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EP0659923A1 - Glass yarns network and reinforced composite materials with this network - Google Patents

Glass yarns network and reinforced composite materials with this network Download PDF

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Publication number
EP0659923A1
EP0659923A1 EP19940403005 EP94403005A EP0659923A1 EP 0659923 A1 EP0659923 A1 EP 0659923A1 EP 19940403005 EP19940403005 EP 19940403005 EP 94403005 A EP94403005 A EP 94403005A EP 0659923 A1 EP0659923 A1 EP 0659923A1
Authority
EP
European Patent Office
Prior art keywords
network
glass
wires
composite material
threads
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.)
Granted
Application number
EP19940403005
Other languages
German (de)
French (fr)
Other versions
EP0659923B1 (en
Inventor
Joseph Gulino
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.)
Saint Gobain Adfors SAS
Original Assignee
Vetrotex France SA
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Filing date
Publication date
Application filed by Vetrotex France SA filed Critical Vetrotex France SA
Publication of EP0659923A1 publication Critical patent/EP0659923A1/en
Application granted granted Critical
Publication of EP0659923B1 publication Critical patent/EP0659923B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B21/00—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B21/14—Fabrics characterised by the incorporation by knitting, in one or more thread, fleece, or fabric layers, of reinforcing, binding, or decorative threads; Fabrics incorporating small auxiliary elements, e.g. for decorative purposes
    • D04B21/16—Fabrics characterised by the incorporation by knitting, in one or more thread, fleece, or fabric layers, of reinforcing, binding, or decorative threads; Fabrics incorporating small auxiliary elements, e.g. for decorative purposes incorporating synthetic threads
    • D04B21/165—Fabrics characterised by the incorporation by knitting, in one or more thread, fleece, or fabric layers, of reinforcing, binding, or decorative threads; Fabrics incorporating small auxiliary elements, e.g. for decorative purposes incorporating synthetic threads with yarns stitched through one or more layers or tows, e.g. stitch-bonded fabrics
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/002—Inorganic yarns or filaments
    • D04H3/004—Glass yarns or filaments
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/10—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically
    • D04H3/115—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically by applying or inserting filamentary binding elements
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/12—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with filaments or yarns secured together by chemical or thermo-activatable bonding agents, e.g. adhesives, applied or incorporated in liquid or solid form
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2403/00—Details of fabric structure established in the fabric forming process
    • D10B2403/02—Cross-sectional features
    • D10B2403/024—Fabric incorporating additional compounds
    • D10B2403/0241—Fabric incorporating additional compounds enhancing mechanical properties
    • D10B2403/02411—Fabric incorporating additional compounds enhancing mechanical properties with a single array of unbent yarn, e.g. unidirectional reinforcement fabrics
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00—Industrial
    • D10B2505/02—Reinforcing materials; Prepregs
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24058—Structurally defined web or sheet [e.g., overall dimension, etc.] including grain, strips, or filamentary elements in respective layers or components in angular relation
    • Y10T428/24074—Strand or strand-portions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24058—Structurally defined web or sheet [e.g., overall dimension, etc.] including grain, strips, or filamentary elements in respective layers or components in angular relation
    • Y10T428/24124—Fibers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24628—Nonplanar uniform thickness material
    • Y10T428/24636—Embodying mechanically interengaged strand[s], strand-portion[s] or strand-like strip[s] [e.g., weave, knit, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/10—Scrim [e.g., open net or mesh, gauze, loose or open weave or knit, etc.]
    • Y10T442/102—Woven scrim
    • Y10T442/172—Coated or impregnated

Definitions

  • the present invention relates to a network of parallel glass strands intended to serve as reinforcement for an organic mixture.
  • Glass strands can be used in a variety of ways to reinforce thermosetting or thermoplastic organic materials.
  • a composite part obtained from such reinforced materials, is mechanically stressed during its use, it is known to produce said part from glass strands oriented in a preferred direction. Often this type of part is produced by impregnating several layers of glass strands of organic material in the form of unidirectional layers.
  • the first resides in the fact that the wires constituting these layers can deform, move relative to one another, during the manipulations which take place between the time of the manufacture of said layers and that of the production of the composite part.
  • the second difficulty resides in the production of a complex composite part, in which the reinforcements arranged in parallel are oriented in a plane in at least two different directions to follow the shape of said part. Indeed, such a part requires the juxtaposition of at least two plies of parallel reinforcements in two different orientations. This distribution of reinforcements results in a discontinuity when passing from one layer to another. If the zone in which this discontinuity is located, whether on the surface or within the composite material, is subjected to stresses, over-stresses will appear in this zone with the consequence of the risk of rapid degradation of the material. On the other hand, the different orientations of the plies of the reinforcement also induce over-stresses over the entire periphery of the part made of composite material.
  • the present invention relates to a network of parallel glass strands such that said strands can be used as reinforcements in a complex composite part, avoiding any discontinuity within said part.
  • the subject of the present invention is a network of parallel wires capable of being deformed and which has sufficient stability to be handled without risking causing the accidental displacement of one or more wires during the production of a complex composite part.
  • the subject of the present invention is a network of parallel glass wires in which the mode of connection of said wires to each other is such that it practically does not affect the fatigue strength of a composite part in which said network serves reinforcement.
  • the present invention also relates to a composite material reinforced by such a network of parallel glass wires.
  • a network of parallel glass wires intended to be associated with an organic mixture to produce a composite material
  • said network being formed of a multiplicity of continuous glass wires, arranged in parallel in the form of a sheet. flat, said threads being connected to each other by threads arranged transversely to said ply according to a binding method called chain, the glass threads being made partially integral by means of an organic thermoplastic binder, and the binding threads having a modulus of elasticity lower than that of glass thread and a melting or softening temperature higher than the melting or softening temperature of the binder.
  • the manipulation of the glass sheet, the deformation of the network of parallel glass wires associated with it and the conservation of this deformation are greatly facilitated by the deposition of an organic material, liquid or in the form of powder on the surface of the tablecloth.
  • the quantity by weight of organic material deposited is generally greater than 0.5% relative to the weight of the sheet and, preferably, less than 2%.
  • the binder is deposited at a temperature below its softening or melting point and reheated on the surface of the web to a temperature above its softening or melting point in order to ensure adhesion of the binder to the surface. of the tablecloth.
  • softening is meant the passage from the solid phase to a sufficiently viscous phase to ensure the adhesion of the binder to the web.
  • the softening or melting temperature of the chosen binder is generally greater than approximately 40 ° C and less than approximately 130 ° C.
  • consolidation is meant a state such that the intrinsic characteristics of the network of parallel glass wires and of the deformed sheet are not altered by successive manipulations.
  • One of the advantageous characteristics of the network of glass strands according to the invention is its ability to be able to deform, for example in a plane, so as to bend, in a determined zone, the orientation of the glass strands constituting the sheet.
  • This change of orientation is carried out, for all of the son of the ply, with respect to one of the transverse son which link said son.
  • these transverse threads will be called in the following description the binding threads.
  • the geometric deformation of the network of parallel glass strands must occur at a temperature above the point of softening or melting of the binder.
  • the binding threads used are made of a material whose melting or softening temperature is higher than the melting or softening temperature of the binder.
  • the network can be deformed and consolidated by cooling several times without ever losing the orientation potential of the wires passing through the loops of the chain.
  • the binding wires when they are made of glass considerably lower the fatigue resistance of this material, because of transverse orientation effects relative to the main direction of mechanical stress of the material.
  • the method of tying the wires of the web of the network according to the invention is a chain and, preferably, a chain with closed meshes. This method of binding by a chain allows the strands of the glass sheet to be held within it, stretched and without ripples, which considerably increases the fatigue strength of a composite material such reinforcement.
  • this method of binding makes it possible to maintain a constant and defined spacing between the glass strands of the sheet in order to ensure good flow of the organic resin within the reinforcement during the molding phase for obtaining the composite material.
  • this method of binding makes it possible to avoid any risk of random displacement of the strands of glass strands during the molding phase when the injection or compression pressure becomes high, which improves the reproducibility of the molded parts.
  • the yarn chosen as the tying yarn or chain is preferably an organic yarn.
  • the binding thread or chain can be made of an identical or similar material.
  • the aptitude for deformation of the network of glass strands according to the invention is closely dependent on the interval separating two consecutive bonding threads or chains. To obtain an inflection of the ply of threads parallel in a plane, without causing folds or undulations, it is preferable that the smallest interval between two consecutive bonding threads is at least equal to 5 millimeters.
  • the binding wires in the network of wires according to the invention are generally regularly spaced.
  • the glass wires can be distributed in the sheet in the form of a series of wicks, each wick being formed by the union of several wires.
  • the wicks forming the sheet have a titer of at least 300 tex.
  • the glass strands, whether or not distributed in the form of wicks, are themselves made up of a multiplicity of continuous filaments whose average diameter is at least equal to 10 micrometers.
  • the network of wires according to the invention is used to reinforce organic thermosetting or thermoplastic materials.
  • the composite material produced comprises at least one layer of such a network.
  • the layer or layers of wires which reinforce it may each consist of a network according to the invention, the web of which is deformed with respect to at least one binding wire, so that the wires are distributed in at least two groups of parallel wires making a determined angle between them.
  • the composite material can comprise one or more plies of parallel wires which, after one or more deformations, have remained flat. Each deformation then simply consisted of a rotation in the initial plane of each thread or wick around the different chain stitches of a determined binding thread.
  • the composite material can also comprise one or more plies which, after one or more deformations, have a curvature, a bending with respect to the initial plane of the ply.
  • Each deformation then consisted of a rotation of each wire or wick around at least one tying wire, chosen as the axis of deformation, so as to form a determined angle with respect to the initial plane of the web.
  • the network of parallel wires according to the invention thus makes it possible to produce three-dimensional composite parts of complex shape.
  • This figure schematically represents a fragment of a network of glass strands according to the invention.
  • This network consists of a series of roving strands 10 arranged parallel to each other in a plane.
  • Each wick has a titer of 1200 tex and it is made up of filaments whose average diameter is of the order of 17 micrometers.
  • the layer of locks 10 is held in place by a closed chain 11 made up of a polyester thread with a count of 50 dtex.
  • the locks 10 are linked to each other by said chain using a loom of the knitted type with thrown stitches.
  • the interval "d" between two consecutive chains is 8 millimeters.
  • this network can be deformed with respect to the chain 12.
  • the locks 10 have pivoted by an angle ⁇ using the loops of the chain 12 as hinges.
  • This change in orientation is carried out without any crease or undulation of the web.
  • the same network can be deformed in relation to several chains to follow complex shapes. Thanks to this great flexibility, the network according to the invention can play the same role as several plies juxtaposed and oriented differently, but without having any discontinuity from one end of the ply of glass strands to the other.
  • a flat plate, curved at its two ends, 70 cm long and 10 cm wide was produced by stacking 10 layers of a network of strands of glass strands as defined above.
  • Each layer is formed by a network of strands of threads onto which a powdered thermoplastic binder has previously been deposited.
  • This binder deposited at a rate of 1% by weight of glass is a polyester sold under the reference NEOXIL 940 HF-2B by the company DSM.
  • the deformation of the network is consolidated by cooling, after a heat treatment at 80 ° C.
  • the stack produced was impregnated with a resin constituted by a system marketed by THE DOW CHEMICAL Co under the trademarks D.E.H. 39 and D.E.R. 332.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)
  • Nonwoven Fabrics (AREA)
  • Woven Fabrics (AREA)

Abstract

The present invention relates to a network of parallel glass yarns intended to serve as a reinforcement for an organic substance and to the composite material resulting from this. This network consists of a multiplicity of continuous glass yarns arranged in parallel in the form of a plane web, the said yarns being connected to one another by means of yarns arranged transversely to the said web by a binding method known as chain stitch, the glass yarns being partially fixed to one another by means of a thermoplastic organic binder, and the binding yarns having a modulus of elasticity lower than that of the glass yarns and a melting or softening temperature higher than the melting or softening temperature of the binder. The invention is used for producing articles subjected to mechanical forces. <IMAGE>

Description

La présente invention concerne un réseau de fils de verre parallèles destiné à servir de renfort d'un mélange organique.The present invention relates to a network of parallel glass strands intended to serve as reinforcement for an organic mixture.

Les fils de verre peuvent être utilisés de multiples manières pour renforcer des matières organiques thermodurcissables ou thermoplastiques. Lorsqu'une pièce composite, obtenue à partir de telles matières renforcées est sollicitée mécaniquement lors de son emploi, il est connu de réaliser ladite pièce à partir de fils de verre orientés selon une direction privilégiée. Souvent ce type de pièce est réalisé en imprégnant de matière organique plusieurs couches de fils de verre se présentant sous la forme de nappes unidirectionnelles.Glass strands can be used in a variety of ways to reinforce thermosetting or thermoplastic organic materials. When a composite part, obtained from such reinforced materials, is mechanically stressed during its use, it is known to produce said part from glass strands oriented in a preferred direction. Often this type of part is produced by impregnating several layers of glass strands of organic material in the form of unidirectional layers.

La réalisation d'une pièce composite complexe à partir d'un tel renfort se heurte à plusieurs difficultés.The production of a complex composite part from such a reinforcement encounters several difficulties.

La première réside dans le fait que les fils constituant ces nappes peuvent se déformer, se déplacer les uns par rapport aux autres, au cours des manipulations qui interviennent entre le moment de la fabrication desdites nappes et celui de la réalisation de la pièce composite.The first resides in the fact that the wires constituting these layers can deform, move relative to one another, during the manipulations which take place between the time of the manufacture of said layers and that of the production of the composite part.

Pour remédier à cet inconvénient, il est connu, d'après la demande de brevet français FR-A-2 594 858 de réaliser une nappe de fils parallèles, par exemple de fils de verre, assemblés à l'aide de fils de liage transversaux thermofusibles. On obtient une nappe dont les fils ne peuvent plus se déplacer les uns par rapport aux autres grâce à un traitement thermique, qui provoque la fusion des fils de liage et, par là même, le collage des fils de verre entre eux. Après ce traitement, la nappe peut être manipulée, découpée sans aucun risque de déformation. La rigidité ainsi conférée à la nappe entrave toute déformation ultérieure qu'il serait souhaitable de lui faire subir lors de la réalisation d'une pièce composite.To remedy this drawback, it is known from French patent application FR-A-2,594,858 to produce a sheet of parallel threads, for example glass threads, assembled using transverse binding threads hot melt. A sheet is obtained whose threads can no longer move relative to one another by means of a heat treatment, which causes the bonding threads to merge and, thereby, the bonding of the glass threads together. After this treatment, the sheet can be handled and cut without any risk of deformation. The rigidity thus imparted to the ply hinders any subsequent deformation that it would be desirable to subject it to during the production of a composite part.

La seconde difficulté réside dans la réalisation d'une pièce composite complexe, dans lequel les renforts disposés parallèlement sont orientés dans un plan selon au moins deux directions différentes pour suivre la forme de ladite pièce. En effet, une telle pièce nécessite la juxtaposition d'au moins deux nappes de renforts parallèles selon deux orientations différentes. Cette répartition des renforts se traduit par une discontinuité lorsqu'on passe d'une nappe à l'autre. Si la zone dans laquelle se trouve cette discontinuité, qu'elle soit en surface ou au sein du matériau composite, est soumise à des efforts, des surcontraintes apparaîtront dans cette zone avec comme conséquence le risque d'une dégradation rapide du matériau. D'autre part, les orientations différentes des nappes du renfort induisent également des surcontraintes sur toute la périphérie de la pièce en matériau composite.The second difficulty resides in the production of a complex composite part, in which the reinforcements arranged in parallel are oriented in a plane in at least two different directions to follow the shape of said part. Indeed, such a part requires the juxtaposition of at least two plies of parallel reinforcements in two different orientations. This distribution of reinforcements results in a discontinuity when passing from one layer to another. If the zone in which this discontinuity is located, whether on the surface or within the composite material, is subjected to stresses, over-stresses will appear in this zone with the consequence of the risk of rapid degradation of the material. On the other hand, the different orientations of the plies of the reinforcement also induce over-stresses over the entire periphery of the part made of composite material.

La présente invention a pour objet, un réseau de fils de verre parallèles tel que lesdits fils puissent être utilisés comme renforts dans une pièce composite complexe, en évitant toute discontinuité au sein de ladite pièce.The present invention relates to a network of parallel glass strands such that said strands can be used as reinforcements in a complex composite part, avoiding any discontinuity within said part.

La présente invention a pour objet, un réseau de fils parallèles susceptibles d'être déformé et qui possède une stabilité suffisante pour être manipulé sans risquer de provoquer le déplacement accidentel d'un ou plusieurs fils lors de la réalisation d'une pièce composite complexe.The subject of the present invention is a network of parallel wires capable of being deformed and which has sufficient stability to be handled without risking causing the accidental displacement of one or more wires during the production of a complex composite part.

La présente invention a pour objet, un réseau de fils de verre parallèles dans lequel le mode de liaison desdits fils entre eux est tel qu'il n'affecte pratiquement pas la résistance à la fatigue d'une pièce composite dans lequel ledit réseau sert de renfort.The subject of the present invention is a network of parallel glass wires in which the mode of connection of said wires to each other is such that it practically does not affect the fatigue strength of a composite part in which said network serves reinforcement.

La présente invention a également pour objet un matériau composite renforcé par un tel réseau de fils de verre parallèles.The present invention also relates to a composite material reinforced by such a network of parallel glass wires.

Ces buts sont atteints grâce à un réseau de fils de verre parallèles destiné à être associé à un mélange organique pour réaliser un matériau composite, ledit réseau étant formé d'une multiplicité de fils de verre continus, disposés parallèlement sous la forme d'une nappe plane, lesdits fils étant reliés les uns aux autres par des fils disposés transversalement à ladite nappe selon un mode de liage appelé chaînette, les fils de verre étant rendus partiellement solidaires au moyen d'un liant organique thermoplastique, et les fils de liage présentant un module d'élasticité inférieur à celui du fil de verre et une température de fusion ou de ramollissement supérieure à la température de fusion ou de ramollissement du liant.These aims are achieved thanks to a network of parallel glass wires intended to be associated with an organic mixture to produce a composite material, said network being formed of a multiplicity of continuous glass wires, arranged in parallel in the form of a sheet. flat, said threads being connected to each other by threads arranged transversely to said ply according to a binding method called chain, the glass threads being made partially integral by means of an organic thermoplastic binder, and the binding threads having a modulus of elasticity lower than that of glass thread and a melting or softening temperature higher than the melting or softening temperature of the binder.

La manipulation de la nappe de verre, la déformation du réseau de fils de verre parallèles qui lui sont associés et la conservation de cette déformation sont grandement facilitées par le dépôt d'une matière organique, liquide ou sous forme de poudre à la surface de la nappe. La quantité pondérale de matière organique déposée est généralement supérieure à 0,5% par rapport au poids de la nappe et, de préférence, inférieure à 2%.The manipulation of the glass sheet, the deformation of the network of parallel glass wires associated with it and the conservation of this deformation are greatly facilitated by the deposition of an organic material, liquid or in the form of powder on the surface of the tablecloth. The quantity by weight of organic material deposited is generally greater than 0.5% relative to the weight of the sheet and, preferably, less than 2%.

Par commodité, cette matière organique de dépôt sera appelée dans la suite de la description «liant».For convenience, this organic deposition material will be called in the following description "binder".

Le liant est déposé à une température inférieure à sa température de ramollissement ou de fusion et réchauffé à la surface de la nappe jusqu'à une température supérieure à son point de ramollissement ou de fusion afin d'assurer l'adhésion du liant à la surface de la nappe. Par ramollissement, on entend le passage de la phase solide à une phase suffisamment visqueuse pour assurer l'adhésion du liant à la nappe. La température de ramollissement ou de fusion du liant choisi est généralement supérieure à environ 40°C et inférieur à environ 130°C.The binder is deposited at a temperature below its softening or melting point and reheated on the surface of the web to a temperature above its softening or melting point in order to ensure adhesion of the binder to the surface. of the tablecloth. By softening is meant the passage from the solid phase to a sufficiently viscous phase to ensure the adhesion of the binder to the web. The softening or melting temperature of the chosen binder is generally greater than approximately 40 ° C and less than approximately 130 ° C.

Après refroidissement et retour au-dessous de cette température de ramollissement ou de fusion du liant et de la nappe, cette dernière présente un état de consolidation tel que sa manipulation en est grandement facilitée. Par consolidation, on entend un état tel que les caractéristiques intrinsèques du réseau de fils de verre parallèles et de la nappe déformée ne soient pas altérées par des manipulations successives.After cooling and returning below this softening or melting temperature of the binder and of the sheet, the latter has a state of consolidation such that its handling is greatly facilitated. By consolidation is meant a state such that the intrinsic characteristics of the network of parallel glass wires and of the deformed sheet are not altered by successive manipulations.

L'une des caractéristiques avantageuses du réseau de fils de verre selon l'invention est son aptitude à pouvoir se déformer, par exemple dans un plan, de manière à infléchir, dans une zone déterminée l'orientation des fils de verre constituant la nappe. Ce changement d'orientation est effectué, pour l'ensemble des fils de la nappe, par rapport à un des fils transversaux qui lient lesdits fils. Par commodité, ces fils transversaux seront appelés dans la suite de la description fils de liage. Par ce changement d'orientation on peut ainsi obtenir l'équivalent de deux nappes liées l'une à l'autre et faisant entre elles un angle bien défini.One of the advantageous characteristics of the network of glass strands according to the invention is its ability to be able to deform, for example in a plane, so as to bend, in a determined zone, the orientation of the glass strands constituting the sheet. This change of orientation is carried out, for all of the son of the ply, with respect to one of the transverse son which link said son. For convenience, these transverse threads will be called in the following description the binding threads. By this change of orientation we can thus obtain the equivalent of two layers linked to each other and forming a well-defined angle between them.

La déformation géométrique du réseau de fils de verre parallèles doit se produire à une température supérieure au point de ramollissement ou de fusion du liant. Le réseau de fils de verre ainsi déformé, après retour à une température inférieure à la température de ramollissement ou de fusion du liant, présente également un état de consolidation tel que sa manipulation en est grandement facilitée et sa géométrie de déformation facilement conservée.The geometric deformation of the network of parallel glass strands must occur at a temperature above the point of softening or melting of the binder. The network of glass strands thus deformed, after returning to a temperature below the softening or melting temperature of the binder, also presents a state of consolidation such that its handling is greatly facilitated and its deformation geometry easily preserved.

L'une des caractéristiques avantageuses du réseau de fils selon l'invention est que les fils de liage utilisés sont constitués d'une matière dont la température de fusion ou de ramollissement est supérieure à la température de fusion ou de ramollissement du liant. Ainsi le réseau peut-il être déformé et consolidé par refroidissement à plusieurs reprises sans jamais perdre la potentialité d'orientation des fils passant à travers les boucles de la chaînette.One of the advantageous characteristics of the network of threads according to the invention is that the binding threads used are made of a material whose melting or softening temperature is higher than the melting or softening temperature of the binder. Thus the network can be deformed and consolidated by cooling several times without ever losing the orientation potential of the wires passing through the loops of the chain.

Lors de la réalisation d'un matériau composite renforcé par un réseau de fils de verre parallèles du type de celui de l'invention, les fils de liage lorsqu'ils sont en verre, abaissent considérablement la résistance à la fatigue de ce matériau, à cause des effets d'orientation transverse par rapport à la direction principale de sollicitation mécanique du matériau.When producing a composite material reinforced by a network of parallel glass wires of the type of that of the invention, the binding wires when they are made of glass considerably lower the fatigue resistance of this material, because of transverse orientation effects relative to the main direction of mechanical stress of the material.

Un tel phénomène est nettement réduit lorsque le fil de liage est constitué d'une matière dont le module d'élasticité est inférieur à celui du verre, et cela d'autant mieux que ce module se rapproche de celui de la matrice organique à renforcer.Such a phenomenon is significantly reduced when the binding wire is made of a material whose modulus of elasticity is lower than that of glass, and this is all the better as this modulus approaches that of the organic matrix to be reinforced.

Le mode de liage des fils de la nappe du réseau selon l'invention est une chaînette et, de préférence, une chaînette à mailles fermées. Ce mode de liage par une chaînette permet aux fils de la nappe de verre d'être maintenus au sein de celle-ci, tendus et sans ondulations ce qui permet d'accroître considérablement la résistance en fatigue d'un matériau composite constitué d'un tel renfort.The method of tying the wires of the web of the network according to the invention is a chain and, preferably, a chain with closed meshes. This method of binding by a chain allows the strands of the glass sheet to be held within it, stretched and without ripples, which considerably increases the fatigue strength of a composite material such reinforcement.

D'autre part, ce mode de liage permet de conserver un espacement constant et défini entre les fils de verre de la nappe afin d'assurer un bon écoulement de la résine organique au sein du renfort durant la phase de moulage pour l'obtention du matériau composite.On the other hand, this method of binding makes it possible to maintain a constant and defined spacing between the glass strands of the sheet in order to ensure good flow of the organic resin within the reinforcement during the molding phase for obtaining the composite material.

Enfin, ce mode de liage, de par sa cohésion, permet d'éviter tout risque de déplacement aléatoire des mèches de fils de verre durant la phase de moulage lorsque la pression d'injection ou de compression devient élevée, ce qui améliore la reproductibilité des pièces moulées.Finally, this method of binding, by virtue of its cohesion, makes it possible to avoid any risk of random displacement of the strands of glass strands during the molding phase when the injection or compression pressure becomes high, which improves the reproducibility of the molded parts.

Le fil choisi comme fil de liage ou chaînette est de préférence un fil organique. Lorsque le réseau de fils selon l'invention est destiné à renforcer une matière organique déterminée, le fil de liage ou chaînette peut être constitué d'une matière identique ou similaire.The yarn chosen as the tying yarn or chain is preferably an organic yarn. When the network of threads according to the invention is intended to reinforce a determined organic material, the binding thread or chain can be made of an identical or similar material.

L'aptitude à la déformation du réseau de fils de verre selon l'invention est étroitement dépendante de l'intervalle séparant deux fils de liage ou chaînettes consécutifs. Pour obtenir une inflexion de la nappe de fils parallèle dans un plan, sans provoquer de plis ou d'ondulations, il est préférable que l'intervalle le plus faible entre deux fils de liage consécutifs soit au moins égal à 5 millimètres. Les fils de liage dans le réseau de fils selon l'invention sont en général régulièrement espacés.The aptitude for deformation of the network of glass strands according to the invention is closely dependent on the interval separating two consecutive bonding threads or chains. To obtain an inflection of the ply of threads parallel in a plane, without causing folds or undulations, it is preferable that the smallest interval between two consecutive bonding threads is at least equal to 5 millimeters. The binding wires in the network of wires according to the invention are generally regularly spaced.

Dans le réseau de fils, les fils de verre peuvent être répartis dans la nappe sous la forme d'une série de mèches, chaque mèche étant formée par la réunion de plusieurs fils. Dans le cadre de l'invention, les mèches formant la nappe ont un titre d'au moins 300 tex. Les fils de verre, répartis ou non sous forme de mèches, sont eux-mêmes constitués d'une multiplicité de filaments continus dont le diamètre moyen est au moins égal à 10 micromètres.In the network of wires, the glass wires can be distributed in the sheet in the form of a series of wicks, each wick being formed by the union of several wires. In the context of the invention, the wicks forming the sheet have a titer of at least 300 tex. The glass strands, whether or not distributed in the form of wicks, are themselves made up of a multiplicity of continuous filaments whose average diameter is at least equal to 10 micrometers.

Le réseau de fils selon l'invention est utilisé pour renforcer des matières organiques thermodurcissables ou thermoplastiques. Le matériau composite réalisé comprend au moins une couche d'un tel réseau. Dans ce matériau la ou les couches de fils qui le renforcent peuvent être constituées chacune d'un réseau selon l'invention dont la nappe est déformée par rapport à au moins un fil de liage, de manière que les fils sont répartis en au moins deux groupes de fils parallèles faisant entre eux un angle déterminé. Ainsi, le matériau composite peut comprendre une ou plusieurs nappes de fils parallèles qui, après une ou plusieurs déformations, sont restées planes. Chaque déformation a alors simplement consisté en une rotation dans le plan initial de chaque fil ou mèche autour des différents points de chaînette d'un fil de liage déterminé.The network of wires according to the invention is used to reinforce organic thermosetting or thermoplastic materials. The composite material produced comprises at least one layer of such a network. In this material, the layer or layers of wires which reinforce it may each consist of a network according to the invention, the web of which is deformed with respect to at least one binding wire, so that the wires are distributed in at least two groups of parallel wires making a determined angle between them. Thus, the composite material can comprise one or more plies of parallel wires which, after one or more deformations, have remained flat. Each deformation then simply consisted of a rotation in the initial plane of each thread or wick around the different chain stitches of a determined binding thread.

Le matériau composite peut également comprendre une ou plusieurs nappes qui, après une ou plusieurs déformations, présentent une courbure, un cintrage par rapport au plan initial de la nappe. Chaque déformation a alors consisté en une rotation de chaque fil ou mèche autour d'au moins un fil de liage, choisi comme axe de déformation, de manière à former un angle déterminé par rapport au plan initial de la nappe. Le réseau de fils parallèles selon l'invention permet ainsi de réaliser des pièces composites tridimensionnelles de forme complexe.The composite material can also comprise one or more plies which, after one or more deformations, have a curvature, a bending with respect to the initial plane of the ply. Each deformation then consisted of a rotation of each wire or wick around at least one tying wire, chosen as the axis of deformation, so as to form a determined angle with respect to the initial plane of the web. The network of parallel wires according to the invention thus makes it possible to produce three-dimensional composite parts of complex shape.

Les avantages de la présente invention seront mieux compris à travers l'exemple décrit ci-après qui est illustré par une figure unique.The advantages of the present invention will be better understood through the example described below which is illustrated by a single figure.

Cette figure représente schématiquement un fragment d'un réseau de fils de verre selon l'invention.This figure schematically represents a fragment of a network of glass strands according to the invention.

Ce réseau est constitué d'une série de mèches de stratifil 10 disposées parallèlement les unes aux autres dans un plan. Chaque mèche a un titre de 1200 tex et elle est constituée de filaments dont le diamètre moyen est de l'ordre de 17 micromètres. La nappe de mèches 10 est maintenue par une chaînette fermée 11 constituée d'un fil polyester d'un titre de 50 dtex. Les mèches 10 sont liées entre elles par ladite chaînette en utilisant un métier du type tricot à mailles jetées. L'intervalle « d » entre deux chaînettes consécutives est de 8 millimètres.This network consists of a series of roving strands 10 arranged parallel to each other in a plane. Each wick has a titer of 1200 tex and it is made up of filaments whose average diameter is of the order of 17 micrometers. The layer of locks 10 is held in place by a closed chain 11 made up of a polyester thread with a count of 50 dtex. The locks 10 are linked to each other by said chain using a loom of the knitted type with thrown stitches. The interval "d" between two consecutive chains is 8 millimeters.

Comme l'indique la figure, ce réseau peut être déformé par rapport à la chaînette 12. En restant dans un plan les mèches 10 ont pivoté d'un angle α en utilisant les boucles de la chaînette 12 comme charnières. Ce changement d'orientation est effectué sans formation de pli ou d'ondulation de la nappe. Le même réseau peut être déformé par rapport à plusieurs chaînettes pour suivre des formes complexes. Grâce à cette grande souplesse, le réseau selon l'invention peut jouer le même rôle que plusieurs nappes juxtaposées et orientées différemment, mais sans présenter de discontinuité d'une extrémité de la nappe de fils de verre à l'autre.As indicated in the figure, this network can be deformed with respect to the chain 12. By remaining in a plane the locks 10 have pivoted by an angle α using the loops of the chain 12 as hinges. This change in orientation is carried out without any crease or undulation of the web. The same network can be deformed in relation to several chains to follow complex shapes. Thanks to this great flexibility, the network according to the invention can play the same role as several plies juxtaposed and oriented differently, but without having any discontinuity from one end of the ply of glass strands to the other.

Ainsi, une plaque plane, incurvée à ses deux extrémités, de 70 cm de longueur de 10 cm de largeur a été réalisée en empilant 10 couches d'un réseau de mèches de fils de verre tel que défini précédemment.Thus, a flat plate, curved at its two ends, 70 cm long and 10 cm wide was produced by stacking 10 layers of a network of strands of glass strands as defined above.

Chaque couche est formée d'un réseau de mèches de fils sur lequel a été déposé préalablement un liant thermoplastique en poudre. Ce liant déposé à raison de 1% en poids de verre est un polyester commercialisé sous la référence NEOXIL 940 HF-2B par la Société DSM. La déformation du réseau est consolidée par le refroidissement, après un traitement thermique à 80°C.Each layer is formed by a network of strands of threads onto which a powdered thermoplastic binder has previously been deposited. This binder deposited at a rate of 1% by weight of glass is a polyester sold under the reference NEOXIL 940 HF-2B by the company DSM. The deformation of the network is consolidated by cooling, after a heat treatment at 80 ° C.

L'empilement réalisé a été imprégné d'une résine constituée par un système commercialisé par la Société THE DOW CHEMICAL Co sous les marques de fabrique D.E.H. 39 et D.E.R. 332.The stack produced was impregnated with a resin constituted by a system marketed by THE DOW CHEMICAL Co under the trademarks D.E.H. 39 and D.E.R. 332.

Claims (9)

Réseau de fils parallèles destiné à être associé à un mélange organique pour réaliser un matériau composite, ledit réseau étant formé d'une multiplicité de fils de verre continus, disposés parallèlement sous la forme d'une nappe plane, lesdits fils étant reliés les uns aux autres par des fils disposés transversalement à ladite nappe selon un mode de liage appelé chaînette, les fils de verre étant rendus partiellement solidaires au moyen d'un liant organique thermoplastique, et les fils de liage présentant un module d'élasticité inférieur à celui du fils de verre et une température de fusion ou de ramollisement supérieure à la température de fusion ou de ramollissement du liant.Network of parallel wires intended to be associated with an organic mixture to produce a composite material, said network being formed of a multiplicity of continuous glass wires, arranged in parallel in the form of a flat sheet, said wires being connected to each other others by wires arranged transversely to said ply according to a binding method called chain, the glass wires being made partially integral by means of an organic thermoplastic binder, and the binding wires having a modulus of elasticity lower than that of the son glass and a melting or softening temperature higher than the melting or softening temperature of the binder. Réseau selon la revendication 1, caractérisé en ce que la température de fusion du liant est comprise entre environ 40 et 130°C.Network according to claim 1, characterized in that the melting point of the binder is between approximately 40 and 130 ° C. Réseau selon la revendication 1 ou 2, caractérisé en ce que les fils de liage sont régulièrement espacés selon un intervalle d'au moins 5 millimètres environ.Network according to claim 1 or 2, characterized in that the binding threads are regularly spaced at an interval of at least about 5 millimeters. Réseau selon l'une quelconque des revendications précédentes, caractérisé en ce que les fils de verre sont répartis dans la nappe sous la forme d'une série de mèches, chaque mèche ayant un titre au moins égal à 300 Tex.Network according to any one of the preceding claims, characterized in that the glass strands are distributed in the sheet in the form of a series of wicks, each wick having a titer at least equal to 300 Tex. Réseau selon l'une quelconque des revendications précédentes, caractérisé en ce que les filaments de verre sont constitués de filaments dont le diamètre moyen est au moins égal à 10 micromètres.Network according to any one of the preceding claims, characterized in that the glass filaments consist of filaments whose average diameter is at least equal to 10 micrometers. Matériau composite formé d'un mélange organique thermodurcissable ou thermoplastique renforcé par des fils de verre, caractérisé en ce qu'il comprend au moins une couche d'un réseau de fils de verre tel que défini par l'une quelconque des revendications 1 à 5.Composite material formed from a thermosetting or thermoplastic organic mixture reinforced with glass strands, characterized in that it comprises at least one layer of a network of glass strands as defined by any one of Claims 1 to 5 . Matériau composite selon la revendication 6, caractérisé en ce que la ou les couches de fils qui renforcent ledit matériau sont constituées chacune d'un réseau dont la nappe de fils de verre est déformée par rapport à au moins un fil de liage, de manière que les fils sont répartis en au moins deux groupes de fils parallèles faisant entre eux un angle déterminé.Composite material according to claim 6, characterized in that the layer or layers of threads which reinforce said material each consist of a network, the sheet of glass threads of which is deformed with respect to at least one bonding thread, so that the wires are divided into at least two groups of parallel wires forming a determined angle between them. Matériau composite selon la revendication 7, caractérisé en ce que la nappe est déformée en demeurant dans un plan, chaque fil ou mèche formant ladite nappe ayant subi une rotation autour de chaque axe perpendiculaire à ladite nappe et passant dans la zone de contact entre ledit fil ou ladite mèche et le fil de liage choisi comme axe de déformation.Composite material according to claim 7, characterized in that the ply is deformed while remaining in a plane, each wire or wick forming said ply having been rotated around each axis perpendicular to said ply and passing through the contact zone between said wire or said wick and the binding wire chosen as the deformation axis. Matériau composite selon l'une des revendications 6 à 8, caractérisé en ce qu'il comprend au moins deux couches d'un réseau formé d'une nappe de fils de verre rendus solidaires par une chaînette polyester, lesdites couches renforçant un mélange à base de résine époxyde.Composite material according to one of claims 6 to 8, characterized in that it comprises at least two layers of a network formed by a layer of glass threads made integral by a polyester chain, said layers reinforcing a base mixture epoxy resin.
EP19940403005 1993-12-24 1994-12-23 Glass yarns network and reinforced composite materials with this network Expired - Lifetime EP0659923B1 (en)

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FR9315604A FR2714398B1 (en) 1993-12-24 1993-12-24 Network of glass wires and composite material reinforced by said network.

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FR2714398B1 (en) 1996-03-08
DE69410967T2 (en) 1999-03-11
DE69410967D1 (en) 1998-07-16
EP0659923B1 (en) 1998-06-10
US5520984A (en) 1996-05-28
JPH07216686A (en) 1995-08-15
ES2119117T3 (en) 1998-10-01

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