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Title:
METHOD FOR LAYER-WISE ADDITIVE MANUFACTURING OF A SHAPED BODY
Document Type and Number:
WIPO Patent Application WO/2020/108821
Kind Code:
A1
Abstract:
The present invention is directed to a Method for layer-wise additive manufacturing of a shaped body made up of slices of processed layers, said method comprising the steps: creating a layer of a slurry, said slurry including binder, a dispersing medium and a particulate filler material, solidifying the slurry layer, directing electromagnetic radiation to the solidified layer for processing it by debinding and/or sintering, and repeating the above-mentioned steps to successively build the shaped body, characterized in that said creating a slurry layer is performed by a laser induced forward transfer (LIFT) process utilizing a laser to direct laser beam pulses to act on a coating of slurry on a carrier to transfer droplets of slurry to a receptor surface to create the slurry layer which is then processed further by above-mentioned steps of solidifying, and debinding and/or sintering.

Inventors:
JOHN HENDRIK (CH)
ZENOU MICHAEL (IL)
RITZBERGER CHRISTIAN (CH)
Application Number:
PCT/EP2019/075562
Publication Date:
June 04, 2020
Filing Date:
September 23, 2019
Export Citation:
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Assignee:
IVOCLAR VIVADENT AG (LI)
IO TECH GROUP LTD (GB)
International Classes:
B22F3/105; B28B1/00; B29C64/153; B29C64/165; B33Y10/00; C03B19/01; C03B19/06; C04B35/111; C04B35/486; C04B35/488; C04B35/626; C04B35/634; C04B35/636; C04B35/638
Domestic Patent References:
WO2010045950A12010-04-29
WO2016207241A12016-12-29
Foreign References:
GB2526328A2015-11-25
EP1268211A12003-01-02
EP1505041A12005-02-09
EP2261184A22010-12-15
EP2377830A12011-10-19
EP2377831A12011-10-19
EP3147707A12017-03-29
Other References:
KENGO JINNO ET AL: "Room temperature impact deposition of ceramic by laser shock wave", JAPANESE JOURNAL OF APPLIED PHYSICS, vol. 57, no. 6S1, 15 May 2018 (2018-05-15), JP, pages 06HJ06, XP055583979, ISSN: 0021-4922, DOI: 10.7567/JJAP.57.06HJ06
CHARIPAR KRISTIN M ET AL: "Laser-induced forward transfer (LIFT) of 3D microstructures", PROCEEDINGS OF SPIE; [PROCEEDINGS OF SPIE ISSN 0277-786X VOLUME 10524], SPIE, US, vol. 10523, 26 February 2018 (2018-02-26), pages 105230R - 105230R, XP060103853, ISBN: 978-1-5106-1533-5, DOI: 10.1117/12.2294578
JIWEN WANG ET AL: "Three-Dimensional Printing of Interconnects by Laser Direct-Write of Silver Nanopastes", ADVANCED MATERIALS, vol. 22, no. 40, 3 September 2009 (2009-09-03), pages 4462 - 4466, XP055121261, ISSN: 0935-9648, DOI: 10.1002/adma.201001729
THEODORAKOS I ET AL: "Selective laser sintering of Ag nanoparticles ink for applications in flexible electronics", APPLIED SURFACE SCIENCE, ELSEVIER, AMSTERDAM, NL, vol. 336, 27 October 2014 (2014-10-27), pages 157 - 162, XP029148723, ISSN: 0169-4332, DOI: 10.1016/J.APSUSC.2014.10.120
T. MUHLER ET AL.: "Slurry-based powder beds for the selective laser sintering of silicate ceramics", J. CERAM. SCI. TECH., vol. 06, no. 02, 2015, pages 113 - 118, XP055295533, doi:10.4416/JCST2015-00007
Attorney, Agent or Firm:
UEXKÜLL & STOLBERG PARTNERSCHAFT VON PATENT- UND RECHTSANWÄLTEN MBB (DE)
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Claims:
Claims

1. Method for layer-wise additive manufacturing of a shaped body made up of slices of processed layers, said method comprising the steps: creating a layer of a slurry, said slurry including binder, a dispersing medium and a particulate filler mate rial, solidifying the slurry layer, directing electromagnetic radiation to the solidified layer for processing it by debinding and/or sintering, and repeating the above-mentioned steps to successively build the shaped body, characterized in that said creating a slurry layer is per formed by a laser induced forward transfer (LIFT) process utilizing a laser (8) to direct laser beam (1) pulses to act on a coating (4) of slurry on a carrier (2) to trans fer droplets of slurry to a receptor surface to create the slurry layer (11) which is then processed further by above-mentioned steps of solidifying, and debinding and/or sintering .

2. Method according to claim 1, characterized in that said solidifying of the slurry layer (11) is performed by ap plying heat from a warm gas flow to act on the slurry layer . 3. Method according to claim 1, characterized in that said solidifying of the slurry layer (11) is performed by di recting electromagnetic radiation to act on the slurry layer .

4. Method according to any of the preceding claims, charac terized in that said directing of electromagnetic radia tion is performed by controlling a laser (8) to direct a laser beam to act on the layer material.

5. Method according to claim 3 and 4, characterized in that said solidifying by directing the laser beam to act on the slurry layer is performed by heating up the slurry layer (11) to vaporize vaporizable components of the slurry.

6. Method according to claim 3 and 4 or 5, characterized in that the laser beam (1) causing solidification of the slurry layer and the laser beam (1) effecting debinding and/or sintering are generated by the same laser (8) .

7. Method according to claim 2 or 3 and 4, characterized in that the laser beam (1) for effecting debinding and/or sintering and the laser beam used for the LIFT process to create a new slurry layer (11) are generated by the same laser ( 8 ) .

8. Method according to claim 3 and 4, characterized in that the laser (8) generating the laser beam (1) for effecting solidification and the laser beam used for the LIFT proc ess to create a new slurry layer are generated by the same laser .

9. Method according to claim 6, characterized in that the la ser (8) generating the laser beams (1) for effecting so lidifying and for effecting debinding and/or sintering are generated by the same laser (8) that is used for the LIFT process to create a new slurry layer (11) .

10. Method according to any of the preceding claims, charac terized in that the slurry further includes an energy transfer component capable of converting energy of the electromagnetic radiation into thermal energy.

11. Method according to any of the preceding claims, charac terized in that the carrier (11) carries a plurality of separate coating zones (4, 4', 4'') arranged next to each other, each coating zone (4, 4', 4'') containing an asso ciated one of a plurality of slurry compositions, and that a control unit is arranged to control a positioning device for positioning the carrier (2) relative to the laser (8) and the receptor surface such that for each layer of slurry being created a selected spatial distribution of slurry compositions selected from the plurality of slurry compositions in the deposited layer is formed by selec tively positioning coating zones (4, 4', 4'') to be effec tive in the LIFT process to achieve a desired spatial pat tern of slurry compositions in the created layer.

12. Method according to claim 11, characterized in that the positioning device is capable of positioning the carrier (2) relative to the laser (8) such that the laser beam of the laser can be directed onto the slurry layer without being affected by the carrier.

13. Method according to any of the preceding claims, charac terized in that said creating a slurry layer and solidify ing it is performed in an area that is larger than the re gion of the slice to be formed from the slurry layer (11), and that debinding and/or sintering of the solidified layer is performed by directing electromagnetic radiation to act on the solidified layer in a spatially selective manner so that debinding and/or sintering takes place only within the contour of the slice to be built.

14. Method according to any of the claims 1 to 12, character ized in that said creating of a slurry layer (11) is per formed by the LIFT process in a spatially selective manner such that the slurry layer is congruent with the contour of the slice to be built, and that support material (21) is applied to surround the region of the slice to be built such that the shaped body to be formed is at least par tially embedded in support material (21) .

15. Method according to any of the preceding claims, charac terized in that the particulate filler material of the slurry is glass-powder, glass-ceramic powder, ceramic pow der or metallic powder.

Description:
Method for layer-wise additive manufacturing of a shaped body

The present invention relates to a method for layer-wise addi tive manufacturing of a shaped body made up of slices of proc essed layers, said method comprising the steps:

creating a layer of a slurry, said slurry including binder, a dispersing medium and a particulate filler material, solidifying the slurry layer,

directing electromagnetic radiation to the solidified layer for processing it by debinding and/or sintering, and

repeating the above-mentioned steps to successively build the shaped body.

Additive manufacturing (AM) describes a class of techniques in which a three dimensional object or shaped body is directly generated from a virtual digital model (e.g. a CAD model) of the shaped body. In this model the shaped body is subdivided into a plurality of successive thin slices, each slice having a contour defined by the model. The construction process is performed by layer-wise adding material in layers, each layer being processed to have a contour defined by the digital model. Eventually the stack of interconnected layers forms the shaped body which in some techniques has to be processed fur ther (e.g. by debinding, sintering etc. to obtain the final product. Generally one distinguishes between the following process types:

Vat Photopolymerisation (Stereolithography SLA, Digital Light Processing DLP, Continuous Digital Light Processing CDLP) ;

Material Extrusion (Fused Deposition Modeling FDM) ;

Material Jetting (Material Jetting MJ, NanoParticle Jetting NPJ Drop on Demand DOD) ; Binder Jetting (BJ) ;

Powder Bed Fusion (Multi Jet Fusion MJF, Selective Laser Sin tering SLS, Direct Metal Laser Sintering / Selective Laser Melting DMLS / SLM, Electron Beam Melting EBM)

Direct Energy Deposition (Laser Engineering Net Shape LENS, Electron Beam Additive Manufacturing EBAM) ; and

Sheet Lamination (Laminated Object Manufacturing LOM) .

For the manufacturing of dental restorations made of glass, glass-ceramic, ceramic or metallic materials stereolitho graphic photopolymerization processes have been proposed, as for example described in WO 2010/045950 A1. The method de scribed utilizes photopolymerizable binder which is mixed with a filler material, in this case ceramic powder. In the de scribed method a construction platform is held vertically moveable above a tank bottom which is at least in part of the bottom area transparent. Below the tank bottom an exposure unit is provided for projecting light to an exposure area in a spatially selective manner. The construction platform is first lowered into the slurry of photopolymerizable material and ce ramic filler material until a layer of slurry with a desired layer thickness remains between the production platform and the tank bottom. This layer is subsequently exposed in an area with a predetermined contour defined by the three-dimensional CAD model which causes solidification of the layer. After the production platform has been raised slurry is replenished from the surroundings and the production platform is lowered again in such a way that a layer with the desired thickness is de fined between the layer formed last and the tank bottom. The latter two steps are repeated until a shaped body having the desired shape defined by the stack of cured layers has been produced. The spatially selective exposure by the exposure unit can be performed by a laser scanning the area to be so lidified under the control of a control unit to solidify layer after layer, with the layer contours being defined by the digital CAD model of the shaped body. Alternatively exposure units with spatial light modulators can be utilized which com prise an array of exposure elements which can be selectively activated, for example in the form of a micromirror device or a liquid crystal display which is illuminated by a light source and spatially selectively project light to picture ele ments contained in the contour of the layer to be processed.

The term "contour" of a layer or of the resulting processed slice in the sense of the present invention does not imply that there is only one simply connected area with the contour as a boundary. The contour may comprise several contour compo nents which define several areas of a layer or slice which are separate from each other or which may include inner boundary contour components surrounding inner void areas not belonging to the layer.

The shaped body formed in this manner is a green body which has to be further processed by debinding. For debinding the green body is heated up in a furnace to a temperature in the range 80 °C to 600 °C, depending on the binder materials. At the elevated temperature the solidified binder (polymerized resin) is thermally decomposed into low molecular weight species which eventually escape as volatile gases such that the ce ramic particulate material remains. This white body is finally subjected to densification by performing sintering by further application of heat in a furnace.

Another technique that can be utilized for manufacturing den tal restorations is for example Selective Laser Sintering (SLS) of ceramic powders. Such technique typically involves spreading of the powder to be sintered to a thin layer as a dry powder by means of a roller or the like, and sintering the powder layer. It is a disadvantage that such powder layers have a relatively low density. For this reason it has already been proposed to form layers of slurry comprising a ceramic powder and a liquid dispersing medium. Such method is for ex ample described in WO 2016/207241 A1. In this method a layer of a slurry is formed which contains ceramic particles sus pended in a dispersing medium and binder. A laser light source projects a laser beam onto the slurry layer to solidify the slurry in an area having the contour of the slice to be added in this step. The laser beam evaporates the dispersing medium to solidify the layer. This deposition of laser energy is con trolled in such a manner that it causes evaporation of the dispersing medium but does not cause sintering of the ceramic particles so that by adding slices successively in this manner a ceramic green body is formed. Eventually this green body has to be further processed by debinding and sintering.

The main disadvantages of existing slurry-based processes is that the debinding and sintering steps are time consuming, typically taking several hours up to days, depending on the size and shape of the green body because the volatile decompo sition products of the binder have to diffuse from the inside to the outside of the shaped body and the diffusion path is not constant and differs from shaped body to shaped body in dependence on the size and shape of the shaped body. There fore, the bigger the body generated the more critical is the debinding process in terms of risks of cracking and deforma tion.

Slurry-based processes which first generate a green body do require further separate process steps, namely debinding and sintering which are usually performed in dedicated furnaces and need, as mentioned above, substantial processing times. A further technology of additive manufacturing that takes ad vantage of the higher particle densities that may be achieved with slurry layers is known as Layer-wise Slurry Deposition (LSD) . LSD processes are for example described in "Slurry- based powder beds for the selective laser sintering of sili cate ceramics", T. Muhler et al . J. Ceram. Sci. Tech., 06 [02] 113-118 (2015) . A layer of slurry is created by applying slurry material on a substrate surface (if the first layer is to be formed) or on the surface of the last layer formed, and the applied slurry is levelled to a desired thickness by a doctor blade. Desiccation of a freshly deposited layer takes place by two main mechanisms: First, during and directly after deposition of the slurry layer the liquid solvent is drawn by capillary forces into the supporting powder compact formed by previously deposited layers and, second, by rapid evaporation of the solvent. The first mechanism ensures that a freshly de posited layer loses its liquid phase immediately after deposi tion. Therefore, the temperature for the supporting dry layers can be kept at a temperature significantly exceeding the boil ing point of the solvent. After solidification by removal of the solvent any remaining binder is removed in a debinding step which is followed by a sintering step for densifying the newly added slice. The preamble of claim 1 is based on such a LSD process.

In LSD processes as described above it is complicated to use slurries of different compositions because this would require that for each type of slurry composition a separate container is provided and that a particular one has to be selected and moved to the application zone to supply the material for the next slurry layer. Even more complicated, if possible at all, are changes of the slurry composition within a slurry layer, e.g. to add a first slurry composition in a central area, and a second and possibly further slurry compositions in outer re gions surrounding the central area of the layer being created. EP 1 268 211 B1 discloses a printing process in which a focus sed laser beam locally supplies energy to a material to be printed which causes an instant temperature increase and vol ume expansion in the material which leads to the ejection of a droplet, in this case ink, which is deposited on a substrate to be printed on. This method is referred to as laser induced forward transfer (LIFT) process. The material to be printed is transferred from a so called donor to a receptor substrate. The donor consists of a carrier on which a thin coating of the material to be printed is applied. A focussed laser beam pulse is acting on this layer which is thereby heated up instantly and partially evaporated. For transparent carriers the laser beam acts on the material to be printed by passing through the backside of the carrier and through the carrier to act on the material coating on the opposite surface of the carrier. If the carrier is not transparent or has a not transparent ab sorption layer at the interface with the material coating, the carrier is heated up at the interface with the material coat ing which leads to the energy transfer to the material to be printed. If the carrier layer is transparent the focussed la ser beam can act directly on the material to be printed. For this purpose the material to be printed may contain an energy transformation component which is capable of absorbing laser radiation and transforming it to thermal energy. By means of the laser energy pulse the material to be printed is locally abruptly heated up and partially evaporated, wherein the ex panding vapour carries away a small amount of the material which is deposited on the receptor substrate which is facing the material coating on the carrier.

The generation of ceramic or glass-ceramic layers by a LIFT process is not known from the prior art.

It is an object of the present invention to provide a method for layer-wise additive manufacturing of a shaped body utiliz- ing layer-wise slurry deposition, which method facilitates use of different slurry compositions in the created slurry layer which is then further processed by solidifying and debinding.

This object is achieved by a method comprising the features of claim 1. Preferred embodiments of the method are set in the dependent claims.

In a method of the present invention a shaped body is build up by adding slices of processed layers, each slice being formed by creating a layer of a slurry which includes binder, a dis persing medium and a particulate filler material, solidifying the slurry of the created layer, and directing electromagnetic radiation to the solidified layer for processing it by debind ing and/or sintering. These steps are repeated for each in newly created layer of slurry on top of the last processed slice. According to the present invention a layer of slurry for the next slice to be formed is created in the following manner. The new slurry layer is added by a laser induced for ward transfer (LIFT) process utilizing a laser to direct laser beam pulses to act on a coating of slurry on a carrier. In a LIFT process each laser beam pulse causes an instant local temperature increase of the slurry in the beam spot which re sults in an explosive ejection of a droplet of slurry mate rial. The droplets are transferred to a receptor surface (a substrate surface in the case of the first created layer or the surface of the last processed slice in subsequent steps of the additive manufacturing method) . The transferred droplets are formed in such a manner that they add up to a continuous layer which is then processed by solidifying, and processed further by debinding and/or sintering.

Said directing of electromagnetic radiation to the solidified layer is performed to deposit energy to increase the tempera ture to cause thermal processing for debinding and/or sinter- ing the solidified layer. The electromagnetic radiation can for example be applied by a laser or by an infrared light source. The thermal processing may include only sintering in cases of slurries having a very low binder content so that there is no separate first debinding step but sintering al ready starts when the electromagnetic radiation is directed onto the solidified layer. Usually, this application of energy by directing electromagnetic radiation onto the solidified layer will be performed in a spatially selective manner so that the solidified layer is only further processed by debind ing and/or sintering within the contour of the slice currently generated .

Utilizing a LIFT process for depositing the slurry for the next layer being added offers particular advantages. For the creation of the next layer laser beam pulses transfer droplets of slurry from a slurry coating on a carrier. The carrier can for example be a film. The carrier can carry slurry coatings of different compositions in different areas of the carrier which are located separately on the carrier. The process of LIFT transfer to the new layer being created can then be con trolled by selectively moving the carrier relative to the re ceptor surface and the laser to bring desired slurry composi tions to the transfer point where the laser beam is acting on the slurry coating to thereby transfer selected slurry compo sitions in a desired pattern to the layer of slurry being cre ated. The principle of changing between different slurry com positions by effectively using different areas of the carrier with different slurry composition coatings for material trans fer is comparable to the principle of a colour ribbon in a traditional colour typewriter, wherein the colour ribbon in the analogy corresponds to the coated carrier with different coating composition in different areas of the carrier. In order to perform the LIFT process, the laser beam pulses act on the slurry coating on the carrier, wherein this inter action can be a direct or indirect interaction. In case of a direct interaction the laser beam pulses are directed onto the slurry coating which absorbs laser energy and is thereby heated up; the absorption can for example be enhanced by add ing an energy transfer component to the binder, which energy transfer component is capable of absorbing laser radiation and of converting absorbed radiation energy into thermal energy. The laser beam can for example be directed onto the slurry layer by utilizing a transparent film as carrier and by di recting the laser beam onto the backside of the carrier film opposite to the slurry coating. After passage through the transparent carrier film the laser beam enters the slurry coating to induce an instant temperature increase to eject slurry coating material. Alternatively, the laser beam can act on the slurry coating in an indirect manner by providing an absorption layer which is sandwiched between the carrier film and its slurry coating. Also in this case the laser beam is directed onto the backside of the transparent carrier film and is, after passage through the carrier film, absorbed in the absorption layer which is thereby rapidly heated up and which by thermal conduction causes a rapid temperature increase in the adjacent slurry coating to effect the ejection of droplets of slurry for the LIFT process.

It is preferred that the slurry layer is solidified by apply ing a gas flow to act on the slurry layer. This can for exam ple be a tempered gas flow which lets vaporizable components of the slurry evaporate.

In an alternative preferred embodiment the slurry layer is so lidified by directing electromagnetic radiation to act on the slurry layer. In a preferred embodiment said directing of electromagnetic radiation is performed by controlling a laser to direct a la ser beam to act on the layer material.

In a preferred embodiment the solidifying by directing the la ser beam to act on the slurry layer is performed by heating up the slurry layer to vaporize vaporizable components of the slurry. For example, water-based slurries which contain a ma jor portion of water as dispersing medium and only a minor amount of other binder materials as additives the evaporation of the water component is effectively drying and solidifying the slurry layer. Alternatively, for other dispersing me- dia/binders which contain a major amount of photopolymerizable resin precursors the solidifying by directing a laser beam to act on the slurry is performed by inducing, by the laser ra diation, polymerisation of the photopolymerizable precursor components of the binder to solidify the slurry layer.

It should be noted that the steps of solidifying and of de binding are not necessarily strictly separate steps. If for example solidification is performed by increasing the tempera ture of the slurry layer to evaporate the vaporizable dispers ing medium the heat supply (for example by laser radiation) can be continuous and there may be an uninterrupted transition from solidifying to debinding, wherein both steps may par tially overlap in time. There may be, depending on the materi als involved, a temperature increase during the transition from the solidifying step to the debinding step. The same ap plies to the debinding and sintering steps, wherein there may be a continuous transition from the increased temperature treatment for debinding to the sintering phase. Also in this case the transition between the two process phases may involve increased laser energy supply to achieve higher temperatures for sintering, depending on the materials involved. In principle the laser beams mentioned-above for effecting so lidifying, and debinding and/or sintering can be generated by separate laser sources. However, in a preferred embodiment the same laser is used for effecting solidification of the slurry layer and for effecting debinding and/or sintering of the so lidified layer.

It is also preferred that the laser generating the laser beam for effecting debinding and/or sintering and the laser beam used for the LIFT process to create a new slurry layer are generated by the same laser, whereas solidification could be effected by warm gas flow, an IR light source, by another la ser or by any other means .

Alternatively the laser beam for effecting solidification and the laser beam used for the LIFT process to create a new slurry layer are generated by the same laser, whereas debind ing and/or sintering is effected by another laser or by any other means .

However, it is particularly preferred that the laser, which is used for generating the laser beams for effecting solidifying, debinding, and/or sintering is the same laser that is used for the LIFT process to create a new slurry layer. In this embodi ment a single laser source is involved in all application and processing steps to add a new slurry layer and to fully proc ess it to the final processed state of the current slice added, and all steps are performed using same laser in the same device which allows to perform the method quickly and ef ficiently.

The combination of the deposition of the slurry using a laser based LIFT process with solidifying, debinding, and sintering allows to combine all process steps in an integrated process ing device, i.e. no transfer of an intermediate state part to separate processing devices such as furnaces is necessary. Furthermore, solidification, debinding, and sintering are per formed layer by layer. In addition, the same laser can be utilized to drive the LIFT process for slurry layer deposi tion, and for solidifying, and for debinding and/or sintering to form a slice of the shaped body before the next slurry layer is transferred and processed by the above-mentioned steps to form the next slice of the shaped body.

In a preferred embodiment the slurry further includes an en ergy transfer component capable of converting energy of the electromagnetic radiation into thermal energy.

In a preferred embodiment the carrier carries a plurality of separate slurry coating zones arranged next to each other, each coating zone containing an associated one of a plurality of slurry compositions. A control unit is arranged to control a positioning device for positioning the carrier relative to the laser beam and receptor surface such that for each layer of slurry being created by the LIFT process a selected spatial distribution of slurry compositions selected from the plural ity of slurry compositions in the deposited layer is formed by selectively positioning coating zones to be effective in the LIFT process. In other words the positioning device allows to control in a spatially selective manner for each position of the slurry layer being created which slurry composition out of the plurality of slurry compositions is deposited. This allows to achieve a desired spatial pattern of slurry compositions in the created layer.

In a preferred embodiment the positioning device is capable of positioning the carrier relative to the laser and receptor such that the laser beam of laser can be directed onto the slurry layer without being affected by the carrier. The car rier can for example be moved by the positioning device to be out of the area of the beam paths from the laser to the slurry layer after the LIFT process. This permits effective applica tion of the laser energy for further processing steps after the application of the slurry layer, namely for solidifying, and for debinding, and/or sintering of the layer.

In a preferred embodiment the slurry layer is created in an area that is larger than the region of the slice which is to be formed from the slurry layer by further processing of so lidifying, debinding, and/or sintering, i.e. the slurry layer extends beyond the contour of the slice to be formed. In such embodiment it is preferred that during debinding and/or sin tering of the solidified slurry layer the electromagnetic ra diation is directed to the solidified slurry layer in a spa tially selective manner so that debinding and/or sintering of the solidified layer takes place only within the contour of the slice to be built.

In the afore-mentioned embodiments the slurry surrounding the contours of the slices formed has the function of support ma terial which laterally embeds the shaped body and which is eventually removed when building of the shaped body is com pleted. The slurry material surrounding the contours of the slices formed generally is solidified when the solidification step is performed in a spatially non-selective manner. In this case the solidified slurry forms a strong support structure embedding the shaped body laterally, which support structure may eventually be removed after completion of the building process, for example by application of a solvent.

Alternatively the creation of a slurry layer by the LIFT proc ess is performed in a spatially selective manner such that the slurry layer is congruent with the contour of the slice to be build, and that support material applied to surround the con tour of the slice to be built such that the shaped body to be formed is imbedded in support material. Typically, also in such cases the direction of electromagnetic radiation for ef fecting debinding and/or sintering is performed in a spatially selective manner to the areas defined by the contour of the slice to be built such that the support material is not af fected by the electromagnetic radiation effecting debinding and/or sintering.

The particulate filler material of the slurry is for example glass-powder, glass-ceramic powder/ceramic powder or metallic powder .

The method of the present invention allows to integrate all processing steps as mentioned above to take place in a single device which can be of compact design and which can be oper ated to generate shaped bodies at high speed. The manufactur ing of the shaped body according to the present invention can be performed in a single device, using the same laser for all process steps, without time consuming post-processing of a green body in additional devices such as a solidify ing/debinding furnace and a sintering furnace. Furthermore, performing all steps of LIFT transfer of slurry, solidifying, debinding and sintering in a layer by layer manner allows to manufacture large shaped bodies, avoids deformation and inner tension as the process steps take place individually for each thin layer, in each case in a nearly 2D manner, and therefore does not involve large diffusion distances for the residual components to leave the thin layer during debinding. Since the debinding is also performed layer-wise, the conditions can be much better controlled since in a thin layer state gradients, such as temperature gradients, can be controlled in a much more effective manner.

For dental applications such as construction of dental resto rations ceramic and metallic filler materials are of main in- terest. In this connection water-based slurries and slurries comprising mainly organic polymer precursor components as binder can be used. In water-based slurries also a certain amount of organic binder material is present. For the water- based slurries the process of solidifying the slurry mainly involves the evaporation of the water by applying heat to the slurry, whereas in slurries comprising mainly organic polymer precursor components solidification is performed by inducing polymerisation which in case of photopolymerizable binder com ponents can be achieved by directing laser radiation on the slurry to be solidified.

An important property of slurries that are preferred to be processed by the method of present invention is a high content of particulate ceramic or glass-ceramic filler material.

In methods according to the present invention preferably slur ries are used which comprise:

(a) ceramic and/or glass ceramic particles as particulate filler material,

(b) at least one binder,

(c) at least one energy transformation component, and

(d) at least one dispersing medium.

As ceramic and/or glass ceramic particles (a) ceramic and/or glass ceramic powders are suitable which, after thermal de binding and sintering, result in ceramic bodies having a de sired strength, for example oxide or glass ceramic particles, such as for example aluminium oxide, zirconium oxide, or lith ium disilicate particles. Preferred are particles having a particle size of less than 20 ym, particularly preferred less than 10 ym and even more preferred less than 5 ym. The parti cles are preferably non-agglomerated . Particularly preferred are particles having particle size from 3 nm to 20 ym, more preferred sizes are from 5 nm to 10 ym, and even more pre ferred are particle sizes from 7 nm to 5 ym.

Ceramics in the sense of the present application are inorganic materials having a crystalline structure which are typically made of corresponding powder materials. Preferred are ceramic particles based on ZrCy or AI2O3, particles based on CaO, Y2O3, La 2 0 3 , CeCy and/or MgO stabilized ZrCy, particles based on other metal oxides or on ceramics made of a plurality of oxides and thus comprising different crystalline oxide phases, preferably ZrCy-A^Cy, ZrCy spinel, ZrCy- AI2O3 spinel, spinels of the type AB2O4, AB12O19, AB11O18, AB2O4, wherein A is preferably an alkali ion or an alkaline earth ion, and B is preferably a transition metal ion having a higher oxidation state than A. Particularly preferred are ceramic particles comprising ZrCy-A^Cy, ZrCy spinel, ZrCy-A^Cy spinel or CaO, Y2O3, La 2 0 3 , Ce0 2 and/or MgO stabilized Zr0 2 -Al 2 0 3 .

Stabilized ceramics include besides a base oxide such as Zr0 2 or AI2O3 a stabilizing agent which is preferably selected from CaO, Y2O3, La203, Ce0 2 , MgO, Er 2 0 3 and mixtures thereof. The sta bilizing agent is preferably used in an amount of 2 to 14 mole %, relative to the mass of the stabilized ceramic. High- strength ceramics include for stabilizing the tetragonal and/or cubic crystal structure preferably 2 to 12 mole % Y2O3 (yttrium oxide), preferably 2 to 10 mole %. This Zr0 2 ceramic is referred to as Y-TZP (yttrium stabilized tetragonal zirco nium dioxide polycrystals) . Particularly preferred are ceramic particles which contain a base oxide and a stabilizing agent only . Glass ceramics are materials which are typically obtained by controlled crystallization of amorphous glasses, in particular silicate glasses, and in which a glass phase and one or more crystal phases coexisting in the solid body. For glass ceram ics one can start from glass powders as well as from glass ce ramic powders. Particularly preferred are glass ceramic parti cles which contain Leucitecrystals , and particularly preferred lithium disilicate crystals. These can be made in a preferred manner from lithium disilicate glass powder or from lithium disilicate glass powders by thermal treatment (crystallization and sinter-firing) . Preferred glass ceramics are described in detail in EP 1 505 041 Al, EP 2 261 184 A1 , EP 2 377 830 A1 and EP 2 377 831 Al .

The optimal particle size of the component (a) depends on the ceramic used. For AI 2 O 3 the size of the particles used as com ponent (a) is in the range from 50 to 500 nm, particularly preferred between 75 and 200 nm; for glass ceramic in the range from 200 nm to 20 ym, particularly preferred in the range from 500 nm to 10 ym, and even more preferred in the range from 1 to 5 ym; for TCB-3Y zirconium dioxide in the range from 3 to 500 nm, particularly preferred in the range from 20 to 350 nm. The particle size is preferably selected such that the obtained slurries show sedimentation stability.

The slurries may contain as binder (b) one or more radically polymerizable monomers, preferably at least one (meth) acrylate and/or (meth) acrylamide, preferably mono or multifunctional (meth) acrylate or their mixtures. Particularly preferred are materials which contain as radically polymerizable monomer at least one multifunctional (meth) acrylate or a mixture of mono- and multifunctional (meth) acrylates . The term monofunctional (meth) acrylates is meant to cover compounds having one radi cally polymerizable group, the term polyfunctional (meth) acrylates is meant to cover compounds having two or more, preferably 2 to 6, radically polymerizable groups. Pre ferred binders of this type are described in EP 3 147 707 A1 in the paragraphs [0036] to [0044] . It is also disclosed there that such binders preferably contain a photo initiator.

It is preferred to use slurries which include a non-reactive binder, i.e. a binder which is not radically polymerizable. In contrast to reactive binders, non-reactive binders do not form a polymer network with covalent bonds upon solidification. For this reason the ceramic and/or glass ceramic particle (a) can shift with respect each other and in this manner at least par tially release tensions during drying and/or debinding.

Binders which in pure form are solid at 25°C are preferred. During the drying process such binders solidify and provide for a higher strength of the green body.

Preferred binders are cellulose derivatives such as methylcel- lulose (MC) , hydroxyethylcellulose (HEC) , hydroxypropylmethyl- cellulose (HPMC) and hydroxybutylmethylcellulose (HBMC) as well as sodium carboxymethylcellulose (NaCMC) and cellulose derivatives .

Further examples of preferred binders are polyvinyl alcohol (PVA) , polyvinyl acetate (PVAc) ; and polyvinyl pyrrolidone (PVPP) . Other examples are polymethylmethacrylate (PMMA) and copolymeres of ethylene glycol and propylene glycol which have a molecular weight which is high enough and/or a relative high amount of polyethylene glycol such that they are solid at room temperature .

The energy transformation component (c) absorbs a major por tion of the energy of the applied energy pulse, for example of the incoming laser beam, and converts the absorbed energy to heat. The heat pulse generated in this manner is transferred to a volume expansion component and causes an instantaneous expansion thereof, for example causes instantaneous generation of microscopic gas bubbles by evaporation of the volume expan sion component. In this manner the transfer of the slurry from the carrier substrate to the receptor substrate in the lift process is induced. The slurry is deposited on the receptor substrate .

The energy transformation component (c) is selected depending on the wavelengths of the laser light to be absorbed. In con nection with the present invention inorganic, and in particu lar organic dyes and pigments are preferred. Particularly pre ferred are dyes and pigments which allow burning off without residues and which after debinding and sintering leave no residues in the built body.

In connection with the present invention the slurries contain as dispersing medium (d) a liquid component in which the ce ramic and/or glass ceramic particles (a) are dispersed. Pre ferred are dispersing media which in pure form are liquid at 25°C. Preferred dispersing media are organic solvents or al ternatively water.

A mixture of different liquids can be used as dispersing me dium. The dispersing medium includes at least one low boiling component and preferably in addition one or more high boiling point components.

Low boiling point components are understood here to be sol vents having a boiling point of less than 200°C (at normal pressure) . Suitable solvents are for example acetic acid bu- tylester and acetic acid-n-hexylester . Preferred low boiling point solvents are 1-octanol, propylene glycol diacetate, eth ylene glycol diacetate, acetone, methyl ethyl ketone (MEK) , isopropanol, ethanol, butanol, p-xylene, cyclohexanone, buty- lacetate, pentylacetate, hexylacetate, and particularly pre ferred water. Water has the advantage that during evaporation no vapours are generated which could be hazardous to health or explosive .

High boiling point components are understood in this applica tion to be solvents having a boiling point above 200°C (at normal pressure) . Preferred high boiling point solvents are liquid poly (ethylene glycols) having a molecular weight be tween 150 and 600 g/mole propylene glycol, dipropylene glycol, tripopylene glycol, poly (propylene glycol) having a molecular weight from 150 to 4000 g/mole, particularly preferred with a molecular weight from 150 to 600 g/mole, ethers thereof such as methyl, ethyl, propyl, isopropyl, butyl, hexyl ether, ei ther as mono ether or di-ether; phthalates such as dimetyl, diethyl, dibutyl phthalates; glycerol; dimethyl, diethyl, dipropyl, dibutyl adipates or glutarates; and diethyl succi nate .

For combining with waters polar, high boiling point solvents such as polyethylenglycol (average molecular weight < 600g/mol) , glycerol and 1,2-propanediol.

Water-based slurries have of course a much lower content of organic binder than polymer precursor based slurries. The lower content of organic binder in water-based slurries has the advantage of a faster debinding process because less binder has to be removed from the slurry, and the temperature needed for thermally decomposing the binder is lower than for cured photopolymers.

The preferred content of organic binder in water-based slur ries is in arrange of 0.1 - 5 weight/, preferred 0.1 - 3 weight/ and a especially preferred 0.1 - 2 weight/ based on the total amount of slurry. In water-based slurries the or- ganic binder has the function as humectants in the slurry and serves to prevent the slurry from drying to fast. These water absorbing binders also need less energy to be removed as they are watersoluble but not volatile polymers, wherein PEG for example has a decomposition temperature of about 150 °C. Due to the fact that the melting temperature of those humectants dif fers depending on their chain length, it makes sense to use a combination of binders with different chain lengths to adjust the debinding process within the material layer. The different binders melt a different temperature and then decompose at different temperature levels which effect a spreading of the melting/decomposition over a longer period of time in which the required temperature increase to the maximal temperature takes place. For this reason less tension is generated during the debinding process.

The invention will now be described with reference to pre ferred embodiments illustrated in the drawings in which:

Figs. 1A - 1C show cross-sectional views illustrating creation of a slurry layer by a laser induced transfer process (LIFT process) ;

Figs. 2A - 2C show cross-sectional views illustrating process ing of the slurry layer by solidifying, debinding, and sinter ing, respectively;

Figs. 3A - 3C show cross-sectional views illustrating the building process of a shaped body;

Figs. 4A - 4C show cross-sectional views illustrating further processing steps after the actual building process has been completed; Figs. 5A - 5C show cross-sectional views illustrating a build ing process using different slurry compositions in the build ing process of shaped body;

Figs. 6A - 6D show cross-sectional views illustrating process ing steps of slurry layer deposition, solidifying, debinding, and sintering;

Fig. 7 shows a schematic side view illustrating components of a device for carrying out the method of the present invention;

Fig. 8 shows a schematic perspective view of a device for car rying out a method of the present invention;

Fig. 9 shows a schematic side view of a further embodiment of a device for carrying out a method of the present invention; and

Fig. 9 shows a schematic side view of a further embodiment similar to the device of Fig. 8 for carrying out a method of the present invention.

The sequences of Figs. 1A-1C, 2A-2C, 3A-3C, and 4A-4C in each case show steps of a layer-wise additive manufacturing method according to embodiments of the present invention.

Figs. 1A-1C schematically illustrate the generation of a slurry layer on a substrate 50 by performing a LIFT process. As shown in Fig. 1A the deposition of a slurry occurs drop by drop. A laser beam 1 is focussed on an interface between a carrier 2 and a slurry coating 4 applied to the carrier. In the illustrated example the carrier 2 is a transparent film. A droplet of the slurry is released and deposited on the sub strate 50 by a laser beam pulse, having a duration of typi cally 100 ns and an energy of less than 1 yj (micro Joule) . To apply a continuous layer it is necessary to move the carrier 2 relative to the laser beam 1 and to move the substrate 50 relative the laser beam 1 to cover an area of the substrate surface continuously with overlapping droplets, as shown in Fig. IB. After the slurry layer has been deposited on the sub strate 50 is smoothed and planarized to form an applied slurry layer 11, for example by moving a rod at a defined level over the surface of the substrate 50, as shown in Fig. 1C.

For effective transfer the energy of the laser beam 1 to the slurry coating 4 the slurry of the slurry coating 4 may in clude an admixture of an energy transfer component which ef fectively absorbs the radiation of the laser beam 1 and con verts it to thermal energy. Alternatively, the carrier may in clude a laser radiation energy absorber and converter, for ex ample in the form of an absorption layer on the surface of the carrier which is facing the slurry coating. In the later case laser radiation energy is converted to thermal energy in the absorption layer directly at the interface of the slurry coat ing and the carrier.

Figs. 2A-2C schematically illustrate further processing steps being performed on the slurry layer 11 applied on the sub strate 50 as shown in Fig. 1C. In this example a water based slurry is considered, i.e. a major portion of the liquid phase of the slurry is water including a minor portion of other binder materials. In this case solidifying the slurry layer is performed by heating up the slurry layer to let the water com ponent of the slurry evaporate. The solidification by drying is effected by uniformly heating the layer in this example, and by removing moisture by gas circulation such as heated gas flow, or the combination of a flash lamp and gas flow. In principle any way of heat supply can be used to evaporate the water from the slurry. In a preferred embodiment, however, heat is supplied by directing the laser beam 1 onto the slurry layer (not shown in Fig. 2A) to heat it up by laser energy ab sorption .

By removing all water a solidified slurry layer 12 is ob tained. The next processing step is illustrated in Fig. 2B, wherein in Fig. 2B the process of debinding is illustrated in which the laser beam 1 is acting on the solidified slurry layer 12 in a spatially selective manner to create debinded areas 14 defined by the contour of the slice to be generated in this step. The process of debinding is performed by heating the solidified slurry layer 12 in the selected areas to cause thermal decomposition of remaining binder, wherein the decom position products of lower molecular weight eventually escape as gases. The debinding is performed by illuminating the area as defined by the contour for this slice to be added by burst of laser pulses, preferably at 10 kHz with a pulses duration of 5 ns and with an energy of 20 yj.

In Fig. 2C the debinded areas 14 shown in Fig. 2B are sub jected to a further process step in which the laser beam is directed onto the layer in a spatially selective manner onto the debinded areas 14 to supply further laser energy there. By further heating up the debinded areas the remaining particu late filler material (for example ceramic or glass-ceramic powder) is densified by sintering to form the sintered areas 16 of Fig. 2C.

The sintering also uses a burst of laser pulses, preferably at 300 kHz with pulse duration of 250 ns and with a pulse energy of less than 5 yJ.

Figs. 3A-3C illustrate how the building process proceeds fur ther. In Fig. 3A the last supplied slurry layer has undergone processing by solidifying the last applied slurry layer, by selectively debinding the area defined by the contour of the slice to be added, and by sintering the debinded area of the layer to form sintered slice 16. Thereafter, a further slurry layer 11 is applied (by the steps as illustrated in Figs. 1A - 1C), and then processed by steps as illustrated in Figs. 2A - 2C to form a further sintered added slice 16 as shown in Fig. 3C .

As has already been indicated in Figs. 1A - 1C and 2A - 2C the slurry layer is applied in an area larger than needed for the shaped body to be built. By selectively processing (debinding and/or sintering) only the desired area defined by the contour of the slice to be added as shown in Figs. 2B and 2C the shaped body continues to be built up slice by slice, wherein solidified slurry material remains to surround the processed slice portions of the shaped body being built, which surround ing solidified slurry serves as support material which later ally embeds the shaped body during the building process. By repeating the steps as illustrated and described before the shaped body is eventually completely built up as shown in Fig. 4A. Thereafter, the solidified material surrounding the con structed shaped body is removed, for example by dissolving it using a solvent, as indicated by the solvent 20 in the vat 22 in Fig. 4B. Eventually, the desired shaped body is obtained in this manner as shown in Fig. 4C.

Figs. 5A-5C illustrate a manufacturing method as described be fore, but in this case using two different slurry compositions 31, 32 in the building process. In Fig. 5A a new slurry layer has been applied which comprises a first slurry composition 31 in an outer or peripheral region of the applied layer, and a second slurry composition 32 in a central region of the layer. This newly added layer 31, 32 is then processed by solidify ing, debinding and/or sintering (as illustrated for a uniform slurry material in Figs. 2A to 2C) . The processed area of the first slurry composition is shown in Fig. 5B in black, and the processed area of the second slurry composition 32 of Fig. 5A is shown in Fig. 5B by oppositely inclined hatching compared to the slurry 32. In this manner a shaped body is built up slice by slice which has a first ceramic or glass-ceramic com position in the outer shell, and has a second ceramic or glass-ceramic composition in the core region of the shaped body as shown in Fig. 5B. In Fig. 5C a new layer of first and second slurry compositions 31, 32 has been deposited which is then processed in the same manner as shown in and described above in connection with Figs. 5A and 5B, and these steps are repeated until the shaped body has been built up completely.

Figs. 6A-6D illustrate a further embodiment of the method of the invention. In Fig. 6A a slurry layer is applied in a man ner corresponding to the LIFT process illustrated in Figs. 1A - 1C, with the difference that in the case of Fig. 6A the slurry layer is not deposited as a continuous layer but in a spatially selective manner only in the areas defined by the contour of the slice to be added, in this case in the slurry layer areas 11. The areas surrounding the slurry layer 11 are filled with support material 21 which is likewise deposited by the LIFT procedure using a different zone of the carrier 2 or a different carrier which has a support material coating. The slurry in this example is a slurry having a binder containing mainly photopolymerizable components and a ceramic filler. The support material 21 may likewise be a photopolymerizable mate rial. In Fig. 6B an exposure unit 40 irradiates the slurry layer 11 and the support material 21 by UV radiation which in duces polymerization of the binder of the slurry and polymeri zation of the support material. In the next step the solidi fied slurry area 11 is processed by applying spatially selec tively laser energy to these areas to cause debinding in a manner corresponding to the process shown in and described in connection with Fig. 2B. In this manner a debinded layer areas 14 are formed in Fig. 6C. The debinded areas 14 of Fig. 6C are then further processed by supplying laser beam pulses in a manner as shown in and described in connection with Fig. 2C to eventually form the sintered slice areas 16 surrounded by sup port material 21. These steps of Fig. 6A - 6D are repeated in a manner corresponding to Figs. 3A - 3C to eventually build up the complete shaped body corresponding to Fig. 4A. Finally the support material is removed, for example by an appropriate solvent in a way corresponding to Fig. 4B to eventually obtain a shaped body as shown in Fig. 4C.

Fig. 7 shows a simplified and schematic side view of a device for carrying out a method of the present invention. The device includes a laser 8 which directs, via an adjustable mirror, laser beam 1 onto carrier 2. The carrier 2 is in this example a transparent film which is unwound from a roller and which is wound up on a spaced apart second roller. The rollers are ro tated, under the control of the control unit (not shown) , in a controlled manner to move the carrier 2 with respect to the laser beam 1 and the substrate 50. The double arrows below substrate 50 are intended to indicate that the substrate is movable by drivers of a positioning device with respect to the carrier 2 and the laser beam 1. A cartridge 6 contains a slurry, which container comprises an applicator capable of ap plying a stripe of slurry coating 4 of defined thickness onto the carrier 2.

A similar device is illustrated in the schematic perspective view of Fig. 8. In this embodiment 2 carrier units are pro vided, each comprising a closed loop of a carrier 2 and three rollers around which the carrier 2 is guided. One carrier unit is provided with a cartridge 6 containing a first slurry com position 4, and the second carrier unit is provided with a second cartridge 6' containing a second slurry composition 4'. The cartridges 6, 6' have applicators which apply a stripe coating of slurry compositions 4, 4', respectively, on the re- spective carriers 2. A positioning device serves to move the carrier units and the substrate relative to each other, as in dicated by the double arrow in order to selectively apply slurry composition 4 or 4' by the LIFT process on the receptor surface (substrate surface or upper surface of the last formed and processed layer) . In these manner slurry compositions 4, 4' can be applied on the receptor surface in a spatially se lective manner to obtain a spatial distribution of the slurry compositions 4, 4' as desired.

Fig. 10 shows a side view of a carrier unit similar to the carrier units of Fig. 8. This view illustrates that the car tridge 6 with its applicator applies slurry composition 4 onto the carrier which is then rotated around the three rollers un der the control of a control unit, wherein the positioning of the carrier effected in this manner is part of the controlled positioning device for controlling the relative position of carrier 2 and substrate 50. Fig. 10 further shows a wiper 5 which wipes off slurry composition 4 left over in the preced ing LIFT process steps which wiped off remaining slurry is collected in a vat 9.

Fig. 9 shows a further schematic illustration for a device for carrying out a method of the present invention, wherein the device is similar to the one shown in Fig. 7. In this case there are three cartridges 6, 6' , 6' ' containing a first, sec ond, are third slurry compositions 4, 4'', 4', respectively which are applied in a selective and controlled manner onto the carrier 2 to provide zones of slurry coatings on the car rier, wherein the zones are provided with different slurry compositions. The rollers shown are rotated by the control unit in a selective manner such that during the LIFT process different slurry compositions are selected in a spatially se lective manner to obtain a desired distribution of slurry com positions in the layer created by the LIFT process.