EP4482632A1 - Procédé de structuration en couches d'un objet tridimensionnel - Google Patents

Procédé de structuration en couches d'un objet tridimensionnel

Info

Publication number
EP4482632A1
EP4482632A1 EP23701837.9A EP23701837A EP4482632A1 EP 4482632 A1 EP4482632 A1 EP 4482632A1 EP 23701837 A EP23701837 A EP 23701837A EP 4482632 A1 EP4482632 A1 EP 4482632A1
Authority
EP
European Patent Office
Prior art keywords
ink
layer
sacrificial
weight
drops
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23701837.9A
Other languages
German (de)
English (en)
Inventor
Stefan WALDNER
Oliver UNGERER
Thomas Sigmund
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
D3-AM GmbH
Original Assignee
D3-AM GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by D3-AM GmbH filed Critical D3-AM GmbH
Publication of EP4482632A1 publication Critical patent/EP4482632A1/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
    • 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
    • B22F10/30—Process control
    • B22F10/38—Process control to achieve specific product aspects, e.g. surface smoothness, density, porosity or hollow structures
    • 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
    • B22F10/40—Structures for supporting workpieces or articles during manufacture and removed afterwards
    • B22F10/43—Structures for supporting workpieces or articles during manufacture and removed afterwards characterised by material
    • 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
    • B22F10/40—Structures for supporting workpieces or articles during manufacture and removed afterwards
    • B22F10/47—Structures for supporting workpieces or articles during manufacture and removed afterwards characterised by structural features
    • 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
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
    • 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
    • B29C64/386—Data acquisition or data processing for additive manufacturing
    • B29C64/393—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
    • 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
    • B29C64/40—Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
    • 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
    • B33Y50/00—Data acquisition or data processing for additive manufacturing
    • B33Y50/02—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
    • 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
    • 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
    • B33Y80/00—Products made by additive manufacturing
    • 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
    • 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
    • B22F12/55—Two or more means for feeding material
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

Definitions

  • the present invention relates to a method for layer-by-layer structuring of a three-dimensional object, in particular by means of inkjet printing. Furthermore, the invention relates to a three-dimensional object that can be obtained by the method according to the invention.
  • the supporting structure For the production of shaped objects with overhanging areas, it has become established in industry that not only the overhanging areas to be formed on a supporting structure, but also the supporting structure itself is built up in layers. The latter has the general task of supporting the individual object layers while maintaining their shape during the layered structuring of the object. In preferred cases, however, the supporting structure can also fulfill the same purpose during further shaping steps of the object, for example a firing step, provided its nature allows this. Depending on the chemical nature of the support structure, taking into account the composition of the manufactured object, one or more known methods can be used to remove it from the finished object without damaging the object.
  • a method is also known from the prior art, in which a support structure is built up in layers in order to support not only overhanging areas but also lateral areas of the object in a shape-retaining manner.
  • Such a method is known from WO2018203331 A1, which comprises the following steps: (A) printing a first mold to define a first layer of the product; (B) filling the first mold with a casting material, thereby forming a first layer; (C) printing a second shape on the first layer to define a second layer; and (D) filling the second mold with the casting material; to thereby form a layered molded product, the respective shapes being printed with an inkjet nozzle by ejecting drops of a first molding material comprising wax, and the respective product layers being cast with a casting nozzle using the molding material comprising ceramic powder.
  • Also known from generic application WO2006078342A2 is a method of forming an object, comprising the steps of: (i) ink jet printing a first material to form a plurality of layers defining a support structure ridge having an inner surface; and (ii) extruding a second material to form a layer of the object, wherein the layer substantially conforms to the interior surface of the support structure ridge and has a thickness greater than the thickness of each layer of the plurality of layers defining the support structure ridge.
  • the object resolution resulting from extrusion is generally about 130 microns and the object resolution resulting from inkjet printing is generally about 50 microns.
  • EP3659547A1 also discloses a method for producing a ceramic dental restoration, in which (A) a slip containing no more than 5% by weight of organic components, based on the total mass of the slip, is applied in layers to give the geometric shape of the desired dental restoration and the individual layers are each dried after printing, and (B) the green body thus obtained is optionally subsequently dried and (C) the green body is then sintered, the layered structure of the green body being produced in step (A) by a layered inkjet printing process takes place.
  • inkjet printers Compared to casting printing and extrusion, the printing speeds of inkjet printers are often significantly lower than those of casting printing devices and extruders, for example. In order to increase the printing speed, it is known to equip inkjet printers with a large number of nozzles and/or inkjet print heads.
  • Inkjet printers also called inkjet printing devices
  • the printing takes place here by the ejection of ink drops according to a predetermined, possibly variable, printing frequency and number of drops.
  • the inkjet print head performs a linear transverse movement, which allows one line to be printed.
  • the substrate to be printed can perform a linear movement during ejection.
  • This (transverse) movement determines the scanning direction.
  • the method known in the state of the art of printing line by line is therefore also called a scanning method. If one or more inkjet print heads extend across the entire width of the medium to be printed, as an alternative to the first-mentioned embodiment above, only the substrate can be moved perpendicularly to a row of nozzles, with the inkjet print head or heads not being moved. This method is known, among other things, as the single-pass method.
  • the print head If the print head only moves across the line once during the scanning process, this is referred to as the single scan process. Runs the print head several times over the same line, this is referred to as the multiscan method.
  • the multiscan process can lead to a higher print quality in selected processes.
  • the substrate to be printed can be moved by one line perpendicularly to the scanning direction executed by the print head in a transport direction and the printing of the next line can begin.
  • monodirectional methods i.e. the print head only prints in one direction when moving transversely and, when it reaches the end of the line, returns to the beginning of the line without printing.
  • bidirectional methods in which the medium to be printed is shifted by one line after the end of the line has been reached and the next line is already printed when the print head is moved back to the starting position.
  • the resolution is determined by the spacing of the droplets deposited by the print.
  • the resolution in a first dimension for example in an x dimension
  • the resolution in the second dimension for example the y dimension, which is oriented perpendicular to the first dimension.
  • the resolution along the transverse movement of the printhead is determined by the speed of the printhead and the drop ejection frequency, while the resolution in the transport direction is determined by the spacing of the nozzles in the nozzle row of the printhead. It should be noted that this resolution can be increased by tilting the row of nozzles.
  • a higher resolution can also be achieved, for example, by arranging a row of nozzles of a first print head offset from a row of nozzles of a second print head on a print carriage such that the resolution is doubled in the transport direction.
  • the resolution in the third dimension for example the z dimension orthogonal to the x-y plane, can differ from the resolution in the first and/or second dimension.
  • the resolution z is determined by the ink application level realized at each pixel.
  • An inking level (0 to KS) of a sacrificial ink for forming a support structure or for forming inner edge regions of respective mold layers of a support structure is defined in the context such that the level KS, i.e. K*S, indicates the amount of ink KS of the sacrificial ink with which each Pixel Di is applied in each row of a first printing raster and K is a drop or a multiple of a drop of sacrificial ink emitted by one or more nozzles of at least one row of nozzles, each individual drop of sacrificial ink having substantially the same drop volume S.
  • An inking level (0 to LT) of an object ink is defined in the context such that the level LT, ie L*T, indicates the amount of ink LT of the object ink with which each pixel D2 in each row of a second printing raster is applied and L is a drop or a multiple of a drop of the object ink emitted by one or more nozzles of at least one row of nozzles, each individual drop of the object ink having essentially the same drop volume T.
  • WO2006078342A2 discloses the realization of object layers and structural layers by means of inkjet printing, which layers each have the same layer thicknesses, as can be seen in FIG.
  • This prior art does not disclose that different ink droplet sizes are used to implement the structural layers or sacrificial layers and the object layers.
  • the droplet volume of the respective ink droplets for realizing the structural layers or sacrificial layers is smaller than the respective droplet volume of the ink drops for realizing the object layers.
  • the present invention is therefore based on the object of specifying a method for structuring three-dimensional objects with which a high degree of imaging accuracy over the entire surface of the object, i.e. also on its cover layer, is achieved in a time-saving manner.
  • the object is achieved with a method that includes the features of claim 1.
  • the dependent claims relate to further advantageous and possibly additionally inventive embodiments.
  • the invention is based on the idea that different native droplet volumes for the sacrificial ink and for the object ink are used to form each sacrificial layer of each mold layer of a supporting structure and to form each object layer.
  • the drop volume of the respective drops of sacrificial ink is ⁇ 100pl, the volume ratio between the volume of the respective drops of sacrificial ink and the volume of the respective drops of object ink being at least 1:15 in each case.
  • Each mold layer for forming a support structure for the three-dimensional object is formed by stacking several sacrificial layers one on top of the other, the sacrificial layers each being formed with a layer thickness that is at least twice smaller than the layer thickness of each object layer.
  • each sacrificial layer is formed by applying a first combination droplet to each pixel Di in each row of an imaginary first printing pattern on the surface to be printed, which is composed of K drops of the sacrificial ink each with a volume S , where K e ⁇ 0, 1, 2, 3, ... ⁇ and thus an ink application level KS is realized for each pixel Di.
  • each object layer is formed by applying a second combination droplet to each pixel D2 in each row of an imaginary second printing screen on the surface to be printed, each consisting of E drops of the object ink, each with one volume T, where L e ⁇ 0, 1, 2, 3, ... ⁇ and thus an ink application level LT is realized for each pixel Ü2.
  • the method according to the invention comprises the following steps: (a) Forming, on a substrate or preferably on a lower layer, a first mold layer with a first gap, which corresponds to the negative of a first object layer, (b) filling in the first gap with object ink, in order to to form the first object layer; (c) forming, on the first mold layer, a second mold layer with a second recess corresponding to the negative of a second object layer, (d) filling the second recess with object ink to form the second object layer, thereby forming an object and a support structure of or comprising sacrificial layers was formed.
  • a first combination drop can be understood in the context of those drops of the sacrificial ink printed in succession with one nozzle or with several nozzles, which essentially have the same drop volume S, which can be understood when using grayscale-capable inkjet print heads in flight and at the latest before impact can unite on the pixel Di to be printed or which, alternatively, generally arise when using Inkjet printheads are merged at different times to a pixel position they were targeting, and essentially have a multiple of the originally printed drop volume S of sacrificial ink.
  • a second combination drop can in turn be understood to mean those drops of the object ink printed with one nozzle or with several nozzles in succession, which essentially have the same drop volume T, which can be understood when using grayscale-capable inkjet print heads in flight and at the latest before the impingement on the pixel to be printed D2, or alternatively which, in general when using inkjet printheads, at different points in time at a pixel position which they aimed at, are combined and essentially a multiple of the originally printed droplet volume T of the object ink exhibit.
  • a combination drop can also consist of zero drops (K or L equal to zero) or one drop (K or L equal to 1).
  • the method according to the invention is a method for layer-by-layer structuring of a three-dimensional object, comprising:
  • each mold layer is formed by stacking a plurality of sacrificial layers one on top of the other, the sacrificial layers each being formed with a layer thickness that is at least a factor of two smaller than the layer thickness of each object layer, such that each sacrificial layer is formed by impinging on each pixel Di in each Row of an imaginary first printing grid on the respective surface to be printed is formed with a first combination drop, which is composed of K drops of the sacrificial ink each with a volume S, where K e ⁇ 0, 1, 2, 3, ... ⁇ and thus an ink application level KS is realized for each pixel Di, and that each object layer is formed by applying a second combination droplet to each pixel D2 in each row of a second imaginary printing grid on the surface to be printed, which consists of E drops of the object ink with each composed of a volume T, where L e ⁇ 0, 1, 2, 3, ...
  • the droplet volume S of the respective K drops of the sacrificial ink being ⁇ 100pl and the volume ratio (S:T) between the volume S of the respective K drops of the sacrificial ink and the volume T of the respective L drops of the object ink is at least 1:15, preferably at least 1:20.
  • a layer means a continuous layer in each case.
  • the drops of sacrificial ink and drops of object ink are applied in such a way that first combination drops of sacrificial ink applied to adjacent pixels Di run into one another with their edge areas and second combination drops of object ink applied to adjacent pixels D2 also run into one another with their edge areas.
  • the method according to the invention is also designed in such a way that the drops of sacrificial ink and object ink are applied in such a way that the X-Y grid widths in the dimension x and in the dimension y of the first printing grid are selected to be smaller than the respective X-Y grid widths in the x dimension and in the y dimension of the second printing screen.
  • the neighboring pixels are typically immediately neighboring pixels that have actually received a combination drop. However, it is also possible for the neighboring pixels to be indirectly neighboring pixels, in which, for example, only every second pixel in the x and y direction was actually acted upon by a combination droplet.
  • a molded layer is understood to mean a molded layer which consists of a side wall enclosing a recess, which side wall comprises a plurality of sacrificial layers stacked on top of one another.
  • the droplet volume S of the respective K drops of the sacrificial ink is ⁇ lOOpl, preferably lOpl ⁇ S ⁇ 80pl, particularly preferably 20pl ⁇ S ⁇ 45pl, with the volume ratio (S:T) between the volume S of the respective K Drops of the sacrificial ink and the volume T of the respective L drops of the object ink are each at least 1:50, preferably at least 1:150, particularly preferably at least 1:300, and very particularly preferably up to 1:1500.
  • the sacrificial layers can be formed, for example, each with a layer thickness that is smaller by at least a factor of four, preferably smaller by a factor of at least eight, than the layer thickness of each object layer.
  • each object layer formed is dried and/or hardened before a further object layer is formed thereon. In this case, the respective object layers are typically not completely dried. This results in improved adhesion between the layers.
  • each object layer that is formed is dried by removing the water, preferably essentially only the water, from each object layer that is formed, before a further object layer is formed thereon.
  • the object ink contains as components (a) water, (b) an organic binder and (c) an organic dispersing agent or (z) an organic dispersing binder instead of components (b) and (c), and (d) ceramic particles and/or metallic particles dispersed in the water, the method further comprising the step of: firing the object to obtain a ceramic and/or metallic fired object.
  • the organic binder (component (b)) is designed in such a way that it has the task of temporarily holding the ceramic and/or metallic particles of the respective object layers in place after the water has been removed by drying the respective object layers and until the particles are bonded to one another by sintering during the firing step.
  • the dispersing agent (component (c)), which differs from the organic binder, promotes the wetting and stabilization of the ceramic and/or metallic particles in the object ink and thus prevents the particles present from floating up and out and from settling, thereby improving the homogeneity the suspension can be maintained over a longer period of time.
  • the organic dispersant is designed accordingly.
  • the organic binder can also be designed to fulfill the function of the organic dispersing agent.
  • Such a binder is referred to in this specification as an organic dispersant binder (component (z)).
  • Suitable organic binders are, for example, first polymers. Such polymers are known to those skilled in the art. Examples of suitable organic dispersants (component (c)) are second polymers. Such polymers are also known to those skilled in the art.
  • Suitable organic binders with a dispersing action are preferably third polymers, for example methylcellulose. Such polymers are also well known to those skilled in the art.
  • the object ink includes the following components:
  • component (a) 10% - 40%, preferably 15% - 25% by weight of component (a);
  • component (b) 0.3% - 5%, preferably 0.5% - 1.5% by weight of component (b); and 0.01% - 5%, preferably 0.2% - 2% by weight of component (c); and 50% - 85%, preferably 70% - 80% by weight of component (d), or
  • component (a) 10% - 40%, preferably 15% - 25% by weight of component (a); and 0.01% - 5%, preferably 0.2% - 2% by weight of component (z); and 50% by weight - 85% by weight, preferably 70% by weight - 80% by weight, component (d), the total organic component content of the object ink being ⁇ 6% by weight, preferably ⁇ 5% by weight, particularly preferably ⁇ 3% by weight .% and where the respective percentages relate to the total weight of the object ink.
  • the object ink comprises at least one additional additive as an additional component (e), for example an organic slip and/or leveling additive, which serves to reduce the surface tension of the object ink.
  • the amount of slip and/or leveling additive in the ink is between 0.2% by weight and 3% by weight, preferably between 0.5% by weight and 1% by weight, based on the total weight of the object ink.
  • conventional object inks with ceramic and/or metallic particles for the production of corresponding objects contain a significantly higher proportion by weight, ie a proportion by weight of more than 15% by weight, usually even more than 30% by weight, of organic components in relation to the total weight of the object ink , including in particular an organic humectant to prevent drying and/or agglomeration of the ceramic and/or metal particles in the nozzles of conventional inkjet print heads with a nozzle diameter of up to 60 ⁇ m. This could successfully eliminate nozzle clogs be minimized, whereby a high printing reliability could be achieved with these print heads.
  • An object produced from the ceramic and/or metallic object ink according to the invention behaves in such a way that - even if no significant organic component content was removed from its layers during the respective drying - a fired ceramic and/or metal object is produced in a significantly shorter time in comparison to the conventional object inks mentioned above can be produced without defects.
  • the object behaves in such a way that it can be brought from room temperature to a temperature at which it begins to sinter within a significantly shorter heating time by means of a temperature ramp, without defects occurring in the object.
  • the object made of layers behaves in such a way that even if, for example, ⁇ 20% by weight, preferably ⁇ 10% by weight of the organic components of the object ink were removed from each layer of the object during the respective drying, a fired ceramic and/or or metal object can be produced without defects in a significantly shorter time compared to the conventional object inks mentioned above.
  • An object produced without defects is understood to mean an object produced after the firing process without cracking and/or bursting of individual object layers.
  • the debinding step is defined in such a way that in this step there is not even partial sintering of the inorganic particles of the object ink, i.e. the ceramic and/or metal particles, in contrast to the firing step.
  • the inventors have observed that the low-organic object inks of the present invention, when formulated as inkjet inks and with nozzles of an inkjet print head, each with an inner diameter in a range from 100 ⁇ m to 400 ⁇ m, enable a surprisingly high printing reliability of the ink jet print head.
  • the low proportion of organic components totaling ⁇ 6% by weight, preferably ⁇ 5% by weight, particularly preferably ⁇ 3% by weight, the risk of drying and/or agglomeration of the ceramic and/or metal particles could be drastically reduced, thereby reducing the risk of nozzles Blockages could be minimized accordingly.
  • the object ink may comprise an object ink A and an object ink B each comprising components (a), (b), (c) and (d) or components (a), (z) and (d) but in different and from each other predetermined weight proportions and compositions, and which are applied to the pixels D2 of the second print screen according to a predetermined print pattern in order to form an object layer.
  • This enables the formation of objects with a wide variety of chemical and/or physical properties.
  • the object ink A may include alumina ceramic particles and the object ink B may include zirconia ceramic particles. If both object inks are used to form the respective object layers according to selected and known printing schemes, the fracture toughness and fracture strength of the individual object layers and thus also that of the object can be significantly increased.
  • the object ink and the sacrificial ink are each designed as inkjet inks and that the K drops of the sacrificial ink are emitted from at least a first inkjet print head with a plurality of nozzles, and that the E drops of the object ink are emitted from at least a second inkjet - Print head each having a plurality of nozzles are output, with a linear relative movement taking place at least between the first inkjet print head and the substrate during the formation of each sacrificial layer, and with a linear relative movement taking place at least between the second inkjet print head and the substrate during the formation of each object layer substrate takes place.
  • the multiple nozzles of the second inkjet print head may each have an internal diameter in a range from 100 ⁇ m to 400 ⁇ m, preferably in a range from 150 ⁇ m to 350 ⁇ m, particularly preferably in a range from 150 ⁇ m to 250 ⁇ m , and that the plurality of nozzles of the first inkjet print head each have an internal diameter of up to 60 ⁇ m, preferably in a range from 20 ⁇ m to 45 ⁇ m.
  • an inkjet print head operated by means of a plunger is provided as the second inkjet print head.
  • the inkjet print head operated by means of a plunger can circulating pump provided outside the print head for pumping the object ink through an ink supply channel of the print head.
  • the inkjet print heads for inkjet printers disclosed in the description of WO 2013/013983 A1, WO 2019/042586 A1 and WO 2019/042585 A1 by the applicant of the same name, which are operated by means of plungers, should be mentioned. Due to the large internal diameter of the nozzles between 250 ⁇ m and 350 ⁇ m, such print heads can, for example, print suspensions with larger particles than with the otherwise typical piezoelectrically operated inkjet printing devices from the prior art, which typically include nozzles with an internal diameter of only up to 60 ⁇ m.
  • At least 95%, preferably at least 99%, of the pixels D2 of the object layer that are actually to be printed are exposed to one and the same second combination droplet, which is composed of L drops of the object ink, where L e ⁇ 1, 2, 3 ⁇ , preferably L e ⁇ 1 ⁇ and thus one and the same ink application level IT, 2T, or 3T, preferably IT, is realized for each of these pixels D2.
  • At least 95%, preferably at least 99% of the pixels Di of the sacrificial layer that are actually to be printed are exposed to one and the same first combination droplet, which is composed of K drops of the sacrificial ink, where K e ⁇ 1, 2, 3 ⁇ , preferably K e ⁇ 1 ⁇ , and thus one and the same ink application level IS, 2S, 3S, preferably IS, is realized for each of these pixels Di.
  • At least 95%, preferably at least 99% of the pixels Di to be actually printed are included either in an area close to the edge of the gap in the sacrificial layer or an inner edge area of a molded layer if there is a gap, or of the entire area of the respective sacrificial layer and applied to the same first combination drop.
  • an area close to the edge of the gap in the sacrificial layers this means an edge area that encloses and within both the actual edge of the gap in the sacrificial layer and a fictitious edge that separates the gap in the object layer the sacrificial layer runs, defined, wherein the Distance between the actual edge and the notional edge is up to 5 cm, preferably up to 1 cm.
  • the method typically includes an additional step of removing the support structure formed from or comprising sacrificial layers from the object, preferably by mechanically abrading, evaporating volatile components, melting, dissolving or burning the support structure.
  • the support structure serves to support lateral and/or overhanging areas of the object.
  • step (a) a sacrificial layer or a plurality of sacrificial layers are formed on the substrate by stacking them one on top of the other. This development is advantageous because it reduces the effort involved in removing the object from the substrate.
  • step (a) also comprises forming, on the substrate or on a lower layer, a first core layer within the recess in question, such that a ring-like recess is formed; and step (c) also comprises forming, on the lower layer, a second core layer such that an annular recess is formed.
  • step (c) a second mold layer is also formed on the first object layer.
  • each sacrificial layer is solidified or dried and/or hardened before a further sacrificial layer, or preferably an object layer and a further sacrificial layer, is formed thereon.
  • the sacrificial ink comprises a wax or the sacrificial ink consists of a wax that has a melting temperature (mp) of >40°C, preferably an mp of >60°C, particularly preferably an mp of >90°C, and which has been previously brought to a temperature that is higher than its melting point in order to act on the pixels Di of the first printing screen.
  • the wax can be solidified by passive or active cooling of the substrate at a temperature that is lower than the melting temperature of the wax.
  • the sacrificial ink comprises a liquid carrier, a dispersant, a UV radiation free radical generating photoinitiator and a polymer, which polymer is free radically curable and is dispersed in the liquid carrier by the dispersant. Drying of each sacrificial layer may be accomplished by exposing the sacrificial ink to thermal energy, such as IR or NIR radiation, and UV curing of each sacrificial layer may be accomplished by exposing the sacrificial ink to UV radiation.
  • thermal energy such as IR or NIR radiation
  • the not yet dried and/or not yet hardened nth object layer is formed with a layer thickness which is less than or equal to the layer thickness of the solidified or dried and/or hardened nth mold layer, which corresponds to the negative of the nth object layer.
  • the letter n of an (n)th mold layer corresponds to the number of mold layers formed so far, and the letter n of an (n)th object layer corresponds to the number of object layers formed so far.
  • the x-y screen rulings, i.e. the screen rulings in an x dimension and in a y dimension, which is aligned vertically to the x dimension, of the first printing screen can each correspond to an ink drop density of >300 dpi, preferably >600 dpi, particularly preferably >1200 dpi, and the grid rulings in the x dimension and in the y dimension of the second printing screen can each correspond to an ink drop density of ⁇ 150 dpi, preferably from 50 dpi to 100 dpi in each case.
  • first type printing cycle comprising:
  • the method according to the invention can also comprise one or more pressure cycles of the so-called second type until the desired object has been completely formed, a pressure cycle of the second type comprising:
  • the (n)th mold layer to which an (n+1)th object layer is to be applied is preferably formed exclusively by stacking the plurality of sacrificial layers one on top of the other.
  • Each object layer may be leveled with a mechanical means for leveling its surface, preferably with a suitable roller or squeegee means, before another object layer is formed thereon. This makes it possible to increase the imaging accuracy of the top layer of the object.
  • each sacrificial layer can be leveled with a mechanical means for leveling its surface, preferably with a suitable roller or doctor blade means, before another sacrificial layer is formed thereon. This makes it possible to increase the imaging accuracy of the cladding layer of the object and possibly an increase in the imaging accuracy of the bottom layer of the object.
  • the object is formed with at least one desired color gradient by forming the respective non-dried and/or non-hardened object layers in such a way that they may be filled with drops, each with a volume of ⁇ 50 pl, of one or more color inks be printed with inorganic or organic color particles according to a predetermined print pattern with at least one third inkjet print head, such that the layer thickness of each non-dried and/or non-hardened object layer does not increase significantly, preferably by no more than 3%, particularly preferably by not more than 1.5%.
  • realistic color gradients of a tooth crown can be reproduced.
  • ceramic and metallic object layers are formed alternately in such a way that insulating and conductive object layers are formed alternately.
  • electronic components can be produced, for example.
  • the sacrificial ink comprises particles, the particles of the sacrificial ink having a volumetric diameter of 0.001 pm ⁇ d50 ⁇ 2.0 pm, preferably 0.1 pm ⁇ d50 ⁇ 1 pm, the particles of the sacrificial ink particularly preferably having 3 from 3% to 30% by weight of the total weight of the sacrificial ink. It is also possible that the ceramic particles and/or metallic particles of the object ink have a volumetric diameter of 0.1 pm ⁇ d50(v) ⁇ 10 pm, preferably 0.35 pm ⁇ d50(v) ⁇ 6 pm, particularly preferably 0.5 pm ⁇ d50(v) ⁇ 4pm.
  • Inks comprising particles with a volumetric diameter of 0.35pm ⁇ d50(v) ⁇ 6pm, preferably 0.5pm ⁇ d50(v) ⁇ 4pm, behave in such a way that an inkjet print head printing such inks has a noticeably higher droplet Ejection frequency can work than would be the case with comparative inks comprising particles with a volumetric diameter of d50(v) ⁇ 0.25 pm, especially since the former can be provided with a significantly lower viscosity than the latter. Consequently, these inks according to the invention may enable an increase in productivity compared to the comparative inks.
  • inks with particles with 0.35 ⁇ m ⁇ d50(v) ⁇ 6 ⁇ m, preferably 0.5 ⁇ m ⁇ d50(v) ⁇ 4 ⁇ m is significantly less expensive than is the case with the said comparison inks, especially since the grinding effort is involved is lower.
  • At least one molded layer can be divided into an outer edge area and an inner edge area, with the inner surface of the inner edge area of the molded layer defining the corresponding recess of the molded layer, with the inner edge area of at least the first and second molded layer passing through stacking the several sacrificial layers on top of one another is formed and the respective outer edge area of at least the first and second mold layer is produced with an ink forming an outer structure, such that the respective outer edge area is imaginary on the respective surface to be printed by impinging on each pixel D3 in each row third printing raster is formed with a third combination droplet, which is composed of M droplets of the ink forming the outer structure, each with a volume U, where M e ⁇ 0, 1, 2, 3, ...
  • the volume ratio (S:U) between the volume S of the respective K drops of the sacrificial ink and the volume U of the respective M drops of the ink forming the outer structure being at least 1:15 in each case.
  • each mold layer can be formed according to said method by stacking the plurality of sacrificial layers one on top of another, and the outer edge portion of each mold layer can be formed according to said method with ink forming the outer structure.
  • the third print screen can correspond to the first print screen.
  • An ink application level (0 to MU) of an exostructure-forming ink for forming the outer edge regions of the respective mold layers of a support structure is defined in the context such that the level MU, i.e.
  • M*U indicates the amount of ink MU of the exostructure-forming ink with which each pixel D3 in each row of a third printing raster is applied and M is a drop or a multiple of a drop of the outer structure-forming ink emitted by one or more nozzles of at least one nozzle row, each individual drop of the outer structure-forming ink having essentially the same drop volume U has.
  • a third combination drop can in turn be understood as those ink that forms the outer structure with a nozzle or with several nozzles printed one after the other, which essentially have the same drop volume U, which can be understood when using grayscale-capable inkjet print heads in flight and at the latest prior to hitting the pixel D3 to be printed, or alternatively, which generally when using inkjet printheads, will combine at different points in time to a pixel position they were aimed at, and essentially a multiple of the originally printed droplet volume U have the object ink.
  • a combination drop can also consist of zero drops (M equal to zero) or one drop (M equal to 1).
  • the droplet volume S of the respective K drops of the sacrificial ink is ⁇ lOOpl, preferably lOpl ⁇ S ⁇ 80pl, particularly preferably 20pl ⁇ S ⁇ 45pl, with the volume ratio (S:U) between the volume S of the respective K drops of the sacrificial ink and the volume U of the respective M drops of the ink forming the outer structure is in each case at least 1:50, preferably at least 1:150, particularly preferably at least 1:300.
  • the width of the inner edge area of a molded layer can be from 20 pm to 5000 pm, preferably from 100 pm to 2000 pm, particularly preferably from 100 pm to 500 pm, and the outer edge area of a molded layer can be greater than 500 pm, preferably greater than 1000 pm, particularly preferably greater than 2000 pm.
  • each molded layer is formed with an inner and outer edge area by first forming the inner edge area of the molded layer and preferably solidifying or drying and/or hardening before the outer edge area one and the same mold layer is formed and is preferably solidified or dried and/or cured.
  • the drop volume T of the respective L drops of the object ink can be essentially identical to the drop volume U of the respective M drops of the ink forming the outer structure.
  • the ink forming the outer structure is embodied as inkjet ink and that the M droplets of ink forming the outer structure are emitted from at least a third inkjet print head with a plurality of nozzles, with the first and third inkjet print heads preferably being the same inkjet -Printhead is.
  • the several nozzles of the third inkjet print head each have an inside diameter in a range from 100 ⁇ m to 400 ⁇ m, preferably in a range from 150 ⁇ m to 350 ⁇ m, particularly preferably in a range from 150 ⁇ m to 250 ⁇ m .
  • an inkjet print head operated by means of a plunger is provided as the third inkjet print head.
  • the inkjet print head operated by means of a plunger can comprise a circulating pump provided outside the print head for pumping the ink forming the outer structure through an ink supply channel of the print head.
  • the outer structure-forming ink for producing an outer edge region of a mold layer contains as components (a) water, (b2) a second organic binder and (c2) a second organic dispersant or (z2) a second organic dispersing agent binder instead of components (b2) and (c2), and (d2) second ceramic particles and/or second metallic particles dispersed in the water, wherein the sacrificial ink is so selected with respect to both the object ink and the ink forming the exterior structure and is configured such that an inner edge portion of a respective mold layer formed by the sacrificial ink resists bonding of the outer edge portion of one and the same mold layer to the object during sintering.
  • a corresponding sacrificial ink according to the invention can comprise wax and non-sinterable particles.
  • Non-sinterable particles of the sacrificial ink are, for example, particles that have a first sintering temperature that is higher than the second sintering temperature of the particles of the object ink and also higher than the third sintering temperature of the ink forming particles.
  • the object is fired at a firing temperature that is higher than the second sintering temperature of the particles of the object ink and also higher than the third sintering temperature of the particles of the ink forming the outer structure, but lower than the first sintering temperature of the particles of the sacrificial ink.
  • a corresponding wax can have a melting temperature (mp) of >40°C, preferably a mp of >60°C, particularly preferably a mp of >90°C, and it can be brought to a temperature beforehand in order to act on the pixels Di of the first print screen which is higher than its melting temperature.
  • mp melting temperature
  • Such sacrificial inks with wax and non-sinterable particles facilitate the mechanical removal of the outer edge area of the support structure from the object after the firing process.
  • At least one of the components b2, c2, d2 and z2 can either differ from their respective component b, c, d and z with the same letter.
  • each component b2, c2, d2 and z2 can be identical to all of its letter-matching components b, c, d and z.
  • the ink forming the outer structure can comprise the following components:
  • the ink forming the ceramic particles and/or metallic particles of the outer structure can have a volumetric diameter of 0.1 pm ⁇ d50(v) ⁇ 1 pm. preferably 0.35 pm ⁇ d50(v) ⁇ 6 pm, particularly preferably 0.5 pm ⁇ d50(v) ⁇ 4 pm.
  • the ceramic particles and/or metallic particles of the object ink and/or the ink forming the second ceramic particles and/or second metallic particles of the outer structure each contain at least two different particle size populations, with the first population (PI) having a volumetric diameter of the particle size of 0.1 pm ⁇ d50(v) ⁇ 4 pm and the second population (P2) has a volumetric diameter of the particle size of 0.8 pm ⁇ d50(v) ⁇ 12 pm, the ratio between the d50( v) value of the population PI and the d50(v) value of the population P2 is in a range of 1:8 to 1:3.
  • the object mentioned at the outset is also achieved by a three-dimensional object according to the invention, preferably a ceramic and/or metal object, which can be obtained by at least one method according to the invention.

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Abstract

L'invention concerne un procédé de structuration en couches d'un objet tridimensionnel, consistant : (a) à former, sur un substrat ou de préférence sur une couche inférieure, une première couche de moule avec une première découpe, qui correspond au négatif d'une première couche d'objet; (b) à remplir la première découpe avec de l'encre d'objet, afin de former la première couche d'objet; (c) à former, sur la première couche de moule, une seconde couche de moule avec une seconde découpe, qui correspond au négatif d'une seconde couche d'objet, moyennant quoi un objet et une structure de support constituée ou comprenant des couches sacrificielles ont été formés; (d) à remplir la seconde découpe avec de l'encre d'objet, afin de former la seconde couche d'objet; chaque couche de moule étant formée par empilement d'un certain nombre de couches sacrificielles les unes sur les autres, les couches sacrificielles étant chacune formées avec une épaisseur de couche qui est inférieure à l'épaisseur de couche de chaque couche d'objet au moins d'un facteur de deux de sorte que chaque couche sacrificielle est formée par une première goutte de combinaison appliquée à chaque pixel D1 dans chaque rangée d'une première trame d'impression imaginée sur la surface qui est respectivement à imprimer, la première goutte de combinaison étant constituée dans chaque cas de K gouttes de l'encre sacrificielle ayant chacune un volume S, où K ϵ {0, 1, 2, 3,...}, et partant un niveau d'application d'encre KS est obtenu pour chaque pixel D1, et que chaque couche d'objet est formée par une seconde goutte de combinaison appliquée à chaque pixel D2 dans chaque rangée d'une seconde trame d'impression imaginée sur la surface qui est respectivement à imprimer, la seconde goutte de combinaison étant constituée dans chaque cas de L gouttes de l'encre d'objet chacune avec un volume T, où L ϵ {0, 1, 2, 3,...}, et partant un niveau d'application d'encre LT est obtenu pour chaque pixel D2, le volume de goutte S des gouttes K respectives de l'encre sacrificielle étant ≤100pl et le rapport volumique (S:T) entre le volume S des gouttes K respectives de l'encre sacrificielle et le volume T des gouttes L respectives de l'encre d'objet étant dans chaque cas d'au moins 1:15.
EP23701837.9A 2022-02-25 2023-01-17 Procédé de structuration en couches d'un objet tridimensionnel Pending EP4482632A1 (fr)

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IT102022000003539A IT202200003539A1 (it) 2022-02-25 2022-02-25 "Metodo per strutturare un oggetto tridimensionale strato per strato"
PCT/EP2023/025011 WO2023160872A1 (fr) 2022-02-25 2023-01-17 Procédé de structuration en couches d'un objet tridimensionnel

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US7236166B2 (en) 2005-01-18 2007-06-26 Stratasys, Inc. High-resolution rapid manufacturing
EP2529694B1 (fr) * 2011-05-31 2017-11-15 Ivoclar Vivadent AG Procédé de génération de formes en céramique par jet d'impression 3D
US20140192117A1 (en) 2011-07-22 2014-07-10 Durst Phototechnik - A.G. Print head for an ink jet printer
JP6642790B2 (ja) * 2015-10-15 2020-02-12 セイコーエプソン株式会社 三次元造形物の製造方法及び三次元造形物の製造装置
JP6669985B2 (ja) * 2015-11-12 2020-03-18 セイコーエプソン株式会社 三次元造形物の製造方法
CN110831711A (zh) 2017-05-01 2020-02-21 三全音科技有限公司 模制方法及设备，特别是适用于金属及/或陶瓷
IT201700098731A1 (it) 2017-09-04 2019-03-04 Durst Phototechnik Ag "Dispositivo per il posizionamento di un attuatore"
IT201700098743A1 (it) 2017-09-04 2019-03-04 Durst Phototechnik Ag "Attuatore per una testina di stampa"
EP3659547B1 (fr) 2018-11-29 2021-11-17 Ivoclar Vivadent AG Procédé et utilisation de barbotine destinés à la fabrication de corps moulés céramiques à partir de l'oxyde de zirconium par impression tridimensionnelle à jet d'encre

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