WO2020104334A1 - Procédé de production d'une pièce constituée de métal ou de matériaux de la céramique technique - Google Patents
Procédé de production d'une pièce constituée de métal ou de matériaux de la céramique techniqueInfo
- Publication number
- WO2020104334A1 WO2020104334A1 PCT/EP2019/081530 EP2019081530W WO2020104334A1 WO 2020104334 A1 WO2020104334 A1 WO 2020104334A1 EP 2019081530 W EP2019081530 W EP 2019081530W WO 2020104334 A1 WO2020104334 A1 WO 2020104334A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- component
- green body
- sintering
- post
- ceramic
- Prior art date
Links
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- 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
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- 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
- B22F10/10—Formation of a green body
- B22F10/18—Formation of a green body by mixing binder with metal in filament form, e.g. fused filament fabrication [FFF]
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- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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- C04B35/638—Removal thereof
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- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
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- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Definitions
- component properties at the upper limit of the values that are possible today can usually be achieved by producing and using ceramic powders with high chemical purity and with a particularly small crystallite size. These powders are processed into a green body with the lowest possible binder content under high pressures.
- One goal is to maintain a high green density and, due to the low binder content ( ⁇ 5%), to create as few or small pores as possible during the subsequent debinding.
- high-quality components can also be produced using the injection molding process if the pressure during injection molding is correspondingly high.
- processes such as uniaxial pressing or cold isostatic pressing are preferably used.
- Isostatic pressing is a pressing process in which the pressing pressure acting on the component is the same in all directions.
- the isostatic process uses an elastic sleeve around the green body.
- further processing of this compact by turning or milling is usually necessary.
- mainly cylindrical molds are used as molds for the pressing process, since geometrically optimized molds would require additional mold construction. Through this mostly only a rough preform, depending on the geometry of the desired component, requires a relatively high “machining effort”, which leads to corresponding losses of the ceramic powder material used.
- Additive manufacturing processes in particular various 3D printing processes, have been developed for the material classes plastic and metals in recent years until they are ready for series production. With these processes, both customer-specific individual parts (e.g. crowns and bridges made of CrCo alloys in the dental sector) and sample parts ("fast prototyping”) can be manufactured in one-off production.
- the bodies made of ceramic materials which are produced using the 3D printing process, have to be processed further by sintering at suitable higher temperatures with a corresponding volume shrinkage.
- An exception to this are components made of silicon in filtered silicon carbide (SiSiC), also called reaction-bonded silicon carbide (RbSiC). These parts no longer experience any significant shrinkage during the actual sintering process, since the pores present after debinding are filled with molten silicon.
- the mechanical properties in the sintered ceramic final state of the components produced by means of 3D printing processes are lower than those for a technical application Mechanical components required and usual values of a high-performance ceramic, which can be achieved with the above-mentioned conventional manufacturing processes.
- oxide-ceramic materials include aluminum oxide AI 2 O 3 in various degrees of purity, zirconium oxide ZrÜ2 with various stabilizing additives and the mixed materials ATZ (alumina toughened zirconia) or ZTA (zirconia toughened alumina).
- SSiC sintered Silicon Nitride
- S13N4 sintered Silicon Nitride
- thermoplastic processes T3DP and FFF require particularly high proportions of additives.
- green densities of up to 55% and thus sintered densities of 99.4% are achieved. With other methods, these values are significantly lower.
- the ceramic powder is always brought into the desired shape without pressure or at low pressure.
- the production without external pressure after debinding of the manufactured components leads to a structure with a relatively high pore content and a low green density.
- These green bodies with a relatively low green density have a relatively high proportion of pores and can subsequently not or only to a very limited extent be processed into a ceramic body with a very high sintered density and very good mechanical properties.
- filigree and thin-walled components are mostly produced using 3D printing with ceramic materials.
- the components often also have internal structures that cannot be produced by other processes.
- the wall thicknesses range from 0.5 mm to a maximum of 6 mm.
- relatively solid components In contrast to the ceramic components that can already be produced using 3D printing processes, relatively solid components with wall thicknesses over 6 mm are required for many applications. These components are usually relatively solid and are in the size range of 20 x 20 x 20 mm to 300 x 300 x 300 mm. There are no complex internal structures, but the wall thicknesses are in the range of 6 to 35 mm.
- Such solid ceramic parts are produced in the prior art by isostatic pressing of the raw powder and subsequent processing of the green body on lathes and milling machines. This is followed by debinding and sintering with a linear combustion shrinkage of about 20%. In the hard-fired state, grinding is usually still required to achieve the required tolerances and surface qualities. Due to the machining of an isostatically pressed full body required in such a conventional manufacture of a ceramic machine component, depending on the geometry, up to 80% of the ceramic material has to be removed and disposed of.
- EP 1 534 461 B1 a 3D object is used to build a metallic object without the addition of a binder. Compaction is achieved when the component is built up in layers by compressing each layer with a pressure roller.
- EP 1 292 413 B1 shows an alternative solution for sintered parts with 98-99% of the theoretical maximum density by adding sugar to the sintered powder in connection with a particular process sequence.
- the object of the invention is to provide a method which enables the production of solid components made of metal or materials of technical ceramics with sintered densities above 99%.
- a method with the following steps is proposed: First, a mixture of a binder and a ceramic or sintered metallurgical powder is produced. This mixture must be suitable for the additive manufacturing of a green body from the mixture. If the mixture is available, a green body is created using additive manufacturing. This is then isostatically compressed to achieve a more homogeneous density distribution and a higher green density. The redensification can take place in the green state or in partially or completely debindered or in a slightly sintered state. Then the densified component is sintered.
- green bodies produced according to the invention are post-compressed using an isostatic pressing process before the sintering process.
- the additive manufacturing enables a very precise and material-saving production of the green body.
- the additive manufacturing enables a near-net-shape production of the raw body and accordingly less material is used.
- components can be produced in an efficient manner from materials of technical ceramics or sintered metals.
- These include e.g. Valve body, valve cone seat rings, valve balls, wear protection sleeves or similar for process control.
- the isostatic pressing is carried out in the form of Nassostatic pressing.
- the body produced in an additive process during the recompression before the penetration of the liquid pressure medium during the nasostatic pressing protect, it is preferably covered with an elastic sleeve before the nasostatic pressing.
- the elastic sleeve must be designed as a double-walled hose.
- the green body produced in an additive process can be coated with an expandable lacquer prior to isostatic pressing.
- Stretchable plastic-based paints e.g. polyurethane-based paints
- Such painting can be done in a simple immersion process.
- the varnish is preferably removed before sintering. This is preferably done by chemical dissolving.
- the green body is preferably at least partially removed after the additive manufacturing and before the isostatic post-compression.
- the binder is preferably removed almost completely.
- the component can be deblocked a second time and further after compression, but before sintering.
- this lacquer Before sintering, this lacquer will be removed again by pyrolysis or by means of a solvent. Depending on the type of paint used, water or organic solvents are suitable as solvents.
- the varnish is preferably removed by thermal treatment between 20 ° C and 650 ° C. In principle, this process corresponds to the "debinding" of the plasticizer / binder of the ceramic green body that has already been carried out. Debinding must, however, be carried out much more slowly, since the resulting gases have to escape from the component through very small pore channels, while the coating is only on the surface.
- the outer edges of the component can have radii
- the foils are thick enough and stretchable enough to close on edges to stay;
- the organic binders When the ceramic green body is heated, the organic binders are expelled or oxidized and expelled in the range between room temperature and about 600 ° C.
- the component does not change its external shape, but is made easier by the escape of the substances. This reduces the macroscopic density of the body and creates a pore volume.
- the actual sintering process begins through liquid phase formation or solid diffusion only at a higher temperature (depending on the material) of around 800 - 1,000 ° C. During this sintering process, the entire body becomes smaller (ceramic shrinkage) and the pore volume is reduced. The macroscopically measurable density of the body increases. If one stops this sintering process shortly after the onset of shrinkage, one speaks of sintering.
- the ceramic component When debinding and sintering, the ceramic component always has a state in which organic binder components have been completely expelled, but there is still no firm ceramic bond. Nevertheless, the component does not fall apart in the firing process.
- the object is also achieved by a component which was produced using the method described and which has a pore fraction of less than 1% of the volume after sintering.
- the coating remains at least partially on the component, the remaining coating can enable or improve a function of the component, in particular through a hydrophilic or oleophilic or electrically conductive or electrically insulating property of the coating.
- the method described is suitable, among other things. for the production of wear protection sleeves, valve seat rings, valve bodies or valve housing parts.
- FIG. 3 shows a seat ring for a ball
- Fig. 4 shows a recirculating ball sleeve
- Fig. 5 is a wear protection sleeve.
- 1A and 2B show two preferred processes of the proposed method for producing a component from, for example, a technical ceramic.
- step 100 a mixture of a binder and a ceramic or sintered tallurgical granulate is produced.
- ABS acrylonitrile butadiene styrene
- PLA Polyactide - polyactid acid
- PVA polyvinyl alcohol
- TPE thermoplastic elastomers
- a green body is then produced additively from the mixture.
- the green body often has about 50 +/- 15% of the maximum achievable density of the ceramic end material.
- the binder is wholly or partly removed from the green body by pyrolysis or another method.
- the ceramic green body is heated, the organic binders are expelled or oxidized and expelled in the range between room temperature and about 600 ° C.
- the component does not change its external shape, but is made easier by the escape of the substances. This reduces the macroscopic density of the body and creates a pore volume.
- the actual sintering process begins through liquid phase formation or solid-state diffusion only at a higher temperature (depending on the material) of around 800 - 1,000 ° C.
- the ceramic component When debinding and sintering, the ceramic component always has a state in which organic binder components have been completely expelled, but there is still no solid ceramic bond. Nevertheless, the component does not fall apart in the firing process.
- the green body is lightly sintered in order to further stabilize it.
- a thermal process step is required between the production of the green body by one of the various additive processes and the post-compression of the component by isostatic pressing and how far the body should be debinded or even sintered depends on the type of 3D printing process selected and from the residual porosity still present in the green body and the type of binder and plasticizer system used. You cannot specify a fixed number for a residual volume share of binder here. The redensification takes place in the green state or in partially or completely debindered or in a slightly sintered state.
- the green body is packed or coated in a watertight manner. This can be done by vacuuming 145 in a suitable plastic film (made of PE or PP or other plastics) or by immersing 140 in a suitable lacquer.
- This coating is intended to prevent the hydraulic fluid from penetrating into the pores. This is typically done using varnishes based on elastic plastic that shows no cracking, e.g. Polyurethane-based paints.
- the stretchable varnish is applied sufficiently thick.
- the paint is applied thicker at the edges, which prevents the paint layer from tearing open during subsequent isostatic compaction.
- the thicker application of paint on unbroken edges is set automatically if the application of paint is carried out in the dipping process.
- This coating process also enables the isostatic pressing of bodies with finer inner contours or (transverse) bores.
- step 150 a cold nasostatic pressing of the green body follows with a pressure fluid.
- the green body After pressing, the green body usually has a density of approximately 55 +/- 15% of the maximum achievable density of the ceramic end material.
- step 160 the waterproof cover is removed.
- This can be in use a coating or a varnish by pyrolysis or by means of a solvent, in the case of vacuumed blanks the covering can be removed mechanically.
- step 170 the green body is further debindered. This is done either by pyrolysis or by means of a solvent.
- step 180 the green body is finally sintered.
- the component should preferably have a density of more than 98% of the maximum achievable density of the ceramic end material.
- step 190 the surfaces are possibly subsequently finished, for example by grinding, sandblasting or machining.
- FIG. 3 shows a seat ring for a ball
- Fig. 4 shows a recirculating ball sleeve
- Fig. 5 is a wear protection sleeve.
- Additive manufacturing also popularly known as 3D printing, refers to processes for manufacturing components by means of point-by-layer or layer-by-layer construction.
- the production takes place on the basis of computer-aided models of the components made of formless (liquids, gels / pastes, powder, etc.) or form-neutral (band, wire, sheet) material by means of chemical and / or physical processes.
- Binder or binder are substances that adhere added solids with a fine degree of division (e.g. powder). Binders are usually added to the fillers to be joined in liquid or pasty form. Both substances are mixed intensively so that they are evenly distributed and all particles of the filler are evenly wetted with the binder.
- the main difference from the FFF process is that instead of filaments, granules are used as the raw material. This means that commercially available raw materials from the injection molding sector can be used.
- FFF Fused Filament Fabrication
- FFF for short, also called Fused Filament Manufacturing
- FFF is a 3D printing process that uses an endless filament made of a thermoplastic material. This is guided by a large spool through a movable, heated printer extruder head. Melted material is pressed out of the nozzle of the print head and placed on the growing workpiece. The head is moved under computer control to define the printing form. Typically, the head moves in layers, moving in two dimensions to deposit one horizontal plane at a time, before moving up slightly to start a new disk.
- ceramic or sintered metallurgical powder has to be introduced into a filament beforehand. By inserting it into a plasticizing filament, almost all ceramic materials can be processed. Relatively simple and inexpensive printing machines can be used. Green body
- a green body or green body is an unsintered blank that is still easy to machine.
- it is powder bonded with binders.
- the green bodies are dimensioned in such a way that they shrink almost completely to the final shape when they burn.
- Isostatic post-compression is a pressing process in which the pressing pressure acting on the component is the same in all directions. This method is well suited for small parts with high isotropy and even compression, and is also inexpensive for demanding prototypes and production in small series.
- Nasostatic post-compression is isostatic post-compression, in which the pressure is transmitted through a liquid, preferably through water.
- the mold enveloping the compact is completely immersed in the pressure medium (e.g. water) and removed from the pressure medium for demolding. 3D extrusion process
- the plastic ceramic mass is pressed through an extruder through a 3D movable nozzle.
Abstract
L'invention concerne un procédé de production d'une pièce constituée de matériaux de la céramique technique ou de matériaux métallurgiques frittés, comportant les étapes suivantes : un mélange d'un liant et d'un granulé céramique ou métallurgique fritté est d'abord produit (100). Ledit mélange doit être approprié pour la fabrication additive d'un corps cru issu du mélange. Une fois le mélange préparé, un agent de corps cru de fabrication additive est généré (110). Ce dernier est ensuite recomprimé isostatiquement (150) à l'état cru ou à l'état d'élimination partielle ou complète du liant, ou à l'état légèrement fritté. La pièce recomprimée est ensuite frittée (180). Grâce à l'augmentation de l'épaisseur avant le processus de frittage propre (180) ainsi qu'à l'homogénéisation supplémentaire suivante de la répartition de l'épaisseur par le pressage isostatique (150), l'invention permet d'obtenir, au cours du processus de frittage consécutif, des épaisseurs de frittage plus élevées et des valeurs de propriétés nettement améliorées concernant la résistance et d'autres paramètres.
Priority Applications (1)
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EP19805277.1A EP3883709A1 (fr) | 2018-11-20 | 2019-11-15 | Procédé de production d'une pièce constituée de métal ou de matériaux de la céramique technique |
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DE102018129162.0 | 2018-11-20 | ||
DE102018129162.0A DE102018129162A1 (de) | 2018-11-20 | 2018-11-20 | Verfahren zum Herstellen eines Bauteils aus Metall oder Werkstoffen der technischen Keramik |
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WO2020104334A1 true WO2020104334A1 (fr) | 2020-05-28 |
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PCT/EP2019/081530 WO2020104334A1 (fr) | 2018-11-20 | 2019-11-15 | Procédé de production d'une pièce constituée de métal ou de matériaux de la céramique technique |
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EP (1) | EP3883709A1 (fr) |
DE (1) | DE102018129162A1 (fr) |
WO (1) | WO2020104334A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN113909490A (zh) * | 2021-09-10 | 2022-01-11 | 华中科技大学 | 一种金属零件及其近净成形方法 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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EP4001243A1 (fr) | 2020-11-17 | 2022-05-25 | Element 22 GmbH | Procédé de fabrication de corps moulés par frittage |
EP4117060A1 (fr) * | 2021-07-09 | 2023-01-11 | Hochschule Rheinmain University of Applied Sciences Wiesbaden Rüsselsheim | Procédé amélioré de fabrication d'une plaque polaire |
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US9139893B2 (en) * | 2008-12-22 | 2015-09-22 | Baker Hughes Incorporated | Methods of forming bodies for earth boring drilling tools comprising molding and sintering techniques |
CN109195776A (zh) * | 2016-04-14 | 2019-01-11 | 德仕托金属有限公司 | 具有支撑结构的增材制造 |
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- 2018-11-20 DE DE102018129162.0A patent/DE102018129162A1/de active Pending
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- 2019-11-15 WO PCT/EP2019/081530 patent/WO2020104334A1/fr unknown
- 2019-11-15 EP EP19805277.1A patent/EP3883709A1/fr active Pending
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JP2000144393A (ja) * | 1998-10-30 | 2000-05-26 | Dowa Mining Co Ltd | Itoスパッタリングターゲットとその製造方法 |
JP2000233299A (ja) * | 1999-02-12 | 2000-08-29 | Dowa Mining Co Ltd | プレス成形用構造体及び成形方法 |
EP1292413B1 (fr) | 2000-06-20 | 2006-06-21 | Honeywell International Inc. | Composition de moulage, en particulier par injection |
EP1534461B1 (fr) | 2002-07-23 | 2010-06-16 | University Of Southern California | Fabrication de pieces metalliques par inhibition selective du frittage |
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DE102016209127A1 (de) * | 2016-05-25 | 2017-11-30 | Robert Bosch Gmbh | Verfahren und Vorrichtung zum Erzeugen eines Formkörpers |
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CN113909490A (zh) * | 2021-09-10 | 2022-01-11 | 华中科技大学 | 一种金属零件及其近净成形方法 |
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DE102018129162A1 (de) | 2020-05-20 |
EP3883709A1 (fr) | 2021-09-29 |
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