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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/12—Powdering or granulating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B7/00—Mixing; Kneading
  • B29B7/002—Methods
  • B29B7/007—Methods for continuous mixing
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  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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  • B29B7/00—Mixing; Kneading
  • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
  • B29B7/58—Component parts, details or accessories; Auxiliary operations
  • B29B7/72—Measuring, controlling or regulating
  • B29B7/726—Measuring properties of mixture, e.g. temperature or density
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  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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  • B29B7/00—Mixing; Kneading
  • B29B7/80—Component parts, details or accessories; Auxiliary operations
  • B29B7/88—Adding charges, i.e. additives
  • B29B7/90—Fillers or reinforcements, e.g. fibres
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  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B9/00—Making granules
  • B29B9/10—Making granules by moulding the material, i.e. treating it in the molten state
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  • B29B9/00—Making granules
  • B29B9/12—Making granules characterised by structure or composition
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B9/00—Making granules
  • B29B9/16—Auxiliary treatment of granules
• • 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
  • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
  • B29C64/10—Processes of additive manufacturing
  • B29C64/141—Processes of additive manufacturing using only solid materials
  • B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
• • 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
  • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
  • B29C64/30—Auxiliary operations or equipment
  • B29C64/307—Handling of material to be used in additive manufacturing
  • B29C64/314—Preparation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y10/00—Processes of additive manufacturing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
  • B33Y40/10—Pre-treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y70/00—Materials specially adapted for additive manufacturing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y70/00—Materials specially adapted for additive manufacturing
  • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
  • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
  • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/203—Solid polymers with solid and/or liquid additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
  • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/346—Clay
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
  • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
  • C08L71/12—Polyphenylene oxides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B9/00—Making granules
  • B29B9/16—Auxiliary treatment of granules
  • B29B2009/165—Crystallizing granules
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2071/00—Use of polyethers, e.g. PEEK, i.e. polyether-etherketone or PEK, i.e. polyetherketone or derivatives thereof, as moulding material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2509/00—Use of inorganic materials not provided for in groups B29K2503/00 - B29K2507/00, as filler
  • B29K2509/02—Ceramics
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
  • C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
  • C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/003—Additives being defined by their diameter
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/005—Additives being defined by their particle size in general
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica

Definitions

• the invention relates to the field of poly-aryl-ether-ketone (s) powders.
• the invention relates to a powder charged with poly-aryl-ether-ketone (s), a process for manufacturing the powder as well as its use in a process for manufacturing three-dimensional objects, in particular in a process for sintering. powder caused by electromagnetic radiation.
• s poly-aryl-ether-ketone
• Poly-aryl ether ketones are well known high performance engineering polymers. They can be used for restrictive applications in temperature and / or in mechanical or even chemical stresses. They can also be used for applications requiring excellent fire resistance and low emission of fumes or toxic gases. Finally, they exhibit good biocompatibility. These polymers are found in fields as varied as aeronautics and space, off-shore drilling, automotive, rail, marine, wind power, sports, construction, electronics and even implants. medical. They can be implemented by all technologies for processing thermoplastics, such as molding, compression, extrusion, spinning, powdering or even prototyping by sintering.
• the laser sintering device 1 comprises a sintering chamber 10 in which are arranged a supply tank 40 containing the sinter powder, a horizontal plate 30 for supporting the three-dimensional object 80 under construction and a laser 20.
• the powder is taken from the feed tank 40 and deposited on the horizontal plate 30, forming a thin layer 50 of powder constituting the three-dimensional object 80 under construction.
• a compactor / scraper roller (not shown) makes it possible to ensure the good uniformity of the powder layer 50.
• the powder layer 50 under construction, is heated by means of infrared radiation 100 to reach a substantially uniform and equal temperature. at a predetermined construction temperature Te.
• Te is generally about 20 ° C below the melting temperature of the powder. In some cases Te may even be lower.
• the energy required to sinter the powder particles at different points of the powder layer 50 is then supplied by laser radiation 200 from the laser 20 mobile in the (xy) plane, according to a geometry corresponding to that of the object.
• the molten powder re-solidifies forming a sintered portion 55 while the remainder of the layer 50 remains as an unsintered powder 56.
• Several passes of laser radiation 200 may be necessary in some cases.
• the horizontal plate 30 is lowered along the (z) axis by a distance corresponding to the thickness of a layer of powder, and a new layer is deposited.
• the laser 20 provides the energy necessary to sinter the powder particles according to a geometry corresponding to this new slice of the object and so on. The procedure is repeated until the object 80 has been made.
• the object 80 is complete, it is removed from the horizontal plate 30 and the unsintered powder 56 can be sieved before being returned, if necessary, in the feed tray 40 to serve as recycled powder.
• the carbon fibers can be mixed with particles of poly-aryl-ether-ketone (s) dry (dry-blend).
• s poly-aryl-ether-ketone
• US2018 / 0201783 describes a composition resulting from a dry mixture of particles of poly-ether-ketone-ketone with carbon fibers whose median length is strictly greater than the average diameter of the particles. More precisely, the mixture used comprises 85% by weight of particles of poly-ether-ketone-ketone having a median diameter of 61.34 mih, measured using a Coulter Counter particle counter according to ISO 13319, and 15% by weight of carbon fibers with median length L50 equal to 77 pm and approximate diameter equal to 7 , 1 pm.
• the mixture is introduced into a high intensity mixer in order to partially incorporate at least part of the carbon fibers in the poly-ether-ketone-ketone particles.
• the dry blending of poly-ether-ketone-ketone particles with carbon fibers has the advantage of being particularly easy to prepare.
• a first disadvantage is that the three-dimensional objects resulting from the laser sintering of these powders have anisotropic mechanical properties, that is to say that they are different from the “Z” axis along which the different layers were printed. or that one places oneself according to the plane (XY) in which each layer was printed. This is because the carbon fibers tend to align in a preferred direction when the compactor / scraper roll passes.
• a second disadvantage is that it is not possible to use a large proportion of carbon fibers in the powder at the risk of impairing the good flowability of the latter, good flowability being necessary for use in laser sintering.
• the carbon fibers since the carbon fibers only incorporate very difficultly into the poly-ether-ketone-ketone particles, a high proportion of carbon fibers in the composition results in few of them arriving. to become sufficiently incorporated into the poly-ether-ketone-ketone particles, which implies that a majority of the carbon fibers remain free in the composition, thus impairing the flowability of the powder.
• the refreshing of the powder that is to say its recycling at least in part, after sieving, into another object construction by laser sintering is not easily achievable because of the difficulties in maintaining a rate.
• powders are known in which carbon fibers are incorporated inside the particles of poly-aryl-ether-ketone (s).
• s poly-aryl-ether-ketone
• application US 2005/0207931 describes poly-ether-ether-ketone particles integrating carbon fibers, the poly-ether-ether-ketone forming a matrix, and the carbon fibers being essentially incorporated in the matrix.
• the “mean diameter D50” (measurement method not detailed) is between 20 ⁇ m and 150 ⁇ m.
• the average length of the carbon fibers is also between 20 and 150 ⁇ m.
• the first method of manufacture described is spray-drying. This method consists of mixing in a liquid phase, such as ethanol or a water / ethanol mixture, a thermoplastic micropowder having a D50 of between 3 ⁇ m and 10 ⁇ m, with carbon fibers. The suspension is sprayed onto a surface, then the liquid phase of the suspension is vaporized or evaporated to form a powder.
• a liquid phase such as ethanol or a water / ethanol mixture
• a thermoplastic micropowder having a D50 of between 3 ⁇ m and 10 ⁇ m
• the second method consists of grinding thermoplastic granules having an initial grain size of 3 mm, in which the carbon fibers are already incorporated. Grinding takes place under cryogenic conditions in a mill equipped with pin discs until the particles reach the desired size and are separated using an air separator.
• the third manufacturing method is melt-spraying. This method involves spraying a mixture of carbon fibers and molten thermoplastic to obtain particles of sizes on the order of a few tens of micrometers.
• thermoplastic is a poly-aryl-ether-ketone, such as poly-ether-ether-ketone.
• the powder loaded with poly-aryl-ether-ketone which would be obtained would have a very high cost price.
• the first method seems very difficult to implement owing to the complexity and the high cost for obtaining polyarylether-ketone particles with a size of the order of a few micrometers used in the starting powder.
• the second method also seems complicated to implement because the presence of carbon fibers in the granules to be ground tends to cause strong abrasion and accelerated aging of the mill.
• the size of the carbon fibers incorporated into the poly-aryl-ether-ketone particles is controlled by the particle size and generally cannot be larger than the particle size.
• the third method is also complicated to implement because the good manufacture of the powder is subject to non-agglomeration of the particles of the spray, which results in particular in the need for an extremely rapid cooling system and specific.
• powder compositions comprising a poly-aryl-ether-ketone, forming a matrix, and carbon fibers essentially incorporated into the matrix, have a much higher production cost than dry blends of poly particles. -aryl-ether-ketone and carbon fiber.
• the reinforcement obtained in three-dimensional objects is generally less for those which were obtained by laser sintering of PAEK particle composition incorporating carbon fibers as compared to those obtained by laser sintering of dry mixtures of PAEK particles and of carbon fibers. This is explained in particular by the fact that in the first case the size of the carbon fibers is generally controlled by the size of the particles, which is not the case in the second case where the carbon fibers can be much longer. .
• the objective of the invention is therefore to provide a charged powder and a method for manufacturing this powder, which at least overcome certain drawbacks of the prior art.
• An objective of the invention is in particular to provide a charged powder based on poly-aryl-ether-ketone (s) leading to objects having better mechanical properties, in particular a higher modulus of elasticity and a higher breaking stress. , than an unfilled powder based on poly-aryl-ether-ketone (s).
• Another objective of the invention is to provide a charged powder based on poly-aryl-ether-ketone (s) resulting in objects whose mechanical properties are substantially isotropic.
• an objective is to provide a charged powder which has a relatively low cost price.
• an objective is to provide a powder which leads to objects which have similar or even improved mechanical properties compared to powders based on poly-aryl-ether-ketone (s) comprising carbon fibers ( dry mix with fibers or incorporated fibers).
• s poly-aryl-ether-ketone
• an objective is to provide a powder which can be used in a powder sintering process by electromagnetic radiation (s) and which can, if necessary, be easily recycled in one or more constructions ( later (s).
• Another object of the invention is also to provide a method for manufacturing the powder according to the invention which is simple and has a relatively low cost price.
• the invention relates to a powder having a particle size distribution, volume weighted, measured by laser diffraction, according to ISO 13320: 2009, with a median diameter D50 ranging from 40 to 120 micrometers.
• the powder comprises at least one poly-aryl-ether-ketone (PAEK) and at least one filler, in which:
• said at least one poly-aryl-ether-ketone forms a matrix incorporating said at least one filler
• said load has a distribution of equivalent Stokes spherical diameters, measured by X-rays with gravity sedimentation in a liquid, according to ISO 13317-3: 2001, with a median diameter of 50 less than or equal to 5 micrometers ,.
• D50 is understood to mean the value of the diameter of the powder particles so that the cumulative function of distribution of the diameters of the particles, weighted by the volume, is equal to 50%. “D50” is measured by laser diffraction according to the ISO 13320: 2009 standard, for example on a Malvern Mastersizer 2000® diffractometer.
• D'50 is meant the value of the diameter of the filler particles so that the cumulative function of distribution of the diameters of the particles, weighted by volume, is equal to 50%. "D'50” is measured by laser diffraction according to ISO 13320: 2009, for example on a Malvern Mastersizer 2000® diffractometer.
• 50 is meant the value of the diameter of the filler particles so that the cumulative distribution function of the spherical equivalent Stokes diameters is equal to 50%. “D'50” is measured by gravity sedimentation in a liquid according to the ISO 13317-3: 2001 standard, for example in a Sedigraph III Plus® device.
• the ISO 9276 standard is used for mathematical and statistical modeling to calculate the particle size distribution.
• a form coefficient C is defined by the following formula:
• Z axis is understood to mean the direction in which the different layers are printed in a layer-to-layer printing process by powder sintering by electromagnetic radiation (s). Conversely, by (XY) is meant the plane in which each layer is printed.
• the powder as claimed made it possible to manufacture three-dimensional objects by a method of constructing layer-by-layer objects by sintering caused by electromagnetic radiation, having mechanical properties. superior to those made from powder based on unfilled poly-aryl ether-ketone (s).
• the powder comprising PAEK (s) and incorporating a filler whose d50 is sufficiently lower than the D50 of the powder makes it possible in particular to obtain three-dimensional objects by laser sintering having greater rigidity and / or resistance. at the top break.
• the powder according to the invention made it possible to manufacture three-dimensional objects by a method of constructing layer-by-layer objects by sintering caused by electromagnetic radiation, having mechanical properties (in particular resistance to breakage and elongation at break) of a similar order, or even greater, than those of objects obtained from powder based on poly-aryl-ether-ketone (s) and carbon fibers (dry mixing of fibers or incorporation of fibers into a matrix).
• the mechanical properties of three-dimensional objects made from the powder according to the invention are isotropic or quasi-isotropic, that is, equivalent in all directions of space.
• the filler has a particle size distribution with a median diameter of 50 less than or equal to 2.5 microns.
• the mass ratio of the load to said at least one PAEK is from 1: 9 to 1: 1.
• the gain in mechanical properties, in particular the increase in the value of the modulus of elasticity, of an article made from the powder is generally not substantial compared to a object made from unfilled powder.
• the object made from the powder is usually too brittle.
• the mass ratio of the charge to said at least one PAEK is from 1: 4 to 3: 7.
• said at least one PAEK and said at least one filler together represent at least 60%, or at least 70%, or at least 80%, or at least 85%, or at least 90%, or at least at least 92.5%, or at least 95%, or at least 97.5%, or at least 98%, or at least 98.5%, or at least 99% or at least 99.5%, or 100% of the total weight of the powder.
• the PAEK is a random poly-ether-ketone-ketone (PEKK) copolymer, essentially consisting of, preferably consisting of, a terephthalic unit and an isophthalic unit, the terephthalic unit (T) having the formula: the isophthalic unit (I) having the formula:
• PEKK poly-ether-ketone-ketone
• the percentage by mass of terephthalic unit relative to the sum of the terephthalic and isophthalic units is from 55 to 65%.
• the percentage by mass of terephthalic unit relative to the sum of the terephthalic and isophthalic units is approximately 60%.
• said at least one PAEK is a copolymer, essentially consisting of, preferably consisting of:
• the filler is a mineral filler.
• Said filler may preferably be chosen from the group consisting of: calcium carbonate, silica, talc, wollastonite, mica, kaolin, and their mixture. More preferably, said filler is a talc.
• Talc has the advantage of having a low production cost and of obtaining advantageous reinforcing properties for an object obtained from a powder according to the invention.
• said load has a form coefficient C greater than or equal to 2, said form coefficient C being defined by the following formula: in which, D'50 denotes the median diameter of the filler particles, weighted in volume and measured according to standard ISO 13320: 2009 and, in which, d'50 denotes the median spherical Stokes equivalent diameter of the filler particles, measured by X-rays with gravity sedimentation in a liquid, according to ISO 13317-3: 2001.
• the present invention also relates to a powder manufacturing process comprising the steps consisting of:
• At least one poly-aryl-ether-ketone (PAEK) and the supply of at least one filler said at least one filler having a distribution of spherical Stokes equivalent diameters, measured by X-rays with sedimentation by gravity in a liquid, according to ISO 13317-3: 2001, with a median diameter of 50 less than or equal to 5 micrometers;
• PAEK poly-aryl-ether-ketone
• the inventors of the present invention have noticed that, surprisingly, the grinding of granules based on PAEK (s) incorporating a filler having a value of 50 less than or equal to 5 micrometers, made it possible to facilitate the grinding in comparison with granules. based on PAEK (s) incorporating fibers of carbon.
• the selection of a filler having a 50 less than or equal to 5 micrometers makes it possible in particular to easily obtain powders having a D50 ranging from 40 to 120 micrometers. The grinding time is therefore short.
• the method further comprises a heat treatment of the granules before the grinding step to allow at least partial crystallization of said at least PAEK of the powder.
• the present invention also relates to a method of constructing layer-by-layer objects by sintering caused by electromagnetic radiation (s), in which a powder according to the invention is used.
• the invention also relates to the use of the powder described above in a method of constructing layer-by-layer objects by sintering caused by at least one electromagnetic radiation.
• the present invention relates to any object capable of being obtained by the method of constructing layer-by-layer objects by sintering caused by electromagnetic radiation (s) in which the powder is used.
• This object is characterized in that it has, in at least one direction, an elastic modulus in tension greater than or equal to 7 GPa, on a 1BA type test piece, at 23 ° C, with a crosshead speed of 1 mm / min, according to the ISO 527-2: 2012 standard.
• the mechanical properties of the object being almost isotropic, it generally has an elastic modulus in tension greater than or equal to 7 GPa in all directions of space, in particular according to the plane (XY) and along the Z axis.
• FIG. 1 schematically represents a device making it possible to implement a method for constructing a three-dimensional object layer-by-layer by sintering in which the powder according to the invention can be used.
• FIG. 1 schematically represents a device making it possible to implement a method for constructing a three-dimensional object layer-by-layer by sintering in which the powder according to the invention can be used.
• the poly-aryl-ether-ketone (s) (PAEK (s)) of the powders according to the invention comprises (s) the following formula units:
• Ar and An each denote a divalent aromatic radical;
• Ar and An can be chosen, preferably, from 1, 3-phenylene, 1, 4-phenylene, 4,4'-biphenylene, 1, 4-naphthylene, 1, 5-naphthylene and 2,6 -naphthylene;
• - X denotes an electron-withdrawing group; it can be chosen, preferably, from the carbonyl group and the sulfonyl group,
• - Y denotes a group chosen from an oxygen atom, a sulfur atom, an alkylene group, such as - (CH) 2- and isopropylidene.
• At least 50%, preferably at least 70% and more particularly, at least 80% of the groups X are a carbonyl group, and at least 50%, preferably at least 70% and more particularly at least. minus 80% of the Y groups represent an oxygen atom.
• 100% of the X groups denote a carbonyl group and 100% of the Y groups represent an oxygen atom.
• the PAEK (s) of the powders can / can be chosen from:
• PEKK poly-ether-ketone-ketone, also called PEKK;
• a PEKK comprises a unit (s) of formula: -Ph-0-Ph-C (0) -Ph-C (0) -;
• a PEEK comprises a unit (s) of formula: -Ph-O-Ph-O-Ph-C (O) -;
• a PEK comprises a unit (s) of formula: -Ph-O-Ph-C (O) -;
• a PEEKK comprises a unit (s) of formula: -Ph-O-Ph-O-Ph-C (O) - Ph-C (O) -;
• PEEEK poly-ether-ether-ether-ketone, also called PEEEK;
• a PEEEK comprises a unit (s) of formula: -Ph-O-Ph-O-Ph-O- Ph-C (O) -;
• a PEDEK comprises a unit (s) of formula: a PEDEK comprises a unit (s) of the formula -Ph-O-Ph-Ph-O-Ph-C (O) -; - their mixture (s); and,
• Ph represents a phenylene group and -C (O) - a carbonyl group, each of the phenylenes possibly being of ortho (1 -2), meta (1 -3) or para (1 -4), preferably of meta or para type.
• defects, end groups and / or monomers can be incorporated in very small amounts in the polymers as described in the list above, without affecting their performance.
• said at least one PAEK is a PEKK.
• the PEKK can be a copolymer essentially consisting of, preferably consisting of, “type I” units (of “isophthalic type”), of formula: “T-type” units (of “terephthalic” type), of formula:
• the proportion by mass of T units relative to the sum of T and I units of PEKK can vary from 0 to 5%; or from 5 to 10%; or from 10 to 15%; or from 15 to 20%; or from 15 to 20%; or from 20 to 25%; or from 25 to 30%; or from 30 to 35%; or from 35 to 40%; or from 40 to 45%; or from 45 to 50%; or from 50 to 55%; or from 55 to 60%; or from 60 to 65%; or from 65 to 70%; or from 70 to 75%; or from 75 to 80%; or from 80 to 85%; or from 85 to 90%; or from 90 to 95%; or 95 to 100%.
• the choice of the mass proportion of T units relative to the sum of T and I units is one of the factors which makes it possible to adjust the melting temperature and the rate of crystallization at a given temperature of the PEKK.
• a given mass proportion of T units relative to the sum of T and I units can be obtained by adjusting the respective concentrations of the reactants during the polymerization, in a manner known per se.
• the sum of the terephthalic and isophthalic units in the PEKK is from 55 to 65%; preferably the percentage by weight of terephthalic unit relative to the sum of the terephthalic and isophthalic units is approximately 60%.
• said at least one PAEK is a PEEK-PEDEK copolymer.
• the PEEK-PEDEK copolymer may consist essentially of, preferably consisting of, units of formula:
• the molar proportion of unit (III) relative to the sum of units (III) and (IV) of PEEK-PEDEK (s) can vary from 0 to 5%; or from 5 to 10%; or from 10 to 15%; or from 15 to 20%; or from 15 to 20%; or from 20 to 25%; or from 25 to 30%; or from 30 to 35%; or from 35 to 40%; or from 40 to 45%; or from 45 to 50%; or from 50 to 55%; or from 55 to 60%; or from 60 to 65%; or from 65 to 70%; or from 70 to 75%; or from 75 to 80%; or from 80 to 85%; or from 85 to 90%; or from 90 to 95%; or 95 to 100%.
• the choice of the molar proportion of unit (III) relative to the sum of units (III) and (IV) is one of the factors which makes it possible to adjust the melting temperature and the rate of crystallization at a given temperature of the PEEK-PEDEK.
• a given molar proportion of unit (III) relative to the sum of units (III) and (IV) can be obtained by adjusting the respective concentrations of the reactants during the polymerization, in a manner known per se.
• the viscosity index of the PAEK (s), measured in solution at 25 ° C in an aqueous solution of sulfuric acid at 96% by mass according to standard ISO 307: 2019 can be from 0.65 dl / g to 1.15 dl / g, preferably from 0.70 dl / g to 1.05 dl / g, and more preferably from 0.70 dl / g to 0.92 dl / g.
• the at least one filler in the powder according to the invention has a distribution of spherical Stokes equivalent diameters, measured by X-rays with gravity sedimentation in a liquid, according to ISO 13317-3: 2001, with a median diameter of 50 less than or equal to 5 micrometers.
• the filler may in particular have a particle size distribution with a median diameter of 50 less than or equal to 2.5 micrometers. In some cases, the filler may have a median diameter of 50 less than or equal to 2 micrometers, or less than or equal to 1.5 micrometers, or even less than or equal to 1 micrometers.
• the median diameter of 50 of the filler is generally not less than 0.1 micrometers.
• the median diameter 50 is 0.1 to 5.0 microns, or 0.25 to 4.0 microns, or even 0.5 to 3.0 microns.
• the median diameter of 50 can in particular be from 0.1 to 0.5 micrometer, or from 0.5 to 1.0 micrometer, or from 1.0 to 1.5 micrometers, or from 1.5 to 2.0. micrometers, or 2.0 to 2.5 micrometers, or 2.5 to 3.0 micrometers, or 3.0 to 3.5 micrometers, or 3.5 to 4.0 micrometers, or 4, 0 to 4.5 micrometers, or 4.5 to 5.0 micrometers.
• the filler is a mineral filler.
• the filler is a reinforcing filler, that is to say making it possible to improve the rigidity, in particular the elastic modulus in traction, and / or the breaking strength of said at least one poly-aryl-ether-ketone ( PAEK).
• PAEK poly-aryl-ether-ketone
• the filler can include calcium carbonate (calcite).
• the filler can also include a silica.
• the filler can in particular be pure silica (S1O2), a synthetic silica, a quartz or a flour of diatoms.
• the filler can also include a talc.
• the filler can also include a wollastonite.
• the filler can finally comprise a clay or an aluminosilicate.
• the filler can in particular be a kaolin, a slate flour, vermiculite or else a mica.
• the filler is advantageously a talc.
• Talc has the advantage of having a low production cost and of providing advantageous reinforcing properties for an article obtained from a powder according to the invention.
• the charge is preferably non-spherical. It can be characterized by its form coefficient C, C being advantageously greater than or equal to 2.
• the form coefficient C is generally not greater than 20.
• the poly-aryl-ether-ketone (s) and the filler (s) are mixed and then extruded.
• the at least one feed and the at least one poly-aryl-ether-ketone are dry mixed and introduced at the main hopper of the extruder.
• the at least one poly-aryl-ether-ketone is introduced at the level of the main hopper while the at least one charge is introduced by lateral force-feeding and added to the poly-aryl-ether- melted ketone.
• extruder suitable for the extrusion of high melting temperature polymers can be used.
• a person skilled in the art is also capable of adapting the extrusion conditions according to the polymer used.
• An example of an extruder is a "Labtech" twin-screw having a screw diameter of 26mm and an L / D ratio of 40. The extruded mixture is subdivided so as to form granules.
• the fraction of PAEK in the powder has an enthalpy of fusion, measured on first heating and using a heating rate at 20 ° C / min according to the ISO 11357-2: 2013 standard, ranging from 20 to 50 J / g ( PAEK), preferably ranging from 25 to 40 J / g (PAEK).
• the heat treatment is advantageously carried out at a temperature much lower than the melting point of the powder.
• the powder is a powder based on PEKK with a percentage by mass of terephthalic unit relative to the sum of the terephthalic and isophthalic units of 55 to 65%
• the heat treatment can be carried out at a temperature of 180 ° C to 220 ° C.
• the granules are then ground into powder until obtaining a powder having a particle size distribution with a median diameter D50 ranging from 40 to 120 micrometers.
• the granules according to the invention are more brittle than PAEK granules (s) incorporating carbon fibers (at the same volume rate of filler): the grinding step is thereby facilitated.
• granules of PAEK (s) incorporating a filler, preferably talc, and having an d'50 of less than or equal to 5 microns are generally much less abrasive during grinding than granules of PAEK (s) incorporating fibers of. carbon.
• the grinding can be carried out at a temperature below -20 ° C, preferably at a temperature below -40 ° C, by cooling with liquid nitrogen, or liquid carbon dioxide, or dry ice, or liquid helium.
• the crusher used is advantageously a pin crusher, in particular a counter-rotating pin crusher, or an impact crusher, such as a hammer crusher, or even a swirl crusher.
• the mill can be equipped with a screen onto which the crushed particles are sent, the particles passing through the screen having the desired size. The particles retained by the screen can be returned to the mill to undergo a longer grinding.
• the mass ratio of the at least one filler to the at least one PAEK can be from 1: 9 to 1: 1.
• the gain in mechanical properties, in particular the increase in the value of the modulus of elasticity, of an article made from the powder is generally not substantial compared to a object made from unfilled PAEK powder.
• the object made from the powder is usually too brittle.
• the mass ratio of the at least one filler to the at least one PAEK is advantageously from 1: 4 to 3: 7.
• the mass ratio of the at least one filler to the at least one PAEK can also be from 3: 7 to 2: 3, or alternatively from 2: 3 to 1: 1.
• the powder may comprise another polymer not belonging to the PAEK family, in particular other thermoplastic polymers.
• the powder can also include additives.
• additives mention may be made of flow agents, stabilizers (light, in particular UV, and heat), optical brighteners, dyes, pigments, energy absorbing additives (including UV absorbers) .
• the additives generally represent less than 5% by weight of the total weight of powder, preferably represent less than 1% by weight of the total weight of powder.
• the powders according to the invention can be used in many applications, including the non-exhaustive applications below.
• the powders according to the invention can be used in methods of constructing layer-by-layer objects by sintering caused by electromagnetic radiation (s).
• sintering caused by electromagnetic radiation (s).
• a sintering process by infrared radiation and by laser radiation is illustrated by FIG. 1 and has already been described in the section dealing with the prior art.
• the powders according to the invention can also be used in processes for coating metal surfaces. Different methods can be used to ultimately obtain a coating on metal parts. Mention may be made of soaking in the fluidized bed for which the metal part is heated and then soaked in the bed of powder in fluidization. It is also possible to carry out a so-called electrostatic powdering (charged powder powdered on a metal part connected to the earth), in this case a thermal post-treatment is carried out to carry out the coating. An alternative is to carry out the powdering on a previously heated part, which makes it possible to eliminate the heat treatment after powdering. Finally, it is possible to carry out a powdering with the flame, in this case the powder is sprayed molten on a metal part possibly preheated.
• the powders according to the invention can also be used in powder compression processes. These methods are generally used to produce thick parts. In these processes, the powder is first loaded into a mold, compacted then there is fusion of the powder to make the part. Finally, suitable cooling is carried out (often quite slow) to overcome the internal constraints in the part.
• the powders of the examples below were manufactured by compounding (extrusion-granulation) of different compositions, heat treatment and then grinding.
• the compounding was carried out on a “Labtech” twin-screw having a screw diameter of 26 mm and an L / D ratio of 40, with a flat temperature profile at 350 ° C. and a screw speed of 400 revolutions per minute. Granules were obtained with a length equal to approximately 2mm.
• the fillers are introduced during the compounding by lateral force-feeding.
• the granules obtained are qualified as “loaded”.
• the granules were then heat treated for 9 hours at 180 ° C.
• the first composition used is a poly-ether-ketone-ketone having a proportion by weight of unit T relative to the sum of units T and I of 60%, having a viscosity index of 0.75 dl / g at 25 ° C. , in an aqueous solution of sulfuric acid at 96% by mass, according to ISO 307: 2019 applied to a PAEK.
• This poly-ether-ketone-ketone is marketed by the company ARKEMA under the name Kepstan®.
• the granules obtained with the composition according to Example 1 could be ground to obtain a D50, measured using a Malvern Mastersizer 2000® diffractometer, of 500 microns.
• Example 2 (comparative)
• the second composition used consists of the poly-ether-ketone-ketone according to Example 1 and of carbon fibers, the carbon fibers representing 23% by weight of the composition.
• the carbon fibers used were Tenax®-A fibers, of the "HT M 100" type, that is to say with fiber lengths of between 60 micrometers and 100 micrometers.
• the granules obtained with the composition according to Example 2 could be ground to obtain a D50, measured using a Malvern Mastersizer 2000® diffractometer, of 160 microns.
• the third composition used consists of the poly-ether-ketone-ketone according to Example 1 and of Jetfine® 0.7C talc, sold by the company IMERYS, the talc representing 30% by weight of the composition (in order to ensure a proportion volume of charge equivalent to that of Example 2).
• Jetfine® 0.7C talc has an of 50, measured on Sedigraph III Plus®, of 0.7 microns and an D'50, measured on a Malvern Mastersizer 2000® diffractometer, of 2.5 microns, i.e. a form coefficient C equal to: 2.6.
• the granules obtained with the composition according to Example 3 could be ground to obtain a D50, measured using a Malvern Mastersizer 2000® diffractometer, of 120 microns.
• the third composition used consists of the poly-ether-ketone-ketone according to Example 1 and of “Steaplus® HAR T77” talc sold by the company IMERYS, the talc representing 30% by weight of the composition (in order to ensure a volume proportion of charge equivalent to that of Example 2).
• Steaplus® HAR T77 talc has a 50, measured on Sedigraph III Plus®, of 2.2 microns and an D'50, measured on a Malvern Mastersizer 2000® diffractometer, of 10.5 microns, i.e. a form coefficient C equal to: 3.8.
• the granules obtained with the composition according to Example 4 could be ground to obtain a D50, measured using a Malvern Mastersizer 2000® diffractometer, of 110 microns.
• the results of grinding the powders according to Examples 3 and 4 (according to the invention) compared with the results of grinding the powders according to Examples 1 and 2 (comparative examples) show that the grinding of PEKK granules incorporating a talc filler having a 50 less than or equal to 5 micrometers is facilitated in comparison with granules of unfilled PEKK or granules of PEKK incorporating carbon fibers at the same volume rate of filler.
• Type 1 BA test pieces according to the ISO 527-2: 2012 standard, were manufactured by laser sintering of powder type 6002 PL®, marketed by the company ARKEMA, in an EOS P800® printer, marketed by the company EOS.
• the powder has a D50 equal to 50 mih, measured using a Malvern Mastersizer 2000® diffractometer, and a viscosity index of 0.96 dl / g at 25 ° C, in a 96% aqueous sulfuric acid solution. by mass, according to ISO 307: 2019 applied to a PAEK.
• Type 1 BA specimens were constructed along the X, Y and Z axes at a build temperature of 290 ° C and with laser energy for sintering of 28 mJ / mm 2 .
• an elastic modulus in tension of 4 GPa was measured at 23 ° C, with a crosshead speed of 1 mm / min, according to the ISO 527- standard. 2: 2012, using an MTS 810® device, marketed by MTS Systems Corporation, equipped with a mechanical extensometer.
• Type 1 BA test pieces according to standard ISO 527-2: 2012, were manufactured by injection of the powder according to example 3, with a supply temperature of 320 ° C, a screw outlet temperature of 340 ° C, a mold temperature of 80 ° C and a cycle time aj plus equal to 1 minute.
• An elastic modulus in tension of 9 GPa was measured, at 23 ° C, with a crosshead speed of 1 mm / min, according to the ISO 527-2: 2012 standard, using a device MTS 810®, marketed by MTS Systems Corporation, equipped with a mechanical extensometer.
• the elastic modulus value obtained for a test piece produced by injection is equal to, or even less than, the value that would be determined for a test piece produced by laser sintering.
• the specimen had been fabricated by laser sintering, it would certainly have a tensile elastic modulus of at least 9 GPa.
• Type 1 BA test pieces according to ISO 527-2: 2012, were manufactured by powder injection according to Example 4, according to the same protocol as that of Example 7.
• the specimen had been fabricated by laser sintering, it would certainly have a tensile modulus of at least 9 GPa.

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