fixed on the glass cloth by softening and then cooling the polymer.
Les grammages et taux de fibres du pré-imprégné obtenu ont été mesurés en 3 points suivant la norme EN2337 par calcination.  The grammages and fiber content of the prepreg obtained were measured at 3 points according to EN2337 standard by calcination.
• Prélèvement 1 : 460.2 g/m2 - 33,1 % en masse de résine • Sampling 1: 460.2 g / m 2 - 33.1% by mass of resin
• Prélèvement 2 : 456.93 g/m2 - 32,6% en masse de résine • Sampling 2: 456.93 g / m 2 - 32.6% by mass of resin
• Prélèvement 3 : 459.4 g/m2 - 33,3% en mase de résine • Sampling 3: 459.4 g / m 2 - 33.3% in resin mase
soit un % de régularité +/-1 %. a% regularity +/- 1%.
Le pré-imprégné décrit ci-dessus est consolidé par l'intermédiaire d'une technologie de compression en continue isobarique, sur une installation comportant des zones de chauffe représentant une longueur d'environ 2,2 m.  The prepreg described above is consolidated via isobaric continuous compression technology on an installation having heating zones of a length of about 2.2 m.
Les conditions de consolidations sont les suivantes :  The consolidation conditions are as follows:
- Température: 370°C  - Temperature: 370 ° C
- Pression dans toutes les zones : 70 bars  - Pressure in all areas: 70 bar
- Vitesse de production : 2 m/min  - Production speed: 2 m / min
Les plaques monoplis consolidées présentent les propriétés suivantes :  Consolidated monoplates have the following properties:
Epaisseur moyenne = 0,270 mm  Average thickness = 0.270 mm
- Taux moyen de fibre : 33,1 %  - Average fiber rate: 33.1%
- Taux de reprise d'acétone : 4,6% en masse  - Acetone recovery rate: 4.6% by weight
- Module de traction sens chaîne : 17,4 GPa  - Chain direction traction module: 17,4 GPa
- Contrainte maximum en traction sens chaîne : 302 MPa  - Maximum tensile stress in the warp direction: 302 MPa
Exemple 2 : Example 2
Cet exemple est basé sur l'utilisation d'un tissu de verre constitué de fibre de verre E de titre 68tex avec un diamètre moyen de 9μηι.  This example is based on the use of a glass fabric made of glass fiber E of 68tex title with an average diameter of 9μηι.
Ce tissu présente une armure de sergé 2/2 avec une contexture moyenne de 22,9 fils/cm en chaîne et 16 fils/cm en trame afin d'obtenir un grammage moyen après traitement proche de 285 g/m2. This fabric has 2/2 twill weave with an average thread count of 22.9 threads / cm in warp and 16 threads / cm in weft to obtain an average basis weight after treatment close to 285 g / m 2 .
Après désensimage, ce tissu est traité avec un bain de finish à base silane à hauteur de 0,1 % en masse pour atteindre 277 g/m2. After desizing, this fabric is treated with a silane-based finish bath at 0.1% by weight to reach 277 g / m 2 .
Ce tissu traité est imprégné de la même poudre PEI MW 55 000 g/mol qu'à l'exemple 1 , par l'intermédiaire d'une technologie de poudrage gravitationnelle à raison de 68 g/m2 par face. La poudre PEI est fixée sur le tissu de verre par ramollissement et refroidissement du polymère. This treated fabric is impregnated with the same MW 55,000 g / mol PEI powder as in Example 1, by means of gravitational powder coating technology. 68 g / m 2 per side. The PEI powder is fixed on the glass fabric by softening and cooling the polymer.
Les grammages et taux de fibres du pré-imprégné obtenu ont été mesurés en 3 points suivant la norme EN2337 par calcination.  The grammages and fiber content of the prepreg obtained were measured at 3 points according to EN2337 standard by calcination.
· Prélèvement 1 :323,8 g/m2 - 33,0% en masse de résine · Sampling 1: 323.8 g / m 2 - 33.0% by mass of resin
• Prélèvement 2 : 324,1 g/m2 - 33,2% en masse de résine • Sampling 2: 324.1 g / m 2 - 33.2% by mass of resin
• Prélèvement 3 : 320,7 g/m2 - 32,6% en mase de résine • Sample 3: 320.7 g / m 2 - 32.6% resin mase
Soit un % de régularité +/-1 ,0%.  That is a% regularity +/- 1, 0%.
Le pré-imprégné décrit ci-dessus est consolidé par l'intermédiaire d'une technologie de compression semi-continue, comportant une zone de chauffe d'une longueur d'environ 0,6 m.  The prepreg described above is consolidated via a semi-continuous compression technology, comprising a heating zone with a length of about 0.6 m.
Les conditions de consolidations sont les suivantes :  The consolidation conditions are as follows:
- Températures : 400°C  - Temperatures: 400 ° C
- Pression dans toutes les zones : 15 bars  - Pressure in all zones: 15 bars
- Vitesse de production : 1 ,2 m/min plaques monoplis présentent les propriétés suivantes  - Production speed: 1, 2 m / min single-sided plates have the following properties
Epaisseur moyenne = 0,236 mm  Average thickness = 0.236 mm
Taux moyen de fibre : 32,3 %  Average fiber rate: 32.3%
Taux de reprise d'acétone : 4,9% en masse  Acetone uptake rate: 4.9% by weight
Module de traction sens chaîne : 21 ,4 GPa  Chain direction traction module: 21, 4 GPa
Contrainte maximum en traction sens chaîne : 353  Maximum tensile stress in warp direction: 353
Exemple 3 (comparatif): Example 3 (comparative):
Cet exemple est basé sur l'utilisation d'un tissu de verre constitué de fibre de verre This example is based on the use of a glass fiberglass fabric
E de titre 68tex avec un diamètre moyen de 9μηι. E of 68tex title with an average diameter of 9μηι.
Ce tissu présente une armure de satin 8H avec une contexture moyenne de 22,9 fils/cm en chaîne et 21 ,1 fils/cm en trame afin d'obtenir un grammage moyen après traitement proche de 309 g/m2. This fabric has an 8H satin weave with an average thread count of 22.9 threads / cm in warp and 21.1 threads / cm in weft in order to obtain an average grammage after treatment close to 309 g / m 2 .
Après désensimage, ce tissu est traité avec un bain de finish à base de silane à hauteur de 0,1 % en masse pour atteindre 303 g/m2. After desizing, this fabric is treated with a silane finish bath at 0.1% by weight to reach 303 g / m 2 .
Ce tissu traité est imprégné de poudre PEI MW 55 000 g/mol (comme aux exemples précédents) par l'intermédiaire d'une technologie de poudrage gravitationnelle à raison de 75 g/m2 par face. La poudre PEI est fixée sur le tissu de verre par ramollissement, puis refroidissement du polymère. Les grammages et taux de fibres du pré-imprégné obtenu ont été mesurés en 3 points suivant la norme EN2337 par calcination. This treated fabric is impregnated with PEI MW 55,000 g / mol powder (as in the previous examples) by means of a gravitational dusting technology at a rate of 75 g / m 2 per side. The PEI powder is fixed on the glass cloth by softening and then cooling the polymer. The grammages and fiber content of the prepreg obtained were measured at 3 points according to EN2337 standard by calcination.
• Prélèvement 1 : 460.2 g/m2 - 33,1 % en masse de résine • Sampling 1: 460.2 g / m 2 - 33.1% by mass of resin
• Prélèvement 2 : 456.63 g/m2 - 32,6% en masse de résine • Sampling 2: 456.63 g / m 2 - 32.6% by mass of resin
• Prélèvement 3 : 459.4 g/m2 - 33,3% en mase de résine • Sampling 3: 459.4 g / m 2 - 33.3% in resin mase
soit un % de régularité +/-1 %.  a% regularity +/- 1%.
Le pré-imprégné décrit ci-dessus est consolidé par l'intermédiaire d'une technologie de compression séquentielle, sur une installation comportant 3 presses dont 2 chauffées à 360°C et une à 80°C.  The prepreg described above is consolidated via sequential compression technology, on an installation comprising 3 presses of which 2 heated to 360 ° C and one to 80 ° C.
Les plaques 2 plis consolidées présentent les propriétés suivantes :  The consolidated 2-ply plates have the following properties:
Epaisseur moyenne = 0,45 mm  Average thickness = 0.45 mm
- Taux moyen de fibre : 32,3 %  - Average fiber rate: 32.3%
- Taux de reprise d'acétone : 1 ,75% en masse  - Acetone uptake rate: 1.75% by weight
- Module de traction sens chaîne : 17,4 GPa  - Chain direction traction module: 17,4 GPa
- Contrainte maximum en traction sens chaîne : 380 MPa  - Maximum tensile stress in the warp direction: 380 MPa
Exemple 4 : Les feuilles composites des exemples 1 à 3 ont été utilisées pour produire des panneaux sandwich moussés, selon un procédé standard comprenant l'imprégnation de film de PEI avec de l'acétone (le cœur), la formation du sandwich en plaçant le cœur entre deux feuilles composites selon l'invention, le placement de l'ensemble entre les deux plateaux d'une presse, le chauffage à une température supérieure à la température de transition vitreuse entre environ 155 et environ 210°C tout en appliquant une pression est appliquée sur l'ensemble, l'obtention du moussage et l'ouverture progressive de la presse pour développer la mousse, puis refroidissement. Example 4: The composite sheets of Examples 1 to 3 were used to produce foamed sandwich panels, according to a standard method comprising the impregnation of PEI film with acetone (the core), the formation of the sandwich by placing the heart between two composite sheets according to the invention, placing the assembly between the two plates of a press, heating at a temperature above the glass transition temperature between about 155 and about 210 ° C while applying pressure is applied on the whole, obtaining the foaming and the progressive opening of the press to develop the foam, then cooling.
Les feuilles composites des exemples 1 et 2 ont permis d'obtenir des panneaux sandwich avec une bonne adhésion entre le cœur en mousse et les feuilles composites de couverture. Au contraire des feuilles composites des exemples 1 et 2, les feuilles composites de l'exemple 3 n'ont pas permis d'obtenir un bon aspect de surface.  The composite sheets of Examples 1 and 2 made it possible to obtain sandwich panels with good adhesion between the foam core and the composite covering sheets. In contrast to the composite sheets of Examples 1 and 2, the composite sheets of Example 3 failed to obtain a good surface appearance.
Le procédé par moulage continu ou semi-continu selon les exemples 1 et 2 s'avère plus performant pour produire des feuilles composites performantes pour l'application sandwich moussé. Une caractéristique des feuilles composites produites par ces procédés qui ressort différente entre ces deux groupes de procédé de moulage (exemples 1 et 2 versus 3) est, à partir d'un même grade de PEI, l'obtention de porosités à l'acétone différentes, les procédés des exemples 1 et 2 conduisant à une porosité à l'acétone supérieure.  The continuous or semi-continuous molding process according to Examples 1 and 2 proves to be more efficient for producing high performance composite sheets for the foamed sandwich application. A characteristic of the composite sheets produced by these processes that emerges different between these two groups of molding process (Examples 1 and 2 versus 3) is, from the same grade of PEI, obtaining different acetone porosities. the processes of Examples 1 and 2 leading to higher acetone porosity.

Claims

REVENDICATIONS
1 - Feuille composite comprenant au moins un tissu et un polyétherimide (PEI), dans laquelle le PEI a une masse molaire en masse (MW) comprise entre environ 20 000 et environ 100 000 g/mol, le PEI imprégnant et densifiant le tissu, la feuille composite ayant une porosité à l'acétone comprise entre environ 3% et environ 8% en masse d'absorption d'acétone, de préférence entre environ 4% et environ 5%, telle que mesurée par la méthode à la prise d'acétone consistant, sur une éprouvette de 40x40 mm de ladite feuille composite, séchée pendant 2 h à 70°C, à peser la masse initiale de l'éprouvette, placer ensuite l'éprouvette dans de l'acétone à recouvrement pendant 24 h, récupérer l'éprouvette, l'essuyer et la peser, comparer à la masse initiale et en déduire la prise d'acétone en masse. 1 - Composite sheet comprising at least one fabric and a polyetherimide (PEI), wherein the PEI has a mass molecular weight (MW) of between about 20,000 and about 100,000 g / mol, the PEI impregnating and densifying the fabric, the composite sheet having an acetone porosity of from about 3% to about 8% by weight of acetone absorption, preferably from about 4% to about 5%, as measured by the setting method; acetone consisting, on a 40x40 mm test piece of said composite sheet, dried for 2 h at 70 ° C, weighing the initial mass of the test piece, then placing the test piece in overlapping acetone for 24 h, recovering the specimen, wipe it and weigh it, compare with the initial mass and deduce the intake of acetone en masse.
2- Feuille selon la revendication 1 , dans laquelle le taux massique de PEI par rapport au poids total de la feuille est compris entre environ 20 et environ 50%, notamment entre environ 23 et environ 43%, de préférence entre environ 30 et environ 36%.  2-sheet according to claim 1, wherein the mass ratio of PEI relative to the total weight of the sheet is between about 20 and about 50%, especially between about 23 and about 43%, preferably between about 30 and about 36 %.
3- Feuille selon la revendication 2, dans laquelle ce taux massique de PEI a une régularité de +/-5%, de préférence de +/-3%, mieux de +/-2%, mieux encore de +/-1 %, en masse de résine sur l'ensemble de la feuille.  3- sheet according to claim 2, wherein the mass ratio of PEI has a regularity of +/- 5%, preferably +/- 3%, better +/- 2%, better still +/- 1% , in mass of resin on the whole of the sheet.
4- Feuille selon l'une quelconque des revendications 1 à 3, dans laquelle le PEI a une masse molaire en masse (MW) comprise entre environ 30 000 et environ 60 000 g/mol ; par exemple environ 47 000 ou 55 000 g/mol.  The sheet of any one of claims 1 to 3, wherein the PEI has a mass molecular weight (MW) of from about 30,000 to about 60,000 g / mol; for example, about 47,000 or 55,000 g / mol.
5- Feuille selon l'une quelconque des revendications 1 à 4, dans laquelle le PEI a une masse molaire en nombre (Mn) comprise entre environ 15 000 et environ 50 000 g/mol, de préférence entre environ 18 000 et environ 30 000 g/mol ; par exemple environ 28 000 g/mol.  The sheet of any one of claims 1 to 4, wherein the PEI has a number-average molecular weight (Mn) of from about 15,000 to about 50,000 g / mol, preferably from about 18,000 to about 30,000. g / mol; for example, about 28,000 g / mol.
6- Feuille selon l'une quelconque des revendications 1 à 5, dans laquelle le tissu est formé de fils de verre, de carbone, de basalte, et mélanges, par exemple verre/carbone.  The sheet of any one of claims 1 to 5, wherein the fabric is formed from glass, carbon, basalt, and blends, eg glass / carbon.
7- Feuille selon l'une quelconque des revendications 1 à 6, dans laquelle la masse surfacique du tissu de verre est comprise entre environ 50 et environ 600 g/m2, de préférence entre environ 100 et environ 400 g/m2. 7. A sheet according to any one of claims 1 to 6, wherein the surface weight of the glass fabric is between about 50 and about 600 g / m 2 , preferably between about 100 and about 400 g / m 2 .
8- Feuille selon l'une quelconque des revendications 1 à 7, dans laquelle les fils ont un titre de 10 à 300 tex en verre et de 60 à 800 tex en carbone. 9- Feuille selon l'une quelconque des revendications 1 à 8, comprenant de 1 à 4 plis de tissu. 8. A sheet according to any one of claims 1 to 7, wherein the yarns have a titer of 10 to 300 tex glass and 60 to 800 tex carbon. 9- Sheet according to any one of claims 1 to 8, comprising 1 to 4 folds of fabric.
10- Feuille selon l'une quelconque des revendications 1 à 9, ayant une épaisseur inférieure ou égale à environ 3 mm, notamment à 2 mm.  10- Sheet according to any one of claims 1 to 9, having a thickness less than or equal to about 3 mm, especially 2 mm.
1 1 - Feuille selon l'une quelconque des revendications 1 à 10, dans laquelle la feuille est susceptible d'être obtenue par un procédé comprenant le fait de disposer d'un pli de tissu ou de plusieurs plis superposés de tissu, de l'imprégner de PEI par poudrage ou dépose d'un film de PEI sur une ou deux faces du tissu ou de l'empilement, en soumettant l'empilement à un ramollissement, puis refroidissement et consolidation, en utilisant un moulage en continu ou en semi-continu avec chauffage à une température comprise entre environ 300 et environ 500°C, notamment entre environ 360 et environ 400°C, pendant une durée comprise entre environ 30s et environ 3 min,  A sheet as claimed in any one of claims 1 to 10, wherein the sheet is obtainable by a process comprising disposing of a fold of fabric or a plurality of superposed folds of fabric, impregnating with PEI by powdering or depositing a PEI film on one or both sides of the fabric or stack, subjecting the stack to softening, then cooling and consolidation, using continuous or semi-continuous molding continuous heating with a temperature of between about 300 and about 500 ° C, in particular between about 360 and about 400 ° C, for a time between about 30s and about 3 min,
12- Feuille selon la revendication 1 1 , dans laquelle la feuille est susceptible d'être obtenue par un procédé de moulage en continu, dans lequel on applique une pression entre environ 20 et environ 100 bars, de préférence entre environ 40 et environ 80 bars, une température entre environ 300 et environ 500 °C, notamment entre environ 360 et environ 400 °C, pour une vitesse de passage d'environ 0,1 à environ 5, de préférence d'environ 1 à environ 2 m/min, pour une durée de traitement à température élevée comprise entre environ 30s et environ 3 min.  12- Sheet according to claim 1 1, wherein the sheet is obtainable by a continuous molding process, wherein a pressure is applied between about 20 and about 100 bar, preferably between about 40 and about 80 bar a temperature between about 300 and about 500 ° C, especially between about 360 and about 400 ° C, for a throughput rate of about 0.1 to about 5, preferably about 1 to about 2 m / min, for a high temperature treatment time of between about 30 seconds and about 3 minutes.
13- Feuille selon la revendication 1 1 , dans laquelle la feuille est susceptible d'être obtenue par un procédé de moulage en continu, dans lequel on applique une pression entre environ 5 et environ 50 bars, de préférence entre environ 10 et environ 25 bars, une température entre environ 300 et environ 500 °C, notamment entre environ 360 et environ 400 °C, pour une vitesse de passage d'environ 0,1 à environ 5, de préférence d'environ 0,4 à environ 1 ,2 m/min, pour une durée de traitement à température élevée comprise entre environ 30s et environ 3 min.  13- Sheet according to claim 1 1, wherein the sheet is obtainable by a continuous molding process, wherein a pressure is applied between about 5 and about 50 bar, preferably between about 10 and about 25 bar a temperature between about 300 and about 500 ° C, especially between about 360 and about 400 ° C, for a throughput rate of about 0.1 to about 5, preferably about 0.4 to about 1.2 m / min, for a high temperature treatment time of between about 30 seconds and about 3 minutes.
14- Procédé de fabrication d'une feuille composite comprenant au moins un tissu et un polyétherimide (PEI), apte à la fabrication d'une feuille composite selon l'une quelconque des revendications 1 à 13, comprenant le fait de disposer d'un pli de tissu ou de plusieurs plis superposés de tissu, de l'imprégner de PEI par poudrage ou dépose d'un film de PEI sur une ou deux faces du tissu ou de l'empilement, en soumettant l'empilement à un ramollissement, puis refroidissement et consolidation, en utilisant un moulage en continu ou en semi-continu avec chauffage à une température comprise entre environ 300 et environ 500°C, notamment entre environ 360 et environ 400°C, pendant une durée comprise entre environ 30s et environ 3 min. 15- Procédé selon la revendication 14, dans lequel, dans le moulage en continu, on applique une pression entre environ 20 et environ 100 bars, de préférence entre environ 40 et environ 80 bars, une température entre environ 300 et environ 500 °C, notamment entre environ 360 et environ 400 °C, pour une vitesse de passage d'environ 0,1 à environ 5, de préférence d'environ 1 à environ 2 m/min, pour une durée de traitement à température élevée comprise entre environ 30s et environ 3 min. 14- A method of manufacturing a composite sheet comprising at least one fabric and a polyetherimide (PEI), suitable for manufacturing a composite sheet according to any one of claims 1 to 13, comprising having a fold fabric or several folds superimposed fabric, impregnate it with PEI by powdering or depositing a PEI film on one or both sides of the fabric or stack, subjecting the stack to softening, then cooling and consolidation, using a continuous or semi-continuous molding with heating at a temperature of between about 300 and about 500 ° C, in particular between about 360 and about 400 ° C, for a period between about 30s and about 3 min. The process according to claim 14, wherein in the continuous molding a pressure is applied between about 20 and about 100 bar, preferably between about 40 and about 80 bar, a temperature between about 300 and about 500 ° C. in particular between about 360 and about 400 ° C, for a flow rate of about 0.1 to about 5, preferably about 1 to about 2 m / min, for a high temperature treatment time of between about 30s. and about 3 min.
16- Procédé selon la revendication 14, dans lequel, dans le moulage en semi- continu, on applique une pression entre environ 5 et environ 50 bars, de préférence entre environ 10 et environ 25 bars, une température entre environ 300 et environ 500 °C, notamment entre environ 360 et environ 400 °C, pour une vitesse de passage d'environ 0,1 à environ 5, de préférence d'environ 0,4 à environ 1 ,2 m/min, pour une durée de traitement à température élevée comprise entre environ 30s et environ 3 min.  16. A process according to claim 14, wherein in semi-continuous molding a pressure is applied between about 5 and about 50 bar, preferably between about 10 and about 25 bar, a temperature between about 300 and about 500 °. C, especially between about 360 and about 400 ° C, for a throughput rate of about 0.1 to about 5, preferably about 0.4 to about 1.2 m / min, for a duration of high temperature between about 30s and about 3 min.
17- Procédé selon l'une quelconque des revendications 14 à 16, dans lequel le PEI a une masse molaire en masse (MW) comprise entre environ 30 000 et environ 100 000 g/mol.  17. A process according to any one of claims 14 to 16 wherein the PEI has a mass molecular weight (MW) of from about 30,000 to about 100,000 g / mol.
18- Procédé selon l'une quelconque des revendications 14 à 17, dans lequel le PEI a une viscosité apparente comprise entre 600 et 1500, notamment entre 800 et 1200 Pa.s à 360 °C, telle que mesurée sous un cisaillement compris entre 10~2 et 1 seconde"1 , telle que mesurée en utilisant un viscosimètre de Couette plan-plan. 18. The process as claimed in claim 14, in which the PEI has an apparent viscosity of between 600 and 1500, in particular between 800 and 1200 Pa.s at 360 ° C., as measured under a shear between ~ 2 and 1 second "1 , as measured using a plane-plane Couette viscometer.
EP17735144.2A 2016-07-05 2017-07-05 Composite sheet made from fabric and polyetherimide with controlled porosity Pending EP3481629A1 (en)

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FR1656394A FR3053627B1 (en) 2016-07-05 2016-07-05 COMPOSITE SHEET BASED ON FABRIC AND CONTROLLED POROSITY POLYETHERIMIDE
PCT/EP2017/066811 WO2018007460A1 (en) 2016-07-05 2017-07-05 Composite sheet made from fabric and polyetherimide with controlled porosity

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US11072146B2 (en) 2021-07-27
FR3053627B1 (en) 2021-07-30
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JP2019524925A (en) 2019-09-05

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