WO2016062896A1 - Mèches poudrées par procédé électrostatique - Google Patents
Mèches poudrées par procédé électrostatique Download PDFInfo
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- WO2016062896A1 WO2016062896A1 PCT/EP2015/074734 EP2015074734W WO2016062896A1 WO 2016062896 A1 WO2016062896 A1 WO 2016062896A1 EP 2015074734 W EP2015074734 W EP 2015074734W WO 2016062896 A1 WO2016062896 A1 WO 2016062896A1
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- WIPO (PCT)
- Prior art keywords
- ribbon
- wick
- width
- polymer
- filaments
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
- B29B15/10—Coating or impregnating independently of the moulding or shaping step
- B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
- B29B15/10—Coating or impregnating independently of the moulding or shaping step
- B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
- B29B15/122—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex
- B29B15/125—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex by dipping
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- 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
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
- B29C43/24—Calendering
- B29C43/245—Adjusting calender parameters, e.g. bank quantity
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- 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
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/58—Measuring, controlling or regulating
-
- 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
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/58—Measuring, controlling or regulating
- B29C2043/5825—Measuring, controlling or regulating dimensions or shape, e.g. size, thickness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2307/00—Use of elements other than metals as reinforcement
- B29K2307/04—Carbon
Definitions
- the present invention relates to the technical field of composites with continuous reinforcement with thermoplastic or thermosetting organic matrix. It relates more particularly to semi-products used in the manufacture of composite materials by automated fiber placement (AFP) or by filament winding, pultrusion, braiding, 3D printer. These composites are intended for "indirect” processes, which means that the entire organic matrix of the final composite is already on the semi-finished product.
- AFP automated fiber placement
- filament winding, pultrusion, braiding, 3D printer 3D printer.
- This type of product is usually obtained in several steps that can be done separately or online.
- the first step is to obtain a unidirectional carbon sheet formed of several strands of carbon. Once the filaments are aligned and the surface weight of carbon adjusted, the sheet is immersed in a polymer dispersion in the liquid phase, it is the impregnation phase. Once the filaments loaded with polymer, the web is heated in order to melt the polymer and to evacuate the liquid phase. Finally, once the web consolidated, it is cut into ribbon width controlled, and then wound on reels.
- the major drawbacks of this method is that the cutting makes that filaments may protrude from the edges of the ribbon and that if the cut is not perfectly parallel to the filaments, the latter are not rigorously oriented in the longitudinal direction of the ribbon.
- EP 1 007 309 describes the production of continuous ribbons by impregnating strands of inorganic material, carbon or glass type, in a polymer bath with application of shear. This process is directed to the production of ribbon for the indirect process, with a polymer content ranging from 25 to 75% by weight.
- Example 1 describes the passage of a wick of glass threads in an impregnation bath, then in a die of rectangular section of dimensions 0.64 cm x 0.023 cm, to produce a ribbon having these dimensions.
- An object of the invention is to produce and provide a large length of reinforcement tape in one piece, without cutting and without splicing, which can reach the length of the wick of the supply reel, for example able to reach and exceed the 1000 meters, while having a very regular width that can be characterized by a very small standard deviation and / or good management of the distribution of the polymer.
- Another object of the invention is to produce and provide such a ribbon with a controlled rate of polymer.
- Another object of the invention is to produce and propose such a ribbon whose constituent filaments are strictly parallel to the longitudinal direction of the ribbon.
- An object of the invention is therefore to provide a method for making such a ribbon continuously.
- Another object of the invention is to produce and provide such a ribbon which is flexible, especially whose flexibility can easily be adjusted, and preferably which is non-brittle.
- Yet another object of the invention is to produce and propose such a ribbon at a competitive cost.
- the subject of the present invention is a process for manufacturing a ribbon of reinforcing filaments impregnated with a thermoplastic or thermosetting polymer matrix, which ribbon has a constant width throughout its length, in which the filaments extend in a parallel direction. to the length of the ribbon.
- This method may apply to the treatment of a wick from a supply coil or, simultaneously and parallel to several (2 or more) wicks from as many feed coils.
- the supply coils can be in particular of a commonly used type, most commonly a cross reel (the wick is wound with a crank and crosswise) or possibly a reel with simple slicing.
- This method is characterized in that it comprises, for each wick (one or more wicks that can be processed simultaneously), the following manufacturing steps, from a wick supply coil to a ribbon storage spool:
- a wick is defined as consisting of a set of filaments (or fibers) and comprises from about 1,000 to about 80,000 filaments, preferably from about 3,000 to about 24,000 filaments.
- the locks used in the context of the invention are preferably made of a material chosen from carbon, ceramics, glasses, silicas, basalts, and aramids, or any other material used in the field of materials.
- composites, for example filaments or metal fibers, the filaments may be of natural or synthetic origin. Carbon is particularly preferred.
- Useful ceramics include silicon carbide and refractory oxides, for example, alumina and zirconia.
- the starting wick may be in a form already flattened or more or less round.
- the locks are presented in coiled bobbin flat bobbins.
- one uses carbon wicks comprising from about 1,000 to about 80,000 filaments, preferably from about 3,000 to about 24,000 filaments.
- the flat composite formed of the wick and the thermoplastic or thermosetting polymer is called a ribbon.
- this ribbon is advantageously stored on a spool or support directly usable on the depositing robots.
- the winding can be of the wire-to-wire type (the ribbon is wound edge to edge, this mode is preferred) or of the crossed type.
- the constituent filaments of the wick or ribbon are preferably continuous.
- the filaments used generally have a substantially circular cross section (round filaments) or, preferably, substantially parallelepipedal or elliptical (flat filaments).
- the locks have irregular widths, as described in the table below, giving the width of the carbon locks according to the number of filaments and their title.
- any type of carbon wire can be used.
- HR High Resistance
- IM Intermediate Module
- HM High Module
- the voltage between the two coils is managed or adjusted, which means that the wick and the resulting continuous ribbon are kept energized between the supply coil and the storage coil. .
- the tension along the line and the process may vary according to the steps and devices that the wick and then the ribbon pass through. This tension can in particular be understood and vary between about 5 and about 50 N.
- the guide of the wick in step b) allows its precise alignment in the machine axis. The guiding step may in particular eliminate the slicing of the wick and / or eliminate the lateral movements associated with the unwinding of a wick wound crosswise on the supply reel.
- the guidance may use in particular at least one set of at least two bars oriented so as to be able to return the wick from the feed reel to a line or path perfectly aligned with the machine axis (positioning in the axis includes positioning at a given height, which is that of the axis machine), at least until the cooling of the impregnated tape.
- a set of two bars can be used at 90 °.
- the first bar is parallel to the axis of the coil, oriented at 90 ° to the direction of travel of the wick, the latter sliding from left to right on the first bar because of the slicing of the supply reel. This first bar allows to adjust the alignment of the wick in the rest of the process.
- the wick goes into contact with the second bar located below the first, oriented at 90 ° relative to the previous and perpendicular to the machine axis, and which keeps the wick flat and adjust the height of the wick to following the process.
- the wick has a width that is constantly greater than the width of the final ribbon.
- the width of the wick is constantly or punctually equal, close to or less than the width of the final ribbon.
- the wick brought back in the machine axis is spread transversely.
- the transverse spreading of the wick is wider than the nominal width of the ribbon.
- This step ensures that the wick, as it is submitted at this stage, always has a width greater than the nominal width of the final ribbon.
- bars having a diameter of between about 10 mm and about 100 mm may be used.
- the bars Preferably, the bars have a low abrasion surface, for example chromium, aluminum or ceramic.
- abrasion surface for example chromium, aluminum or ceramic.
- the width of the wick is controlled or adjusted in d), which means that the width of the wick is reduced to a predetermined value by passing through a calibration device.
- the width is reduced to a predetermined value, in particular between the maximum spreading width and the nominal width of the final ribbon.
- the width after spreading is from about 1.5 to about 4.5, for example from about 2 to about 3 times the nominal width of the final ribbon.
- the calibration width is from about 10 mm to about 29 mm for a nominal ribbon of about 6.35 mm.
- step e Downstream of this stage, at a time of its course in which the wick is under high tension (there may be a tension of up to 5 kg per wick), it is preferable in step e) to pull the wick in order to maintain its width and to apply to the wick a forward movement towards the storage reel.
- This step can in particular be done using a device for gripping the wick and forcing it to move in the opposite direction to the supply reel. In particular, it is possible to use a scarf or similar device.
- the work done on the wick so far allows to work with initial wicks of very different qualities, having for example a variable width, to ensure a regular powder level and significantly improve the dispersion of width of the final ribbon.
- a step of measuring the width can be performed with a laser, as will be described later.
- the running speed of the wick and ribbon may be in particular between about 5 and about 50 m / min, especially between about 10 and about 40 m / min, typically between about 15 and about 35 m / min. This speed is adapted to the different steps, in particular to the dusting step.
- the grounding f) of the wick, to allow the electrostatic powdering, is advantageously carried out as close as possible to the powdering, so just upstream of this step.
- the g) powdering step determines the distribution of the matrix in the final ribbon and the fiber / matrix rate in the final composite product.
- an electrostatic powdering method is used.
- the wick is grounded, in particular by passing in contact with one or more bars connected to the ground, for example one or more bars of docking.
- This dusting step comprises a first dry fluidization step. Fluidization involves passing a gas between small polymer particles. When the friction of the gas creates a force sufficient to compensate for the weight of all particles in the bed, it is said that the bed of particles is fluidized. The use of the dry fluidized bed makes it possible to deposit larger amounts of powder and to work with more powder compared to the pressure pots.
- One or more electrostatic powder spray guns or nozzles using the corona discharge principle is preferably used. This involves applying a high potential difference between the tip of the gun and the part to be covered, which is connected to the ground. The electric field at the tip accelerates the electrons of the surrounding medium by the Coulomb force and ionizes the molecules present in the air. By avalanche effect, a self-sustaining process is obtained which makes the surrounding medium conductive. The powder particles passing through this ionized medium are charged by the accumulation of electrons on their surface. They are then driven by the electric field towards the wick which is connected to the mass. For strands of non-conductive filaments, the conductive surface is made before dusting by misting, metallization or use of a conductive polymer.
- the deposition of the powder is via the use of one or two gun (s) on which a nozzle, preferably flat, is mounted.
- a gun s
- This type of installation creates a cloud of powder around the wick which is itself connected to the ground.
- the powder that is around the fiber is then attracted by the wick changing its path to create a thin layer of deposit all around the wick.
- a gun is disposed above the wick, the other below.
- the guns are controlled via a central unit that allows the two guns to be independently driven.
- the parameters that can be set are:
- the adjustment of these parameters makes it possible to adjust the rate of powder deposited on the fiber and the regularity of the deposit.
- the settings are to be adapted for each wick / die pair.
- the carbon ribbon is divided into several bundles of filaments during the dusting.
- a first dusting pass is carried out vertically or in the vicinity of the wick separated in bundles, and that a second dusting pass is carried out a little further, at a location where the line where the ribbon is again joined (the adjacent bundles then tend to come closer together to tend towards the ribbon structure as it was before the bundle separation, except that the polymer was deposited part of which can separate, more or less distinctly, the adjacent beams), to ensure the sheathing of the wick.
- the number of beams and how to obtain them are discussed below. More details of this embodiment are given in Example 4.
- ribbon which therefore consists of a fibrous reinforcement oriented in the longitudinal direction impregnated with a polymeric matrix.
- the length of a ribbon spool may be equal to or substantially equal to the spool of which the thread is issued, with no limit on the length of the thread.
- the weight ratio of the polymeric matrix applied to the spread wick may especially be between about 20, 25 or 30% and about 75%, especially between about 20, 25 or 30% and about 50% and more particularly between about 30% and about 40%.
- This particularly high rate makes it possible to use the ribbon in the indirect process. This rate can reach significant values, greater than 30 or 40%, while being flexible and well consolidated, as will be seen below.
- the polymer that impregnates the fiber is in the form of powder whose grains have a diameter in particular between about 10 ⁇ and about 300 ⁇ and preferably between about 30 ⁇ and about 200 ⁇ .
- thermoplastic and thermosetting polymers polyamides (in particular PA6, PAI2, PAU, PA6.6, PA 6.10, PA 6.12), copolyamides (CoPA), polyamide-blocks ether or ester (PEBAX, PEBA), polyphthalamides (PPA), polyesters (especially polyethylene terephthalate-PET-, polybutylene terephthalate-PBT-), copolyesters (CoPE), thermoplastic polyurethanes (TPU), polyacetals (POM, ...), polyolefins (especially PP, HDPE, LDPE, LLDPE), polyethersulfones (PES), polysulfones (PSU, ...), polyphenylenesulfones (PPSU, etc.), polyetheretherketones (PEEK) , polyetherketones (PEEK) , polyetherketones (PEEK) , polyetherketones (PEEK) , polyetherketones (PEEK) , polyetherket
- the thermoplastic material is a thermoplastic material.
- it may be a high performance thermoplastic material that is to say having a melting point and / or a transformation temperature of greater than or equal to 280 ° C. It can be chosen in particular from PEEK, PPS, PEKK, PEI, or a mixture of at least two of them.
- thermosetting polymers in powder form having a softening temperature lower than their crosslinking temperature.
- This type of powder is obtained by uncrosslinked thermosetting polymer formulation and provides a ribbon with a non-crosslinked thermosetting polymer content of between 20, 25 or 30% and 75%.
- This tape can then be used in a method of automated fiber placement or filament winding, where the crosslinking will be activated once the crosslinking temperature reached.
- This tape impregnated with thermosetting polymer makes it possible to produce composite parts without an injection or infusion step after placement of the ribbon and also allows storage of unlimited duration at ambient temperature.
- the melting or softening of the powder can in particular be carried out by passing through one or more, especially 2 ovens, preferably short or medium infrared ovens, just after the dusting step.
- the regulation of the furnace (s) is preferably in power for a better stability of the process.
- the settings are to be adapted for each pair wick / matrix but also depending on the speed of travel and the target powder rate.
- the temperature applied to the polymer is in all cases higher than its melting point (eg for semi-crystalline polymers) or sufficient to pass the powdery polymer in the viscous state for impregnation.
- the temperature may especially be between 300 and 450 ° C., more particularly between 350 and 450 ° C.
- Calibration of the ribbon in step i) at a target width is a decisive feature since, for example, variations in width result in non-qualities at the time of automated deposition of the ribbon by the deposition robots to form. Too small a width generates "gap” while a too large width generates "overlap” and jams at the deposition head.
- the ribbon can be calendered.
- This calendering can allow alignment on the machine axis or contribute to it.
- the calendering makes it possible to ensure the impregnation of the wick by the thermoplastic or thermosetting material, which is still in the molten state.
- the calender is cooled.
- the temperature of the material at this stage may allow it to be sufficiently fluid to be shaped.
- the calendering can be achieved by passing the ribbon between at least two cooled rollers whose pressure and temperature can be regulated. In this device, the calendering allows to penetrate more or less the matrix in the ribbon but also, possibly, to spread the ribbon.
- the impregnation rate accounts for the distribution of the matrix in the transverse direction of the ribbon.
- a low impregnation rate amounts to having, according to one embodiment, a hollow strip with a distribution of the polymer only at the periphery of the wick (eg carbon), thus forming a polymer sheath (or continuous layer) which protects the filaments and guarantees a very high flexibility to the ribbon.
- the calender pressure is preferably less than 1 bar, typically it is between about 0.1 and about 0.9 bar, especially between about 0.1 and about 0.6. bar. This type of product is particularly interesting for the draping of complex shapes with very small radii of curvature.
- a high impregnation rate will correspond, in another embodiment, to a ribbon where the polymer is distributed substantially uniformly between the filaments (e.g., carbon) in the width and thickness direction.
- the polymer protects the filaments of the ribbon with a sheath, but it does not necessarily form a continuous outer layer as in the previous case.
- the calender pressure is preferably greater than or equal to 1 bar, typically it is between about 1 and about 4 bar.
- the temperature parameter can be continuously monitored by the temperature measurement, for example using an infrared pyrometer, at the outlet of the oven and / or before calendering.
- Step i) may comprise a width calibration of the ribbon by passing through a transverse calibration device or width, or calibration both width and thickness.
- step i) comprises, on the one hand, the calendering and, on the other hand, the calibration in width, or in width and in thickness.
- one caliber both in the transverse direction and in thickness Preferably, one caliber both in the transverse direction and in thickness.
- the calibration is advantageously set to the desired nominal width for the ribbon. Various embodiments will be described later.
- the cooling takes place gradually between the exit of the oven and the winding. It is not essential to provide a cooling device. It has been seen that the calender at calibration step i) is performed at a sufficient temperature, e.g., between the glass transition temperature and the melting point of the semicrystalline polymer. Before winding, the temperature reached is such that the polymer is no longer deformable, for example it is less than the glass transition temperature Tg of the semicrystalline polymer.
- the width and / or thickness of the tape can be measured in j) continuously, preferably with its standard deviation, during the manufacture of the tape using the following method. Downstream of its calibration and upstream of its reel storage, spot measurements of width and / or thickness are carried out every x cm (for example every 50 cm or every 1 meter) with the aid of a Laser, the data is processed by a computer processing unit or a computer collecting width values and calculating the standard deviation.
- a laser formed of a transmitter emitting a line of laser light and a receiver having a line of receptor cells. The transmitter is placed on one side of the ribbon, facing one of its flat faces if the width is measured. The receiver is placed on the other side of the ribbon, facing its other flat face always for width measurement. The shadow of the ribbon projected on the receiver makes it possible to know the width (or the thickness) with a great precision.
- the winding in step k) consists in winding the ribbon onto supports that are preferably compatible with automated dispensing robots. It can be done in two different ways: in tension or in speed.
- the spindle carrying the storage spool adapts its speed of rotation according to the tension information of the ribbon, for example raised by a dancer arm.
- This type of winding makes it possible to have a very clean winding and does not require speed control with the device, such as the scarf, which tows the ribbon at the beginning of the line.
- the speed of the spindle is entered in setpoint, it is then necessary to slave the winder and the drive device such as the scarf to avoid any problem of tension due to the speed difference. between the two devices. Voltage winding is preferred.
- the winding and thus the speed of production of the tape may be between about 5 and about 50 m / min, especially between about 10 and about 40 m / min, typically between about 15 and about 35 m / min.
- the method described in the invention makes it possible to produce a ribbon both from a single lock and from several (2 or more) locks.
- the surface weight of carbon is increased.
- at least two, preferably two, carbon ribbons are superimposed to obtain a given mass per unit area.
- the combination of the two son can be done before dusting at the level of the spreading or after dusting, once the polymer melted. In both cases it is necessary to reproduce the unwinding and guiding elements described earlier. Then, in the first case, the mixture of the filaments of the two threads is made throughout the jams used to spread the threads.
- a continuous reinforcing tape formed from unidirectional inorganic material filaments, substantially uniformly coated and / or substantially impregnated with a thermoplastic polymer core or thermosetting at a mass ratio of from about 20, 25 or 30% to about 75%, especially from about 20, 25 or 30% to about 50% and more preferably from about 30% to about 40%.
- the ribbon is of predetermined constant width and controlled, preferably with a standard deviation of between 0.02 and 0.15 mm, preferably between 0.02 and 0.05 (inclusive), over a length of one piece (without splicing) greater than or equal to 100, 500, 1000 or 5000 m, or more.
- This standard deviation is actually the entire length of ribbon produced from a continuous feed wick length. From a reel of x meters of wick, a ribbon of substantially equal length is produced with the standard width and standard deviation. This standard deviation is typically measured as described above by laser measurement.
- the ribbon is also continuous throughout its length, without cutting filament and in one piece, ie without splice or "splice". Its component filaments are substantially parallel to the longitudinal direction of the ribbon (or perfectly aligned in the longitudinal direction).
- This product is intended for indirect processes for making composite parts from one or more tapes.
- the ribbon has a constant width, which may be in particular between about 2 mm and about 75 mm and more particularly between about 5 mm and about 10 mm.
- the rate of thermoplastic or thermosetting material can reach significant values, greater than 30 or 40%, while being flexible and well consolidated, as will be seen later.
- the standard deviation is calculated using the following formula:
- the width of the ribbon can be measured with its standard deviation continuously during the manufacture of the ribbon using the method described above, which makes it possible to obtain the standard deviation over the total length of the ribbon or on a fraction.
- outside the production line to characterize a ribbon according to the invention, it is possible to proceed in the same manner, by unwinding the ribbon and by making spot width measurements, for example every 1 m by the laser measurement.
- the subject of the invention is also an impregnated and / or consolidated continuous ribbon formed of unidirectional inorganic material filaments, preferably made of carbon, uniformly coated and / or impregnated with a core of a thermoplastic or thermosetting polymer, comprising a polymer content included from about 20, 25 or 30% to about 75%, especially from about 20, 25 or 30% to about 50% by weight and preferably from about 30% to about 40% by weight, based on the weight of the strip.
- This ribbon can be presented in particular in the three forms that will be described, namely hollow, impregnated and substantially consolidated at heart, impregnated and substantially consolidated at heart. with bundles of filaments.
- the ribbon has a constant width, in particular with a standard deviation of between 0.02 and 0.15 mm, preferably between 0.02 and 0.05 mm (inclusive).
- the width of this tape may be in particular between about 2 mm and about 75 mm and more particularly between about 5 mm and about 10 mm.
- the ribbon has an average width in the specification of 6.35 mm ⁇ 0.15 mm with a standard deviation of 0.02 to 0.05 mm, preferably a length of a single piece. , that of the starting wick, especially greater than or equal to 100, 500, 1000 or 5000 m.
- a ribbon with an average width of 6.35 mm and a standard deviation of between 0.02 and 0.05 mm can be used.
- the tape is impregnated and consolidated at the periphery, including on its two longitudinal edges (or longitudinal edges), the thermoplastic or thermosetting material impregnating the filaments at the periphery forming a substantially continuous sheath, including the long ribbon edges.
- this tape has a particular surface state, corresponding to the fact that it is completely or mostly coated with molten or softened polymer which substantially forms a polymer continuum across the ribbon in the direction of the width and in the direction of the length, as illustrated by way of example in FIG. 6.
- the average thickness of the surface polymer (outer layer) may advantageously be between approximately 10 and approximately 100 ⁇ , preferably between about 25 and about 100 ⁇ .
- the ribbon comprises a certain proportion of non-polymer impregnated filaments (taken in the polymer) within it.
- This proportion can in particular represent from about 20, 25 or 30 to about 50% of the total of the ribbon filaments (this can be determined by analysis of the impregnated and non-impregnated surfaces by image processing of sections with adequate magnification; microscopically or any other digital imaging device (camera, camera, etc.) makes it possible to distinguish the bare fiber zones from the impregnated fiber zones taken in the polymer, as well as the polymer zones which are substantially or totally filament-free )).
- This ribbon is said to be hollow, insofar as the heart of the ribbon is formed of non-impregnated filaments, the heart being thereby non-impregnated or unconsolidated.
- the tape is impregnated and / or substantially solidified to the core, i.e., it comprises a high proportion of polymer impregnated filaments within it.
- This proportion can in particular represent from about 80 to about 100% of the total of the ribbon filaments.
- this ribbon has a particular surface condition, corresponding to the fact that it is partly covered with molten or softened polymer, forming discontinuous phases across the ribbon in the direction of its width and in the direction of its length, as illustrated by way of example in Figure 7.
- This tape is said impregnated to heart.
- the proportion of filaments taken in the polymer is between 80% and 99, 98, 97, 96, 95 or 90%. Typical ranges are 90 to 100%, especially 95 to 100%.
- the average thickness of the surface polymer (outer layer) may advantageously be between about 10 and about 100 ⁇ , preferably between about 25 and about 100 ⁇ .
- the filaments are distributed in the form of bundles.
- the filaments extend in the longitudinal direction of the strip in the form of at least two bundles of separate filaments coated with polymer.
- the beams are notably more or less individualized on the transverse plane. It will be readily understood that the number of beams can be adapted according to the width of the ribbon. Typically 2 to 50, especially 5 to 50, preferably 10 to 30, beams can be provided. The beams are separated from each other by the polymer alone or possibly containing sparse filaments.
- the impregnated product may be characterized by a distribution of filaments in the form of bundles with a width of between about 200 ⁇ m and about 6000 ⁇ m and a height of between about 50 ⁇ m and about 250 ⁇ m, the spacing of which is between about 25 ⁇ m and about 100 ⁇ m.
- the fiber bundles are totally or partially impregnated with polymer to form a ribbon which has a strong cohesion in the direction transverse to the fibers.
- this product retains a thin sheath (outer layer) of polymer.
- the average thickness of the surface polymer may advantageously be between about 10 and about 100 ⁇ , preferably between about 25 and about 100 ⁇ .
- the measurement of the impregnation rate can be carried out by image analysis (use of a micrioscope or camera or digital camera, in particular), of a cross-section of the ribbon, by dividing the surface of the tape impregnated with the polymer. by the total surface of the product (impregnated surface + surface of the porosities).
- image analysis use of a micrioscope or camera or digital camera, in particular
- impregnation rates typically: hollow product: from about 30% to about 70% and preferably from about 40% to about 60%; impregnated product: from about 70% to about 100% and preferably from about 90 to about 98%; impregnated product with bundle structure: from about 70% to about 100% and preferably from about 90 to about 100%.
- the thickness measurement of the polymer sheath is performed by the same tools, in particular using a microscope from a cross section of the ribbon (the sample preparation is identical to that intended for the measurement impregnation rate).
- the flexibility of the ribbon can be characterized by a Taber Model 150D stiffness meter (Taber Industries, North Tonawanda, New York, USA) in accordance with NF ISO 2493-2 (Part 2: Taber Tester). All measurements are made with the No. 1 gauge, referred to as extreme sensitivity, the bending angle used is 7.5 ° and the average of the reference pad is 88.3TSU (Taber Stiffness Unit) for a nominal from 88TSU.
- Taber Model 150D stiffness meter Tiber Industries, North Tonawanda, New York, USA
- NF ISO 2493-2 Part 2: Taber Tester
- the Taber rigidity of the hollow tape with a mass of 250 UT is between about 5 TSU and about 25 TSU and more specifically between about 10 TSU and about 20 TSU.
- the rigidity of the tape impregnated at heart is between about 45 TSU and about 65 TSU and more specifically between about 50 TSU and about 60 TSU.
- the same measurement can be carried out with a mass of 500UT on the impregnated tape at heart, the Taber rigidity is then between about 20 TSU and about 40 TSU and more precisely between about 25TSU and about 35TSU.
- a ribbon according to the invention with a proportion of filaments taken from the polymer matrix of less than 100% has the remarkable characteristic of not breaking when it is folded on itself, unlike ribbons obtained by standard impregnation in the liquid phase. .
- a proportion of filaments, in particular of carbon, which are not embedded in the matrix can slide on each other during the deformation of the ribbon.
- the ribbon according to the invention having a proportion of filaments taken in the polymer matrix of less than 100%, preferably less than or equal to 99, 98, 97, 96, 95 or 90%, does not break during a folding operation. which is not the case of ribbons obtained by standard impregnation which can break when folded on themselves.
- the tapes according to the invention have an unequaled bending capacity, with a very small radius of curvature.
- the invention also relates to an installation for implementing the method according to the invention and to produce a ribbon according to the invention.
- This installation includes the following elements.
- At least one spool pin with brake At least one spool pin with brake.
- the device is a machine-axis yarn alignment device; the device may for example comprise a set of two bars at 90 °, a first bar parallel to the axis of the coil, oriented at about 90 ° relative to the direction of travel of the wick leaving the coil, and a second bar located below the first, oriented at about 90 ° to the previous and perpendicular to the machine axis, as described supra.
- a device for transverse spreading of the wick in particular a loading device operating on the principle of the application of a tension on the wick causing the transverse spreading of the filaments, in particular of the type comprising at least 1, of preferably several (typically from 2 to 7) bars perpendicular to the machine axis and of which at least 1 is above or below this machine axis (which allows to impose a tension on the wick, causing its opening );
- the bars may in particular have a diameter of between about 10 mm and about 100 mm; they preferably have a low abrasive surface, for example chromium, aluminum or ceramic; they can be heated and / or vibrating; they can have a regular cylindrical, oval or elliptical shape or with a non-constant section, they can be rectilinear or bent, they can be braked or not
- a calibration device in width, to manage or adjust the width of the wick may in particular comprise a piece provided with a groove bringing the filaments of the wick to the width of the groove.
- the width of the groove may advantageously be determined by the width of the ribbon to be produced, for example the calibration width (or throat) is from 1.5 to 4.5, in particular from 2 to 3 times the nominal width of the ribbon to be produced. final ribbon.
- a device for gripping and pulling the wick preferably comprising two rollers, at least one of which is rotated, for example a scarf or the like, for gripping the wick to maintain its width and applying to the wick a forward movement towards the storage spool;
- the scarf or similar device may in particular comprise at least two rollers arranged one above the other, at least one of them is movable towards the other in order to apply pressure to a material in this case the wick, which would pass between them, and of which at least one is rotated.
- a device for measuring the width of the wick in particular a laser, as described above.
- At least one metal part (preferably of good electrically conductive and non-abrasive surface metal) grounded.
- This metal part can advantageously be placed as close as possible to the powder which will be described. It can be one or more (typically 2) metal bars.
- the powder former comprises a fluidizer or dry fluidization device with a powder storage chamber maintained in the fluidized state.
- the powder duster comprises a control unit of the gun or guns, making it possible to regulate in particular the injection pressure, the dilution pressure, the voltage and the intensity released at the cathode. Operating details are given supra.
- This initial ribbon splitting system can be made using a comb or other grooved element (for example a bar whose surface has threads or grooves extending over the circumference of the bar) permitting the separation of the filaments in a regular manner (examples number of beams above, and therefore grooves or the like).
- the objective is to deposit the powder in the heart of the ribbon to increase the impregnation rate.
- this dividing device makes it preferable for the first powdering gun to be placed plumb with or in the vicinity of the strip separated in bundles, thus at the plumb or in the vicinity of the separating device or immediately downstream, and that the second is further downstream in the dusting device, at a place where the beams are closer, the second gun for the cladding of the tape.
- the precise location within the powder duster is easily determinable.
- At least one heating unit such as an oven.
- one or short or medium infrared furnaces are used.
- the regulation of the furnace (s) is preferably in power. Their power is adapted to the polymer used.
- a ribbon alignment device to make it coincide with the machine axis and in particular with the calibrator that will be described.
- a grille Possibly, a grille.
- the calender is cooled.
- the pressure applied by the calender is preferably adjustable.
- a calibration device in the transverse direction and in thickness may especially comprise at least two forms of calibration, in particular grooves, antagonists, that is to say that one of forms comes act in contact with a first face of the ribbon, the other in contact with the other ribbon face.
- the width of the shapes is advantageously set to the desired nominal width for the ribbon.
- a first groove is flared at the beginning and then has a nominal width equal to the desired nominal width for the final ribbon, for example 6.35 mm.
- This groove is in contact with the underside or upper side of the ribbon.
- a second groove is in contact with the other face of the ribbon, it also has a nominal width equal to the desired nominal width for the final ribbon, for example 6.35 mm.
- This groove may for example be machined on a wheel.
- the two grooves must be perfectly aligned and can for example be mounted on verniers which allow a very fine adjustment of their position, one with respect to the other but also with respect to the scrolling of the ribbon. Different embodiments will be described in the examples.
- a device for measuring the width of the ribbon in particular a laser, as described above and in the examples.
- This measuring device can preferably be connected to a computer or processor programmed to adjust the measurement rate (for example every x cm, eg every 50 cm or every 1 meter), record the measured values throughout the measurement. producing a tape reel and / or calculating the standard deviation.
- this pin is offset relative to the machine axis in the direction of the height, for example by one or more (typically 2) return bars.
- This spindle can be part of a conventional winding device, allowing for cross winding or wire to wire, for example.
- the pin can be enslaved in particular speed or voltage.
- the elements b), c), d), e), g), h), i), j), k) and I), preferably also n), are aligned on the machine axis so that the wick, then the ribbon does not undergo significant lateral movement movement. More preferably, the elements e), g), h), i), j), and k), preferably also d) are perfectly aligned on the machine axis, so that the wick, then the ribbon undergoes no lateral movement movement or sensitive height
- the setting device c) is itself preferably arranged so that the entry and the exit of the wick is done being perfectly aligned on the machine axis, laterally and preferably also in height.
- Driving devices include devices for rotating the pin of the formed ribbon winding device. They also include the scarf or the like in e). These drive devices can advantageously be enslaved, to manage the tension of the wick, then the ribbon, all along the production line.
- the installation can include several production lines allowing to simultaneously produce several ribbons from several wicks.
- the invention also relates to composite parts or articles made from a ribbon according to the invention or produced according to the method of the invention.
- These parts or articles are formed in whole or part of tape, the part or article having been consolidated hot, for example in an autoclave or in an oven, after placing the tape to form the blank.
- the part or article is formed exclusively or mainly of ribbon according to the invention or produced according to the method of the invention.
- the invention also relates to the use of a ribbon according to the invention for the manufacture of an article or composite part, and such a manufacturing method, comprising the placement of the ribbon to form a blank, and then the consolidation of the piece or article hot, especially in an autoclave or in an oven.
- the ribbon can be placed edge to edge and / or superimposed, the superposition can be done according to one or angle (s) adapted (s).
- Placement can be achieved by Automated Fiber Placement (AFP) or by filament winding, pultrusion, braiding, 3D printer.
- AFP Automated Fiber Placement
- the placement can be done on a support or mold.
- Figure 1 is a schematic representation of an installation according to the invention.
- FIGS 2, 3 and 4 are schematic representations of different calibration devices according to the invention.
- FIG. 5 is a schematic representation of a ribbon produced by the standard method by bath impregnation.
- Figure 6 is a schematic representation of a ribbon produced by a first embodiment of the invention.
- Figure 7 is a schematic representation of a ribbon produced by a second embodiment of the invention.
- Figures 8 and 9 are graphs showing the width measurements made every 1 m of tape as a function of the footage in m produced.
- Figure 10 is a schematic cross-sectional representation of a ribbon having bundles of filaments.
- the numeral 1 denotes a wick coil 2, for example a wick of carbon filaments.
- This coil is mounted on a spindle (not shown), provided with an adjustable brake.
- a first bar 3 is parallel to the axis of the coil 1 and oriented at 90 ° to the direction of travel of the wick 2, the latter sliding from left to right on the first bar because of the slitting of the coil of supply 2.
- a second bar 4 is located below the first, oriented at 90 ° relative to the previous and perpendicular to the machine axis. A series of seven docking bars is shown.
- a calibration device 7 has a groove through which the wick passes, which is calibrated to the desired width.
- a scarf 8 is disposed later, this scarf being designed to pinch the wick 2 and force it to move in the opposite direction to the supply reel.
- a laser device for measuring the width of the wick is shown under 9. Two metal bars 10 and 1 1 connected to the ground are in contact for one, 10, of the lower face of the wick, for the other , 1 1, of its upper face. These bars apply some pressure on the wick.
- an electrostatic powdering unit comprising two powdering guns 13, fed with fluidized polymer powder from a fluidization device (not shown).
- One of the guns has its spray nozzle oriented towards one side of the wick, the other toward the other side of the wick.
- the unit is controllable to ensure the continuous removal of a predetermined amount of thermoplastic or thermosetting material on the wick 2 which scrolls inside the enclosure.
- the numeral 14 designates two infrared furnaces, preferably short or medium, located one behind the other, which are controlled by temperature and this control is power.
- the wick impregnated with molten polymer then passes into a cooled calender.
- the shell has two rollers and a device for adjusting the pressure exerted by the rollers on the wick which passes between them.
- the wick then passes into a calibration device 16 which will be described with reference to FIGS. 2-4.
- a Laser Wavelength Measuring Device is shown at 17, which is connected to a computer or processor for recording the width and calculating the standard deviation. The device performs punctual measurements, at regular intervals, according to the desire of the user.
- the ribbon 18 itself is formed.
- the ribbon is then taken over by a ribbon winding device, comprising two return rollers 19 and 20 and a storage spool 21 mounted on a spindle (not shown) rotated.
- the active surfaces (in contact with the wick or ribbon) of the elements 4, 5, 7, 8, 14, 15, and 16 are perfectly aligned on the machine axis, so that the wick, then the ribbon when it is formed, does not undergo lateral movement or in sensible height.
- Figure 2 a first embodiment of a calibration device that can be used, in particular as a device 16 in the installation of Figure 1. It comprises a plate 22 hollowed with a groove 23 formed of a flared portion 24 and a straight portion 25.
- the width of the groove is equal to the width of the ribbon to be produced.
- the numeral 26 denotes a wheel having a planar surface of revolution slightly smaller in width than that of the rectilinear portion 25 of the groove in which it is inserted in part.
- a device (not shown), for example a vernier, allows to perform this operation. This adjusts the pressure on the wick.
- FIG 3 there is the same plate 22.
- a wheel 27 having a groove 28 peripheral flat bottom, whose width is equal to the width of the ribbon to produce.
- the wick 2 passes to the bottom of the groove 23, then into the groove 28 of the roller 27, which comes to apply pressure on it.
- a device for example vernier, not shown, allows to position the flat bottom of the groove in height relative to the machine axis to adjust the pressure exerted on the wick.
- a succession of three rollers 29 is used, each having a flat bottom peripheral groove 30 whose width is equal to the width of the ribbon to be produced.
- the first and third wheels are placed above the machine axis, the second below.
- the wick 2 passes in contact with the bottoms of the grooves 30, in the lower part of the first wheel, then in the upper part of the second, and finally in the lower part of the third.
- a device for example a vernier, not shown, makes it possible to position the flat bottom of the grooves in height with respect to the machine axis in order to adjust the pressure exerted on the bit.
- the carbon fiber wick is heated before spreading to a width of between 8 mm and 12 mm by loading, at a post-loading tension of between 4.5 kg and 2.5 kg.
- the fibers then pass through a groove 10 mm wide, then into the scarf that pulls the fiber. Before entering the dust box, the fiber passes into contact with two grounded bars.
- the dusting step is carried out using a SAMES installation comprising a fluidization tank, 2 guns and a control unit. To obtain the target powder rate, only one gun is used, its settings are reported in the following table:
- the pressure of the fluidization tank is set at 2 bars, which makes it possible to have a uniform and regular fluidization regime.
- the polymer is melted by passing the ribbon under two SOPARA infrared ribbon radials (IR average), set between 50% and 70% of their power.
- IR average SOPARA infrared ribbon radials
- Calibration is carried out by first calendering the ribbon and then passing it through a groove with a nominal width of 6.35 mm +/- 0.05 mm.
- the measurement of the width is performed by a Mike Model 91 1 LASER (measurement accuracy of 0.003 m), the data collected every 1 m during the production of a 1000 m coil is shown in Figure 8.
- the average width of the ribbon is 6.37 mm with a standard deviation of 0.04 mm.
- the winding takes place in tension, at a speed between 15 m / min and 20 m / min with a SAHM winder.
- Figure 6 is a schematic view of the surface of the ribbons observed at 0.6x3 magnification binocular magnification.
- the reference numeral 104 denotes the polymer coating, relatively continuous, and leaving the carbon filaments appear on discrete areas designated by the numerals 105.
- Example 2 obtaining a carbon / PEEK tape with a polymer mass ratio of 34% and width 6.35 mm using the installation of Figure 1.
- the carbon fiber wick is heated before spreading to a width of between 5 mm and 8 mm by insertion, at a post-loading tension of between 4.5 kg and 2.5 kg.
- the fibers then pass into a throat 8 mm wide, then into the scarf that pulls the fiber.
- the fiber Before entering the dust box, the fiber passes into contact with two grounded bars.
- the dusting step is carried out as in Example 1.
- the pressure of the fluidization tank is set at 2 bars, which makes it possible to have a uniform and regular fluidization regime.
- the polymer is melted by passing the ribbon under the two infrared radials SOPARA lamp (length of 75 cm and a power of 3 kW each), set between 50% and 70% of their power.
- Calibration is carried out by first calendering the ribbon and then passing it through a groove with a nominal width of 6.35 mm +/- 0.05 mm.
- the average width is 6.16 mm with a standard deviation of 0.13 mm.
- the winding takes place in tension, at a speed between 5 m / min and 20 m / min with a SAHM winder.
- Figure 7 is a schematic view of the surface of the ribbons observed with a 0.6x3 magnification binocular magnifier.
- the reference numeral 106 denotes the carbon filaments and this time, the polymer remained on the surface does not form a quasi-continuous coating, but discrete areas 107.
- FIG. 5 shows what is obtained by the standard impregnation method by immersion in a bath.
- Reference numeral 101 denotes continuous zones of polymer at the surface
- reference numeral 102 denotes discrete clusters of polymer
- reference numeral 103 denotes bare filaments.
- Example 3 Production of a composite article
- An Automated Fiber Placement (AFP) robot is programmed to deposit the ribbon according to Example 1 or Example 2 on a support, until forming the blank of the part to be manufactured.
- the robot places the ribbon edge to edge to form a fold, then superimposes another fold on the previous one, the superposition can be done according to one or angle (s) adapted (s), according to the production program of the draft .
- the blank formed is then placed according to a first sub-example in an oven and according to a second sub-example in an autoclave.
- the consolidation is completed and the consolidated composite part is obtained.
- Example 4 Production of a filament bundle ribbon
- a bar with circumferential grooves is installed, the grooves having a width which depends on the width of the beams concerned; typically, this width may be between about 0.25 and about 2 mm.
- the tape is brought into contact with this bar, permanently or intermittently, to ensure the separation of the wick into bundles.
- the first powdering gun projects the powder on the wick separated into bundles, especially immediately downstream of the bar.
- the second gun is placed a little downstream, including a few centimeters further, in a location where the beams have moved closer.
- the impregnated product resulting from this implementation is characterized by a distribution of the filaments in the form of bundles 108 with a width of between 200 ⁇ m and 6000 ⁇ m and a height of between 50 ⁇ m and 250 ⁇ m, of which spacing (polymer zone 109) is between 25 ⁇ and 100 ⁇ .
- this product retains a thin sheath 1 10 of polymer with a thickness between 25 ⁇ and 100 ⁇ .
- This product has a strong cohesion in the transverse direction to the filaments. Its surface condition may be similar to that observed with the hollow product.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Reinforced Plastic Materials (AREA)
- Moulding By Coating Moulds (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Working Measures On Existing Buildindgs (AREA)
Abstract
Description
Claims
Priority Applications (13)
Application Number | Priority Date | Filing Date | Title |
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CA2965448A CA2965448C (fr) | 2014-10-24 | 2015-10-26 | Meches poudrees par procede electrostatique |
BR112017008256-0A BR112017008256B1 (pt) | 2014-10-24 | 2015-10-26 | Fitas contínuas, método para fabricar uma fita, parte de compósito consolidada e instalação |
MX2017005352A MX2017005352A (es) | 2014-10-24 | 2015-10-26 | Hebras pulverizadas mediante metodo electrostatico. |
RU2017113762A RU2703213C9 (ru) | 2014-10-24 | 2015-10-26 | Стренги, покрытые порошком электростатическим способом |
JP2017521566A JP6730270B2 (ja) | 2014-10-24 | 2015-10-26 | 静電的方法により駆動されるストランド |
US15/521,473 US10538015B2 (en) | 2014-10-24 | 2015-10-26 | Strands powdered by electrostatic method |
CN201580062689.3A CN107107395B (zh) | 2014-10-24 | 2015-10-26 | 通过静电方法粉化的股线 |
EP15785102.3A EP3209473B1 (fr) | 2014-10-24 | 2015-10-26 | Mèches poudrées par procédé électrostatique |
ES15785102T ES2859728T3 (es) | 2014-10-24 | 2015-10-26 | Hebras recubiertas con polvo por procedimiento electrostático |
CN202011079562.1A CN112454736B (zh) | 2014-10-24 | 2015-10-26 | 一种连续带 |
DK15785102.3T DK3209473T3 (da) | 2014-10-24 | 2015-10-26 | Bundter, der er pulvercoatet med en elektrostatisk fremgangsmåde |
IL251752A IL251752B (en) | 2014-10-24 | 2017-04-18 | Strands dusted by an electrostatic method |
US16/731,927 US11518068B2 (en) | 2014-10-24 | 2019-12-31 | Strands powdered by electrostatic method |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1460259A FR3027546B1 (fr) | 2014-10-24 | 2014-10-24 | Meches poudrees par procede electrostatique |
FR1460259 | 2014-10-24 |
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US15/521,473 A-371-Of-International US10538015B2 (en) | 2014-10-24 | 2015-10-26 | Strands powdered by electrostatic method |
US16/731,927 Division US11518068B2 (en) | 2014-10-24 | 2019-12-31 | Strands powdered by electrostatic method |
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US (2) | US10538015B2 (fr) |
EP (1) | EP3209473B1 (fr) |
JP (2) | JP6730270B2 (fr) |
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BR (1) | BR112017008256B1 (fr) |
CA (1) | CA2965448C (fr) |
DK (1) | DK3209473T3 (fr) |
ES (1) | ES2859728T3 (fr) |
FR (1) | FR3027546B1 (fr) |
IL (1) | IL251752B (fr) |
MX (1) | MX2017005352A (fr) |
PT (1) | PT3209473T (fr) |
RU (1) | RU2703213C9 (fr) |
WO (1) | WO2016062896A1 (fr) |
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WO2018115736A1 (fr) | 2016-12-22 | 2018-06-28 | Arkema France | Procédé de fabrication d'un matériau fibreux pré-imprégné de polymère thermoplastique en lit fluidise |
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WO2019180370A1 (fr) | 2018-03-23 | 2019-09-26 | Arkema France | MATERIAU FIBREUX IMPREGNE DE POLYMERE THERMOPLASTIQUE D'EPAISSEUR INFERIEURE OU EGALE A 100µM ET SON PROCEDE DE PREPARATION |
EP3670127A1 (fr) | 2018-12-18 | 2020-06-24 | Arkema France | Procede de fabrication d'un materiau fibreux impregne de polymere thermoplastique |
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JP7245186B2 (ja) | 2023-03-23 |
US11518068B2 (en) | 2022-12-06 |
IL251752B (en) | 2020-11-30 |
IL251752A0 (en) | 2017-06-29 |
CA2965448C (fr) | 2023-04-18 |
CN112454736B (zh) | 2022-09-23 |
FR3027546A1 (fr) | 2016-04-29 |
US20200139587A1 (en) | 2020-05-07 |
MX2017005352A (es) | 2018-01-09 |
RU2703213C9 (ru) | 2019-11-25 |
JP2020090103A (ja) | 2020-06-11 |
PT3209473T (pt) | 2021-04-22 |
US20170334094A1 (en) | 2017-11-23 |
JP2017533983A (ja) | 2017-11-16 |
BR112017008256B1 (pt) | 2022-04-05 |
CN112454736A (zh) | 2021-03-09 |
JP6730270B2 (ja) | 2020-07-29 |
DK3209473T3 (da) | 2021-04-26 |
CN107107395A (zh) | 2017-08-29 |
ES2859728T3 (es) | 2021-10-04 |
EP3209473A1 (fr) | 2017-08-30 |
RU2703213C2 (ru) | 2019-10-15 |
EP3209473B1 (fr) | 2021-03-03 |
CN107107395B (zh) | 2021-01-08 |
RU2017113762A3 (fr) | 2019-04-22 |
CA2965448A1 (fr) | 2016-04-28 |
BR112017008256A2 (pt) | 2018-01-02 |
US10538015B2 (en) | 2020-01-21 |
FR3027546B1 (fr) | 2017-07-21 |
RU2017113762A (ru) | 2018-10-23 |
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