Classifications

• • 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
  • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
  • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
  • D04H1/44—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling
  • D04H1/46—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
  • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
  • B29C70/06—Fibrous reinforcements only
  • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
  • B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
  • B29C70/24—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in at least three directions forming a three dimensional structure
• • 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
  • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
  • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
  • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
  • D04H1/4209—Inorganic fibres
  • D04H1/4218—Glass fibres
• • 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
  • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
  • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
  • D04H1/44—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling
  • D04H1/46—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres
  • D04H1/48—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres in combination with at least one other method of consolidation
  • D04H1/488—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres in combination with at least one other method of consolidation in combination with bonding agents
• • 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
  • D04H18/00—Needling machines
  • D04H18/02—Needling machines with needles
• • 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
  • D04H3/105—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 needling
• • 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

Definitions

• the invention relates to the manufacture of glass fiber mats which can be used for the reinforcement of composite materials prepared in particular by injection (process known as RTM from English "Resin Transfer Molding") or prepared from prepreg sheet ( synonymous with SMC from the English Sheet Molding Compound). It is also possible to directly impregnate the mat according to the invention with a thermosetting resin, in particular for producing translucent plates.
• a mat for reinforcing composite materials should preferably have the following properties: - have sufficient cohesion to be rollable, unrollable (for storage and transport), - have sufficient cohesion to be cut into pieces, held by hand and placed by hand in the mold (RTM), - do not prick your hands when handling it or place it in the mold (RTM), - let yourself be easily deformed by hand when you place it manually in the mold (RTM) ), ⁇ correctly keep the shape given by hand in the mold (RTM), - let yourself be impregnated with injection resin or SMC (generally polyester type and sometimes epoxy type) as easily as possible, - have a the most homogeneous structure possible, in particular without holes or other peculiarity on the surface which can cause a mark on the surface of the final composite, - reinforce the composite as much as possible.
• injection resin or SMC generally polyester type and sometimes epoxy type
• the final composite must generally have the best possible impact resistance, the least uncontrolled porosity possible (no gas bubbles involuntarily imprisoned), and the best possible surface appearance, in particular the edge (narrow face) of the final pieces.
• the use of continuous yarns leads to an unexpected advantage in terms of surface appearance and more particularly of the edge of the final composites, and in terms of the homogeneity of the distribution of the fibers in the final composite. Indeed, the Applicant has discovered that the edge of the molded parts was much sharper, smoother and better formed than when cut wires were used.
• cut threads implies that a significant quantity of ends of cut threads are found on the surface or just below the surface of the edges of pieces. .
• This phenomenon originates from the fact that the cut wires naturally have an orientation parallel to the main faces of the composite.
• This accumulation of ends of threads cut at the edges seems to favor the presence of porosities at the edges at the start of the process.
• the bubbles formed then expand under the effect of temperature (of the order of 200 ° C for the solidification of the thermosetting resin), which tends to distort the appearance of the surface of the edges. It seems that the use of continuous wires considerably reduces this phenomenon.
• the surface of SMC before pressing generally only represents around 30% of the surface of the final composite. We go from 30% to 100% under the effect of pressing.
• chopped strands are projected onto a moving sheet of resin-based dough, and another dough sheet is deposited on top to trap the cut strands as in a sandwich.
• the SMC is then rolled up and stored.
• We unroll it to cut a part (generally called "prepreg blank") whose surface represents only 30% of the surface of the final part, the said part is placed in a mold and hot molding is carried out in a press.
• the thermosetting resin hardens during this treatment.
• the Applicant has discovered that the edge of the molded parts was much sharper, smoother and better formed than when cut wires were used.
• the necessary creep of the SMC during molding leads to a preferential orientation of the wires, which can cause surface undulations.
• the cut wires are independent, they follow the flows too easily and orient themselves along the flow lines. The threads can even agglomerate or form bundles "n following these flows too much.
• the continuous wires resist any orientation because of their length, while sufficiently following the expansion of the SMC during pressing. Consequently, the use of continuous wire leads to a better homogeneity of the reinforcement of the composite.
• the use of continuous wire generally leads to a composite having a stiffness greater by 5 to 12% greater in comparison with the use of cut wire.
• the manufacture of a mat for reinforcing composites via the RTM process generally involves the deposition or projection of freshly sized threads on a moving carpet.
• the wire bed at this stage has no consistency and cannot be handled. Nor can it be rolled up or unwound because its different layers of threads would mix. We must therefore link it, either chemically or mechanically.
• we apply a chemical binder of the thermoplastic or thermosetting type generally in powder form, and we proceed then a heat treatment which melts the thermoplastic or polymerizes the thermosetting and finally after cooling creates bridges between the wires.
• this binder gives a spring effect to the structure of the mat which then tends not to maintain certain less progressive forms (in the corners of the mold for example).
• the heat treatment for melting the thermoplastic is at a relatively high temperature (220-250 ° C) which leads to severe baking of the size making the wires therefore the mat stiffer and more difficult to deform (the network glass is blocked).
• the heat treatment for melting the thermoplastic is at a relatively high temperature (220-250 ° C) which leads to severe baking of the size making the wires therefore the mat stiffer and more difficult to deform (the network glass is blocked).
• To mechanically bond a mat it can be subjected to a conventional needling. However, this generally leads to breakage of the wires, causing a reduction in the mechanical properties, as well as to the formation of spikes emerging from at least one face of the mat. These points then prick the hands of the manipulators.
• Mats comprising a central core made of curly fibers of polypropylene (PP) and external layers of cut glass threads, the whole being linked by a seam of synthetic thread like polyester (PET).
• PP polypropylene
• PET synthetic thread like polyester
• US 4335176 (or FR 2494632) teaches a needle mat of continuous glass threads produced by passing a mat of continuous, unbound glass threads through a felting loom or a conventional needling machine equipped with needles. beards. During the passage through the needling machine, the mat is perforated by a series of rows of these needles to entangle the glass strands and to cut the strands in order to provide a mechanically assembled mat containing short strands and filaments. After needling, one of the mat surfaces has a denser accumulation of fibers protruding from the surface, called "points". The other side has 25 to 50% fewer tips than the dense surface.
• US 4404717 (or FR 2502199) teaches a process for manufacturing a needle felt from a continuous sheet of glass fibers containing a significant amount of moisture, the sheet being subjected to an air treatment to dry it. before going into the needling machine equipped with hook needles. This treatment results in lower fouling of the needling machine because of the binder in the size of the fibers. ". - The invention solves the above-mentioned problems. According to the invention, a very particular needling is carried out on the mat, giving it sufficient consistency, not breaking or only very few threads, and not forming too large holes.
• the mat according to the invention is sufficiently deformable by hand at room temperature and it is very permeable to resin.
• needling is carried out by needles moving at the same time as the mat, with substantially the same speed as the mat in a direction parallel to the direction of movement of the mat.
• the number of needle strikes is reduced and is at most 25 strokes per cm 2 , and preferably at most 15 strokes per cm 2 , and more preferably at most 10 strokes per cm 2 .
• the number of needle impacts is at least 1 stroke per cm 2 and preferably at least 2 strokes per cm 2 .
• a mat has generally a thickness ranging from 0.8 to 5 mm, and more generally from 1 to 3 mm, while a felt is much thicker, and generally has a thickness greater than 1 cm.
• a felt usually has a density ranging from 85 to 130 kg / m 3 .
• a mat is much denser since its density can be of the order of 300 kg / m 3. However, we never express the density of a mat in density but in surface mass, as planar reinforcement.
• the invention relates firstly to a method for preparing a mat comprising a) the deposition or projection of threads on a moving belt to form a sheet of said threads entrained by said mat, then b) the needling by barbs crossing said sheet and moving in the direction of the sheet at substantially the same speed as when they cross it, with a stroke density ranging from 1 to 25 strokes per cm 2 .
• the barbs of the needles are directed towards their support
• the penetration depth of the needles ranges from 5 to 20 mm.
• the needles have a diameter (smallest circle - entirely containing any section of the needle including the barbs) ranging from 0.2 to 3 mm and more preferably 0.5 to 1.5 mm.
• the mat can be advanced at high speeds, for example at least 2 meters per minute and even at least 5 meters per minute and even at least 8 meters per minute. Generally, the speed is at most 35 or even at most 30 meters per minute, or at most 20 meters per minute.
• the needles pass through the mat, threads are caught in the beards and entrained to form loops across the mat, without breaking the threads. These loops bind the mat and can easily be deformed while retaining the function of binder during installation in the mold. These loops do not bite hands due to the non-breakage of the wires.
• the needles describe an elliptical movement with a horizontal component allowing the needles in the mast to follow it in its movement.
• the mat according to the invention generally has a surface mass ranging from 50 to 3000 g / m 2 . It can be a chopped strand mat or a continuous strand mat.
• the cut threads are deposited or projected onto the moving belt in the direction of the needling machine.
• continuous threads these, the number of which can range from 5 to 1200, are projected onto the moving belt by means of an arm oscillating transversely with respect to the direction of movement of the belt.
• the technique of projection of continuous threads one can for example refer to WO 02084005.
• Each of the projected threads can comprise 20 to 500 unitary fibers (in fact, continuous filaments).
• the wire has a titer ranging from 12.5 to 100 tex (g / km).
• the material constituting the fibers (continuous filaments) and therefore the yarns may comprise a fiber glass such as glass E or the glass described in FR2768144 or an alkaline-resistant glass called AR glass, which comprises at least 5 mol% of ZrO 2 .
• AR glass an alkaline-resistant glass
• the use of AR glass leads to a mat which effectively reinforces the cement matrices or which can reinforce the composites with thermosetting matrix which must come into contact with a corrosive environment. Glass can also be free of boron.
• the yarns used to make the mat therefore comprise glass fibers (filaments).
• the invention also relates to a method of manufacturing a mat comprising the needling step already described.
• the cut or continuous threads are deposited or projected on a moving belt.
• the threads can be dry, either because they come from rovings (or coils), or because they have been dried after sizing and before needling according to the invention.
• the Applicant has observed that it is advantageous for the wires to be wet to pass through the needling machine. Indeed, the passage of the carpet (having served to receive the fibers) to the needling machine is easier because the threads stick a little between them thanks to the sticky effect imparted by the liquid permeating them. This sticky effect can in particular be that coming naturally from the sizing of the fibers just after fiberizing.
• the jump or passage from the carpet to the needling machine is carried out in a better way due to the consistency of the sheet thanks to its impregnated state.
• the threads are dry at the start, they can even be impregnated voluntarily before needling so as to facilitate the passage from one device to another, more particularly the jump from the fiber receiving mat to the needling machine.
• the mat according to the invention can undergo at least drying, as the case may be. If the yarns used are initially dry and the yarns are not impregnated with any liquid, drying is not necessary. Drying is necessary if the threads are impregnated with a liquid at a time during the manufacture of the mat according to the invention.
• the threads are freshly sized when they are used in the process according to the invention.
• the drying can be carried out by passing the moving carpet through an oven at a temperature ranging from 40 to 170 ° C. and more particularly from 50 to 150 ° C.
• Such a heat treatment does not produce too strong hardening of the size of the wires which keep all their flexibility.
• the mat according to the invention can be integrated into a complex comprising several juxtaposed layers.
• the mat according to the invention in its variant using continuous threads, can constitute the layer with continuous threads randomly distributed of the fibrous structure which is the subject of WO 03/060218, the text of which is incorporated herein by reference. More particularly, the mat according to the invention can be incorporated into a multilayer complex with the following structure: mat according to the invention + layer of threads cut on one side of the mat according to the invention or mat according to the invention + layer of threads cut on both sides of said mat (complex with 2 or 3 layers).
• a first layer of fibers for example: threads cut for example to a length between 12 and 100 mm
• this layer the threads to form the mat according to the invention
• a third layer for example: threads cut for example to a length between 12 and 100 mm
• the invention leads in particular to a needle mat of continuous threads or cut threads (preferably continuous threads) consisting of glass fiber possibly sized and without needle holes visible to the naked eye.
• This mat therefore contains a maximum of glass to reinforce the composite as much as possible, in the absence of synthetic materials based on polymers (PP, polyester, etc.) which are not reinforcing for the composite, apart from any organic components of fiber sizing.
• This mat is advantageously used to reinforce a composite in the closed mold injection process (RTM) or in the context of SMC technology, or to be directly impregnated with resin to make plates, in particular particularly translucent.
• the mat obtained by the process according to the invention can be integrated into a sheet prepreg (SMC).
• SMC sheet prepreg
• the mat according to the invention is then inserted continuously between two layers of thermosetting resin paste.
• One unwinds then integrates said mat directly entered two layers of resin paste.
• other reinforcing layers in the SMC such as for example cut son, in particular of glass.
• the SMC sheet can be used for the manufacture of a composite material by molding the sheet by pressure on its main faces leading to an enlargement of the sheet in the mold before solidification of the resin.
• the cut sheet of SMC has, before pressure molding, preferably a surface representing 50 to 80% of the surface of the mold (and therefore of the surface of the final part).
• a support film 41 (generally made of polyester) is unwound, to which a layer 42 of gelcoat (generally a polyester resin) is applied. ). Then the mat 43 according to the invention is unwound on said gelcoat layer.
• Another support film 44 is unwound to receive a layer of gelcoat 45, this assembly 44/45 being applied to the mat according to the invention on the side of the layer of gelcoat.
• the assembly is then subjected to a heat treatment by the unit 46 to harden the gelcoat, then the two support films 41 and 44 are peeled off and the solid composite is received at 47.
• FIG. 1 shows very schematically the principle of needling with which the needles accompany the mat when they penetrate it.
• the mat 1 advances under the board 2 provided with needles 3 with beards oriented towards their support (needle board), said board being driven by a movement with two components, one horizontal CH and the other vertical CV, thanks to a system of connecting rods rotating around a fixed point 4.
• These different elements of the machine are dimensioned so that the horizontal component CH is substantially identical to the speed of the mast VM when the needles are in the mast.
• FIG. 1 represents a needle 3 fixed in the needle board 2. It can be seen that the needle is provided with barbs 5 directed towards the needling board, that is to say upwards when the mat is under the board with needles (the beards are directed as for a hook).
• FIG. 2 represents a needle 3 fixed in the needle board 2. It can be seen that the needle is provided with barbs 5 directed towards the needling board, that is to say upwards when the mat is under the board with needles (the beards are directed as for a hook).
• the needling machine comprises two large perforated cylindrical elements 9 and 9 'driven in rotation in coherence with the speed of the belt 6. These two cylindrical elements enclose the sheet to make it advance without distortion or elongation thereof.
• the needle board 2 is located inside the upper cylindrical element (the same system in the lower cylinder) and is animated by an elliptical movement 10, the horizontal component of which corresponds substantially to the forward speed VM of the mast.
• the needles pass through the upper cylindrical element which is provided with suitable orifices, then the ply to needle it, then possibly the lower cylindrical element, then rise upwards along an elliptical trajectory.
• the mat passes (or jumps) again at 11 on another mat 12 which takes it into the oven 13.
• the mat can be rolled up and stored. At the time of its use, it can be unrolled, cut, moved, manipulated, placed and deformed in the injection mold in the most satisfactory manner. It is well permeated by the injection resin. It has good resin permeability, especially if it is obtained from continuous threads.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Mechanical Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Composite Materials (AREA)
• Nonwoven Fabrics (AREA)
• Reinforced Plastic Materials (AREA)
• Moulding By Coating Moulds (AREA)

Applications Claiming Priority (2)

Publications (1)

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• 2003
  • 2003-11-28 FR FR0313977A patent/FR2862987B1/fr not_active Expired - Fee Related
• 2004
  • 2004-10-07 BR BRPI0416955-7A patent/BRPI0416955A/pt not_active IP Right Cessation
  • 2004-10-07 JP JP2006540550A patent/JP4974221B2/ja not_active Expired - Fee Related
  • 2004-10-07 EA EA200601057A patent/EA007699B1/ru not_active IP Right Cessation
  • 2004-10-07 US US10/580,936 patent/US7509714B2/en not_active Expired - Fee Related
  • 2004-10-07 EP EP04805738A patent/EP1689924A1/fr not_active Withdrawn
  • 2004-10-07 CA CA002547340A patent/CA2547340A1/fr not_active Abandoned
  • 2004-10-07 AU AU2004295511A patent/AU2004295511A1/en not_active Abandoned
  • 2004-10-07 CN CNA2004800353385A patent/CN1886542A/zh active Pending
  • 2004-10-07 WO PCT/FR2004/050495 patent/WO2005054559A1/fr active Application Filing
• 2006
  • 2006-05-23 ZA ZA200604127A patent/ZA200604127B/xx unknown

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