EP4622764A1 - Verfahren zum beschichten einer oberfläche - Google Patents
Verfahren zum beschichten einer oberflächeInfo
- Publication number
- EP4622764A1 EP4622764A1 EP23828685.0A EP23828685A EP4622764A1 EP 4622764 A1 EP4622764 A1 EP 4622764A1 EP 23828685 A EP23828685 A EP 23828685A EP 4622764 A1 EP4622764 A1 EP 4622764A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- welding
- coated
- laser
- track
- coating
- 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
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/34—Laser welding for purposes other than joining
- B23K26/342—Build-up welding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/08—Devices involving relative movement between laser beam and workpiece
- B23K26/0823—Devices involving rotation of the workpiece
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2101/00—Articles made by soldering, welding or cutting
- B23K2101/006—Vehicles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2101/00—Articles made by soldering, welding or cutting
- B23K2101/34—Coated articles ; Surface treated articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/02—Iron or ferrous alloys
- B23K2103/04—Steel or steel alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/02—Iron or ferrous alloys
- B23K2103/06—Cast-iron alloys
Definitions
- the invention relates to a method for coating a surface using a laser coating device, the method comprising at least the following steps: a. providing a base body with a surface to be coated; b. providing laser optics; c. moving the surface to be coated relative to the laser optics; and d. providing welding filler material and carrying out a coating process by heating the welding filler material provided using laser light from the laser optics to connect a web-shaped first welding track to the surface to be coated, step c. being carried out during a coating process according to step d.
- the method is primarily characterized in that the first welding track is produced in step d.
- the invention further relates to a laser coating device.
- Additive manufacturing processes are becoming increasingly interesting for large-scale production.
- the aim of additive coating processes is usually to provide a base body with a coating that is better suited to the respective application. This opens up the possibility of using a base body that is made of a mechanically and/or thermally more suitable material and/or can be produced more cost-effectively. This is known, for example, in the area of brake discs, cylinder barrels in engine blocks and pistons for external applications.
- Coating processes including laser spraying and laser cladding, such as extremely high-speed laser cladding [EHLA] as used in the
- the present invention is based on the object of at least partially overcoming the disadvantages known from the prior art.
- the features according to the invention arise from the independent claims, for which advantageous embodiments are shown in the dependent claims.
- the features of the claims can be combined in any technically reasonable manner, whereby the explanations from the following description and features from the figures can also be used, which include additional embodiments of the invention.
- the invention relates to a method for coating a surface by means of a laser coating device, wherein the method comprises at least the following steps: a. Providing a base body with a surface to be coated; b. Providing a laser optics which is movable relative to the provided base body and by means of which laser light can be provided in a focused manner for connecting a welding filler material to the surface to be coated; c. Moving the surface to be coated relative to the laser optics; and d.
- step c. is carried out during a coating process according to step d.
- the method is characterized in particular in that the first welding track in step d. is produced on the surface to be coated with an overlap with itself of less than 10% of the track width or without overlap, and a further welding track is applied at the earliest after completion of a relative 360° turn between the surface to be coated and the laser optics.
- a method is now proposed in which a time saving for cooling is achieved without causing a disadvantage in the process times.
- This is achieved by applying the individual welding tracks at a distance from each other on the surface to be coated and not in the final state or relating to a respective layer and its final state, the desired overlap of the welding tracks with one another.
- Such an overlap is, for example, up to 90% [ninety percent], preferably 60% [sixty percent] to 80%.
- With only a slight overlap of less than 10% it is necessary to place at least one further welding track between these two slightly overlapping welding tracks. Due to the small overlap and thus a small amount of material, in an advantageous embodiment this overlapping material is melted again and thus any inadequate connection between the welding tracks and/or the surface to be coated is improved.
- the method is designed for coating a surface of a base body, wherein the surface to be coated is preferably provided with a coating over its entire surface with the aid of a welding filler material and the thermal energy of laser light from the laser optics.
- a base body is made, for example, of a gray cast iron material, preferably lamellar gray cast iron
- the coating, which is formed from the welding filler material is made of a steel, for example stainless steel or tool steel, with a high proportion of additives, such as carbon [C], chromium [Cr], molybdenum [Mo], vanadium [V], titanium [Ti], tungsten [W], manganese [Mn], boron [B] and/or niobium [Nb].
- the welding filler material is already provided on the surface to be coated as a so-called powder bath (selective laser welding) and in another embodiment, the welding filler material is fed to the welding process in-situ, preferably via a nozzle.
- the above-mentioned extremely high speed laser cladding [EHLA] is used.
- a base body is provided, for example clamped in a workpiece holder, whereby a surface to be coated is aligned as required.
- a laser optic is provided, which is usually supplied with laser light from an external laser source. Laser light can be appropriately focused using the laser optic, for example in extremely high-speed Laser cladding [EHLA] with a laser focus just above the surface to be coated.
- the base body or the surface to be coated and the laser optics are movable relative to one another, whereby the surface to be coated is preferably movable in a fixed plane and the laser optics itself is alignable relative to it and/or movable along another spatial axis relative to the surface to be coated.
- a corresponding laser coating device has an actuator device, which usually has a plurality of individual actuators or feed axes.
- step c. the relative movement between the base body and the laser optics is now carried out, for example by the actuator device of the executing laser coating device.
- the surface to be coated is moved relative to the laser optics in such a way that a welding track is created.
- step d. welding filler material is now provided, whereby, as already described above, this is either already held on the surface to be coated before the welding energy is supplied using the laser light or is fed in situ into the laser focus of the laser optics. Due to the movement and the welding process before step c. and step b., a web-like first welding track is applied to the surface to be coated and connected to it.
- the welding filler material is melted or completely melted and at the same time a molten pool is formed on the surface to be coated, so that an excellent bond quality is achieved between the welding filler material and the surface to be coated.
- first welding track be created that has little or no overlap with itself, in such a way that no final coating is created with the first welding track. Rather, further welding tracks are necessary in order to achieve a final coating result. It should be noted at this point that a coating often is produced from several layers, each additional layer being formed from weld tracks which are applied to a previously applied complete layer consisting of several weld tracks.
- a further welding track is applied with a considerable delay, which then has a greater overlap than the first welding track with itself.
- a further welding track is applied with the final desired overlap of, for example, 40% [forty percent] to 60%.
- a meandering welding track first an outward path, a cross path and a return path and then another cross path of the first welding track are created before another welding track with a greater overlap is placed next to the part of the first welding track already created. Overall, this process only results in a small time delay as a result of the time offset between the start of the application of the first welding track and the further welding tracks.
- the method proposed here can achieve an overall time saving because, as a result of the improved weld joint, an intermediary layer, a so-called adhesive layer or buffer layer, can be dispensed with.
- step c. the laser optics rotate relative to the surface to be coated about the axis of rotation and are moved radially with respect to the axis of rotation, and in step d. the first welding track is generated in a spiral shape, a further welding track is applied during step d. at the earliest after a full relative rotation of the surface to be coated.
- a further welding track is only applied when a full relative rotation of the surface to be coated has been carried out, i.e. the first welding track has already made a complete circuit on the surface to be coated.
- a further welding track is then applied to the surface to be coated with a larger overlap than the first welding track has with itself (preferably with the final overlap).
- a subsequent welding track is only applied after completion of the previously generated welding track. It is now proposed that the subsequent welding track is only applied when the previously created welding track has been completely applied to the surface to be coated. For example, in the case of a spiral-shaped welding track that is applied from radially outside to radially inside or vice versa, the subsequent welding track is only applied to the surface to be coated when this spiral has been applied from the starting point (e.g. radially outside) to the end point (e.g. radially inside) and is thus completed.
- the coating of the surface to be coated is not yet complete when the first weld trace is created, but at least one more weld trace still has to be applied to the surface to be coated. The same applies to the completion of each layer in a multi-layer coating structure.
- all welding tracks in the final state form a complete covering of the surface to be coated.
- a desired (partial) covering of the surface to be coated is achieved.
- a partial covering of the surface to be coated is created by the first welding track, in such a way that the remaining partial surfaces are covered by the at least one subsequently applied welding track.
- a desired overlap of all of the welding tracks is taken into account. It should be noted that part of the surface to be coated is not necessarily still visible if all of the welding tracks necessary for a desired overlap have not yet been applied.
- the first welding tracks are applied radially offset from one another without overlapping with the immediately adjacent one or with a small overlap (for example less than 10% [ten percent]) on the surface to be coated.
- the welding tracks of the same ordinal number are applied offset from one another (for example by 90° [ninety degrees of 360°]) on the surface to be coated and have the same overall length from the starting point to the end point.
- the welding tracks are started differently offset from one another and/or have a different length between their respective starting point and end point.
- all welding tracks created on the surface to be coated are provided with an equal length between the starting point and the end point.
- a welding track is only applied over a partial section (for example in a dead end formed by previous welding tracks or subsequently formed welding tracks).
- a distance between two generated by means of the method adjacent sections of the first weld track is equal to or greater than twice, preferably three times, the difference between the track width and the desired overlap of weld tracks in the final state of the coated surface.
- the distance between the first welding tracks is twice the difference between the track width and the desired overlap of all welding tracks, which in the final state (the respective layer) corresponds to the surface to be coated.
- the distance is greater than twice, preferably exactly three times or even a factor greater than three times.
- the respective factor is an integer factor and corresponds to the number of welding tracks in the final state.
- the ordinal number here also relates to the simultaneous creation, i.e. to the time of creation. It should be noted that the number of welding traces applied one after the other results from the desired small overlap of the first welding trace with itself and the desired final overlap of all welding traces, provided that these are also to be created one after the other like the first welding trace.
- the distance to the generated adjacent section of the same first welding track is defined. In an embodiment with multiple first welding tracks, the distance to the generated adjacent section of the next adjacent first welding track is defined.
- the distance is defined in the radial direction to the axis of rotation.
- the distance is defined transversely to the center line or longest extension of the respective welding track, for example between two sections of the welding track which are parallel to each other in an x-direction. and their track width extends in the y-direction.
- a cross connection between the parallel sections of the meander has no distance, another at least no smaller distance to another cross connection.
- a meander is not necessarily formed with a non-spiral welding track.
- several welding tracks preferably running parallel to one another (for example also curved, jagged and/or wavy), are formed, preferably applied to the surface to be coated simultaneously with a plurality of laser optics.
- the surface to be coated is cooled during or after step d., preferably by means of air cooling and/or activated heat conduction.
- active cooling in addition to cooling down the welding track produced due to the time offset until the next welding track is produced (overlapping by equal to or more than 10% of the track width), active cooling is used, namely air cooling (i.e. convection) and/or activated heat conduction, whereby this activated heat conduction not only uses the material conduction, but also actively dissipates the heat within the material via a fluid.
- air cooling i.e. convection
- activated heat conduction is formed, for example, by a so-called heat pipe, in which an enclosed coolant evaporates at the end providing cooling and is liquefied again at the end dissipating heat.
- a cavity or a line is formed in a component of the laser coating device (for example the workpiece holder) for a circulating liquid and/or a coolant.
- the base body is that of a brake disc, wherein a friction surface is to be formed on the surface to be coated.
- the base body is that of a brake disc, for example a cast body, on whose surface (to be coated) a friction surface is created by means of a coating.
- a brake disc is designed for a motor vehicle and has an inner and an outer friction surface, which are each designed to interact with a brake pad.
- a laser coating device comprising at least the following components:
- the laser coating device is set up to carry out a method according to an embodiment according to the above description, wherein preferably the laser coating device is set up for extremely high-speed laser deposition welding.
- the laser coating device is a selective laser deposition welding machine, a laser spraying machine for thermal coating, or a laser welding machine, for example for deposition welding, preferably for the above-mentioned extremely high-speed laser deposition welding [EHLA].
- the coating for example for surface finishing, is carried out with a material which is provided as a wire, (liquefied) drop-shaped or (solid) powder-shaped via the feed device as a welding filler material.
- the welding filler material is put into the liquid state by means of the laser light of the laser optics or is kept in the liquid state, i.e. melted or only melted on the outside and/or in a melt pool formed by means of the laser light in the introduced into the surface to be coated and thus bonded to the surface to be coated at an atomic or molecular level.
- the laser optics are fed from and/or comprise one or more laser sources.
- the laser beam or the multiple laser beams of the laser optics are bundled onto one or more laser focuses, wherein the energy density (intensity) for the desired (maximum) thermal input is preferably only present in this area when, controlled by a control device, a predetermined power limit or more power is emitted by means of the laser optics.
- the laser focus has a spatial extent, for example with a diameter (in a plane parallel to the surface to be coated) of 1 mm [one millimeter] to 12 mm, for example from 1.2 mm to 8 mm, particularly preferably from 3 mm to 4 mm.
- the surface to be coated in one embodiment of the method for coating is a surface of the fixed workpiece (i.e. the base body), which in one embodiment is arranged on the workpiece with the surface to be subsequently coated, for example within the surface to be coated.
- a surface of the fixed workpiece is referred to here for simplicity as the surface to be coated.
- the Surface of the fixed workpiece a surface outside an area to be coated (for the desired function), for example in the case of a brake disk or a piston on the continuous and/or uniformly aligned surface for the respective function but outside the functional surface, i.e. outside the braking surface or the sliding surface.
- the surface to be coated with the laser optics is arranged in a section which is not continuous with the functional surface and/or uniformly aligned, but for example on a surface that is angled and/or offset therefrom.
- This is, for example, a shoulder or, for example, in the case of a brake disk, its cylindrical outer peripheral surface and, in the case of a piston, one of its cover surfaces.
- the coating method is used to process an area of the functional surface to be coated.
- the feed device for welding filler material is set up for wire or powder material, for example.
- a powder nozzle for transporting powder material for powder deposition welding has one (for example lateral) or several outlets and/or an annular gap outlet, wherein the powder material is transported by means of a gas flow (for example air or an inert carrier gas).
- the powder material is thus transported as a powder flow by means of the shape of the at least one outlet and (at least approximately) the speed of the gas flow along a powder trajectory.
- a gas flow for example air or an inert carrier gas
- the powder focus is defined, for example, in a design coaxial to the laser beam by a conical (or running along an imaginary conical surface) arrangement of the plurality of nozzle channels (powder ring as an imaginary ring line through a plurality of points and/or line sections) or by an annular nozzle (circumferential powder ring). Due to the conical structure, the coaxial powder ring tapers concentrically to a powder focus. After passing through the powder focus, the powder gas jet diverges along the propagation direction (of the laser beam). In one embodiment, the powder focus is to be aligned relative to the laser focus.
- the workpiece holder is designed to clamp, i.e. to fix, a workpiece (i.e.
- the base body whereby a defined spatial axis, for example a central axis of rotation, of the workpiece can be precisely aligned.
- the base body is already finished, except for the coating to be applied or, if necessary, other smaller post-processing processes. Precise positioning is therefore necessary.
- This is preferably supported by a gripping arm and defined gripping surfaces on the workpiece and/or appropriate measuring technology.
- the workpiece holder comprises a detection device for imbalances, whereupon a clamping can be corrected or, if balancing of the workpiece has not yet been carried out or can still be added (for example within the scope of admissibility), at least a corresponding material removal or material application is carried out.
- the actuator device is designed to position the laser optics (or their laser focus) and, if applicable, the feed device for welding filler material (or their powder focus) relative to the workpiece or its surface to be coated.
- the actuator device comprises at least one actuator, preferably a plurality of actuators, for the translational and/or rotational movement of the laser optics and, if applicable, the feed device for welding filler material and/or the base body.
- the actuator device rotates the brake disk about its axis of rotation (fixed in the workpiece holder) and guides the laser optics and the feed device for welding filler material radially, so that an (at least approximate) spiral shape of the application track is produced.
- a movement axis aligned normal to the surface of the base body is often provided, which is used for different sized base bodies are provided and/or for a possibility of clamping the base body in the workpiece holder of the device for the laser coating process without collision and/or to be able to easily maintain or replace the laser optics and the feed device.
- the actuator device per spatial axis
- the actuator device can only be moved with sufficient precision for the coating process, for example in the range of a few millimeters, preferably from 0.1 mm [a tenth of a millimeter] to 1 mm.
- the laser coating device is set up to carry out the method for coating a surface of a base body, as described above.
- the laser coating device is set up for the above-mentioned extremely high-speed laser deposition welding [EHLA].
- EHLA extremely high-speed laser deposition welding
- the high deposition speed is combined with the necessary cooling of the welding tracks, which is beneficial for material pairs that are difficult to weld together. In one embodiment, this can also result in a time saving compared to conventional deposition methods with EHLA, because an intermediary layer, a so-called adhesive layer or buffer layer, can be dispensed with.
- Fig. 1 a laser coating device in a schematic view with a base body
- Fig. 2 a (rotational) base body in a plan view
- Fig. 3 a sectional view of a brake disc with welding traces
- Fig. 4 a motor vehicle with brake discs in a schematic plan view
- Fig. 1 shows a laser coating device 3 in a schematic view with a base body 4 (i.e. workpiece).
- the base body 4 is clamped here by means of the workpiece holder 20 of the laser coating device 3 and is, for example, a brake disk 17.
- the base body 4 has a surface 2 to be coated (as shown, upper) and optionally an opposite rear side 22 (as shown, lower). In the state shown, a layer can be applied to the surface 2 to be coated for coating 1 the surface 2 of a base body 4.
- the base body 4 is clamped in a workpiece holder 20 of the laser coating device 3 and is held in exact position by it.
- the workpiece holder 20 is, for example, a chuck with a rigid axis of rotation 5 and the base body 4 is aligned coaxially to the axis of rotation 5.
- the axis of rotation 5 is thus aligned normally to the surface 2 to be coated.
- the workpiece holder 20 is optionally driven by a rotary drive 23, so that the base body 4 can rotate about the axis of rotation 5.
- the base body 4 can preferably be repeatedly and precisely adjusted to coordinates by the rotary drive 23 according to a coordinate system.
- the rotary drive 23 is part of the actuator device 21.
- Fig. 2 shows a (rotational) base body 4, for example a brake disk 17 according to Fig. 1, in a plan view of the surface 2 to be coated, wherein three spiral-shaped welding tracks 9, 10, 11 (for example their center lines) are indicated here purely schematically for better understanding.
- Each of the welding tracks 9, 10, 11 begins (or ends) at the outer edge 41 of the base body 4 and ends (or begins) at the inner edge 42.
- the beginning and the end of the welding tracks 9, 10, 11, each of equal length are offset from one another by 90° [ninety degrees out of 360°].
- additional welding tracks must be provided accordingly.
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Mechanical Engineering (AREA)
- Laser Beam Processing (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102022130764.6A DE102022130764A1 (de) | 2022-11-21 | 2022-11-21 | Verfahren zum Beschichten einer Oberfläche |
| PCT/DE2023/100903 WO2024109990A1 (de) | 2022-11-21 | 2023-11-21 | Verfahren zum beschichten einer oberfläche |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4622764A1 true EP4622764A1 (de) | 2025-10-01 |
Family
ID=90923295
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP23828685.0A Pending EP4622764A1 (de) | 2022-11-21 | 2023-11-21 | Verfahren zum beschichten einer oberfläche |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP4622764A1 (de) |
| DE (1) | DE102022130764A1 (de) |
| WO (1) | WO2024109990A1 (de) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011100456B4 (de) | 2011-05-04 | 2015-05-07 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Extremes Hochgeschwindigkeitslaserauftragsschweißverfahren |
| DE102013008396B4 (de) * | 2013-05-17 | 2015-04-02 | G. Rau Gmbh & Co. Kg | Verfahren und Vorrichtung zum Umschmelzen und/oder Umschmelzlegieren metallischer Werkstoffe, insbesondere von Nitinol |
| ES2930232T3 (es) * | 2014-10-24 | 2022-12-09 | Laserbond Ltd | Método y aparato para revestir una superficie de un artículo |
| DE102018130798A1 (de) * | 2018-12-04 | 2020-06-04 | Trumpf Laser- Und Systemtechnik Gmbh | Geregeltes Pulverauftragsschweißverfahren |
| DE102019132191A1 (de) * | 2019-11-27 | 2021-05-27 | HPL Technologies GmbH | Vorrichtung zum Laserauftragschweißen mit mehreren Laserauftragschweißköpfen |
| CN111334789B (zh) * | 2020-02-02 | 2022-04-26 | 江苏大学 | 一种用于超高速激光熔覆盘类零件端面的方法 |
| DE102020106822B4 (de) * | 2020-03-12 | 2022-10-13 | HPL Technologies GmbH | Vorrichtung und Verfahren zum Nachbearbeiten von Schichten aufgetragen durch Laserauftragschweißen |
-
2022
- 2022-11-21 DE DE102022130764.6A patent/DE102022130764A1/de active Granted
-
2023
- 2023-11-21 WO PCT/DE2023/100903 patent/WO2024109990A1/de not_active Ceased
- 2023-11-21 EP EP23828685.0A patent/EP4622764A1/de active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE102022130764A1 (de) | 2024-05-23 |
| WO2024109990A1 (de) | 2024-05-30 |
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