METHOD FOR IMPREGNATING A FIBROUS MATERIAL WITH AN OPTIMISED SYSTEM FOR RESUPPLYING AND CLEANING FINE PARTICLES

Abstract

A method for manufacturing an impregnated fibrous material comprising at least one fibrous material made of continuous fibres and at least one thermoplastic polymer matrix comprises a step of pre-impregnating the fibrous material with a thermoplastic polymer matrix in powder form. This step is carried out dry in a tank comprising a fluidized bed, while keeping the level h of the powder and the mass m of the powder present in the tank substantially constant. The level h is from hi to hi−3%, during implementation of the pre-impregnation step, and hi is the initial level of the powder in the tank at the start of implementation of the pre-impregnation step, the mass m is from mi to mi±0.5% during implementation of the pre-impregnation step, and mi is the initial mass of the powder in the tank at the start of implementation of the pre-impregnation step.

Claims

1. A process for manufacturing an impregnated fibrous material comprising at least one fibrous material made of continuous fibers and at least one thermoplastic polymer matrix, said process comprising: a step of pre-impregnating said fibrous material with a thermoplastic polymer matrix in powder form, wherein said pre-impregnation step is carried out dry in a tank comprising a fluidized bed, said pre-impregnation step being carried out while keeping the level h of the powder and the mass m of the powder present in the tank substantially constant, said level h being from hi to hi−3% during an implementation of the pre-impregnation step, where hi is an initial level of the powder in said tank at a start of the implementation of the pre-impregnation step, said mass m being from mi to mi±0.5% during the implementation of the pre-impregnation step, where mi is an initial mass of the powder in said tank at the start of the implementation of the pre-impregnation step, with the exclusion of any electrostatic process with intentional charging.

2. The process as claimed in claim 1, wherein a volume mean diameter D50 of thermoplastic polymer powder particles of the powder is from 30 to 300 μm.

3. The process as claimed in claim 1, wherein the tank is replenished with the thermoplastic polymer matrix in powder form to compensate for a consumption of said thermoplastic polymer matrix by the pre-impregnation of said fibrous material.

4. The process as claimed in claim 1, wherein a particle size of said powder is substantially constant in said tank, such that a D50 of the thermoplastic polymer powder particles of the powder varies by a maximum of +20%.

5. The process as claimed in claim 1, wherein a particle size of the fine particles of said powder is substantially constant in said tank, such that a D10 of the thermoplastic polymer powder particles of the powder varies by a maximum of +30%.

6. The process as claimed in claim 1, wherein a particle size of the large particles of said powder is substantially constant in said tank, such that a D90 of the thermoplastic polymer powder particles of the powder varies by a maximum of +10%.

7. The process as claimed in claim 1, wherein said tank comprises a fluidized bed and said pre-impregnation step is carried out with simultaneous spreading of a roving or rovings between an inlet and an outlet of said fluidized bed.

8. The process as claimed in claim 1, wherein said tank is equipped with a scraper.

9. The process as claimed in claim 8, wherein said scraper is used automatically when the level h<hi−3%.

10. The process as claimed in claim 1, wherein said tank is equipped with a transverse suction system which sucks up fine particles having a diameter of 0.01 to 60 μm which leave said tank during the fluidization.

11. The process as claimed in claim 10, wherein said suctioned particles are continuously reintroduced into said tank.

12. The process as claimed in claim 1, wherein said tank is equipped with a scraper and a transverse suction system which sucks up fine particles having a diameter of 0.01 to 60 μm which leave said tank.

13. The process as claimed in claim 1, wherein said fluidized bed comprises at least one tension device, a roving or rovings being in contact with a portion or the whole of a surface of said at least one tension device.

14. The process as claimed in claim 13, wherein a spreading of said roving or of said rovings is carried out at least at a level of said at least one tension device.

15. The process as claimed in claim 13, wherein said at least one tension device is a compression roller of convex, concave or cylindrical shape.

16. The process as claimed in claim 15, wherein said at least one compression roller is of cylindrical shape and a percentage of spreading of said roving or of said rovings between the inlet and the outlet of said fluidized bed is from 1% to 400%.

17. The process as claimed in claim 1, wherein said thermoplastic polymer is a non-reactive thermoplastic polymer.

18. The process as claimed in claim 17, comprising a step of heating the pre-impregnated fibrous material to melt the thermoplastic polymer and to finalize the impregnation of said fibrous material.

19. The process as claimed in claim 1, wherein said thermoplastic polymer is a reactive prepolymer capable of reacting on itself or with another prepolymer, depending on the chain ends borne by said prepolymer, or else with a chain extender.

20. The process as claimed in claim 19, comprising a step of heating the pre-impregnated fibrous material to melt and polymerize the thermoplastic prepolymer optionally with said extender and to finalize the impregnation of said fibrous material.

21. The process as claimed in claim 1, wherein said at least one thermoplastic polymer is selected from: poly(aryl ether ketone)s (PAEKs), in particular poly(ether ether ketone) (PEEK); poly(aryl ether ketone ketone)s (PAEKKs), in particular poly(ether ketone ketone) (PEKK); aromatic polyetherimides (PEIs); polyaryl sulfones, in particular polyphenylene sulfones (PPSUs); polyaryl sulfides, in particular polyphenylene sulfides (PPSs), polyamides (PAs), in particular semiaromatic polyamides (polyphthalamides) optionally modified by urea moieties; PEBAs, polyacrylates, in particular polymethyl methacrylate (PMMA); polyolefins, in particular polypropylene, polylactic acid (PLA), polyvinyl alcohol (PVA), and fluoropolymers, in particular polyvinylidene fluoride (PVDF) or polytetrafluoroethylene (PTFE) or polychlorotrifluoroethylene (PCTFE); and blends thereof.

22. The process as claimed in claim 1, wherein said at least one thermoplastic polymer is a polymer having a glass transition temperature such that Tg≥80° C., or a semicrystalline polymer having a melting temperature Tm≥150° C.

23. The process as claimed in claim 1, wherein said at least one thermoplastic polymer is selected from polyamides, aliphatic polyamides, cycloaliphatic polyamides and semiaromatic polyamides (polyphthalamides), PEKK, PEI and a blend of PEKK and PEI.

24. The process as claimed in claim 1, wherein a content of fibers in said impregnated fibrous material is from 45% to 65% by volume.

25. The process as claimed in claim 1, wherein a degree of porosity in said impregnated fibrous material is less than 10%.

26. The process as claimed in claim 1, wherein said thermoplastic polymer further comprises carbon-based fillers.

27. The process as claimed in claim 1, wherein said fibrous material comprises continuous fibers selected from carbon fibers, glass fibers, silicon carbide fibers, basalt-based or basalt fibers, silica fibers, natural fibers in particular flax or hemp fibers, lignin fibers, bamboo fibers, sisal fibers, silk fibers, or cellulose fibers in particular viscose fibers, or amorphous thermoplastic fibers having a glass transition temperature Tg above the Tg of said polymer or of said blend of polymers when the latter is amorphous or above the Tm of said polymer or of said blend of polymers when the latter is semicrystalline, or semicrystalline thermoplastic fibers having a melting temperature Tm above the Tg of said polymer or of said blend of polymers when the latter is amorphous or above the Tm of said polymer or of said blend of polymers when the latter is semicrystalline, or a mixture of two or more of said fibers.

28. The process as defined in claim 1, performed for manufacture of calibrated ribbons suitable for manufacture of three-dimensional composite parts, by automated layup of said ribbons using a robot.

29. The process as claimed in claim 28, wherein said composite parts relate to any of the fields of transport, of oil and gas, of hydrogen, of gas storage, aeronautical, nautical and railroad transport; or of renewable energy, energy storage devices, solar panels; or thermal protection panels; sports and leisure, health and medical, and electronics.

30. A three-dimensional composite part, which results from the process as defined in claim 28.

31. A tank comprising a fluidized bed, and a scraper or a transverse suction system configured to suck up fine particles, configured for use in a process as defined in claim 1.

32. A tank comprising a fluidized bed, a scraper and a transverse suction system configured to suck up fine particles, configured for use in a process as defined in claim 1.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0253] FIG. 1 presents a partial diagram of a unit for implementing the process for manufacturing a pre-impregnated fibrous material according to WO 2018/115736.

[0254] FIG. 2 presents a tank comprising a fluidized bed provided with at least one tension device (E′) which may be a compression roller.

[0255] FIG. 3 presents a photo of the tank with a scraper.

[0256] FIG. 4 is the presentation of the automated scraper system for the fuzz and the unpacking of the powder over time. The fuzz is automatically recovered in an inoperative area of the tank that does not disrupt the rest of the tank. FIG. 4 and FIG. 5 below are only one figure, but for visibility reasons, it has been split into two parts; FIG. 4 represents the left part and FIG. 5 represents the right part.

[0257] FIG. 5 is the right part as explained above.

[0258] FIG. 6 presents a cyclone making it possible to recover the powders sucked up above the fluidized bed.

[0259] FIG. 7 shows the decrease in the level of the fluidized bed and the percentage by weight of thermoplastic polymer (BACT/10T) in the fibrous material AS4 from Hexcel as a function of time. Left scale: bed height Right scale: weight in % of thermoplastic polymer (BACT/10T).

EXAMPLES

Example 1

[0260] A production test was carried out on a pilot line for the pre-impregnation of an AS4 12k fibrous material from Hexcel with a BACT/10T thermoplastic polymer matrix having a particle size of D50=106 μm in a transparent parallelepipedal tank with dimensions L×l×h=500×500×400 mm.sup.3, only adding powder manually as the pre-impregnation progresses. The powder added has a particle size equal to that in the tank at the start. This situation is therefore the worst-case scenario, in which nothing in terms of particle size is controlled or readjusted. [0261] 4 families of powders are obtained, the particle sizes of which may be analyzed: [0262] the one carried away by the fibrous material and the particle size distribution of which is substantially equivalent to that present in the tank.fwdarw.G0 [0263] the one that flies away and falls back down next to the tank and the one that is carried away by the fibrous material and falls from the fibrous material before being melted.fwdarw.G1 [0264] the one initially present in the tank.fwdarw.G2 [0265] the one present in the tank at the end of production.fwdarw.G3

[0266] After 1 week of production, the volume of powder of particle size G1 found next to the tank was measured as equal to 1/20 of that of the volume of powder initially present in the tank.

[0267] After 1 week of production, the following table is thus obtained:

TABLE-US-00001 TABLE 1 D10 D50 D90 G0 27 110 268 G1 36 147 294 G2 27 110 268 G3 87 191 333 Without recycling this gives Difference G3&G2 69% 42% 20% [0268] With recycling, a G4 particle size is obtained in the tank substantially equivalent to G0.

Example 2

[0269] Tank with automated scraper and automatic system for supplying the powder during production.

[0270] Fiber material: carbon fiber AS4 12k from Hexcel

[0271] Thermoplastic polymer: BACT/10T (40/60 in molar percentage) having a Tg of 140° C. and a particle size D50=106 μm.

[0272] Raking is carried out with the scraper every 15 minutes, which makes it possible to return to the initial bed height and to maintain the amount of BACT/10T carried away without adding powder for 1 h 40, thereby making it possible to recover the generated fuzz which accumulates at the surface of the frit.

[0273] The results are presented in FIG. 7.