Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
  • B22F1/05—Metallic powder characterised by the size or surface area of the particles
  • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
  • B22F1/06—Metallic powder characterised by the shape of the particles
  • B22F1/065—Spherical particles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
  • B22F10/20—Direct sintering or melting
  • B22F10/25—Direct deposition of metal particles, e.g. direct metal deposition [DMD] or laser engineered net shaping [LENS]
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
  • B22F10/20—Direct sintering or melting
  • B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
  • B22F10/30—Process control
  • B22F10/34—Process control of powder characteristics, e.g. density, oxidation or flowability
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
  • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
  • B23K26/34—Laser welding for purposes other than joining
  • B23K26/342—Build-up welding
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B28—WORKING CEMENT, CLAY, OR STONE
  • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
  • B28B1/00—Producing shaped prefabricated articles from the material
  • B28B1/001—Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D 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
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
  • C04B35/628—Coating the powders or the macroscopic reinforcing agents
  • C04B35/62802—Powder coating materials
  • C04B35/62828—Non-oxide ceramics
  • C04B35/62839—Carbon
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/71—Ceramic products containing macroscopic reinforcing agents
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C1/00—Making non-ferrous alloys
  • C22C1/04—Making non-ferrous alloys by powder metallurgy
  • C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
  • B22F1/14—Treatment of metallic powder
  • B22F1/148—Agglomerating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F12/00—Apparatus or devices specially adapted for additive manufacturing; Auxiliary means for additive manufacturing; Combinations of additive manufacturing apparatus or devices with other processing apparatus or devices
  • B22F12/40—Radiation means
  • B22F12/44—Radiation means characterised by the configuration of the radiation means
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F12/00—Apparatus or devices specially adapted for additive manufacturing; Auxiliary means for additive manufacturing; Combinations of additive manufacturing apparatus or devices with other processing apparatus or devices
  • B22F12/40—Radiation means
  • B22F12/49—Scanners
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F12/00—Apparatus or devices specially adapted for additive manufacturing; Auxiliary means for additive manufacturing; Combinations of additive manufacturing apparatus or devices with other processing apparatus or devices
  • B22F12/50—Means for feeding of material, e.g. heads
  • B22F12/53—Nozzles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F9/00—Making metallic powder or suspensions thereof
  • B22F9/02—Making metallic powder or suspensions thereof using physical processes
  • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
  • B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F9/00—Making metallic powder or suspensions thereof
  • B22F9/02—Making metallic powder or suspensions thereof using physical processes
  • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F9/00—Making metallic powder or suspensions thereof
  • B22F9/02—Making metallic powder or suspensions thereof using physical processes
  • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
  • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
  • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y10/00—Processes of additive manufacturing
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
  • C04B2235/52—Constituents or additives characterised by their shapes
  • C04B2235/5296—Constituents or additives characterised by their shapes with a defined aspect ratio, e.g. indicating sphericity
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
  • C04B2235/54—Particle size related information
  • C04B2235/5463—Particle size distributions
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
  • C04B2235/54—Particle size related information
  • C04B2235/5463—Particle size distributions
  • C04B2235/5481—Monomodal
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
  • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
  • C04B2235/665—Local sintering, e.g. laser sintering
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C33/00—Making ferrous alloys
  • C22C33/02—Making ferrous alloys by powder metallurgy
  • C22C33/0207—Using a mixture of prealloyed powders or a master alloy
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C33/00—Making ferrous alloys
  • C22C33/02—Making ferrous alloys by powder metallurgy
  • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P10/00—Technologies related to metal processing
  • Y02P10/25—Process efficiency

Definitions

• the present invention relates to the field of manufacturing parts made of metallic material, intermetallic ceramic, Ceramic Matrix Composite (CMC) or Metallic Matrix Composite (CMM) with discontinuous reinforcement, in particular ceramic or intermetallic reinforcement, by melting or sintering powder particles (s) by means of a high beam energy.
• CMC Ceramic Matrix Composite
• CMM Metallic Matrix Composite
• discontinuous reinforcement reinforcing elements such as short fibers (whiskers or whiskers), particles, in particular monocrystalline particles, and not continuous reinforcing elements of the long fiber type.
• the laser beam and the electron beam.
• the laser it can be either pulsed or continuous.
• the invention aims in particular the rapid manufacture of parts by laser projection or by selective melting of powder beds by laser or by selective sintering of powder beds by laser.
• SLS Selective Laser Sintering
• SLM Selective Laser Melting
• a first layer 10 of powder of a material is deposited on a construction support 80 (it can be a massive support , from part of another part or a support grid used to facilitate the construction of certain parts).
• This powder is transferred to the construction support 80 from a feed tank 70 during a forward movement of the roll 30, then it is scraped, and possibly slightly compacted, during one (or more) movement (s) of return of the roll 30.
• the powder is composed of particles 60.
• the excess powder is recovered in a recycling bin 40 located adjacent to the building tank 85 in which the construction support 80 moves vertically.
• a laser beam generator 90 and a driver 50 capable of directing the beam 95 over any region of the building support 80 so as to scan any region of a powder layer.
• the shaping of the laser beam and the variation of its diameter in the focal plane are done respectively by means of a beam expander or "Beam Expander" 52 and a focusing system 54, the assembly constituting the optical system .
• this first powder layer 10 is scanned with a laser beam 95 at a temperature above the melting temperature T F of this powder.
• the SLM process can use any high energy beam in place of the laser beam 95, as long as this beam is sufficiently energetic to melt the powder particles and a part of the material on which the particles rest (also called diluted zone making integral part of the liquid bath).
• This scanning of the beam is carried out for example by a galvanometric head forming part of a control system 50.
• this control system comprises, in a nonlimiting manner, at least one orientable mirror 55 on which the laser beam 95 is reflected before to reach a powder layer where each point of the surface is always located at the same height relative to the focusing lens, contained in the focusing system 54, the angular position of this mirror being controlled by a galvanometric head so that the laser beam scans at least one region of the first layer of powder, and thus follows a predetermined part profile.
• the galvanometric head is controlled according to the information contained in the computer tool database used for computer-aided design and manufacturing of the part to be manufactured.
• the powder particles 60 of this region of the first layer 10 are melted and form a first integral element 15, integral with the construction support 80.
• the support 80 is lowered by a height corresponding to the thickness of the first layer (20 to 100 ⁇ and in general from 30 to 50 ⁇ ).
• a second layer 20 of powder is then deposited on the first layer 10 and on this first element in one piece or consolidated 15, and a region of the second layer 20 which is located partially or completely is heated by exposure to the laser beam 95.
• this first element in one piece or consolidated in the case illustrated in Figure 1 so that the powder particles of this region of the second layer 20 are melted with at least a part of the element 15 and form a second element in one piece or consolidated 25, all of these two elements 15 and 25 forming, in the case illustrated in Figure 1, a block in one piece.
• the aforementioned region of the first layer 10 is not, even partially, below the aforementioned region of the second layer 20, so that in this case the first consolidated element 15 and the second consolidated element 25 do not then form a block in one piece.
• This process of building the piece layer by layer is then continued by adding additional layers of powder to the already formed assembly.
• the scanning with the laser beam 95 makes it possible to construct each layer by giving it a shape in accordance with the geometry of the part to be produced.
• the lower layers of the room cool more or less quickly as the upper layers of the room are built.
• the "laser projection” or “direct deposition” (DMD) deposition process is explained below with reference to FIG. 2.
• a first layer 110 of material is formed by spraying powder particles 60, under an inert gas, onto a construction support 180, through a nozzle 190.
• This nozzle 190 conveys, simultaneously with the projection of particles 60 of powder, a laser beam 195 which originates from a generator 194.
• the first orifice 191 of the nozzle 190 through which the powder is projected on the construction support 180 is coaxial with the second orifice 192 through which the laser beam 195 is emitted, so that that the powder is projected into the laser beam 195.
• coaxial nozzle therefore means a powder beam concentric to the laser beam with the alignment of the Focal Laser point (F L ) and the Focal Powder point (F P ) on the axis of symmetry of the nozzle 190 (the Focal Laser point (F L ) being adjustable relative to the point Focal Powder (F P )).
• the powder forms a conical envelope, and the laser beam is conical in shape.
• the laser beam 195 carries the powder at a temperature higher than its melting temperature T F / so that this powder forms a bath 102 on the surface of the support 180 under the laser beam 195.
• the bath 102 may also have begun to be formed on the support 180 by melting the region of the support 180 exposed to the laser beam 195, to a certain depth: in this case the powder feeds the bath 102 in which it reaches the fully molten state.
• the position of the nozzle 190 can be adjusted with respect to the position of the laser beam so that the powder does not pass for example enough time in the laser beam 195 or the speed of the powder particles at the nozzle outlet either too large or this laser beam is not sufficiently energetic so that the powder particles are completely melted upstream of the bath, and completely melt after only having reached the bath 102 formed beforehand on the surface of the support 180 by melting the region of this support 180 exposed to the laser beam 195.
• the powder may also, upstream of the bath, not be melted by the laser beam 195 or be only partially because the size of certain particles constituting the powder is too great or that their mass flow is too big for them to be completely melted before arriving in the bath.
• the powder may not be brought to temperature before arriving then cold in the previously formed bath on the surface of the support 180 because the setting of the nozzle 190 relative to the laser beam is such that there is no intersection between the powder beam and the laser beam at the right of the work plane.
• the bath 102 is maintained and solidifies step by step to form a first bead of solidified material 105 on the support 180.
• the process is continued to form another solidified bead on the support 180, this other bead being for example juxtaposed and parallel to the first bead.
• first layer 110 of material which solidifies a first element 115 integrally whose geometry conforms to that defined by the information contained in the database of the computer tool used for computer-aided design and manufacture of the part to be manufactured.
• a second scan of the nozzle 190 is then performed to similarly form a second layer 120 of material on the first previously consolidated member 115.
• This second layer 120 forms a second consolidated element 125, all of these two elements 115 and 125 forming a block in one piece.
• the baths 102 formed step by step on the first element 115 during the construction of this second layer 120 generally comprise at least a portion of the first element 115 which has been remelted by exposure to the laser beam 195 (also called diluted zone forming part of integral of the liquid bath), and the particles of the powder feed the baths 102.
• This process of developing the layer-by-layer part is then continued by adding additional layers to the already formed assembly.
• the scanning with the laser beam 195 makes it possible to give each layer a shape independent of the adjacent layers. Layers The lower parts of the room cool down more or less quickly as the upper layers of the room are formed.
• SLS Selective Laser Sintering
• this manufacture In order to reduce the contamination of the part, for example oxygen, oxide (s) or another pollutant during its manufacture layer by layer as described above, this manufacture must be carried out inter alia in a chamber to degree hygrometry and oxygen content controlled and adapted to the process / material pair.
• an oxide film (s) is formed with a release of hydrogen inside porosities (occluded gas) within a fused aluminum alloy according to the reaction:
• the selective laser melting process when using, for example, the selective laser melting process without a drastic control of the dew point of the surrounding atmosphere (in this case the ratio between the partial pressures of H 2 and H 2 0 corresponding to a quantity of water vapour).
• the ratio between the partial pressures of H 2 and H 2 0 corresponding to a quantity of water vapour For example, at a dew point of -50 ° C is associated a water vapor content of 38.8 ppm.
• the chamber is filled with a neutral gas (non-reactive) with respect to the material in question such as nitrogen (N 2 ), argon (Ar) , carbon monoxide (CO), carbon dioxide (CO2), or helium (He) with or without the addition of a small amount of hydrogen (H 2 ) known for its reducing power.
• a neutral gas non-reactive
• nitrogen N 2
• Ar argon
• CO carbon monoxide
• CO2 carbon dioxide
• He helium
• H 2 hydrogen
• selective laser melting or laser projection makes it possible to construct, with good dimensional accuracy, weakly polluted parts whose three-dimensional geometry can be complex but whose mechanical strength is still insufficient for certain applications and therefore requires a better optimization of the process and in particular a better optimization of the constitution of the powders.
• the selective laser melting or the laser projection also uses and preferably a powder composed of particles of spherical morphology, homogeneous composition, clean (ie not contaminated with residual elements from the synthesis of the powder) and fine (the dimension each particle is between 1 and 100 ⁇ m and preferably between 1 and 50 ⁇ m or even between 1 and 25 ⁇ m), which makes it possible to obtain an excellent surface state of the finished part.
• Selective laser melting or laser spraying also reduces manufacturing time, costs and fixed costs, compared to a molded, injected, compacted and sintered, wrought or machined piece.
• the current practice is to use, when possible, a pre-alloyed powder (FIG. 6A) with single-component particles of substantially spherical (or quasi-spherical) shape, dense (absence of intraparticle porosity, that is, ie absence of occluded gas in the particle), uncontaminated and unoxidized at the surface, whose composition is homogeneous, that is to say the same in any elemental volume of the particle, and identical to that referred to for the part resulting from the process of melting powder particles.
• the particles are formed of continuous material, of homogeneous composition and are, according to the invention, quasi-spherical and dense. They can be composed of a single chemical element (single-element powder), or of several chemical elements (multi-element powder).
• FIGS. 4A to 4C This situation is illustrated on the micrographs of FIGS. 4A to 4C showing fracture facies of test pieces obtained from a first AISilOMg alloy powder supplemented by a low volume proportion of a second powder consisting of reactive and refractory particles of different compositions (based on iron and chromium for FIG. 4A, nickel, chromium and cobalt for FIG. 4B and based on iron, nickel and chromium for FIG. 4C), carried out under a scanning electron microscope different settings so that one of the two views of each micrograph shows the topography (secondary electron image, denoted by SE) and the other view highlights the differences in chemical composition (electron-retro-scattered image, designated by BSE).
• SE secondary electron image
• BSE electro-retro-scattered image
• the phenomenon described above can be accentuated by a broad particle size distribution of the second powder and by a large average size for the second powder, having the highest melting temperature among the various powders making up the reactive mixture.
• non-reactive particles completely melted and / or dissolved in the supernatant liquid for larger ones on the surface of the bath. It can especially be particles of refractory material such as intermetallics or ceramics.
• the micrographs of FIG. 5 relate to the case of a steel part reinforced with particles of titanium carbide in which some of these particles of the most refractory powder of the mixture do not have been completely implemented solution in the liquid bath, and thus concentrated on the surface of the bath, encircling and sometimes trapping even pockets of gas.
• the object of the present invention is to provide a method of manufacturing a desired composition and microstructure part in a metallic, intermetallic, ceramic, ceramic matrix composite (CMC) or intermittently reinforced metal matrix composite (CMM), by melting powder particles (s) by means of a high energy beam, which overcomes the disadvantages of the prior art.
• CMC ceramic matrix composite
• CMM intermittently reinforced metal matrix composite
• this invention it is intended to obtain a homogeneous composition of the part conforming to the desired composition, the absence of manufacturing defects, a macro- and microstructure (size and morphology of the grains, then morphology, fineness and composition of the phases ) adapted from the raw material (at the end of the melt manufacturing stage), a good dimensional quality (ensured by a perfect bath stability), a minimization of the residual stresses, a total mass yield of the process (fusion + recycling) the greatest possible and an optimal manufacturing speed or optimal manufacturing time, whatever the materials envisaged.
• the powder used is a single powder whose particles have a sphericity between 0.8.
• each particle of powder having a substantially identical average composition and in the particle size distribution of said powder is tightened around the average diameter value d 5 o% such that: (dg 0 oa - dso%) / dso % ⁇ 0.66 and (d 5 o% - dio %) / d 5 o% ⁇ 0.33 with (dgo% - dio%) / d 5 o% ⁇ 1.00.
• this particle size distribution defined by the value of "span", (dgo% - dio%) / dso%, must be less than or equal to 0.50 with (dg 0 % - d 50 %) / d 5 o% ⁇ 0.33 and (d 5 o% - di 0 %) / d 50 % ⁇ 0.17.
• sphericity is meant the sphericity factor (a dimensionless number) as defined by Wadell as follows: the ratio between the sphere area of the same volume as the particle and the surface of the particle in question ( ⁇ ⁇ ), Equivalent squared equivalent of the ratio of volume equivalent diameter to surface equivalent diameter.
• this sphericity factor is greater than 0.82, advantageously greater than 0.85, and still more preferably greater than 0.90 with an even more advantageous situation when this sphericity factor is greater than 0.95.
• all the particles of the single powder used according to the invention have a form factor between 1 (corresponding to a sphere) and V2 (corresponding to a cube).
• This form factor which gives a good indication of the slenderness of the particles, is defined as the ratio between maximum Feret diameter (maximum distance between two parallel tangents at opposite sides of the particle) and the minimum Feret diameter (minimum distance between two parallel tangents at opposite sides of the particle).
• this form factor is less than 1.3, advantageously less than 1.25, and still more preferably less than 1.15 with an even more advantageous situation when this form factor is less than 1.05.
• the term "particle” corresponds to a physical entity isolated from the other physical entities of the powder considered and may correspond to different situations among which those of FIGS. 6A to 61
• one does not use a mixture in bulk (non-bound powders particles) of two or more different powders.
• the "particles" (which are optionally isolated macro-particles from each other) all have on average the same composition.
• the identical average composition of all the "particles" of the single powder used according to the process of the present invention corresponds to a chemical composition that is close to or identical to that of the material that is intended to be obtained in the part of the additive manufacturing process.
• a single powder of suitable composition which forms a pre-alloyed powder taken in the broad sense (single-component powder, (atomized powders, coated powders, kneaded powders, kneaded and milled powders, encrusted powders, ...) or multi-component powder (agglomerated powders, ..)), the "particles" of which have a high degree of sphericity (sphericity greater than 0.7, preferably greater than 0.8 and advantageously greater than 0, 9).
• the “particles" of this single powder are mono-components that is to say consist of a single component, namely formed of a continuous material of homogeneous composition (FIG. 6A) or heterogeneous composition, that is to say non-homogeneous, at the scale of the "particle” (FIGS. 6B, 6C, 6D, 6E, 6F, 6G and 6H).
• the powder used is obtained by atomization or centrifugation (in particular by rotating electrode) of a parent alloy and its composition is then homogeneous at the particle scale but not necessarily at the scale of the microstructure.
• the pre-alloyed powder consists of single-component "particles" formed of a continuous material of homogeneous composition at the scale of "Particle", composed of a single chemical element (single-element powder) or most often of several chemical elements (multi-element powders), of spherical or quasi-spherical morphology (FIG. 6A) and used according to the method of The present invention is obtained by gas atomization ("Gas Atomization” in English) or by spinning-type centrifugation ("Rotating Electrode Process” in English) of a mother alloy in rotation and in fusion from which droplets are formed and formed. cool in flight in a chamber under a protective or neutral atmosphere, to form the particles of the powder.
• Such parent alloy is for example metallic.
• pre-alloyed powders can be produced by different processes or combination of different synthesis processes, in particular processes based on mechanical or thermomechanical treatment in the dry, wet or inert gas (in particular by conventional grinding by means of balls, balls, knives, hammers, discs or rollers, ... or by co-grinding at higher or lower energy and preferably between a ceramic powder and a metal powder using a high energy planetary ball mill (grinding mechanically).
• cryogenic grinding reactive grinding between reactive solid particles or solid particles and reactive gas or by mechanofusion
• a chemical or thermo-chemical treatment in particular by CVD coating "Chemical Vapor Deposition”, PECVD or PACVD "Plasma Enhanced (Assisted!) Chemical Vapor Deposition” and OMCVD "Organo-Metallic Chemical Vapor Deposition” in English
• a reactive synthesis in particular by self-propagating combustion better known under the acronym SHS "Self-propagating High Temperature Synthesis”” in English).
• the mechanical or thermomechanical grinding or the mechano-synthesis of metal powders preferably introduce impurities from the grinding elements and do not allow rigorous control of the morphology and size of the particles.
• the particle morphology is usually isotropic and fairly spherical.
• the powder used is obtained by coating or incrustation.
• FIG. 6B shows such a particle of pre-alloyed powder formed by a mono- or multi-element particle of homogeneous composition coated or coated, the core of which is continuous and made of a first material and whose envelope is continuous, made of a second material of a composition different from the first, and deposited, for example, under vacuum in the chemical vapor phase (CVD deposition) or physically (PVD deposition, "Physical Vapor Deposition") or by a thermo-chemical treatment in beds fluidized dry or wet or by a thermo-mechanical treatment of the mechanofusion type.
• CVD deposition chemical vapor phase
• PVD deposition Physical Vapor Deposition
• Hard particle mechanofusion metal coating will improve the ductility and toughness of high fraction CMM volume of ceramic reinforcements non-oxides (carbides, nitrides, silicides and borides) or intermetallic because for such voluminal fractions the fusion of such a metal coating by means of a high energy beam greatly facilitates its distribution between the ceramic reinforcements which remain strong.
• the coating of the pre-alloyed particles by these same synthetic processes mentioned above may be of the multilayer type.
• the powder used is obtained by grinding / kneading, namely by grinding / mechanical kneading by impact or attrition (frictional wear) or by shearing or compression or a combination of two or more of these efforts.
• the final average size of the particles depends on the grinding technique used, the characteristics of the grinding elements (type of material, shape, size), the grinding time, the grinding medium (dry grinding with or without controlled atmosphere, in the middle aqueous or non-aqueous, with or without dispersant), the charge ratio (mass of the grinding elements on powder mass) and the speed of rotation of the grinding elements and / or the jar.
• FIG. 6C illustrates the case of a particle of pre-alloyed powder obtained by incrustation.
• incrustation of fine hard particles of a first powder on the surface of mono- or multi-element ductile particles of homogeneous composition of much larger size from a second pre-alloyed powder.
• mechano-synthesis (“mechanical alloying" in English) of mixing at high energy in the desired volume proportions a second fine powder of high hardness with a first ductile and coarse powder. This can be ensured by attrition and / or under the impact of balls by means of a planetary mill.
• the energy released is by an opposite rotation of the grinding vessel (jar) and the support disc under a protective gas.
• the particle of pre-alloyed powder which is visible in FIG. 6C, consists of a metal alloy core T16AI4V of homogeneous composition, and of an envelope formed of ceramic elementary fine particles (for example TiB 2 or TiC). ) or non-metallic (for example B for boron) which have encrusted on the surface of T6A4V.
• FIG. 6D illustrates the case of a particle of pre-alloyed powder of dispersed type whose material is continuous and obtained from the intimate mixing of two or more particles of original powders of different chemical composition, preferably comprising metal alloys.
• FIG. 6E illustrates the case of a particle of pre-alloyed powder of dispersed type but whose material is continuous and obtained from the intimate mixing of two or more particles of original powders of very different size and of different chemical composition, comprising preferably a ductile metal alloy and hard elementary particles, especially oxides (ODS materials "Oxide Dispersion Strengthened” materials): for example, one distinguishes the parts, respectively clear and dark, of the two original powders whose particles are of homogeneous composition but different, the clear particles of the first powder having plastically deformed and having repeatedly bonded with the hard and dark particles of the second powder, to form the pre-alloyed powder particle of Figure 6E.
• ODS materials Oxide Dispersion Strengthened
• FIG. 6F illustrates the case of a particle of pre-alloyed powder combining the characteristics of the powder particles of FIGS. 6D and 6E: this particle of pre-alloyed powder is of dispersed type but whose material is continuous and obtained from the intimate mixing of three original powders of different chemical composition, comprising two powders of ductile metal alloys: for example in FIG. 6F, there is a white matrix resulting from one or more large particles, the large dark parts each coming from a single particle of average size, even close to that of the first powder and dark elementary particles of much smaller hard size, including oxides.
• FIG. 6G illustrates the case of a pre-alloyed powder particle combining the characteristics of the powder particles of FIGS. 6B and 6D:
• a first production step makes it possible to obtain pre-alloyed powder particles such as those in FIG. 6D, namely of dispersed type but whose material is continuous and obtained from the intimate mixing of two or more particles of original powders of different chemical composition, preferably comprising ductile metal alloys, consisting of multi-elements: it is is the heart of the particle of Figure 6G.
• a second development step makes it possible to form the continuous envelope, made of a second material of different composition from the first material forming the core.
• FIG. 6H illustrates the case of a pre-alloyed powder particle combining the characteristics of the powder particles of FIGS. 6D and 6C:
• a first production step makes it possible to obtain pre-alloyed powder particles such as those in FIG. 6D, namely of dispersed type but whose material is continuous and obtained from the intimate mixing of two or more particles of original powders of different chemical composition, preferably comprising ductile metal alloys, consisting of multi-elements: it is is the heart of the particle of Figure 6H.
• a second development step makes it possible to form the discontinuous envelope by inlaying fine hard particles of a second powder on the surface of ductile particles of heterogeneous composition of much larger size resulting from a first pre-alloyed powder, such as those in FIG. 6D.
• the "particles" of this single powder are multi-components, namely each formed identically by several components (or elementary particles) of different chemical composition, interconnected by an organic or inorganic binder within a "macroparticle".
• the particles are formed of discontinuous material, of heterogeneous composition and are, according to the invention, quasi-spherical.
• the use of a binder in the synthesis of this agglomerated powder confers discontinuous matter character to the agglomerates and justifies the name of multi-component particle powder.
• this binder is removed after the agglomeration step by the use of a consolidation step of pyrolyzing or evaporating the binder by bringing the agglomerated powders into temperature.
• Such "particle” type “macro-particle” can be obtained by granulation comprising an agglomeration of components or elementary particles of different sizes, shapes and / or chemical compositions in the presence of moisture followed by drying.
• the development of particles of "macro-particle” type powders by agglomeration-drying or spray-drying of a slip requires, however, to master the following phases:
• the formulation of the slip in particular the choice of the solvent, the dispersant, the plasticizer and the binder (stability, homogeneity, rheological behavior and sedimentation),
• this granulation of the mixture of elementary particles in the form of a suspension makes it possible to transform it by atomization at low temperature (in a stream of air or hot inert gas) in spherical agglomerates of comparable size, often greater than 50 ⁇ and whose flowability is excellent,
• a consolidation step of the granules thus formed may sometimes be considered if denser and cohesive agglomerates are desired.
• the binder can cause problems during additive manufacturing from unembedded agglomerated powders, hence the interest of removing this binder.
• the furnace treatment makes it possible to consolidate the structure of the granules without modifying their characteristics while the oxyacetylene flame treatment leads to partial melting, sintering and spheronization of the granules modifying their morphology.
• this unique powder is formed of "macro-particles”, also referred to as “agglomerates”, “aggregates” or still “granules”, and is a powder referred to under the generic name of "engineered owders”.
• the powder used is obtained by granulation from a suspension also called slip.
• the slip is an aqueous or non-aqueous suspension of fine powders consisting of a mixture or not of different elementary particles different in shape, composition and / or size.
• the solvent should have a low boiling point and low viscosity. It must ensure the dissolution of the binder which may be organic or inorganic, that of the plasticizer and various additions such as deflocculants or dispersants and wetting agents. On the other hand, the solvent must not be soluble or reactive with the elementary particles of the composite powder.
• Particles formed of granulated composite particle macro-particles are visible in FIGS. 61 and 6J, they are granules consisting of components or elementary particles essentially connected to each other by a binder, for example water-soluble polymers such as vinyl polymers, acrylic polymers, polyimines and polyoxides, but also emulsion polymers and polymers of natural origin.
• a binder for example water-soluble polymers such as vinyl polymers, acrylic polymers, polyimines and polyoxides, but also emulsion polymers and polymers of natural origin.
• elementary metal particles ductile clear, of different sizes and fragile elementary components formed of dark short fibers (or "whiskers” in English).
• ceramic or intermetallic type refractory fibers acting as reinforcement to increase the mechanical strength of the metal matrix, insofar as the volume fraction of reinforcement is sufficiently large.
• These fragile and refractory elementary components of ceramic and / or intermetallic type may also be of equiaxed or spherical shape.
• FIG. 63 there are several elementary particles or elementary components of the same types, in particular metallic but sometimes also ceramic or intermetallic, of different size, shape and chemical composition, namely in the case represented three metallic elementary particles: small clear elementary particles (eg aluminum), clear elementary particles of larger size (eg titanium) and dark ovoid elementary particles (eg niobium).
• metallic elementary particles eg aluminum
• clear elementary particles of larger size eg titanium
• dark ovoid elementary particles eg niobium
• composite powders For the formation of these composite powders, one generally starts from a homogeneous mixture of several types of particles (several powders mono-element and / or multi-elements, "element” relating to the chemical element) having an average size, a size distribution and morphology suitable for macro-particle synthesis by known mixing and agglomeration techniques, using a binding additive (eg an organic binder) and other additions with or without densification (or consolidation) and spheroidization.
• a binding additive eg an organic binder
• FIGS. 6A to 6J relate to the illustration of the structure or constitution of powder particles falling within the scope of the present invention and are of course not limiting.
• the possible size range of the macro-particles of the composite powder (defined by dgo% - dio% or even preferably by di 0 o% - d 0 %), referred to the diameter value medium or median (d 5 o%) is low so as not to have too much size difference between these macro-particles as well as too coarse granules (d 50 % close to 50 ⁇ ).
• the granulation process results in the narrowest particle size distribution and the coarsest powder.
• this agglomerated composite powder is more suitable for the DMD process than for the SLM process. Recall that in practice a better compactness of the powder bed deposited on the production plate is obtained by considering a wide particle size distribution, accessible by atomization.
• (d 90 % - d 5 %) / d 5 % and (d 5 % - di 0 %) / d 5 % are two terminals, the first of which is less than or equal to 0.66 (66%), or even less than or equal to 0.33 (33%), and preferably less than or equal to 0.17 (17%), and the second is less than or equal to 0.33 (33%), or even less than or equal to 0.17 (17%), and preferably less than or equal to 0.08 (8%).
• composite powders also called granules, aggregates or agglomerates
• desired composition having a spherical morphology
• the granulation of the homogeneous mixture of elementary particles of different powders, to form the single powder consisting of macro-particles, also facilitates its handling, transport and storage by avoiding the segregation or sedimentation of particles of different sizes and / or masses. of these different powders (the smaller and / or heavier particles tend to flow easily through the interstices of the granular edifice).
• Granulation techniques are numerous in the science of powder metallurgy and are well known to those skilled in the art.
• a composite powder consisting of macro-particles makes it possible to envisage among the various powders to be mixed a powder composed of refractory particles, preferably fine and in a moderate amount.
• the technique of manufacturing this composite powder requires that the mixing of these different powders is homogeneous before it is followed by a suitable granulation technique.
• this technique not only makes it possible to avoid, on the one hand, problems of layering and homogeneity of the powder bed in SLM and, on the other hand, problems of flow through the nozzle, but also prevents dispersion (scattering) of these fine particles at the outlet of the DMD nozzle, especially since they are not very dense (low density), thus guaranteeing a repeatable (or reproducible) composition of the liquid bath.
• the particles of the different powders are mixed homogeneously before the granulation process. Otherwise, it may result in granules or macro-particles of different composition, which affects the composition of the final part which is then heterogeneous.
• the mixture is even more difficult to homogenize than the volume proportion of one of these powders is low compared to the others (for example additions to the rare earth mixture as deoxidizing elements or surfactant elements to facilitate the wetting between solid and liquid).
• the use of such a pre-alloyed powder by these techniques, in the straight line of the atomization, makes it possible in particular to ensure the obtaining of a homogeneous chemical composition in each particle and between all the particles.
• the solution according to the invention therefore makes it possible to very substantially reduce the heterogeneity of composition and microstructure of the material forming the part resulting from the additive manufacturing process by melting powder particles by means of a high energy beam.
• FIGS. 1 and 2 are explanatory diagrams of two additive manufacturing processes by melting of powder particles, known and preferably used in the context of the present invention
• FIG. 3 already described, illustrates the formation of a film of oxide (s) which forms with the presence of occluded gas porosity during the melting of an aluminum alloy in the presence of water vapor
• FIGS. 4A, 4B and 4C already described, are micrographs of fracture facies of specimens exhibiting intermetallic inclusions following the reaction of an aluminum-rich liquid with refractory particles based on iron or nickel which play. the role of complements to obtain the desired composition of the aluminum alloy
• FIG. 5 already described, corresponds to micrographs representing a steel part reinforced with particles of titanium carbide of lower density, some of which could not be completely dissolved and could not be solidified in the form of primary dendrites, and
• FIGS. 6A to 6J already described, represent different mono-component pre-alloyed powders (both of homogeneous composition, FIG. 6A, and of heterogeneous composition, FIGS. 6B, 6C, 6D, 6E, 6G, 6G and 6H) or multi -composantes (also called composite powders, Figures 61 to 6J) whose constitution or structure differs according to the methods of synthesis of these pre-alloyed powders.
• the powder used has a composition enriched in at least one chemical element of the composition of said material forming the part resulting from said process.
• the average chemical composition of the powder is slightly different from that of the material, in particular of the metal alloy, of the part resulting from the process according to the invention because the loss of a quantity of one or more chemical elements during manufacture, especially by evaporation.
• This evaporation is all the more favored by the use of an additive manufacturing process under vacuum, in particular by electron beam selective melting (EBM), unlike the SLM process, which The manufacturing enclosure is generally placed in overpressure.
• EBM electron beam selective melting
• said chemical element or one of its oxides is volatile at the implementation temperature by said high energy beam.
• said material is a metal alloy which is
• Ti6Al4V and said volatile element is aluminum.
• This alloy T ⁇ 6AI4V or TA6V is composed of titanium, 6% by weight of aluminum and 4% by weight of vanadium.
• An enrichment of the aluminum powder is preferably considered, which is between 0.15 and 3% by weight relative to the composition of the TiAl4V alloy, and preferably between 0.15 and 1.5% by weight.
• said material is a metal alloy based on aluminum and lithium (especially alloys with mass composition 2.7% ⁇ Cu ⁇ 4.3% - 0.8% ⁇ Li ⁇ 1.6% - 0.25% ⁇ Ag ⁇ 0.45% - 0.01% ⁇ Mn ⁇ 0.45% - 0.3% ⁇ Mg ⁇ 0.8% - Zn ⁇ 0.63% - Si ⁇ 0.12% - Fe ⁇ 0.15% and the remainder being Al) and said volatile element is lithium, the evaporated amount of which can be from 0.1 to 0.5% by weight.
• said material is a metal alloy based on titanium, preferably 6242 (ie Ti-6Al-2Sn-4Zr-2Mo-O, lSi in% by weight), and said volatile element which is enriched is Sn, this enrichment being between 0.15 and 1.5% by weight relative to the composition of the alloy.
• said material is an aluminum-based metal alloy, preferably 6061 whose main alloying elements are Mg and Si, and said volatile element which is enriched is Mg and / or Cu , this enrichment being between 0.05 and 0.40% by weight relative to the composition of the alloy for Cu and 0.05 to 1% by mass for Mg.
• said material is an intermetallic TiAl type, preferably TiAl 48-2-2 (ie Ti-48Al-2Cr-2Nb atomic%), and said volatile element which is enriched is Al, this enrichment being between 0.15 and 3% by weight relative to the composition of the intermetallic.
• said material is a nickel-based metal alloy, precipitation hardening type ⁇ '-Ni 3 (AI, ⁇ n) and said volatile element which is enriched is Al, this enrichment being between 0 , 05 and 3% by mass relative to the composition of the alloy.
• said material is an iron-based metal alloy and more specifically a martensitic stainless steel with a Cu-structured hardening, preferably 17-4PH (Z6CNU 17-04 or X5CrNiCuNbl7-4 or 1.4542) of mass composition C: 0.07% max, Mn: 1.00% max, P: 0.040% max, S: 0.03% max, Si: 1.00% max, Cr: between 15.00 and 17.00%, Ni: between 3.00 and 5.00%, Cu: between 2.8 and 5.00%, Nb + Ta: between 0.15 and 0.45% and the remainder being Fe, and said volatile element which is enriched is Cu this enrichment being between 0.15 and 3% by weight relative to the composition of the alloy.
• 17-4PH Z6CNU 17-04 or X5CrNiCuNbl7-4 or 1.4542
• the 15-5 PH alloy which is a precipitation-hardened martensitic stainless steel (Z7CNU 15-05 or X5Cr1 / CuNbl5-5 or 1.4540) of mass composition C: 0.07% max, Mn: 1.00 % max, P: 0.040% max, S: 0.03% max, Si: 1.00% max, Cr: between 14.00 and 15.50%, Ni: between 3.50 and 5.50%, Cu: between 2.50 and 4.50%, Nb + Ta: between 0.15 and 0.45% and the remainder being Fe.
• An enrichment in Cu (total quantity between 1500ppm and 2.5%), of this element likely to volatilize under a high energy beam, should be considered in order to maintain the desired volume fraction.
• magnesium alloy RZ5 which is designated according to the French standard AFNOR by GZ4TR and by ZE41 (or Mg-Zn-RE-Zr) according to the ASTM standard. Its mass composition is as follows: Cu: ⁇ 0.10%, Mn: ⁇ 0.15%, Ni: ⁇ 0.01%, Zn: between 3.50 and 5.00%, Zr: between 0.40 and 1.00%, Ce (rare earth): between 0.75 and 1.75% and the rest being Mg.
• the composition of the powder used has at least one additional chemical element in a reasonable amount (non-zero, in particular greater than 0.001% by mass, ie 10 ppm or 10 mg / kg but less than 0.5% by weight, ie 5000 ppm or 5 g / kg) and able to modify the microstructure of said material of the resulting part of said process with respect to the case where this additional chemical element is absent from the composition of the powder.
• said material is a metal alloy and said additional chemical element is able to modify the morphology of the metallurgical phase or phases of said metal alloy.
• the Al-Si hypo-eutectic aluminum alloys it is the additional chemical elements sodium (Na) and / or strontium (Sr) and / or calcium (Ca) and / or antimony (Sb) which have in effect to refine the morphology of the lamellar or fibrous eutectic.
• Na sodium
• strontium Sr
• Ca calcium
• antimony Sb
• this refining effect of the eutectic microstructure which increases the ductility of the alloy is reduced by the addition of the phosphorus element (P) which reacts with the modifying elements, and in particular sodium, to form phosphures.
• the phosphorus content should be kept low ( ⁇ 15 to 30 ppm).
• another way to refine the eutectic microstructure is to use process parameters to generate a high rate of solidification which also already characterizes these rapid manufacturing processes by melting powder particles by means of a beam high energy.
• said material is a metal alloy and said additional chemical element is capable of refining the size of the grains of said metal alloy without systematically modifying the morphology of the grains: it is a question of carrying out a refining the grain size by adding inoculant.
• the equiaxed fine grain structure offers the best combination of strength and ductility.
• the morphology and size of the grains formed after solidification of the bath are determined by the composition of the alloy, the rate of solidification and the small addition of additional chemical elements known as "refiners", in particular titanium and boron in the form of Ti, B or Ti-B salts or Al-Ti, Al-B or Al-Ti-B alloys.
• refining chemical elements form, in contact with liquid aluminum, intermetallic compounds with a high melting point which constitute sites of heterogeneous germination of grains and increase the number of grains.
• inoculants such as Nb, Zr and Cu-P (where the phosphorus element acts in particular on Si germination) are also used for the refining of aluminum alloys.
• said parent metal alloy is an aluminum-based alloy of the AISilOMg type close to the 43000 alloy according to the NF EN 1706 standard or is still close to the A360 alloy according to the "Aluminum Association" in the USA.
• This alloy is composed of aluminum, 9.5% by weight of silicon, 0.5% by weight of magnesium and 1.3% by mass of iron and said element is titanium and / or boron and / or zirconium (preferably 100 to 300 ppm Ti, and / or 20 to 50 ppm B and / or 100 to 500 ppm Zr).
• These three elements can be introduced into the parent alloy in the form of an Al-Ti or Al-Zr binary alloy containing from 3 to 10% by mass of Ti or Zr, or else in the form of a ternary alloy Al -Ti-B or Al-Zr-B consisting of the said same Al-Ti or Al-Zr binary alloy with in addition 0.2 to 1% by mass of B.
• the direct introduction of TiB 2 or ZrB 2 particles into the aluminum-rich parent alloy is to be discarded because of its high melting point making it difficult to dissolve, especially since the particles are large.
• aluminides essentially TiAl 3 or ZrAl 3
• borides essentially TiB 2 or ZrB 2 and sometimes AIB 2
• aluminides essentially TiAl 3 or ZrAl 3
• borides essentially TiB 2 or ZrB 2 and sometimes AIB 2
• titanium and / or boron are two chemical elements which are introduced, alone or together, preferably in the form of binary (Al-Ti) or (Al-B) or ternary (Al-Ti) alloys. -B) with a low melting point, close to that of the aluminum-based alloy.
• said parent metal alloy is a titanium-based alloy which is TiAl4V or TA6V and said additional chemical element or refining element is boron (10 to 5000 ppm of B) or TiB 2 type borides (10 to 5000 ppm of TiB 2 ).
• these chemical elements are introduced in the form of elementary fine particles by incrustation (discontinuous coating as in the case of FIG. 6C) and / or by kneading (as in the case of FIG. 6E). .
• either Ca and / or Zr may be added, which, in a small quantity (total of between 10 to 5000 ppm), may have a beneficial effect on the refining of the grain.
• the enrichment of additional chemical elements known as "refiners” comprises one or more chemical elements from C, B, N, TiC, TiN, TiB 2 , Fe 3 C and FeSi, for a total addition of between 50 and 5000 ppm.
• said element is able to deoxidize the bath of said metal alloy.
• said metal alloy is an iron-based alloy which is preferably 16NCD13, 32CDV13 or 15CDV6 and said additional chemical element or deoxidizing element is titanium introduced in the form of TiC and / or TiB 2 particles ( less than 1% by volume, preferably 50 to 5000 ppm TiC and / or TiB 2 and preferably 50 to 500 ppm TiC and / or TiB 2 ).
• the addition of rare earths in the synthesis of metal matrix composites (CMM) or oxygen-hungry materials has the effect of limiting the dissolved oxygen in the liquid bath during additive manufacturing.
• the most common rare earths are Scandium (Se), Neodyne (Nd), Yttrium (Y) and Lanthanum (La). They have the particularity of fixing the dissolved oxygen in the form of oxides, which oxides are chemically stable with respect to the matrix of CMM and oxygen-hungry materials.
• said additional chemical element is added by adding fine particles of TiC, TiB 2 and / or hexaborides of rare earths for Ti, Fe and Al-based alloys.
• it can be enriched from 50 to 5000ppm RZ5 magnesium alloy aforementioned rare earth which in addition to act as a deoxidizer bath, can increase the resistance to galvanic corrosion and can reduce the microporosity and cracking on solidification of the liquid bath.
• said additional chemical element is capable of facilitating the wetting of the reinforcements (discontinuous) by the liquid formed by the melting of a part of the particles of the composite powder by means of a high energy beam: in particular it is is the fusion by the beam of high energy of other metallic elementary particles of the composite powder.
• the dissolved Mg element increases the wetting of SiC by the liquid aluminum while the Cu element decreases it.
• Si in small quantities (50 to 5000ppm) makes it possible to control the Fe content of the aluminum-rich liquid bath and lowers its melting temperature somewhat, thus improving the wettability of the liquid with respect to the SiC reinforcement.
• said element is capable of improving the absorptivity of the radiation provided by the high energy beam so as to facilitate on the one hand the sinter densification if the compactness of the powder bed is sufficiently important (case of the SLS process) or on the other hand the melting of the powders (in the case of the SLM and DMD processes) of the material in question.
• said material is a ceramic that is almost transparent to the radiation of the high energy beam, preferably oxides (Al 2 O 3 , SiO 2 , ZrO 2 , Y 2 O 3 , MgO, TiO 2, etc.) or mixtures more oxides (Al 2 0 3 -Si0 2, Al 2 0 3 -Zr0 2, Zr0 2 -Y 2 0 3, Al 2 0 3 -Si0 2 -Y 2 0 3 ...) some of which may play the role of melting (reducing the solidus temperature of the mixture by the formation of a small amount of low melting point liquid facilitating the densification and consolidation of the material during its additive manufacturing), and the said element is carbon - or any another absorbent element vis-à-vis the wavelength of the laser used - preferably introduced in the form of a continuous coating (50 to 5000 ppm carbon or its derivatives and preferably 100 to 1000 ppm carbon ) of an atomized or centrifuged powder (powder of FIG. 6B) or
• said element or additional chemical compound is capable of reinforcing the metal alloy from a mechanical point of view for high application.
• temperature in particular, said additional chemical compound is used with a sufficiently large volume fraction, between 3 and 30% by volume, and a sufficiently fine size and a sufficiently homogeneous distribution, both close to those of the elementary metal particles of the composite powder presented in Figure 61
• CMM metal matrix composites
• ductility is reduced and requires an optimization of the volume fraction of the reinforcements so as to limit this decrease in ductility.
• titanium alloys such as TA6V may be reinforced by additions of TiB and / or TiC with a volume fraction of these reinforcements, which preferably does not exceed 15% by volume. These additions can be obtained by reacting the titanium alloy with the reinforcement B 4 C.
• SiC reinforcements in 5000 series aluminum alloys and Al 2 0 3 reinforcements in 6000 series aluminum alloys is envisaged.
• the introduction of SiC reinforcements into magnesium alloys is also considered.

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