WO1986000323A1 - Method for fabricating thermo-hardenable or thermo-reactive pre-impregnated materials enabling the fabrication of composite articles - Google Patents

Method for fabricating thermo-hardenable or thermo-reactive pre-impregnated materials enabling the fabrication of composite articles Download PDF

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Publication number
WO1986000323A1
WO1986000323A1 PCT/FR1985/000168 FR8500168W WO8600323A1 WO 1986000323 A1 WO1986000323 A1 WO 1986000323A1 FR 8500168 W FR8500168 W FR 8500168W WO 8600323 A1 WO8600323 A1 WO 8600323A1
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Prior art keywords
powder
thermo
roving
composite
powders
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PCT/FR1985/000168
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French (fr)
Inventor
Jean Philippe Galichon
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Jean Philippe Galichon
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Publication of WO1986000323A1 publication Critical patent/WO1986000323A1/en

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    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/241—Preventing premature crosslinking by physical separation of components, e.g. encapsulation
    • 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
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres

Definitions

  • the composites are made up of a combination of fibers of all metallic, mineral, polymeric natures and currently predominantly thermosetting matrices such as polyesters, epoxies, phenolics.
  • the object of the present invention is to produce a flexible filament prepreg in which the thermosets or thermostats are in solid form, stable at ordinary temperature, consisting of two elements reacting during processing at temperature.
  • the prepregs of the prior art consist of fibrous elements such as mats, plates, sheets into which resins are introduced in the form of powder by polymerization or electrostatic powdering. These resins, to be maintained in these elements are melted and not crosslinked, otherwise these elements could not be handled. This fusion leads to a bond of the fibers and these elements become rigid or semi-rigid.
  • the prepreg according to the invention is mainly characterized by the interpenetration in solid powder form constituting n ° I at the level of the unitary filament (6 to 20 microns) constituting the rovings of the dies without any connection between the unitary fibers and these dies and the sheathing of this roving interpenetrated by a second flexible product constituting No. I.
  • the sheath obtained by extrusion, coating or covering covering has 3 main functions:
  • thermoset type products which would only be heated until softening without crosslinking would already give a bond between the fiber and the matrix stiffening the entire roving.
  • a single cladding of products by simple or multiple extrusion of reactive products as indicated in other patents would only be a coating of roving and not an interpenetration to the core alone capable of giving a compeeite with important properties.
  • This roving remains flexible and can be manipulated to obtain semi-finished products.
  • These semi-finished products are made by transforming a basic prepreg yarn to form mats, fabrics, knits or cut.
  • the core matrix gives products different from those obtained by a posterior impregnation on mats or fabrics.
  • the products constituting the element interpenetrating the wick in powder form and the sheathing products must be compatible, reactive or complementary according to the aim sought in the final compesite so that during the constitution of the composite obtained by raising the temperature the final product comprises the properties of a homogeneous matrix composite.
  • the installation for making such a prepreg includes, by way of description and without limitation, the following devices:
  • a tank making it possible to produce a fluidized bed of powder with a particle size compatible with the unitary fibers (from 10 to 40 microns). Can this fluidized bed be simple or will it be possible to be electrostatically charged by incorporating an electrode in the case where the base fiber is conductive and should be earthed? In this case the powder would be charged.
  • the roving goes into this tank. Being in full bloom, it loads powder to the core, each unitary filament is interpenetrated.
  • a square extruder allows to extrude a sheath around a loaded roving.
  • the extrusion is carried out in such a way that the extruded sheath cools very quickly as soon as it leaves the extruder over a very short distance of a few centimeters (this distance depends on the polymer considered). Thanks to this cooling, the point of contact between the inner face of the sheath and the powder situated outside the prepreg roving have no possibility of reaction in this state of the prepreg.
  • An additional cooling device can be envisaged: water bath or cold air blowing.
  • a winding device allowing the production of reels. This device also serves to drive the entire system.
  • a cutting device can be envisaged.
  • the fibers used will be metallic, mineral, polymetric.
  • Epoxy powders are particularly suitable for implementing the invention. However, it is understood that other powders of thermosetting or thermostable materials such as phenolics, polyesters, thermoplastic or thermosetting polyimides, acrylics, polyurethanes can be used.
  • thermoplastics allowing a solution for sheathing by coating and having free groups capable of reacting with the resins constituting the powder such as polyamides with NH2 end groups .
  • free groups capable of reacting with the resins constituting the powder
  • other prepolymeric or non-thermoplastic or thermosetting thermoplastic matrices such as reactive acrylics can be used.
  • This powder has the particularity of reacting only at a temperature close to 230 ° C and having the combined elements within each grain. Percentage by weight of powder: 25%.
  • EXAMPLE II Idem I, but the coating in the solvent phase is replaced by an extrusion of an experimental copolyamide 6-12 with NH 2 end groups.
  • the extrusion takes place at 180 ° C.
  • the extrusion speed is 100 m / minute and the cooling of the sheath takes place in a stream of air in a fraction of a second, which avoids the melting of the epoxy powder.

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

Pre-impregnated filamentary product comprised of continuous reinforcement fibres interpenetrated by a matrix of solid thermo-hardenable or thermo-reactive polymers arranged at the level of the unitary fibre and not bound with that fibre and protected by a shielding reacting with the polymer providing for the solid interpenetration during a temperature rise, and fabrication method thereof. The fabrication method comprises the following steps: introduction of thermo-hardenable or thermo-reactive material in the form of a powder having a grain size which is compatible with the dimensions of the unitary filaments of the fibre rovings; covering of said core impregnated roving by a polymer layer by coating, extrusion or lapping, which has the property of being compatible, to be combined or react in temperature with the powder polymer impregnating the roving. The assembly remains flexible since there is no binding between the fibre and the matrix and the composite is obtained only during the implementation which involves the temperature. The pressure and the time may be a complementary element for good achievements according to the resins in question. During the step which is the object of the invention, the pre-impregnated and shielded roving remains flexible and is characterized by a good handling for the making of flexible semi-products such as braides, knitted material, woven material or mats.

Description

PROCEDE DE FABRICATION DE FREIMPREGNES THERMODURCISSABLES OU THERMOREACTIFS PERMETTANT LA FABRICATION D'OBJETS COMPOSITES. Les composites sont constitués d'association de fibres de toutes natures métalliques, minérales,polymeriques et de matrices actuellement à majorité thermodurcissables tels que polyesters, epoxys, phénoliques. PROCESS FOR THE MANUFACTURE OF THERMOSETTING OR THERMOREACTIVE FREIMPREGNES FOR THE MANUFACTURE OF COMPOSITE OBJECTS. The composites are made up of a combination of fibers of all metallic, mineral, polymeric natures and currently predominantly thermosetting matrices such as polyesters, epoxies, phenolics.
Ces produits se présentent généralement sous forme liquide résine de base et durcisseur réagissant lors de leur mise en oeuvre. Ces produits très réactifs doivent se stocker séparément à des températures basses (chambres froides) et ont des temps de stockage limités. Ils ont également l'inconvénien étant réalisés avec des produits contenant des solvants lourds qui sont difficiles à extraire, de donner des compoéites à porosités.These products are generally in liquid base resin and hardener form which reacts during their use. These highly reactive products must be stored separately at low temperatures (cold rooms) and have limited storage times. They also have the disadvantage, being produced with products containing heavy solvents which are difficult to extract, of giving compounds with porosities.
Le but de la présente invention est de réaliser, un préimprégné filamentaire souple dans lequel les thermodurcissables ou thermostables se présentent sous forme solide, stables à température ordinaire, constitués de deux éléments réagissant pendant la mise en oeuvre à température.The object of the present invention is to produce a flexible filament prepreg in which the thermosets or thermostats are in solid form, stable at ordinary temperature, consisting of two elements reacting during processing at temperature.
Ce matériau a déjà été partiellement décrit dans le brevet principal àe la demanderesse n° 84.10021 du 26 juin 1984.This material has already been partially described in the main patent to the Applicant No. 84.10021 of June 26, 1984.
Les préimprégnés de l'état antérieur de la technique sont constitués à partir d'éléments fibreux tels que mats, plaques, feuilles dans lesquelles sont introduites des résines sous forme de poudre par syntérisation ou poudrage électrostatique. Ces résines, pour être maintenues dans ces éléments sont fondues et non réticulées,autrement ces éléments ne pourraient être manipulables. Cette fusion entraine une liaison des fibres et ces éléments deviennent rigides ou semi-rigides.The prepregs of the prior art consist of fibrous elements such as mats, plates, sheets into which resins are introduced in the form of powder by polymerization or electrostatic powdering. These resins, to be maintained in these elements are melted and not crosslinked, otherwise these elements could not be handled. This fusion leads to a bond of the fibers and these elements become rigid or semi-rigid.
D'autres cas d'éléments réagissants ont été également envisagés, comme des empilements de produits filmogènes ou en poudre mis en empilement avec des tissus ou mats. Dans ces deux cas, la réaction obtenue pendant la réalisation du composite nedsnne qu'un enrobage de roving, c-à-d la viscosité de ces produits à l'état fondu est trop importante pour pénétrer à l'intérieur des rovings et de la fibre unitaire. Le préimprégné selon l'invention est principalement caractérisé par l'interpénétration sous forme solide poudre constituant n°I au niveau du filament unitaire (6 à 20 microns) constituant les rovings des matrices sans aucune liaison entre les fibres unitaires et ces matrices et le gainage de ce roving interpénétré par un second produit souple constituant nº I. La gaine obtenue par extrusion, enduction ou guipage de recouvrement a 3 fonctions principales:Other cases of reactants have also been envisaged, such as stacks of film-forming or powdered products stacked with fabrics or mats. In these two cases, the reaction obtained during the production of the composite is only a coating of roving, i.e. the viscosity of these products in the molten state is too great to penetrate inside the rovings and the single fiber. The prepreg according to the invention is mainly characterized by the interpenetration in solid powder form constituting n ° I at the level of the unitary filament (6 to 20 microns) constituting the rovings of the dies without any connection between the unitary fibers and these dies and the sheathing of this roving interpenetrated by a second flexible product constituting No. I. The sheath obtained by extrusion, coating or covering covering has 3 main functions:
- Maintenir les poudres au sein du roving,- Maintain the powders within the roving,
- Protéger ce roving interpénétré pendant des manipulations ultérieures éventuelles pour obtenir des semi produits (tissus, tresses, tricots, mats) ou réaliser de l' enroulement filamentaire.- Protect this interpenetrating roving during possible subsequent manipulations to obtain semi-products (fabrics, braids, knits, mats) or carry out filament winding.
- Sert d'agent de réticulation dans certains cas en se combinant ou en étant compatible avec la poudre de base.- Acts as a crosslinking agent in certain cases by combining or being compatible with the base powder.
Ces deux éléments: poudre et gaines sont inséparables et primordiaux. En effet:These two elements: powder and sheaths are inseparable and essential. Indeed:
. Une poudre seule simplement dispersée ne saurait être maintenue au sein du roving pendant les manipulations ultérieures.. A powder, simply dispersed, cannot be maintained within the roving during subsequent manipulations.
. Une poudre de produits type thermodurs qui ne serait chauffée que jusqu'au ramollissement sans réticulation donnerait déjà une liaison entre la fibre et la matrice rigidifiant l'ensemble du roving.. A powder of thermoset type products which would only be heated until softening without crosslinking would already give a bond between the fiber and the matrix stiffening the entire roving.
. Un gainage seul de produits par extrusion simple ou multiple de produits réagissants tel qu'indiqué dans d' autres brevets ne serait qu'un enrobage de roving et non une interpénétration à coeur seule susceptible de donner un compeeite à propriétés importantes .. A single cladding of products by simple or multiple extrusion of reactive products as indicated in other patents would only be a coating of roving and not an interpenetration to the core alone capable of giving a compeeite with important properties.
Ce roving reste souple et peut être manipulé pour obtenir des semi-produits. Ces semi-produits sont constitués par transformation d'un fil préimprégné de base pour former des mats, tissus, tricots ou coupés.This roving remains flexible and can be manipulated to obtain semi-finished products. These semi-finished products are made by transforming a basic prepreg yarn to form mats, fabrics, knits or cut.
La matrice à coeur donne des produits différents de ceux obtenus par une imprégnation a posteriori sur mats ou tissus. Les produits constituant l'élément interpénétrant la mèche sous forme de poudre et les produits de gainage doivent être compatibles, réagissants ou complémentaires suivant le but recherché dans le compesite final pour que lors de la constitution du composite obtenu par élévation de température le produit final comporte les propriétés d'un composite à matrice homogène.The core matrix gives products different from those obtained by a posterior impregnation on mats or fabrics. The products constituting the element interpenetrating the wick in powder form and the sheathing products must be compatible, reactive or complementary according to the aim sought in the final compesite so that during the constitution of the composite obtained by raising the temperature the final product comprises the properties of a homogeneous matrix composite.
L'installation pour réaliser un tel préimprégné comprend à titre descriptif et non limitatif les appareillages ci-après:The installation for making such a prepreg includes, by way of description and without limitation, the following devices:
- Un dispositif de déroulement des fibres: dévidoir.- A fiber unwinding device: reel.
- Des rouleaux métalliques ou de matières plastiques résistantes type teflon permettant un épanouissement des fibres aiasi que la possibilité de charger ces fibres électro- statiquement.- Teflon-type metallic or resistant plastic rollers allowing fibers to flourish as well as the possibility of charging these fibers electrostatically.
- Un bac permettant de réaliser un lit fluidisé de poudre de granulométrie compatible avec les fibres unitaires (de 10 à 40 microns). Ce lit fluidisé pourra être simple ou aura la possibilité d'être chargé électrostatiquement par incorporation d'électrode dans le cas où la fibre de base est conductrice et devrait être mise à la terre? Dans ce cas la poudre serait chargée. Le roving passe dans ce bac. Etant épanoui, il se charge de poudre à coeur, chaque filament unitaire est interpénétré.- A tank making it possible to produce a fluidized bed of powder with a particle size compatible with the unitary fibers (from 10 to 40 microns). Can this fluidized bed be simple or will it be possible to be electrostatically charged by incorporating an electrode in the case where the base fiber is conductive and should be earthed? In this case the powder would be charged. The roving goes into this tank. Being in full bloom, it loads powder to the core, each unitary filament is interpenetrated.
- Une extrudeuse d'équerre permet d'extruder une gaine autourdéœ roving chargé. L'extrusion se fait de telle façon que la gaine extrudée se refroidit très rapidement dès sa sortie de l'extrudeuse sur une distance très courte de quelques centimètres (cette distance dépend du polymère considéré). Grâce à ce refroidissement, le point de contact entre la face intérieure de la gaine et la poudre située à l'extérieur du roving préimprégné n'ont aucune possibilité de réaction dans cet état du préimprégné. - Un dispositif de refroidissement complémentaire peut être envisagé: bain d'eau ou soufflage d'air froid.- A square extruder allows to extrude a sheath around a loaded roving. The extrusion is carried out in such a way that the extruded sheath cools very quickly as soon as it leaves the extruder over a very short distance of a few centimeters (this distance depends on the polymer considered). Thanks to this cooling, the point of contact between the inner face of the sheath and the powder situated outside the prepreg roving have no possibility of reaction in this state of the prepreg. - An additional cooling device can be envisaged: water bath or cold air blowing.
- Un dispositif d'enroulement permettant la fabrication de bobine. Ce dispositif sert également d'entraînement de l' ensemble du système. - Si nécessaire pour fabrication de sous produit type mat réalisé par préimprégné coupé, un dispositif de coupe peut être envisagé. Selon les exigences du composite recherché pour les applications, les fibres employées seront métalliques, minérales, polymétriques. Conviennent particulièrement pour la mise en oeuvre de l'invention les poudres epoxydiques. Mais il est bien entendu que d'autres poudres de matières thermodurcissables ou thermostables telles que phénoliques, polyesters, polyimides thermoplastiques ou thermodurcissables, acryliques, polyurethanes peuvent être mises en oeuvre. Conviennent particulièrement pour la mise En oeuvre de l'invention des gainages de thermoplastiques à bas poids moléculaire permettant une mise en solution pour gainage par enduction et possédant des groupes libres aptes à réagir avec les résines constituant la poudre tels que les polyamides à groupes terminaux NH2. Mais il est bien entendu que d'autres matrices thermoplastiques prépolymères ou non ou thermdurcissables tels que acryliques réactifs peuvent être utilisés.- A winding device allowing the production of reels. This device also serves to drive the entire system. - If necessary for the manufacture of a mat type by-product produced by cut prepreg, a cutting device can be envisaged. Depending on the requirements of the composite sought for the applications, the fibers used will be metallic, mineral, polymetric. Epoxy powders are particularly suitable for implementing the invention. However, it is understood that other powders of thermosetting or thermostable materials such as phenolics, polyesters, thermoplastic or thermosetting polyimides, acrylics, polyurethanes can be used. Particularly suitable for the implementation of the invention sheathings of low molecular weight thermoplastics allowing a solution for sheathing by coating and having free groups capable of reacting with the resins constituting the powder such as polyamides with NH2 end groups . However, it is understood that other prepolymeric or non-thermoplastic or thermosetting thermoplastic matrices such as reactive acrylics can be used.
Dans le cas de produits où la température de mise en oeuvre du procédé ne permettrait pas d'installer par enduction ou extrusion une gaine autour de la fibre préimprégnée de poudre sera utilisé le procédé par guipage, c'est-à-dire l'enroulement en continu d'un fil qui peut être appliqué à la température ambiante ou à des températures suffisamment éloignées des températures de réaction des poudres constituant la préimprégnation. EXEMPLE I Mèche de fibre de verre de 1200 tex de Owens Corning Fiber Glass disposant de l'ensimage expérimental particulier R 28 permettant le défibrage pour arriver en passant sur des embarrages à la fibre unitaire de 20 microns. Foudre epoxyde type pipe de 3 M référence 206 N. Imprégnation de la fibre par passge dans un lit fluidisé de poudre epoxyde de qualité, "pipe line" mise au point par la société 3 M et référencée 206 N de laquelle on n'aura conservé que les particules de granulométrie moyenne de 20 microns.In the case of products where the temperature of implementation of the process would not allow to install by coating or extrusion a sheath around the fiber pre-impregnated with powder will be used the process by wrapping, that is to say the winding continuously of a wire which can be applied at room temperature or at temperatures sufficiently distant from the reaction temperatures of the powders constituting the prepreg. EXAMPLE I Wick of 1200 tex glass fiber from Owens Corning Fiber Glass having the specific experimental size R 28 allowing defibration to arrive while passing over tethers to the unitary fiber of 20 microns. 3M type epoxy lightning pipe, reference 206 N. Impregnation of the fiber by passge in a fluidized bed of quality epoxy powder, "pipe line" developed by the company 3M and referenced 206 N from which only the particles with an average particle size of 20 microns have been kept.
Cette poudre a la particularité de ne réagir qu'à la température voisine de 230°C et possédant les éléments combinés au sein de chaque grain. Pourcentage en poids de poudre : 25%.This powder has the particularity of reacting only at a temperature close to 230 ° C and having the combined elements within each grain. Percentage by weight of powder: 25%.
Gainage par passage dans une solution de polymère acrylique PARALOID B 44 à 20% dans le Méthyl-éthyl cétone. Le solvant est évaporé par passage du produit gaine dans un tunnel infrarouge. Le produit final est constitué de: verre 60% poudre epoxy 25% résine acrylique 15%Sheathing by passage through a solution of acrylic polymer PARALOID B 44 at 20% in Methyl ethyl ketone. The solvent is evaporated by passing the sheath product through an infrared tunnel. The final product consists of: glass 60% epoxy powder 25% acrylic resin 15%
EXEMPLE II Idem I, mais le gainage en phase solvant est remplacé par une extrusion d'un copolyamide expérimental 6-12 à groupements terminaux NH2.L'extrusion a lieu à 180°C. La vitesse d'extrusion est de 100 m/minute et le refroisissement de la gaine a lieu dans un courant d'air en une fraction de seconde, ce qui permet d'éviter la fusion de la poudre epoxy.EXAMPLE II Idem I, but the coating in the solvent phase is replaced by an extrusion of an experimental copolyamide 6-12 with NH 2 end groups. The extrusion takes place at 180 ° C. The extrusion speed is 100 m / minute and the cooling of the sheath takes place in a stream of air in a fraction of a second, which avoids the melting of the epoxy powder.
Composition finale : Verre 60% Epoxy 20% POLYAMIDE 20% EXEMPLE IIIFinal composition: Glass 60% Epoxy 20% POLYAMIDE 20% EXAMPLE III
Idem 2, mais la poudre epoxy est remplacée par une poudre de polyméthane.Same as 2, but the epoxy powder is replaced by a polymethane powder.
EXEMPLE IV Idem 2, mais la poudre epoxy est remplacée par une poudre polyester à groupements terminaux - COOH obtenue à partir de la résine 9000 de CARGILL. EXAMPLE IV Same as 2, but the epoxy powder is replaced by a polyester powder with end groups - COOH obtained from CARGILL resin 9000.

Claims

REVENDICATIONS
1. Procédé de fabrication de filaments préimprégnés constitués de fibres de renforcement continues interpénétrées au niveau du filament unitaire constituant la mèche sous une forme solide en poudre mais sans aucune liaison entre la fibre et la poudre et gainage de ce roving interpénétré par un produit qui reste souple, compatible ou réagissant avec la poudre de base interpénétrant le roving et caractérisé par les étapes suivantes:1. Method for manufacturing prepreg filaments consisting of continuous reinforcing fibers interpenetrated at the level of the unitary filament constituting the wick in a solid powder form but without any connection between the fiber and the powder and sheathing of this roving interpenetrated by a product which remains flexible, compatible or reactive with the base powder interpenetrating the roving and characterized by the following stages:
- Introduction des poudres thermodurcissables ou thermoréactives au sein du roving préalablement épanoui pour permettre d'atteindre la fibre unitaire.- Introduction of thermosetting or thermoreactive powders within the roving previously bloomed to allow the unitary fiber to be reached.
- Recouvrement de ladite mèche au moyen d'une couche plastique à une température qui ne permet aucune réaction avec la poudre de base.- Covering of said wick by means of a plastic layer at a temperature which does not allow any reaction with the base powder.
La réaction se produit quand ce préimprégné sous sa forme initiale ou sous sa forme serai produits est rais en oeuvre pour réaliser un composite, c'est-à-dire à une température permettant la réaction des produits gaine et poudre.The reaction occurs when this prepreg in its initial form or in its form is produced is used to make a composite, that is to say at a temperature allowing the reaction of the sheath and powder products.
2. Procédé selon I caractérisé en ce que l'interpénétration dans les fibres unitaires se fait par passage dans un lit fluidisé de poudres.2. Method according to I characterized in that the interpenetration in the unitary fibers is done by passage through a fluidized bed of powders.
3. Procédé selon I caractérisé en ce que l'interpénétration dans les fibres unitaires se fait par passage dans une suspension aqueuse ou solvante, puis par séchage ou élimination du solvant avant gainage.3. Method according to I characterized in that the interpenetration in the unitary fibers is done by passage through an aqueous or solvent suspension, then by drying or elimination of the solvent before sheathing.
4. Procédé selon I caractérisé en ce que la couche de matière de recouvrement est appliquée par enduction. 5. Procédé selon I caractérisé en ce que la couche de matière de recouvrement est appliquée par extrusion.4. Method according to I characterized in that the layer of covering material is applied by coating. 5. Method according to I characterized in that the layer of covering material is applied by extrusion.
6. Procédé selon I caractérisé en ce que la couche de matière de recouvrement est appliquée par guipage.6. Method according to I characterized in that the layer of covering material is applied by covering.
7. Procédé selon l'une des revendications I à 6 caractérisé en ce que les fibres appartiennent au groupe constitué par les fibres métalliques, minérales ou polymeriques synthéticrues. 7. Method according to one of claims I to 6 characterized in that the fibers belong to the group consisting of metallic, inorganic or polymeric synthetic fibers.
8. Procédé selon l'une des revendications I à 7 caractérisé en ce que la matière constituant la poudre appartient au groupe constitué par les epoxydes, les polyesters, les phénoliques, les polyuréthanes, les polyoléfines modifiées maléiques ou acryliques.8. Method according to one of claims I to 7 characterized in that the material constituting the powder belongs to the group consisting of epoxides, polyesters, phenolics, polyurethanes, maleic or acrylic modified polyolefins.
9. Procédé selon l'une des revendications I à 8 caractérisé en ce que la matière constituant la gaine protectrice appartient au groupe constitué par les thermoplastiques à groupements réactifs avec les thermodurcissables par élévation de température non pendant la constitution du préimprégné mais lors de la constitution du composite final, tels que polyamides à groupements terminaux - COOH ou - NH2, polyols, polyacryliques,etc.... IO. Procédé selon l'une des revendications I à 9 caractérisé en ce que la matière constituant le gainage protecteur appartient au groupe des polymères pouvant être mis en solution et pouvant constituer une gaine par évaporation du solvant de base. il. Procédé selon l'une des revendications I à 10 caractérisé en ce que les matières constituant poudre et gaine seront une action des peroxydes sur des terpolymères.9. Method according to one of claims I to 8 characterized in that the material constituting the protective sheath belongs to the group consisting of thermoplastics with reactive groups with thermosets by raising the temperature not during the constitution of the prepreg but during the constitution of the final composite, such as polyamides with end groups - COOH or - NH2, polyols, polyacrylics, etc. .... IO. Method according to one of claims I to 9 characterized in that the material constituting the protective sheathing belongs to the group of polymers which can be dissolved and which can constitute a sheath by evaporation of the base solvent. he. Method according to one of claims I to 10 characterized in that the materials constituting powder and sheath will be an action of peroxides on terpolymers.
12. Procédé selon l'une des revendications I à 10 caractérisé en ce que les matières constituant poudre et gaine seront une réaction de polycondensation ou d'addition pendant la fabrication du composite de produit maléisé avec des diamines, polyols, epikotes ou diisocyanates.12. Method according to one of claims I to 10 characterized in that the materials constituting powder and sheath will be a polycondensation or addition reaction during the manufacture of the composite of maleized product with diamines, polyols, epikotes or diisocyanates.
13. Procédé selon l'une des revendications I à 10 caractérise en ce que les matières constituant poudres et gaines seront une réaction pendant la fabrication du composite des oligomères diamines de polyamides avec les epikotes, les polyamides dicarboxyliques.13. Method according to one of claims I to 10 characterized in that the materials constituting powders and sheaths will be a reaction during the manufacture of the composite of oligomer diamines of polyamides with epikotes, dicarboxylic polyamides.
14. Procédé selon l'une des revendications I à 10 caractérisé en ce que les matières constituant poudres et gaines seront une réaction pendant la fabrication du composite, de polyoléfines modifiés maléiques avec des polymères acryliques. 14. Method according to one of claims I to 10 characterized in that the materials constituting powders and sheaths will be a reaction during the manufacture of the composite, of maleic modified polyolefins with acrylic polymers.
15. Procédé selon l'une des revendications I à I0 caractérisé en ce que les matières constituant poudres et gaines seront pendant la fabrication du composite une combinaison de résines phénoliques ou epoxyphénoliques avec des résines polyamides compatibles.15. Method according to one of claims I to I0 characterized in that the materials constituting powders and sheaths will be during the manufacture of the composite a combination of phenolic or epoxyphenolic resins with compatible polyamide resins.
16. Procédé selon l'une des revendications I à I0 caractérisé en ce que les matières constituant poudres et gaines font partie du groupe de produits constituant les systèmes (RIM) et préférentiellement à base de caprolactame.16. Method according to one of claims I to I0 characterized in that the materials constituting powders and sheaths are part of the group of products constituting the systems (RIM) and preferably based on caprolactam.
17. Procédé selon l*une des revendications I à I0 caractérisé en ce que les produits disposés sous forme de poudre peuvent être chargés de poudres métalliques (Fe, Cu,Al,etc...).17. Method according to one of claims I to I0 characterized in that the products arranged in powder form can be loaded with metal powders (Fe, Cu, Al, etc.).
18. Procédé selon l'une des revendications I à I0 caractérisé en ce que les produits disposés sous forme de poudre peuvent être chargés ou additionnés de billes de verre pleines ou creuses. 19. Procédé selon l'une des revendications I à I8 caractérisé en ce que le préimprégné est découpé en morceaux pour servir d'éléments de moulage ou d'injection ou disposé de manière à constituer un mat de fibres coupées.18. Method according to one of claims I to I0 characterized in that the products arranged in powder form can be loaded or added with solid or hollow glass beads. 19. Method according to one of claims I to I8 characterized in that the prepreg is cut into pieces to serve as molding or injection elements or arranged so as to constitute a mat of cut fibers.
20. Procédé selon l'une des revendications I à I8 caracterisé en ce que le fil préimprégné est déroulé d'une manière aléatoire par défilement continu pour constituer un mat. Par empilement, élévation de température et ces mats coaatitueront des objets compθβites.20. Method according to one of claims I to I8 characterized in that the prepreg wire is unwound in a random manner by continuous scrolling to constitute a mat. By stacking, rise in temperature and these mats will coaatituate compθβites objects.
21. Procédé selon l'une des revendications I à I8 caractérisé en ce que les fils coupés sont alliés ou fil déroulé pour constituer des mats mixtes. 21. Method according to one of claims I to I8 characterized in that the cut son are alloyed or unwound wire to form mixed mats.
PCT/FR1985/000168 1984-06-26 1985-06-24 Method for fabricating thermo-hardenable or thermo-reactive pre-impregnated materials enabling the fabrication of composite articles WO1986000323A1 (en)

Applications Claiming Priority (2)

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FR8410021A FR2566416B1 (en) 1984-06-26 1984-06-26 PROCESS FOR THE MANUFACTURE OF THERMOSETTING OR THERMOREACTIVE PREPREGNATES FOR THE MANUFACTURE OF COMPOSITE OBJECTS
FR84/10021 1984-06-26

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AU (1) AU4496285A (en)
FR (1) FR2566416B1 (en)
WO (1) WO1986000323A1 (en)

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EP0585992A1 (en) * 1992-07-31 1994-03-09 ENICHEM S.p.A. Mixed-matrix composite material reinforced with continuous fibres
EP0590702A1 (en) * 1992-07-31 1994-04-06 ENIRICERCHE S.p.A. Reinforced composite material with a matrix composed of a mixture of thermoplastic and thermosetting resin
EP0700952A2 (en) * 1994-09-06 1996-03-13 ENICHEM S.p.A. Process for the preparation of a flexible thermoplastic composite filament containing continuous fibres

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EP0274899B1 (en) * 1986-12-25 1994-02-09 Toray Industries, Inc. Highly tough composite materials

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FR1306656A (en) * 1960-08-17 1962-10-19 Leicester Process for producing reinforced synthetic resin articles comprising a reinforcing material coated with a meltable resinous composition
US3305417A (en) * 1963-12-03 1967-02-21 Shell Oil Co Process for preparing preimpregnated strands of fibers and use of resulting productsin making reinforced composites
US3837981A (en) * 1971-05-10 1974-09-24 T Flint Epoxy tape
FR2224516A1 (en) * 1973-04-09 1974-10-31 Ciba Geigy Ag
FR2463159A1 (en) * 1979-08-10 1981-02-20 Inst Nat Rech Chimique Rheologically stable semi-finished prods. contg. thermosetting resins - fibres and fillers, and having good mechanical and electrical properties

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FR1306656A (en) * 1960-08-17 1962-10-19 Leicester Process for producing reinforced synthetic resin articles comprising a reinforcing material coated with a meltable resinous composition
US3305417A (en) * 1963-12-03 1967-02-21 Shell Oil Co Process for preparing preimpregnated strands of fibers and use of resulting productsin making reinforced composites
US3837981A (en) * 1971-05-10 1974-09-24 T Flint Epoxy tape
FR2224516A1 (en) * 1973-04-09 1974-10-31 Ciba Geigy Ag
FR2463159A1 (en) * 1979-08-10 1981-02-20 Inst Nat Rech Chimique Rheologically stable semi-finished prods. contg. thermosetting resins - fibres and fillers, and having good mechanical and electrical properties

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Publication number Priority date Publication date Assignee Title
EP0585992A1 (en) * 1992-07-31 1994-03-09 ENICHEM S.p.A. Mixed-matrix composite material reinforced with continuous fibres
EP0590702A1 (en) * 1992-07-31 1994-04-06 ENIRICERCHE S.p.A. Reinforced composite material with a matrix composed of a mixture of thermoplastic and thermosetting resin
US5380583A (en) * 1992-07-31 1995-01-10 Eniricerche, S.P.A. Mixed-matrix composite thermoplastic and thermosetting material reinforced with continuous fibres
EP0700952A2 (en) * 1994-09-06 1996-03-13 ENICHEM S.p.A. Process for the preparation of a flexible thermoplastic composite filament containing continuous fibres
EP0700952A3 (en) * 1994-09-06 1996-05-01 Enichem Spa Process for the preparation of a flexible thermoplastic composite filament containing continuous fibres
US5658510A (en) * 1994-09-06 1997-08-19 Enichem S.P.A. Process for the preparation of a flexible thermoplastic composite filament containing continuous fibres

Also Published As

Publication number Publication date
AU4496285A (en) 1986-01-24
EP0195776A1 (en) 1986-10-01
FR2566416A1 (en) 1985-12-27
FR2566416B1 (en) 1987-03-20

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