WO2023007094A1 - Tube comportant un élément cylindrique pultrudé - Google Patents
Tube comportant un élément cylindrique pultrudé Download PDFInfo
- Publication number
- WO2023007094A1 WO2023007094A1 PCT/FR2022/051515 FR2022051515W WO2023007094A1 WO 2023007094 A1 WO2023007094 A1 WO 2023007094A1 FR 2022051515 W FR2022051515 W FR 2022051515W WO 2023007094 A1 WO2023007094 A1 WO 2023007094A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fibers
- tube
- polyamide
- cylindrical element
- tube according
- Prior art date
Links
- 239000000835 fiber Substances 0.000 claims abstract description 158
- 230000002787 reinforcement Effects 0.000 claims abstract description 71
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 55
- 239000011159 matrix material Substances 0.000 claims abstract description 45
- 239000002657 fibrous material Substances 0.000 claims abstract description 38
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 31
- 239000004952 Polyamide Substances 0.000 claims description 40
- 229920002647 polyamide Polymers 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 26
- 229920000571 Nylon 11 Polymers 0.000 claims description 21
- 229920001652 poly(etherketoneketone) Polymers 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims description 16
- 229920001601 polyetherimide Polymers 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- -1 polyphenylene Polymers 0.000 claims description 15
- 150000004985 diamines Chemical class 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 230000009477 glass transition Effects 0.000 claims description 12
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 239000004917 carbon fiber Substances 0.000 claims description 11
- 229920006375 polyphtalamide Polymers 0.000 claims description 11
- 239000004954 Polyphthalamide Substances 0.000 claims description 10
- 239000003365 glass fiber Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000011955 best available control technology Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 229920006152 PA1010 Polymers 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 229920002530 polyetherether ketone Polymers 0.000 claims description 8
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 7
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 7
- 229920000299 Nylon 12 Polymers 0.000 claims description 6
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002748 Basalt fiber Polymers 0.000 claims description 4
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 4
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 claims description 4
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 229920005992 thermoplastic resin Polymers 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 229920002614 Polyether block amide Chemical group 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 239000004626 polylactic acid Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 125000001174 sulfone group Chemical group 0.000 claims description 3
- 150000003568 thioethers Chemical class 0.000 claims description 3
- GHOKWGTUZJEAQD-ZETCQYMHSA-N (D)-(+)-Pantothenic acid Chemical compound OCC(C)(C)[C@@H](O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-ZETCQYMHSA-N 0.000 claims description 2
- 229920003189 Nylon 4,6 Polymers 0.000 claims description 2
- 229920002292 Nylon 6 Polymers 0.000 claims description 2
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 2
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 2
- 229920000393 Nylon 6/6T Polymers 0.000 claims description 2
- XZAHJRZBUWYCBM-UHFFFAOYSA-N [1-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1(CN)CCCCC1 XZAHJRZBUWYCBM-UHFFFAOYSA-N 0.000 claims description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 229920002313 fluoropolymer Polymers 0.000 claims description 2
- 150000003951 lactams Chemical class 0.000 claims description 2
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 claims description 2
- 229920006396 polyamide 1012 Polymers 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 claims description 2
- 238000004804 winding Methods 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims 1
- 239000002131 composite material Substances 0.000 description 20
- 238000005470 impregnation Methods 0.000 description 16
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 239000004959 Rilsan Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000012783 reinforcing fiber Substances 0.000 description 3
- 229920006135 semi-crystalline thermoplastic polymer Polymers 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004093 laser heating Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- 229920001643 poly(ether ketone) Polymers 0.000 description 2
- 229920006260 polyaryletherketone Polymers 0.000 description 2
- 229920006126 semicrystalline polymer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 244000198134 Agave sisalana Species 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229920001872 Spider silk Polymers 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 229920006017 homo-polyamide Polymers 0.000 description 1
- 238000013003 hot bending Methods 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- VPRUMANMDWQMNF-UHFFFAOYSA-N phenylethane boronic acid Chemical compound OB(O)CCC1=CC=CC=C1 VPRUMANMDWQMNF-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001660 poly(etherketone-etherketoneketone) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L9/00—Rigid pipes
- F16L9/14—Compound tubes, i.e. made of materials not wholly covered by any one of the preceding groups
-
- 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
- B29C63/00—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
- B29C63/24—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor using threads
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
- B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
- B29C70/525—Component parts, details or accessories; Auxiliary operations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D23/00—Producing tubular articles
- B29D23/001—Pipes; Pipe joints
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L9/00—Rigid pipes
- F16L9/12—Rigid pipes of plastics with or without reinforcement
Definitions
- the present invention relates to a tube comprising a pultruded cylindrical element.
- the invention also relates to its method of manufacture, as well as to its use in structures, in particular in the field of mobility.
- the invention relates to a tube comprising:
- the invention also relates to a process for manufacturing the tube as defined above, characterized in that it comprises the following successive steps: a) pultrusion of the cylindrical element, b) depositing additional fibrous reinforcement .
- the invention relates to the use of the tube as defined above to form structures including, in particular, bicycle frames, reinforcements, battery pack reinforcements, vehicle chassis reinforcements.
- the tube according to the invention is light. It has excellent mechanical resistance in bending, compression and traction. Furthermore, it has excellent properties for hot bending, thus making it possible to envisage various shapes. However, this deformed tube after bending and after possible reconsolidation in a closed mould, retains its mechanical strength properties.
- FIG 1 is a diagram illustrating the process for preparing the tube according to the invention.
- FIG 2 is a diagram illustrating another process for preparing the tube according to the invention.
- the tube according to the invention comprises:
- At least one cylindrical element made of a pultruded fibrous material impregnated with a thermoplastic matrix
- the cylindrical elements and at least one additional fibrous reinforcement, enveloping partially or totally, preferably totally, the cylindrical elements, the fibers contained in the additional fibrous reinforcement being positioned in a different axis from the longitudinal axis of the cylindrical element, the total fiber content of the tube being between 40 and 70% by volume with respect to the volumes of the matrix and fibers contained in the tube.
- the cylindrical element is manufactured using a pultrusion process. It is thus made up of fibers impregnated with a thermoplastic matrix. Pultrusion is a generally continuous process, which imposes traction of the fibers through a die in the axis of the cylindrical element, the fibers not necessarily being oriented in the axis of traction. Pultrusion covers the impregnation of dry fibers, for example dry fiber braids, dry fiber fabrics or uni-directional rovings. It also covers the implementation in the form of composite fiber profiles, pre-impregnated fibers, braids pre-impregnated with resin. According to the latter case, the fibers can be pre-impregnated before the pultrusion step.
- the tube according to the invention may contain a liner. But, this liner is not essential.
- tube is meant in the sense of the present invention a hollow body with constant section, of circular, square, rectangular, oval shape, or other shape, preferably of circular shape.
- the number of fibers per strand is for carbon fibers greater than or equal to 12K, greater than 24K, in particular greater than or equal to 50K, in particular comprised from 24 to 36K.
- the grammage for the fiberglass is greater than or equal to 1200 Tex per strand, in particular less than or equal to 4800 Tex, in particular comprised from 1200 to 2400 Tex.
- fibers of mineral origin mention may be made of carbon fibers, glass fibers, basalt fibers or fibers based on basalt, silica fibers, or silicon carbide fibers for example.
- fibers of organic origin mention may be made of fibers based on a thermoplastic or thermosetting polymer, such as semi-aromatic polyamide fibers, aramid fibers or polyolefin fibers for example.
- they are based on an amorphous thermoplastic polymer and have a glass transition temperature Tg higher than the Tg of the polymer or mixture of thermoplastic polymer constituting the impregnation matrix when the latter is amorphous, or higher than the Tm of the polymer or mixture of thermoplastic polymer constituting the impregnation matrix when the latter is semi-crystalline.
- they are based on semi-crystalline thermoplastic polymer and have a melting point Tf higher than the Tg of the polymer or mixture of thermoplastic polymer constituting the impregnation matrix when the latter is amorphous, or higher than the Tm of the polymer or mixture of thermoplastic polymer of constitution of the impregnation matrix, when the latter is semi-crystalline.
- the organic fibers of constitution of the fibrous material during the impregnation by the thermoplastic matrix of the final composite.
- the fibers of plant origin mention may be made of natural fibers based on flax, hemp, lignin, bamboo, silk, in particular spider silk, sisal, and other cellulosic fibers, in particular viscose. These fibers of plant origin can be used pure, treated or even coated with a coating layer, in order to facilitate adhesion and impregnation of the thermoplastic polymer matrix.
- constituent fibers can be used alone or in mixtures.
- organic fibers can be mixed with mineral fibers to be impregnated with thermoplastic polymer and form the impregnated fibrous material.
- the rovings of organic fibers can have several basis weights. They may also have several geometries.
- the fibers are in the form of continuous fibers, which make up 2D fabrics, nonwovens (NCF), braids or rovings of unidirectional fibers (UD) or nonwovens.
- the fibers of constitution of the fibrous material may also be in the form of a mixture of these reinforcing fibers of different geometries.
- the fibers included in the pultruded fibrous material of the cylindrical element are a braid of dry fibers.
- the fibrous material is chosen from glass fibers, carbon fibers, basalt fibers and basalt-based fibers.
- the fibrous material is chosen from glass fibers.
- the fibrous material is chosen from carbon fibers.
- the fibrous material is chosen from fibers based on basalt.
- the fibers are used in the form of a roving or several rovings.
- thermoplastic matrix The thermoplastic matrix
- Thermoplastic, or thermoplastic polymer means a material which is generally solid at room temperature, which may be semi-crystalline or amorphous, and which softens when the temperature rises, in particular after passing its glass transition temperature. (Tg) and flows at a higher temperature when it is amorphous, or can present a frank melting on passing its so-called melting temperature (Tf) when it is semi-crystalline, and which becomes solid again during a decrease in temperature below its crystallization temperature (for a semi-crystalline) and below its glass transition temperature (for an amorphous).
- Tg glass transition temperature
- Tf melting temperature
- the glass transition temperature denoted Tg below and the melting temperature denoted Tf below are determined by differential scanning calorimetry (DSC) according to standard ISO 11357-2:2013 and 11357-3:2013 respectively.
- the thermoplastic polymer may be an amorphous polymer having a glass transition temperature Tg greater than or equal to 50° C., in particular greater than or equal to 100° C., in particular greater than or equal to 120° C., in particular greater than or equal to 140°C, or a semi-crystalline thermoplastic polymer whose melting point Tm is greater than 150°C.
- the matrix is qualified as "thermoplastic", this means that the majority component of the matrix is a polymer thermoplastic or a mixture of thermoplastic polymers.
- said at least one thermoplastic polymer is selected from: poly(aryl etherketones) (PAEK), in particular poly(etheretherketone) (PEEK); poly(aryl etherketoneketone) (PAEKK), in particular poly(etherketoneketone) (PEKK); aromatic polyetherimides (PEI); polyarylsulphones, in particular polyphenylene sulphones (PPSU); polyarylsulphides, in particular polyphenylene sulphides (PPS); polyamides (PA), in particular semi-aromatic polyamides (polyphthalamides) optionally modified with urea units; PEBAs whose Tm is greater than 150° C., polyacrylates, in particular polymethyl methacrylate (PMMA); polyolefins, excluding polypropylene, polylactic acid (PLA), polyvinyl
- said at least thermoplastic polymer is selected from polyamides, aliphatic polyamides, cycloaliphatic polyamides and semi-aromatic polyamides (polyphthalamides), PEKK, PEI and a mixture of PEKK and PEI.
- polyphthalamides polyphthalamides
- PEKK poly(ethylene glycol)
- PEI poly(ethylene glycol)
- the nomenclature used to define polyamides is described in standard NF EN ISO 1874-1:2011 "Plastics - Polyamide (PA) materials for molding and extrusion - Part 1: Designation", in particular on page 3 (tables 1 and 2) and is well known to those skilled in the art.
- the polyamide can be a homopolyamide or a copolyamide or a mixture of these.
- PAEKs are advantageously used according to the invention.
- Poly(ArylEtherketone) such as PEK poly(etherketones), PEEK poly(etheretherketone), PEKK poly(etherketone ketone), PEKEKK poly(etherketoneetherketone) or high glass transition temperature Tg PAs.
- said polyamide is chosen from aliphatic polyamides, cycloaliphatic polyamides and semi- aromatics (polyphthalamides).
- the aliphatic polyamide is chosen from polyamide 6 (PA6), polyamide 11 (PAU), polyamide 12 (PA12), polyamide 66 (PA66), polyamide 46 (PA46), polyamide 610 ( PA610), polyamide 612 PA612), polyamide 1010 (PA1010), polyamide 1012 (PA1012), polyamide 11/1010 (PA11/1010) and polyamide 12/1010
- PA12/1010 PA12/1010
- PBA polyamide/polyether
- the semi-aromatic polyamide is a semi-aromatic polyamide, optionally modified with urea units, in particular an PA MXD6 and an PA MXD10 or a semi-aromatic polyamide of formula X/YAr, as described in EP1505099, in particular a semi-aromatic polyamide of formula A/XT in which
- -A is chosen from a unit obtained from an amino acid, a unit obtained from a lactam and a unit corresponding to the formula (diamine in Ca).(diacid in Cb), with a representing the number of carbon atoms of the diamine and b representing the number of carbon atoms of the diacid, a and b each being between 4 and 36, advantageously between 9 and 18, the unit (diamine in Ca) being chosen from aliphatic diamines, linear or branched, cycloaliphatic diamines and alkylaromatic diamines and the (Cb diacid) unit being chosen from aliphatic, linear or branched diacids, cycloaliphatic diacids and aromatic diacids;
- -XT denotes a unit obtained from the polycondensation of a Cx diamine and terephthalic acid (T), with x representing the number of carbon atoms of the Cx diamine, x being between 6 and 36 , advantageously between 9 and 18.
- a semi-aromatic polyamide is of formula A/6T, A/9T, A/10T or A/11T, A being as defined above, in particular a polyamide PA 6/6T , a PA 66/6T, a PA 6I/6T, a PA MPMDT/6T, a PA PA11/10T, a PA 11/6T/10T, a PA MXDT/10T, a PA MPMDT/10T, a PA BACT/10T , a PA BACT/6T, PA BACT/10T/6T or a PA 11/BACT/10T; T stands for terephthalic acid, MXD stands for m-xylylene diamine, MPMD stands for methylpentamethylene diamine and BAC stands for bis(aminomethyl)cyclohexane.
- said thermoplastic polymer is a semi-crystalline polymer.
- said semi-crystalline polymer has a glass transition temperature such that Tg 3 80°C, in particular Tg 3 100°C, in particular 3 120°C, in particular 3 140°C and a Tf 3 150°C .
- said at least semi-crystalline thermoplastic polymer is selected from: poly(aryl etherketones) (PAEK), in particular poly(etheretherketone) (PEEK); poly(aryl etherketoneketone) (PAEKK), in particular poly(etherketoneketone) (PEKK); aromatic polyetherimides (PEI); polyarylsulphones, in particular polyphenylene sulphones (PPSU); polyarylsulphides, in particular polyphenylene sulphides (PPS); polyamides (PA), in particular semi-aromatic polyamides (polyphthalamides) optionally modified with urea units; polyacrylates, in particular polymethyl methacrylate (PMMA); polyolefins, excluding polypropylene, polylactic acid (PLA), polyvinyl alcohol (PVA); polyvinyl chloride (PVC) and acrylonitrile-butadiene-styrene (ABS) polymer and mixtures thereof, in particular a mixture of PEKK
- said at least thermoplastic polymer is selected from polyamides, aliphatic polyamides, cycloaliphatic polyamides and semi-aromatic polyamides (polyphthalamides), PEKK, PEI and a mixture of PEKK and IEP.
- impregnated materials also called “ready-to-use” materials
- the impregnating polymer or mixture of thermoplastic polymers is distributed uniformly and homogeneously around the fibers.
- the impregnating thermoplastic polymer must be distributed as homogeneously as possible within the fibers in order to obtain a minimum of porosities, that is to say a minimum of voids between the fibers.
- porosities can act as stress concentration points, when placed under mechanical tensile stress for example, and which then form break initiation points of the impregnated fibrous material. and weaken it mechanically.
- a homogeneous distribution of the polymer or mixture of polymers therefore improves the mechanical strength and the homogeneity of the composite material formed from these impregnated fibrous materials.
- the content of fibers in said impregnated fibrous material is between 45 and 70% by volume, preferably 50 and 70% by volume, preferably between 50 and 60% by volume, in particular 54 and 60% by volume. volume relative to the volume of the impregnated fibrous material.
- the measurement of the fiber content can be carried out by image analysis (use of a microscope or camera or digital camera, in particular), of a cross section of the tube, by dividing the surface of the fibers by the surface of the tube (impregnated surface plus surface of the pores).
- image analysis use of a microscope or camera or digital camera, in particular
- the image size to be analyzed is between 10-12 times the fiber diameter. Between 5 and 40 images at different locations (sections) are taken. The average is taken over all the images and recalculated in volume.
- the measurement of the carbon fiber content can be determined according to ISO 14127:2008. [0049] If the fibers are glass fibers, the measurement of the fiber content is determined according to ISO 1172:1999.
- the porosity rate of said impregnated fibrous material is less than 10%, in particular less than 5%, in particular less than 2%.
- the porosity rate is greater than 0% but less than the rates mentioned above.
- the porosity rate corresponds to the closed porosity rate and can be determined either by electron microscopy, or as being the relative difference between the theoretical density and the experimental density of said impregnated fibrous material as described in the examples part of EP3418323, especially example 4.
- the composite material is waterproof, inert and resistant.
- the tube according to the invention comprises fibrous materials comprising, as fibers, fibers chosen from among glass fibers, carbon fibers, basalt fibers and basalt-based fibers and, as thermoplastic matrix, polymers chosen from polyamides, aliphatic polyamides, cycloaliphatic polyamides, semi-aromatic polyamides (polyphthalamides), PEKK, PEI and a mixture of PEKK and PEI.
- the impregnated fibrous material is thus manufactured by pultrusion in the form of a cylinder.
- the inside diameter of the cylindrical element can be between 10 mm and 100 mm, preferably between 15 mm and 50 mm.
- the length of the tube can be between 10 cm to 1 m, preferably between 15 cm to 50 cm.
- the manufacturing process is a continuous process, which leads to tubes that can range from 50 cm to 3 m in length, depending on the size of the production site. These tubes can then be reworked and shortened to suit the intended application.
- the final tube that is to say ready to be used, is generally less than 1 m, and can range from 15 cm to 50 cm.
- the ratio of the thickness of the wall of the tube to its internal diameter can be less than 0.20, preferably less than 0.10.
- the tube according to the invention also comprises at least one additional fibrous reinforcement, enveloping partially or totally, preferably totally, the cylindrical element or elements.
- fibrous reinforcement is meant in the sense of the present invention a material comprising fibers, which gives the final part a higher mechanical strength.
- the additional fibrous reinforcement is chosen from continuous dry fibers, a fibrous material based on continuous fibers impregnated with a thermoplastic matrix, and their mixture.
- the additional fibrous reinforcement is dry fibers, these can be chosen from those defined above.
- the additional fibrous reinforcement is a fibrous material based on continuous fibers impregnated with a thermoplastic matrix, it may be identical to or different from the fibrous material constituting the cylindrical element.
- the additional fibrous reinforcement is a fibrous material based on continuous fibers impregnated with a thermoplastic matrix
- the total fiber content of the reservoir which is between 40 and 70% by volume relative to the volumes of the matrix and the fibers contained in the tube, takes into account the matrix of the thermoplastic impregnated pultruded fibrous material and the matrix of the additional fibrous reinforcement.
- the total fiber content of the reservoir is between 40 and 70% by volume relative to the volumes of the matrices and the fibers contained in the tube.
- the additional fibrous reinforcement is chosen from a braid of dry fibers, a braid of fibrous ribbons impregnated with thermoplastic resin, and a mixture thereof.
- the fibers included in the fibrous material can be a braid of dry fibers and the additional fibrous reinforcement can also be a braid of dry fibers.
- the fibers included in the fibrous material can be rovings of continuous fibers and the additional fibrous reinforcement can also be a braid of dry fibers.
- the fibers included in the fibrous material can be a braid of fibers and the additional fibrous reinforcement can also be rovings of continuous fibers.
- the fibers included in the fibrous material can be a braid of fibers and the additional fibrous reinforcement can also be rovings of impregnated continuous fibers.
- the fibers included in the fibrous material can be rovings of continuous fibers and the additional fibrous reinforcement can also be rovings of impregnated continuous fibers.
- the thermoplastic matrix of the additional fibrous reinforcement may be identical to or different from that of the cylindrical element.
- the thermoplastic matrix of the cylindrical element is completely or partially miscible with the thermoplastic matrix of the additional fibrous reinforcement. This total or partial miscibility makes it possible to increase the adhesion between the wall of the cylindrical element and the layer of additional fibrous reinforcement.
- the tube may comprise a cylindrical element, the thermoplastic matrix of which is made of PVC and a fibrous reinforcement, the polymer matrix of which is made of acrylic.
- the tube may comprise a cylindrical element, the thermoplastic matrix of which is made of ABS and a fibrous reinforcement, the polymer matrix of which is made of acrylic.
- the tube may comprise a cylindrical element, the thermoplastic matrix of which is made of polyamide and a fibrous reinforcement, the polymer matrix of which is made of polyphthalamide.
- thermoplastic matrix of the additional fibrous reinforcement has a melting temperature above 150°C.
- thermoplastic matrix of the additional fibrous reinforcement has a glass transition temperature above 80°C, preferably above 100°C, and more particularly above 120°C.
- thermoplastic matrix of the additional fibrous reinforcement has a melting temperature greater than 150° C., and a glass transition temperature greater than 80° C., preferably greater than 100° C., and more particularly greater than 120°C.
- the thickness of the fiber reinforcement layer may be between 0.5 mm and 10 mm, preferably between 0.5 mm and 5 mm
- the total fiber content is between 40 and 70% by volume per relative to the sum of the volume of the matrix and the fibers, preferably between 50 and 70% by volume.
- the total fiber content is meant within the meaning of the present invention the sum of the fiber content contained in the tube, that is to say in the cylindrical element and in the reinforcement extra fibrous.
- the additional fibrous reinforcement comprises fibers positioned along an axis different from the longitudinal axis of the cylindrical element, preferably at an angle of between +/-10° and +/-89° relative to the axis longitudinal of the cylindrical element.
- an angle comprised between +/-25° and +/-89° from the axis of the cylindrical element, more preferably between +/-45° and +/-89°.
- the longitudinal axis of the cylindrical element constitutes the 0° axis
- the direction of the fibers of the additional reinforcement constitutes a second axis.
- the angle between these two axes is as defined above.
- the +/- signs indicate whether the fibers of the additional fibrous reinforcement are positioned on the right or on the left depending on the axis of the tube.
- a portion of the fibers included in the material of the cylindrical element is positioned in the longitudinal axis of the cylindrical element. More particularly, all of the fibers included in the material of the cylindrical element are positioned along the axis of the cylindrical element.
- the tube may comprise a second cylindrical element composed of one or more layers of thermoplastic resin, not comprising fibers, also called liner.
- This second cylindrical element can make it possible to increase the tightness of the tube. Depending on the application, it can also increase the pressure resistance of the tube, or even reinforce the chemical resistance of the final part.
- the tube according to the invention may comprise a liner, then above it a cylindrical element as defined above, then an additional fibrous reinforcement as defined above.
- the length and the diameter of the tube can be larger or smaller, depending on the intended application.
- the tube according to the invention comprises -one or more cylindrical elements, the fibers of which are positioned in the axis of the cylindrical element and -one or more additional fibrous reinforcements, the fibers of which are positioned in a axis different from the axis of the cylindrical element,
- the tube according to the invention comprises
- the tube according to the invention comprises
- the fibers of which are a braid of dry fibers
- the fibers of which are a braid of dry fibers positioned along an axis different from the axis of the braid of the cylindrical element.
- the invention also relates to the process for manufacturing the tube according to the invention.
- the method comprises the following successive steps: a) pultrusion of the cylindrical element, b) depositing additional fibrous reinforcement.
- the step of depositing the additional fibrous reinforcement can be done by winding the additional fibrous reinforcement tape around the cylindrical element. This removal can be done under a certain mechanical stress so as to exert pressure on the cylindrical element.
- the invention finally relates to the use of the tube according to the invention to form structures, such as bicycle frames, reinforcements, more particularly battery pack reinforcements, vehicle chassis reinforcements, fishing rod elements, camera or camera stands, photovoltaic panel supports, structures for camping elements, such as tent structures, ski poles, pipes for transporting fluids.
- structures such as bicycle frames, reinforcements, more particularly battery pack reinforcements, vehicle chassis reinforcements, fishing rod elements, camera or camera stands, photovoltaic panel supports, structures for camping elements, such as tent structures, ski poles, pipes for transporting fluids.
- any structure of tubular shape can be made from the tube according to the invention.
- FIG. 1 The method according to the invention can be illustrated by FIG. 1
- FIG. 1 illustrates a pultrusion process.
- Element 1 is an extruded tube, which will give shape to the final pultruded element.
- the dry fibers 3 emerge from the coils supported by the creel 2 and pass into the impregnation zone 4.
- This zone 4 comprises a bath of liquid resin or else a resin injection head.
- the pultrusion die 5 guides the pultruded impregnated fibers leading to the pultruded layer 6.
- the pultruded impregnated fibers undergo heating generated by a heating element 7.
- a coil 8 supports the additional fibrous reinforcement, which is wound around the pultruded tube , at an angle 9.
- the entire pultruded tube is pulled by 10 pullers.
- the pultruded tube is then cut by a cutting device 11.
- FIG. 2 illustrates another pultrusion process.
- the element 21 is an extruded tube, which will make it possible to give shape to the final pultruded element.
- the resin-impregnated fibers 23 leave the coils supported by the creel 22 and pass through the pultrusion die 24. This guides the impregnated fibers and conforms them, leading to the pultruded layer 25.
- the pultruded impregnated fibers undergo heating generated by a heating element 26.
- a coil 27 supports the additional fibrous reinforcement, which wraps around the pultruded tube, at an angle 28.
- the entire pultruded tube is pulled by pullers 29.
- the pultruded tube is then cut by a cutting device 30.
- a composite tube of circular section, having an outside diameter of 50 mm and a thickness of 2 mm is manufactured by pultrusion, at a speed of 0.5 m/min, by means of a process of impregnation in the molten route, using a tubular die connected to a single-screw extruder.
- the resin used for the pultrusion is a grade of low viscosity polyamide 11 (reference Rilsan® FMNO) allowing good impregnation of the fibers to be obtained.
- This polyamide 11 resin had a Tm of 190°C (measured according to the ISO 11357-3:2013 standard) and the temperature in the pultrusion die was 250°C.
- the fibers used were Hypertex S4550 glass fibers, marketed by the company 3B.
- the fiber content was 58% vol (fiber content relative to the volume of the pultruded tube).
- the orientation of fibers in the pultruded tube was exclusively along the axis of the tube.
- the tube was tested in 3-point bending, at ambient temperature, with a difference between supports of 1 m and a crosshead speed of 1 mm/min: the rupture occurred prematurely along the axis of the tube.
- We speak of premature rupture because the tensile stress measured in the tube at the time of rupture was 550 MPa (Table 1) or about half of the expected theoretical value, which corresponds to a rupture along the axis of the tube, i.e. that is to say a mode of rupture transverse to the fibres. This is explained by the absence of reinforcement perpendicular to the axis of the tube, making it possible to prevent this type of rupture transverse to the axis of the reinforcing fiber.
- a composite tube of circular section having an outside diameter of 50 mm and a thickness of 2 mm is manufactured by pultrusion, at a speed of 0.5 m/min, by means of a process of impregnation in the molten way, using a die tube connected to a single-screw extruder.
- the resin used for the pultrusion is a grade of low viscosity polyamide 11 (reference Rilsan® FMNO) allowing good impregnation of the fibers to be obtained.
- This polyamide 11 resin had a Tm of 190°C (measured according to the ISO 11357-3:2013 standard) and the temperature in the pultrusion die was 250°C.
- the fibers used were Hypertex S4550 glass fibers, marketed by the company 3B.
- the fiber content was 58% vol (fiber content relative to the volume of the pultruded tube).
- the orientation of the fibers in the pultruded tube was exclusively along the axis of the tube.
- An additional reinforcement consisting of Hyosung H2550 G10 carbon fibers not impregnated with resin (ie dry fiber reinforcement) was wound at 85° from the axis of the tube, to a thickness of 1 mm.
- the composite tube obtained was tested in 3-point bending, at ambient temperature, with a difference between supports of lm and a crosshead speed of lmm/min: the stress measured was 800 MPa: the presence of additional reinforcing fibers makes it possible to delay the fracture transverse to the fibers of the pultruded tube, but does not eliminate it.
- a composite tube having an outer diameter of 170 mm and a thickness of 2mm is manufactured by pultrusion, at a speed of 0.5m/min, by means of a melt impregnation process, using a tubular die connected to a single-screw extruder.
- the resin used for the pultrusion is a grade of low viscosity polyamide 11 (reference Rilsan® FMNO) allowing good impregnation of the fibers to be obtained.
- This polyamide 11 resin had a Tm of 190°C (measured according to the ISO 11357-3:2013 standard) and the temperature in the pultrusion die was 250°C.
- the fibers used were Hypertex S4550 glass fibers, marketed by the company 3B.
- the fiber content was 58% vol (fiber content relative to the volume of the pultruded tube).
- the fiber orientation of the pultruded tube was exclusively along the axis of the tube.
- An additional fibrous reinforcement consisting of a composite tape with a width of 1 ⁇ 2'', was wound perpendicular to the axis of the tube, (taking into account the width of the tape and the diameter of the pultruded tube the angle of the fibers was approximately 85°) over a thickness of 1mm.
- the composite tape was made of Hyosung H2525 G10 carbon fiber, impregnated with a polyamide 11 resin (reference Rilsan® FMNO) with a glass transition temperature of 50°C (measured by DSC according to ISO 11357- 2:2013). The fiber content was 55% by volume (based on the volume of the composite ribbon).
- the composite tape was implemented using an automatic process of removal with Coriolis® Solo brand laser heating, at a temperature of 270°C and a speed of 0.3m/s.
- the composite tube obtained was tested at 3 points, at room temperature, with a difference between supports of 1 m and a crosshead speed of 1 mm/min: the stress measured was 1000 MPa. Breakage in transverse mode to the fibers of the pultruded tube is completely eliminated. The rupture is then perpendicular to the axis of the tube and therefore to the axis of the fibers of the tube: we then say that the mode of rupture is axial.
- a composite tube, of circular section, having an outer diameter of 170 mm and a thickness of 2 mm is manufactured by pultrusion, at a speed of 0.5 m/min, by means of a process of impregnation in the molten route, using a tubular die connected to a single-screw extruder.
- the resin used for the pultrusion is a grade of low viscosity polyamide 11 (reference Rilsan® FMNO) allowing to obtain a good impregnation of the fibres.
- This polyamide 11 resin had a Tm of 190°C (measured according to the ISO 11357-3:2013 standard) and the temperature in the pultrusion die was 250°C.
- the fibers used were Hypertex S4550 glass fibers, marketed by the company 3B.
- the fiber content was 58% vol (fiber content relative to the volume of the pultruded tube).
- the orientation of the fibers in the pultruded tube was exclusively along the axis of the tube.
- An additional fibrous reinforcement consisting of a composite tape with a width of 1 ⁇ 2'', was wound perpendicular to the axis of the tube, (taking into account the width of the tape and the diameter of the pultruded tube the angle of the fibers was approximately 85°) over a thickness of 1mm.
- the composite ribbon was made of a Hyosung H2525 G10 carbon fiber, impregnated with a PPA type resin
- the fiber content was 55% by volume (based on the volume of the composite tape).
- the composite tape was implemented using an automatic process of removal with Coriolis® Solo brand laser heating, at a temperature of 330°C and a speed of 0.3m/s.
- the composite tube obtained was tested in bending, at ambient temperature, with a difference between supports of 1 m and a crosshead speed of 1 mm/min: the stress measured was 1200 MPa. Breakage in transverse mode to the fibers of the pultruded tube is completely eliminated; the failure mode is axial.
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Abstract
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Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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CN202280052754.4A CN117729992A (zh) | 2021-07-27 | 2022-07-27 | 包含拉挤的圆柱形元件的管 |
EP22764442.4A EP4377065A1 (fr) | 2021-07-27 | 2022-07-27 | Tube comportant un élément cylindrique pultrudé |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR2108128A FR3125742B1 (fr) | 2021-07-27 | 2021-07-27 | Tube comportant un élément cylindrique pultrudé |
FR2108128 | 2021-07-27 |
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WO2023007094A1 true WO2023007094A1 (fr) | 2023-02-02 |
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Family Applications (1)
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PCT/FR2022/051515 WO2023007094A1 (fr) | 2021-07-27 | 2022-07-27 | Tube comportant un élément cylindrique pultrudé |
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EP (1) | EP4377065A1 (fr) |
CN (1) | CN117729992A (fr) |
FR (1) | FR3125742B1 (fr) |
WO (1) | WO2023007094A1 (fr) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1505099A2 (fr) | 2003-08-05 | 2005-02-09 | Arkema | Polymides semi aromatiques souples à faible reprise en humidité |
WO2007025288A1 (fr) * | 2005-08-24 | 2007-03-01 | Kusek Walter W | Procede de production de resine de plastisol en pvc renforce, et produits prepares avec le procede |
GB2523204A (en) * | 2014-02-18 | 2015-08-19 | Sigma Prec Components Uk Ltd | Fibre reinforced thermoplastic composite rigid pipe |
EP3418323A1 (fr) | 2017-06-22 | 2018-12-26 | Arkema France | Materiau fibreux impregne de polymere thermoplastique |
EP3458767A1 (fr) * | 2016-05-19 | 2019-03-27 | Gilles Rocher | Reservoir en matériau composite pour contenir un fluide sous pression |
-
2021
- 2021-07-27 FR FR2108128A patent/FR3125742B1/fr active Active
-
2022
- 2022-07-27 WO PCT/FR2022/051515 patent/WO2023007094A1/fr active Application Filing
- 2022-07-27 CN CN202280052754.4A patent/CN117729992A/zh active Pending
- 2022-07-27 EP EP22764442.4A patent/EP4377065A1/fr active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1505099A2 (fr) | 2003-08-05 | 2005-02-09 | Arkema | Polymides semi aromatiques souples à faible reprise en humidité |
WO2007025288A1 (fr) * | 2005-08-24 | 2007-03-01 | Kusek Walter W | Procede de production de resine de plastisol en pvc renforce, et produits prepares avec le procede |
GB2523204A (en) * | 2014-02-18 | 2015-08-19 | Sigma Prec Components Uk Ltd | Fibre reinforced thermoplastic composite rigid pipe |
EP3458767A1 (fr) * | 2016-05-19 | 2019-03-27 | Gilles Rocher | Reservoir en matériau composite pour contenir un fluide sous pression |
EP3418323A1 (fr) | 2017-06-22 | 2018-12-26 | Arkema France | Materiau fibreux impregne de polymere thermoplastique |
Also Published As
Publication number | Publication date |
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EP4377065A1 (fr) | 2024-06-05 |
CN117729992A (zh) | 2024-03-19 |
FR3125742B1 (fr) | 2024-03-01 |
FR3125742A1 (fr) | 2023-02-03 |
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