Method of producing a fibrous material pre-impregnated with thermoplastic polymer in a fluid bed

Abstract

A method of producing a pre-impregnated fibrous material including a fibrous material of continuous fibres and a thermoplastic polymer matrix, wherein the pre-impregnated fibrous material is produced in a single unidirectional strip or in a plurality of parallel unidirectional strips, the method including the following steps: (i) impregnating the fibrous material in the form of a strand or a plurality of parallel strands with the thermoplastic polymer in the form of a powder in a fluid bed; and (ii) shaping the strand or parallel strands of the fibrous material impregnated as in step (i) by calendering by at least one heating calender in the form of a single unidirectional strip or of a plurality of parallel unidirectional strips, the heating calender, in the latter case, including a plurality of calendering grooves, and the pressure and/or a spacing between the rollers of the calender being regulated by an auxiliary system.

Claims

1. A method of producing a pre-impregnated fibrous material comprising a fibrous material of continuous fibres and a thermoplastic polymer matrix, wherein said pre-impregnated fibrous material is produced in a plurality of parallel unidirectional ribbons, wherein the method comprises the following steps: i) impregnating said fibrous material, in the form of several parallel rovings, said rovings not being in contact with each other, with said thermoplastic polymer or a mixture of thermoplastic polymers, in the form of a fluidised bed powder, the powder having powder particles with a mean diameter of less than 125 μm, and ii) forming said parallel rovings of said fibrous material impregnated at step i), via calendering by means of at least one heating calender, into the form of a plurality of parallel unidirectional ribbons, said heating calender comprises a plurality of calendering grooves conforming to the number of said ribbons, the pressure and/or spacing between the rollers of said calender being regulated by a servo system.

2. The method according to claim 1, wherein the method further comprises a step iii) of spooling said ribbons on a plurality of spools, the number of spools being identical to the number of ribbons, one spool being allocated to each ribbon.

3. The method according to claim 1, wherein said impregnating said fibrous material in step i) is completed by a coating step of said single roving or said plurality of parallel rovings after impregnation with the powder at step i), with a molten thermoplastic polymer, wherein the polymer is the same or different from said polymer in fluidised bed powder form, said coating step being performed before said calendering in step ii).

4. The method according to claim 1, wherein said polymer in fluidised bed powder form is a thermoplastic polymer or mixture of thermoplastic polymers.

5. The method according to claim 4, wherein said thermoplastic polymer or mixture of thermoplastic polymers further comprises carbon fillers.

6. The method according to claim 4, wherein the thermoplastic polymer or mixture of thermoplastic polymers comprises liquid crystal polymers or cyclic polybutylene terephthalate, or mixtures containing the liquid crystal polymers or cyclic polybutylene terephthalate, as additive.

7. The method according to claim 1, wherein said thermoplastic polymer, or mixture of thermoplastic polymers, is selected from among amorphous polymers having a glass transition temperature Tg≥80° C. and/or from among semi-crystalline polymers having a melting temperature Tf≥150° C.

8. The method according to claim 7, wherein the thermoplastic polymer or mixture of thermoplastic polymers is selected from among: polyaryl ether ketones; polyaryl ether ketone ketones; aromatic polyether-imides; polyaryl sulfones; polyarylsulfides; polyamides; polyacrylates; or fluorinated polymers; or mixtures thereof.

9. The method according to claim 1, wherein said fibrous material comprises continuous fibres selected from among carbon, glass, silicon carbide, basalt, silica fibres, natural fibres, or thermoplastic fibres having a glass transition temperature Tg higher than the Tg of said polymer or a mixture of polymers when the latter are amorphous, or having a melting temperature Tf higher than the Tf of said polymer or said mixture of polymers when the latter are semi-crystalline, or a mixture of two or more of said fibres.

10. The method according to claim 1, wherein the volume percentage of said polymer or mixture of polymers relative to said fibrous material varies from 40 to 250%.

11. The method according to claim 1, wherein the volume percentage of said polymer or a mixture of polymers relative to said fibrous material varies from 0.2 to 15%.

12. The method according to claim 1, wherein the calendering in step ii) is performed using a plurality of heating calenders.

13. The method according to claim 1, wherein said heating calender(s) in step ii) comprise an integrated heating system via induction or microwave, combined with the presence of carbon fillers in said thermoplastic polymer or mixture of thermoplastic polymers.

14. The method according claim 1, wherein said heating calender(s) in step ii) are coupled to an additional rapid heating device positioned before and/or after said calender(s).

15. A unidirectional ribbon of pre-impregnated fibrous material, wherein the ribbon is obtained using the method according to claim 1.

16. The ribbon according to claim 15, wherein the ribbon has a width (I) and thickness adapted for depositing by a robot for the manufacture of three-dimensional parts, without the need for slitting.

17. The use of the method according to claim 1, for the production of calibrated ribbons adapted to the manufacture of three-dimensional composite parts via automated deposit of said ribbons by a robot.

18. The use of the ribbon of pre-impregnated fibrous material defined in claim 15 for the manufacture of three-dimensional composite parts.

19. The use according to claim 18, wherein said manufacture of said composite parts concerns the transport sectors; renewable energies; energy storage systems; thermal protection panels; sports and leisure equipment, health and medicine; ballistics with parts for weapons or missiles; safety and electronics.

20. A three-dimensional composite part, wherein the part results from the use of at least one unidirectional ribbon of pre-impregnated fibrous material according to claim 15.

21. A unit for implementing the method according to claim 1, wherein the unit comprises: a) a device for continuous impregnation of a roving or plurality of parallel rovings of fibrous material, comprising a tank of a fluidised bed of powder polymer; and b) a device for continuous calendering of said roving or said parallel rovings, with forming into a single ribbon or into several parallel unidirectional ribbons, comprising: b1) at least one heating calender, said calender having a calendering groove or several calendering grooves, and b2) a system for regulating pressure and/or spacing between calender rollers.

22. The unit according to claim 21, wherein the unit further comprises a device for spooling the ribbons of pre-impregnated fibrous materials, wherein said device for spooling comprises a number of spools identical to the number of ribbons, one spool being allocated to each ribbon.

23. The unit according to claim 21, wherein said device for continuous impregnation, following after said fluidised bed tank, further comprises a device for coating said roving(s) of fibrous material impregnated at step i), with a molten polymer.

24. The unit according to claim 21, wherein said heating calender(s) comprise an integrated heating system via induction.

25. The unit according to claim 21, wherein said heating calender(s) are coupled to an additional rapid heating device, positioned before and/or after said calender(s), said rapid heating device being selected from among a microwave or induction device.

Description

(1) Other particular aspects and advantages of the invention will become apparent on reading the description that is non-limiting and given for illustrative purposes, with reference to the appended Figures illustrating:

(2) FIG. 1, a schematic of a unit to implement the method of producing a pre-impregnated fibrous material according to the invention;

(3) FIG. 2, a cross-sectional schematic of two constituent rollers of a calender such as used in the unit in FIG. 1,

(4) FIG. 3, a photo taken under scanning electron microscope of a cross-sectional view of a glass fibre roving of 1200 Tex, impregnated to the core with a PA11 polyamide powder of mean size 100 μm;

(5) FIG. 4, a photo taken under scanning electron microscope of a cross-sectional view of a composite ribbon obtained by calendering the glass fibre roving in FIG. 3,

(6) FIG. 5, a photo taken under scanning electron microscope of a cross-sectional view of a composite ribbon obtained by calendering a roving of 12K carbon fibres, pre-impregnated with PA11 polyamide powder.

DETAILED DESCRIPTION OF THE INVENTION

(7) Polymer Matrix

(8) By thermoplastic or thermoplastic polymer is meant a material generally solid at ambient temperature, possibly being crystalline, semi-crystalline or amorphous, which softens on temperature increase, in particular after passing its glass transition temperature (Tg), flows at higher temperature and may melt without any phase change when it passes its melting temperature (Tf) (if it is semi-crystalline); it returns to the solid state when the temperature drops to below its melting temperature and below its glass transition temperature.

(9) With regard to the constituent polymer of the fibrous material impregnation matrix, it is advantageously a thermoplastic polymer or mixture of thermoplastic polymers. This thermoplastic polymer or mixture of thermoplastic polymers is ground to a powder so that it can be used in a fluidised bed. The powder particles preferably have a mean diameter of less than 125 μm so that they can penetrate the fibre roving (s).

(10) Optionally, the thermoplastic polymer or mixture of thermoplastic polymers further comprises carbon fillers, carbon black in particular or carbon nanofillers, preferably selected from among carbon nanofillers in particular graphenes and/or carbon nanotubes and/or carbon nanofibrils or the mixtures thereof. These fillers allow conducting of electricity and heat and therefore allow improved lubrication of the polymer matrix when it is heated.

(11) According to another variant, the thermoplastic polymer or mixture of thermoplastic polymers may further comprise additives such a liquid crystal polymers or cyclic polybutylene terephthalate, or mixtures containing the same such as CBT100 resin marketed by CYCLICS CORPORATION. These additives particularly allow fluidisation of the polymer matrix in the molten state, for better penetration into the core of the fibres. Depending on the type of thermoplastic polymer or polymer mixture used to prepare the impregnation matrix, in particular the melting temperature thereof, one or other of these additives will be chosen.

(12) Advantageously, the thermoplastic polymer, or mixture of thermoplastic polymers, is selected from among amorphous polymers having a glass transition temperature such that Tg≥80° C. and/or from among semi-crystalline polymers having a melting temperature Tf≥150° C.

(13) More particularly, the thermoplastic polymers entering into the composition of the fibrous material impregnation matrix can be selected from among: polymers and copolymers of the polyamide family (PA), such as high density polyamide, polyamide 6 (PA-6), polyamide 11 (PA-11), polyamide 12 (PA-12), polyamide 6.6 (PA-6.6), polyamide 4.6 (PA-4.6), polyamide 6.10 (PA-6.10), polyamide 6.12 (PA-6.12), aromatic polyamides, optionally modified by urea units, in particular polyphthalamides and aramid, and block copolymers in particular polyamide/polyether, polyureas, aromatic in particular, polymers and copolymers of the acrylic family such as polyacrylates, and more particularly polymethyl methacrylate (PMMA) or the derivatives thereof, polymers and copolymers of the polyarylether ketone family (PAEK) such as polyether ether ketone (PEEK), or polyarylether ketone ketones (PAEKK) such as polyether ketone ketone) (PEKK) or the derivatives thereof, aromatic polyether-imides (PEI), polyarylsulfides, in particular polyphenylene sulfides (PPS), polyarylsulfones, in particular polyphenylene sulfones (PPSU), polyolefins, in particular polypropylene (PP); polylactic acid (PLA), polyvinyl alcohol (PVA), fluorinated polymers, in particular polyvinylidene fluoride (PVDF), or polytetrafluoroethylene (PTFE) or polychlorotrifluoroethylene (PCTFE), and the mixtures thereof.

(14) Preferably the constituent polymers of the matrix are selected from among thermoplastic polymers having a high melting temperature Tf, namely on and after 150° C., such as Polyamides (PA), in particular aromatic polyamides optionally modified by urea repeat units and the copolymers thereof, Polymethyl methacrylate (PPMA) and the copolymers thereof, Polyether imides (PEI), Polyphenylene sulfide (PPS), Polyphenylene sulfone (PPSU), Polyetherketoneketone (PEKK), Polyetheretherketone (PEEK), fluorinated polymers such as polyvinylidene fluoride (PVDF).

(15) For fluorinated polymers, a homopolymer of vinylidene fluoride (VDF of formula CH.sub.2═CF.sub.2) can be used, or a VDF copolymer comprising at least 50 weight % VDF and at least one other monomer copolymerisable with VDF. The VDF content must be higher than 80 weight %, even better higher than 90 weight % to impart good mechanical strength to the structural part, especially when subjected to thermal stresses. The comonomer may be a fluorinated monomer such as vinyl fluoride for example.

(16) For structural parts that are to withstand high temperatures, in addition to fluorinated polymers advantageous use can be made according to the invention of PAEKs (PolyArylEtherKetone) such as polyether ketones (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether ketone ether ketone ketone (PEKEKK), etc.

(17) Fibrous Material:

(18) Regarding the constituent fibres of the fibrous material, these are fibres of mineral, organic or plant origin in particular. Among the fibres of mineral origin, mention can be made of carbon fibres, glass fibres, basalt fibres, silica fibres or silicon carbide fibres for example. Among the fibres of organic origin, mention can be made of fibres containing a thermoplastic or thermosetting polymer such as aromatic polyamide fibres, aramid fibres or polyolefin fibres for example. Preferably they are thermoplastic polymer-based and have a glass transition temperature Tg higher than the Tg of the constituent thermoplastic polymer or thermoplastic polymer mixture of the impregnation matrix if the polymer(s) are amorphous, or a melting temperature Tf higher than the Tf of the constituent thermoplastic polymer or thermoplastic polymer mixture of the impregnation matrix if the polymer(s) are semi-crystalline. There is therefore no risk of melting of the constituent organic fibres of the fibrous material. Among the fibres of plant origin, mention can be made of natural flax, hemp, silk in particularly spider silk, sisal fibres and other cellulose fibres particularly viscose. These fibres of plant origin can be used pure, treated or coated with a coating layer to facilitate adhesion and impregnation of the thermoplastic polymer matrix.

(19) These constituent fibres can be used alone or in a mixture. For example, organic fibres can be mixed with mineral fibres for impregnation with thermoplastic polymer and to form the pre-impregnated fibrous material.

(20) The chosen fibres can be single-strand, multi-strand or a mixture of both, and can have several gram weights. In addition they may have several geometries. They may therefore be in the form of short fibres, then producing felts or nonwovens in the form of strips, sheets, braids, rovings or pieces, or in the form of continuous fibres producing 2D fabrics, fibres or rovings of unidirectional fibres (UD) or nonwovens. The constituent fibres of the fibrous material may also be in the form of a mixture of these reinforcing fibres having different geometries. Preferably, the fibres are continuous.

(21) Preferably, the fibrous material is composed of continuous fibres of carbon, glass or silicon carbide or a mixture thereof, in particular carbon fibres. It is used in the form of one or more rovings.

(22) Depending on the volume ratio of polymer relative to the fibrous material, it is possible to produce so-called “ready-to-use” pre-impregnated materials or so-called “dry” pre-impregnated materials.

(23) In so-called “ready-to-use” pre-impregnated materials, the thermoplastic polymer or polymer mixture is uniformly and homogeneously distributed around the fibres. In this type of material, the impregnating thermoplastic polymer must be distributed as homogenously as possible within the fibres to obtain minimum porosities i.e. voids between the fibres. The presence of porosities in this type of material may act as stress-concentrating points when subjected to a mechanical tensile stress for example and then form rupture initiation points in the pre-impregnated fibrous material causing mechanical weakening. Homogeneous distribution of the polymer or polymer mixture therefore improves the mechanical strength and homogeneity of the composite material produced from these pre-impregnated fibrous materials.

(24) Therefore, with regard to so-called “ready-to-use” pre-impregnated materials, the volume percentage of thermoplastic polymer or polymer mixture relative to the fibrous material varies from 40 to 250%, preferably from 45 to 125%, and more preferably from 45 to 80%.

(25) So-called “dry” pre-impregnated fibrous materials comprise porosities between the fibres and a smaller amount of impregnating thermoplastic polymer coating the fibres on the surface to hold them together. These “dry” pre-impregnated materials are adapted for the manufacture of preforms for composite materials. These preforms can then be used for the infusion of thermoplastic resin or thermosetting resin for example. In this case, the porosities facilitate subsequent conveying of the infused polymer into the pre-impregnated fibrous material, to improve the end properties of the composite material and in particular the mechanical cohesion thereof. In this case, the presence of the impregnating thermoplastic polymer on the so-called “dry” fibrous material is conducive to compatibility of the infusion resin.

(26) With regard to so-called “dry” pre-impregnated materials therefore, the volume percentage of polymer or mixture of polymers relative to the fibrous material advantageously varies from 0.2 to 15%, preferably between 0.2 and 10% and more preferably between 0.2 and 5%. In this case the term polymeric web is used having low gram weight, deposited on the fibrous material to hold the fibres together.

(27) The method of producing a fibrous material according to the invention advantageously comprises two steps: a first step to impregnate the fibrous material with the thermoplastic polymer, followed by a step to form the pre-impregnated fibrous material into one or more unidirectional ribbons having calibrated width and thickness.

(28) Impregnation Step:

(29) The production method and unit to implement this method are described below with reference to FIG. 1 which, in very simple manner, schematises the constituent elements of this unit 100.

(30) Advantageously, the impregnation step of the fibrous material is performed by passing one or more rovings through a continuous impregnating device comprising a tank 20 of a polymer powder fluidised bed.

(31) Each roving to be impregnated is unwound from a reel 11 device 10, under traction generated by cylinders (not illustrated). Preferably the device 10 comprise a plurality of reels 11, each reel allowing the unwinding of one roving to be impregnated. It is therefore possible to impregnate several fibre rovings simultaneously. Each reel 11 is provide with a braking system (not illustrated) to tension each fibre roving. In this case an alignment module 12 allows the fibre rovings to be arranged parallel to one another. In this manner the fibre rovings cannot come into contact with each other, thereby particularly avoiding mechanical degradation of the fibres.

(32) The fibre roving or parallel fibre rovings then pass through a tank 20 of a fluidised bed 22, such as described in patent EP0406067. The powder of polymer(s) is placed in suspension in a gas G (e.g. air) added to the tank and circulating inside the tank through a hopper 21. The roving(s) are set in circulation in this fluidised bed 22. The mean diameter of the polymer powder particles in the fluidised bed is preferably smaller than 125 μm, so that they can penetrate the fibre roving(s). This impregnation is performed to allow adhesion of the polymer powder to the fibres. The roving(s) pre-impregnated with the powder then leave the tank and are directed towards the heating calender device, possibly with preheating before calendering and with optional post-calender heating.

(33) Optionally, this impregnation step can be completed by a step to coat the pre-impregnated roving or rovings, immediately after leaving the tank 20 in which they were impregnated with fluidised bed powder 22, and just before the forming step via calendering. In this case, the airlock at the outlet of the fluidised tank 20 (fluidised bed 22) can be connected to a coating device 30 which may comprise a coating crosshead as also described in patent EP0406067. More particularly, said coating device comprises a crosshead supplied with molten thermoplastic polymer by an extruder 30. The coating polymer may the same or different from the polymer powder in the fluidised bed. Preferably it is of same type. Said coating not only allows completion of the fibre impregnation step to obtain a final volume percentage of polymer within the desired range, in particular to obtain so-called “ready-to-use” fibrous materials of good quality, but also allows improvement in the performance of the composite material obtained.

(34) Forming Step

(35) Immediately on leaving the fluidisation tank 20, the pre-impregnated roving or parallel rovings, optionally coated with molten polymer, are formed into a single unidirectional ribbon or into a plurality of parallel unidirectional ribbons, by means of a continuous calendering device comprising one or more heating calenders.

(36) Up until the present time, hot calendering could not be envisaged for a forming step but only for a finishing step since it was not able to heat up to sufficient temperatures, in particular if the thermoplastic polymer or polymer mixture comprises polymers with a high melting temperature.

(37) Advantageously, the heating calenders of the calendering device are coupled to rapid heating means which allow the material to be heated not only on the surface but also at the core. The mechanical stress of the calenders coupled to these rapid heating means allows porosities to be removed and the polymer to be distributed homogeneously, in particular if the fibrous material is a so-called “ready-to-use” material.

(38) Advantageously, this hot calendering not only allows the impregnation polymer to be heated so that it penetrates into, adheres to and uniformly coats the fibres, but also provides control over the thickness and width of the ribbons of pre impregnated fibrous material.

(39) To produce a plurality of parallel unidirectional ribbons i.e. as many ribbons as pre-impregnated parallel rovings passed through the fluidised bed, the heating calenders referenced 51, 52, 53 in the schematic in FIG. 1 advantageously comprise a plurality of calendering grooves conforming to the number of ribbons. This number of grooves may total up to 200 for example. A SYST servo system allows regulation of the pressure and/or of the spacing E between the rollers 71, 75 of the calender 70, so as to control the thickness ep of the ribbons. Said calender 70 is schematised in FIG. 2 described below.

(40) The calendering device comprises at least one heating calender 51. Preferably it comprises several heating calenders 51, 52, 53 mounted in series. The fact that there are several calenders in series means that it is possible to compress the porosities and reduce the number thereof. This plurality of calenders is therefore of importance if it is desired to produce so-called “ready-to-use” fibrous materials. On the other hand, to produce so-called “dry” fibrous materials, a fewer number of calenders will be sufficient, even a single calender.

(41) Advantageously, each calender of the calendering device has an integrated heating system via induction or microwave, preferably microwave, to heat the thermoplastic polymer or polymer mixture. Advantageously if the polymer of polymer mixture comprises carbon fillers such as carbon black or carbon nanofillers, preferably selected from among carbon nanofillers in particular graphenes and/or carbon nanotubes and/or carbon nanofibrils or the mixtures thereof, the heating effect via induction or microwave is amplified by these fillers which then convey the heat into the core of the material.

(42) Advantageously, each calender 51, 52, 53 of the device is coupled to a rapid heating device 41, 42, 43 positioned before and/or after each calender for rapid transmission of thermal energy to the material and for perfecting of fibre impregnation with the molten polymer. The rapid heating device can be selected for example from among the following devices: a microwave or induction device, an infrared IR or laser device or other device allowing direct contact with a heat source such as a flame device. A microwave or induction device is most advantageous, in particular when combined with the presence of carbon nanofillers in the polymer or polymer mixture since carbon nanofillers amplify the heating effect and transmit this effect to the core of the material.

(43) According to one variant of embodiment it is also possible to combine several of these heating devices.

(44) The method may further comprise a step to heat the fibre rovings before said impregnation using microwave heating as preferred heating means, as for the heating system of said heating calender.

(45) Optionally, a subsequent step is to spool the pre-impregnated, formed ribbon(s). For this purpose a unit 100 to implement the method comprises a spooling device 60 comprising as many spools 61 as there are ribbons, one spool 61 being allocated to each ribbon. A distributor 62 is generally provided to direct the pre-impregnated ribbons towards their respective spool 61 whilst preventing the ribbons from touching one another to prevent any degradation.

(46) FIG. 2 schematises cross-sectional details of the groove 73 of a calender 70. A calender 70 comprises an upper roller 71 and a lower roller 75. One of the rollers e.g. the upper roller 71 comprises a castellated part 72, whilst the other roller i.e. the lower roller 75 in the example comprises a grooved part 76, the shape of the grooves matching the protruding parts 72 of the upper roller. The spacing E between the rollers 71, 75 and/or the pressure applied by the two rollers against one another allows defining of the dimensions of the grooves 73, and in particular the thickness ep thereof and width I. Each groove 73 is designed to house a fibre roving which is then pressed and heated between the rollers. The rovings are subsequently transformed into parallel unidirectional ribbons, the thickness and width of which are calibrated by the grooves 73 of the calenders. Each calender advantageously comprises a plurality of grooves the number of which may total up to 200, so that as many ribbons can be produced as there are grooves and pre-impregnated rovings. The calendering device also comprises a central device referenced SYST in FIG. 1, driven by a computer programme provided for this purpose and which allows simultaneous regulation of the pressure and/or spacing between the calender rollers of all the calenders in the unit 100.

(47) The unidirectional ribbon(s) thus produced have a width I and thickness ep adapted for depositing by a robot for the manufacture of three-dimensional parts without the need for slitting. The width of the ribbon(s) is advantageously between 5 and 100 mm, preferably between 5 and 50 mm, and more preferably between 5 and 10 mm.

(48) The method of producing a pre-impregnated fibrous material just described therefore allows pre-impregnated fibrous materials to be produced with high productivity whilst allowing homogeneous impregnation of the fibres, providing control over porosity which is reproducible and hence providing controlled, reproducible performance of the targeted end composite product. Homogeneous impregnation around the fibres and the absence of porosities are ensured by the fluidised bed impregnation step coupled with the use of a forming device under mechanical loading itself coupled to rapid heating systems, thereby allowing heating of the material on the surface as well as at the core. The materials obtained are semi-finished products in the form of ribbons with calibrated thickness and width used for the manufacture of three-dimensional structural parts in transport sectors such as automobile, civil or military aviation, nautical, rail; renewable energies in particular wind energy, hydrokinetic energy; energy storage devices, solar panels; thermal protection panels; sports and leisure equipment, health and medicine, weaponry and ballistics (parts for weapons or missiles), safety—using a method entailing the deposition of strips assisted by a robot head for example and known as Automatic Fibre Placement (AFP).

(49) This method therefore allows the continuous manufacture of ribbons of calibrated size and long length, with the result that it avoids slitting and stubbing steps that are costly and detrimental to the quality of subsequently manufactured composite parts. The savings related to elimination of the slitting step represent about 30-40% of the total production cost of a ribbon of pre-impregnated fibrous material.

(50) The association of rapid heating devices with the heating calenders facilitates forming of the ribbons to the desired dimensions, and allows a significant increase in the production rate of these ribbons compared with conventional forming methods. In addition this association allows densification of the material by fully eliminating the porosities in so-called “ready-to-use” fibrous materials.

(51) The rapid heating devices also allow the use of numerous grades of polymers, even the most viscous, thereby covering all the desired ranges of mechanical strength.

(52) For the specific manufacture of ribbons of so-called “dry” fibrous materials, the fluidised bed impregnation step allows a polymer gram weight to be obtained that is homogenously distributed, controlled and reproducible with a preferred content of deposited polymer in the order of 5 to 7 g/m.

(53) The method therefore allows the production of calibrated ribbons of pre-impregnated fibrous material adapted for the manufacture of three-dimensional composite parts via automated deposition of said ribbons.

(54) The following examples give a non-limiting illustration of the scope of the invention.

EXAMPLES

Example 1

(55) A glass fibre roving of 1200 Tex was immersed in a fluidised powder bed composed of PA11 polyamide powder having a mean particle size of 100 μm. The PA11 powder was previously dry mixed with 0.2% (by weight) of carbon black powder of 50 μm particle size.

(56) On leaving the fluidised bed the glass fibre roving was heated up to the softening temperature of the polymer (150° C.) to fix the powder on the glass fibres. The impregnation method allowed impregnation to the core of the fibre rovings. The force applied to the roving was low and just sufficient to tension the fibre roving.

(57) Before being placed in the calender, the powder pre-impregnated roving was heated by means of an infrared (IR) oven until melting of the polymer and then placed in the heating calender having a wall temperature (i.e. the temperature of the surface of the castellated portion and grooved portion) brought to 110° C. The fluidised bed through-rate and calender through-rate were the same since the roving is tensioned and both items of equipment are in series. The linear speed of the roving was 20 m/mn. The calender was essentially characterized by a groove of width 6.35 mm in which a castellated portion was inserted under pressure. The pressure was controlled by an adapted device and maintained constant at 5 bars throughout the calendering test.

(58) Results:

(59) The photo in FIG. 3, taken under scanning electron microscope SEM, gives a cross-sectional view of the pre-impregnated glass fibre roving before calendering. It can be seen that the polymer powder is truly present at the core of the fibre roving, which proves the efficacy of the fluidised bed impregnation mode. The powder particles are still visible even after the fixing phase via softening of the polymer.

(60) Table 1 below gives the width measurements that were obtained with 30 samples representing the pre-impregnated roving before calendering. It can be observed that the roving width is quite variable with a minimum of 1.26 mm and maximum of 4.54 mm.

(61) TABLE-US-00001 TABLE 1 Width measurements of samples representing the pre-impregnated roving before calendering. Width (mm) Mini 1.26 Maxi 4.54 Mean 2.98 Std. deviation 0.77

(62) Table 2 below gives the width measurements obtained on 30 samples representing the ribbon after calendering. It can be seen that the variation in roving width is much narrower than for the pre-impregnated roving before calendering, with a minimum of 5.01 mm and maximum of 6.85. It is also observed that the mean value of the calendered ribbon is much higher than that of the pre-impregnated roving before calendering (2.98 mm compared with 6.19) and is close to the target of 6.35 mm (size of the calender groove) which shows the efficacy of calendering to finish the production of the composite ribbon after the pre-impregnation phase of the glass fibre roving.

(63) TABLE-US-00002 TABLE 2 Width measurements of samples representing the ribbon calendered from a glass fibre roving of 1200 Tex, pre-impregnated with PA11 powder. Width (mm) Mini 5.01 Maxi 6.85 Mean 6.19 Std. deviation 0.34

(64) FIG. 4 is a cross-sectional view of the composite ribbon after calendering, observed under scanning electron microscope, after preparation of the surface by polishing following the rules of the art. It can be seen that the PA11 powder particles have disappeared giving way to a homogeneous polymer matrix of the composite having scarce porosity. This proves that calendering allows melting of the powder and consolidation of the composite ribbon as was desired.

(65) This example demonstrates the efficacy of the impregnation method using a dry powder in a fluidised bed in association with calendering, to obtain a glass fibre unidirectional composite ribbon (UD) impregnated with a thermoplastic matrix and having a width of 6.35 mm (¼ inch), without having recourse to slitting of a unidirectional composite sheet.

Example 2

(66) The operating conditions were identical to Example 1. The particle size of the PA11 powder differed (30 μm on average compared with 100 μm in Example 1). In this example carbon fibres were used forming a 12K roving. FIG. 5 gives a cross-sectional view of the composite ribbon obtained, after calendering, observed under scanning electron microscope (SEM). As in Example 1 the powder particles melted to give way to a polymer matrix of composite ribbon that is homogeneous and scarcely porous.

(67) Width measurements of the calendered composite ribbon are given in Table 3, following the same measuring protocol as in Example 1.

(68) TABLE-US-00003 TABLE 3 Width measurements of samples representing a ribbon calendered from the 12K carbon fibre roving pre-impregnated with PA11 powder. Width (mm) Mini 6.00 Maxi 6.75 Mean 6.36 Std. deviation 0.13

(69) This demonstrates the efficacy of the impregnation method using a dry powder in a fluidised bed in association with calendering, to obtain a composite, unidirectional (UD) carbon fibre ribbon having a width of 6.35 mm (¼ inch), without having recourse to slitting a unidirectional composite sheet.