EP3997253B1 - Verfahren zum herstellen eines blechproduktes - Google Patents

Verfahren zum herstellen eines blechproduktes Download PDF

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Publication number
EP3997253B1
EP3997253B1 EP20737116.2A EP20737116A EP3997253B1 EP 3997253 B1 EP3997253 B1 EP 3997253B1 EP 20737116 A EP20737116 A EP 20737116A EP 3997253 B1 EP3997253 B1 EP 3997253B1
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EP
European Patent Office
Prior art keywords
sheet metal
depressions
product
rolled
coated
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.)
Active
Application number
EP20737116.2A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP3997253A1 (de
Inventor
Oliver Vogt
Benjamin LAUER
Stefan Wischmann
Sascha Sikora
Martin Koch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ThyssenKrupp Steel Europe AG
Original Assignee
ThyssenKrupp Steel Europe AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ThyssenKrupp Steel Europe AG filed Critical ThyssenKrupp Steel Europe AG
Publication of EP3997253A1 publication Critical patent/EP3997253A1/de
Application granted granted Critical
Publication of EP3997253B1 publication Critical patent/EP3997253B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/22—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length
    • B21B1/222—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length in a rolling-drawing process; in a multi-pass mill
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236—Cold rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils

Definitions

  • the present invention is based on a method for producing a sheet metal product, the sheet metal product being produced from a sheet metal pre-product by mechanical forming.
  • Sheet metal pre-products are usually further processed using mechanical forming processes such as deep drawing.
  • the forces introduced into the sheet metal material are transferred to the sheet metal pre-product via the sheet metal surface.
  • the geometry of the sheet metal product and the frictional forces occurring during the forming process between the sheet metal surface and the forming tool result in very high local stresses on the sheet metal surface. These local stresses, which are made up of normal and shear forces, can be subject to significant changes during forming. For an optimal forming result, it is necessary to be able to control the sheet metal flow during the forming process.
  • the sheet metal flow is controlled in particular by influencing the retention forces, which counteract the drawing force of the forming process. This influence occurs, for example, through additional lubrication with lubricants. This leads to a local reduction in frictional forces and thus to a reduction in restraining forces.
  • the retention forces can be increased, for example, by using drawbeads.
  • the functionality of the lubricants used is essentially determined by the additives added to the lubricant.
  • the additives can bring about the formation of a boundary layer, for example by adding polymer chains or by chemical reactions on the metallic surfaces of the forming tool and sheet metal product, and prevent direct contact between the surfaces of the forming tool and sheet metal product.
  • the bond between the polymer chains is based on van der Waals forces. Therefore, these can be moved comparatively easily against each other.
  • the bonding of the polymer chains to the surfaces of the forming tool and the sheet metal pre-product is based on a dipole bond.
  • the boundary layer is usually a few nanometers thin and can be easily detached from the surfaces of the forming tool and the sheet metal product.
  • the invention is therefore based on the technical task of providing a manufacturing method for sheet metal products which does not have the disadvantages of the prior art but instead offers effective lubrication during the forming of the sheet metal pre-product while at the same time using less lubricant.
  • This object is achieved by a method for producing a sheet metal product from a sheet metal pre-product, at least one surface of the sheet metal pre-product being coated with a coating, the sheet metal pre-product being rolled, depressions being rolled into the surface during rolling, with lubricant after the coating and rolling is introduced into the depressions, the sheet metal pre-product being mechanically formed with a forming tool after the introduction of lubricant, characterized in that that the surface is coated in such a way that the coating in the forming tool is elastically deformable under loads of 0.5 MPa to 20 MPa and plastically deformable under loads above 20 MPa during the forming process, in particular with relative movement between the sheet metal and tool surface.
  • the method according to the invention makes it possible for the lubricant in the depressions to be transported in a targeted manner as lubricant pockets to the critical areas of the forming tool.
  • the indentations enable the surface of the sheet metal pre-product to absorb the lubricant and to transport it largely without loss. Only under high loads, i.e. where the lubricant is needed to lubricate between the sheet metal pre-product and the forming tool, is it released locally through plastic deformation of the depressions.
  • Relative movements between the sheet metal pre-product and the forming tool occur during forming, such as deep drawing, in particular in the flange or support of the forming tool and on the drawing edge of the forming tool. These areas differ significantly in terms of the loads acting on the sheet metal pre-product. While in the flange or support there is a predominantly surface stress in the single-digit MPa range, very heavy loads occur on the drawing edge, which can be in the mid-double-digit MPa range and beyond. The indentations are plastically deformed in accordance with the locally occurring loads, releasing the lubricant. Due to the flow of sheet metal during forming, further depressions filled with lubricant are continuously conveyed into the areas with very high loads, so that these areas are constantly wetted with new lubricant.
  • the volumes of the depressions correspond to the required amount of lubricant. It is conceivable that the amount of lubricant required is between 0.5 g/mm 2 and 1 g/mm 2 . It is also conceivable that sheet metal blanks or sheet metal in strip form is provided as the sheet metal preliminary product. It is also conceivable that a skin-passing roll is used as the roll for rolling the indentations into the sheet metal pre-product, to which a geometric texture has been applied in particular using a laser texturing process. Any type of sheet metal forming is conceivable as mechanical forming of the sheet metal pre-product into a sheet metal product. Examples include bending, deep-drawing, twisting, pressing and stretch-forming. The coating is preferably between 1 ⁇ m and 30 ⁇ m, in particular between 2 ⁇ m and 15 ⁇ m, thick.
  • the surface is coated in such a way that the coating is elastically deformable in the forming tool during the forming process, in particular with relative movement between the sheet metal and tool surface, under loads of 0.5 MPa to 15 MPa and under loads is plastically deformable above 25 MPa.
  • the loads present in the forming tool are expressed as pressure, i.e. force per area, on the surface of the sheet metal pre-product.
  • a correspondingly favorable design of the indentations makes it possible to manipulate the surface on which the force acts. Accordingly, the deformability of the coating can be controlled in this way.
  • the depressions are rolled in as closed depressions in relation to a main extension plane of the sheet metal pre-product. This advantageously allows the lubricant to be transported safely and largely without loss. Due to the closed shape in relation to the main extension plane of the sheet metal pre-product, no lubricant can run out of the recess at the side. Furthermore, it is ensured in this way that the lubricant is released in the event of a plastic deformation of the depression and is not pressed away from the area of the plastic deformation along a non-closed depression.
  • the indentations are rolled in an I-shape, rectangular or square in relation to the main extension plane of the sheet metal pre-product. This results in trough-shaped depressions, for example. It has been shown that a very effective lubricant transport is possible in this way. However, it is also conceivable for the depressions to be round, oval, triangular or cross-shaped in relation to the main extension plane of the sheet metal pre-product.
  • the depressions are rolled in with a depth of 2 ⁇ m to 15 ⁇ m, preferably 2 ⁇ m to 10 ⁇ m and particularly preferably 2 ⁇ m to 5 ⁇ m. This enables the volume of the depressions to be adapted well to the required volume of lubricant.
  • the depth of the indentation in the sense of the present invention is the depth of the recess after the coating of the surface.
  • the depressions are rolled in with a ratio of depth to volume of the depression of 1:3 to 1:15 and preferably 1:5 to 1:10. A corresponding ratio also has a positive effect on the lubricant transport and the targeted local wetting with lubricant.
  • the volume of the depression in the context of the present invention is the volume of the depression after the surface has been coated.
  • indentations are rolled into at least 30% of the area of the surface of the sheet metal pre-product. This ensures that lubricant is actually transported everywhere where high loads in the forming tool make it necessary to introduce lubricant.
  • the depressions are rolled in such that a bottom of the depression has a smaller area than the projection of the depression onto the main plane of extension of the surface.
  • the depressions are rolled in, for example, in the form of a trough or bowl. This is particularly advantageous when the lubricant is released when the depression is deformed.
  • the angles between the walls of the depressions and the main extension plane of the surface With the angle between the walls of the depressions and the main extension plane of the surface, the changes in volume of the depressions due to the load can be adjusted in a targeted manner.
  • Correspondingly designed angles between the walls of the depressions and the main plane of extension of the surface have proven to be advantageous.
  • the coating is used as the coating.
  • Zinc is excellently suited as a cathodic anti-corrosion coating. If the zinc is processed accordingly, the yield point of the zinc is exceeded at the highly stressed points in the forming tool, which means that the lubricant is advantageously released in a targeted manner.
  • the sheet metal pre-product is coated by hot-dip galvanizing, with the sheet metal pre-product being coated before rolling (rolling in of the indentations). Hot-dip galvanizing is well mastered and already highly integrated into manufacturing processes.
  • the surface is preferably coated with a continuous coating, the coating not being punctured when the depressions are rolled in.
  • the sheet metal pre-product is coated electrolytically, the sheet metal pre-product being coated after rolling (rolling in of depressions).
  • the coatings follow the uncoated course of the surface to be coated very precisely. The coating can therefore be carried out after the depressions have been rolled in. This sequence enables a very even coating, even within the depressions.
  • the sheet metal pre-product 2 is provided as a strip (coil material) or blank and rolled with skin-pass rollers 3 .
  • the skin-pass rollers 3 roll trough-shaped indentations (see Figure 2 ) into the surface of the sheet metal pre-product 2.
  • the indentations are several micrometers deep, several micrometers long and wide, regularly arranged and are rolled into about 40% of the surface.
  • the tempering rollers 3 have been processed beforehand, preferably using a laser texturing method, in such a way that they have a corresponding negative for rolling in the depressions on their surface.
  • the negative has an elevation for each indentation, with the elevation being higher than the indentation rolled in by the elevation. This is due, among other things, to the fact that the skin-passing rolls 3 do not rest over their entire surface on the surface of the sheet metal product 2 during rolling, which would have negative effects on the rolling/skin-passing process.
  • a skin-pass liquid for example, is preferably introduced between the sheet metal product 2 and skin-pass roll 3 .
  • the surfaces are electrolytically coated with zinc to a thickness of about 7 ⁇ m in the coating system 4 .
  • the zinc layer follows the surface geometry of the underlying surface, in particular the rolled indentations.
  • the coating with zinc is carried out by means of hot-dip galvanizing. In this case, however, the coating would have to be carried out before the rolling/dress-passing, since a coating applied by hot-dip galvanizing follows the surface geometry of the underlying surface, in particular the rolled indentations, less well than electrolytic coating.
  • rolling in the indentations after hot-dip galvanizing would compensate for this disadvantage.
  • the lubricant 8.1 is now introduced into the depressions on the coated surface.
  • essentially only as much lubricant 8 is introduced as the depressions can hold.
  • the rolled and coated sheet metal pre-product 2 is cut to length from the strip to form a blank and then subjected to forming in a forming tool 5 . Deep drawing is shown here as an example of a possible form of forming.
  • the sheet metal pre-product 2 which is still in the form of a blank, is placed in the forming tool 5 . Outer edges of the sheet metal product 2 are held by hold-down devices 5.3 of the forming tool 5 on supports 5.4 of the forming tool 5, while the punch 5.1 presses the inner area of the sheet metal product 2 into the die 5.2. This creates loads acting on the sheet metal pre-product 2, including on the hold-down devices 5.3, on the supports 5.4 and on the stamp 5.1. These loads are in the single-digit MPa range.
  • Loads also act on the sheet metal pre-product 2 at the drawing edges 5.5.
  • the loads here are significantly higher and are in an area in which the coating is plastically deformed, the depressions are leveled and the lubricant 8.1 contained in the depressions is released for lubrication.
  • the flow of sheet metal from the supports 5.4 in the direction of the drawing edges 5.5 during the deep-drawing process repeatedly transports new depressions to the drawing edges 5.5, which are also leveled there by plastic deformation and release the lubricant 8.1 contained therein.
  • a continuous and very precisely targeted local lubrication is possible.
  • the person skilled in the art understands that the method according to the invention can also be used in other forming methods. Bending, twisting, spinning and stretch-forming are only mentioned as further examples, the examples mentioned not being a complete list of the possible forming processes.
  • FIG 2 a section of a sheet metal pre-product 2 according to an exemplary embodiment of the present invention is shown schematically.
  • a section orthogonal to the skin extension plane of the surface 7 of the sheet metal product 2 can be seen.
  • the regularly arranged indentations 6 are several micrometers deep and have the bottom 6.1 and the walls 6.2.
  • the walls 6.2 enclose an angle ⁇ with the main extension plane of the surface 7 of 110° to 120°.
  • figure 3 1 schematically shows a section of the surface 7 of a sheet metal pre-product 2 according to an exemplary embodiment of the present invention.
  • Recesses 6 can be seen, whose projections onto the main extension plane of the surface 7 are I-shaped.
  • the surface 7 has the depressions 6 on more than 30% of its area.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Shaping Metal By Deep-Drawing, Or The Like (AREA)
  • Metal Rolling (AREA)
  • Laminated Bodies (AREA)
  • Powder Metallurgy (AREA)
  • Mounting, Exchange, And Manufacturing Of Dies (AREA)
EP20737116.2A 2019-07-09 2020-07-02 Verfahren zum herstellen eines blechproduktes Active EP3997253B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102019118578.5A DE102019118578A1 (de) 2019-07-09 2019-07-09 Verfahren zum Herstellen eines Blechproduktes und Blechprodukt
PCT/EP2020/068623 WO2021004872A1 (de) 2019-07-09 2020-07-02 Verfahren zum herstellen eines blechproduktes und blechprodukt

Publications (2)

Publication Number Publication Date
EP3997253A1 EP3997253A1 (de) 2022-05-18
EP3997253B1 true EP3997253B1 (de) 2023-04-19

Family

ID=71523123

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20737116.2A Active EP3997253B1 (de) 2019-07-09 2020-07-02 Verfahren zum herstellen eines blechproduktes

Country Status (7)

Country Link
US (1) US20230279574A1 (pl)
EP (1) EP3997253B1 (pl)
CN (1) CN114080468B (pl)
DE (1) DE102019118578A1 (pl)
ES (1) ES2948492T3 (pl)
PL (1) PL3997253T3 (pl)
WO (1) WO2021004872A1 (pl)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102024107448A1 (de) 2024-03-15 2025-09-18 Thyssenkrupp Steel Europe Ag Verfahren zum Herstellen eines schmelztauchbeschichteten Kaltbands

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1651444A1 (ru) * 1987-02-05 1996-08-27 Московский автомеханический институт Способ изготовления деформирующего элемента протяжки
FR2805200B1 (fr) * 2000-02-18 2002-10-11 Usinor Tole composite stratifiee emboutissable et resistante a la chaleur
JP3854469B2 (ja) * 2000-03-31 2006-12-06 新日本製鐵株式会社 高耐食性を有し加工性に優れためっき鋼材およびその製造方法
SI2006037T1 (sl) * 2007-06-22 2010-12-31 Thyssenkrupp Steel Europe Ag Ploĺ äśat izdelek iz kovinskega materiala, zlasti jeklenega materiala, uporaba takega ploĺ äśatega izdelka ter valj in postopek za izdelavo takih ploĺ äśatih izdelkov
DE102010007840A1 (de) * 2010-02-11 2011-08-11 Wieland-Werke AG, 89079 Elektromechanisches Bauelement oder Gleitelement
CN101875059B (zh) * 2010-05-20 2013-02-13 宝钢集团上海二钢有限公司 一种制造ф5.0mm1860MPa超高强度热镀锌钢丝的方法
DE102012017703A1 (de) 2012-09-07 2014-03-13 Daetwyler Graphics Ag Flachprodukt aus Metallwerkstoff, insbesondere einem Stahlwerkstoff, Verwendung eines solchen Flachprodukts sowie Walze und Verfahren zur Herstellung solcher Flachprodukte
DE102013100730B3 (de) * 2013-01-25 2014-06-05 Thyssenkrupp Rasselstein Gmbh Verfahren und Vorrichtung zum Herstellen von verzinktem Fein- oder Feinstblech mit hoher Korrosionsbeständigkeit sowie Verwendung des verzinkten Fein- oder Feinstblechs
BR112017007273B1 (pt) * 2014-10-09 2021-03-09 Thyssenkrupp Steel Europe Ag produto de aço plano laminado a frio e recozido, recristalizado, e método para a fabricação de um produto de aço plano formado

Also Published As

Publication number Publication date
CN114080468A (zh) 2022-02-22
DE102019118578A1 (de) 2021-01-14
CN114080468B (zh) 2024-03-15
ES2948492T3 (es) 2023-09-13
PL3997253T3 (pl) 2023-09-04
WO2021004872A1 (de) 2021-01-14
EP3997253A1 (de) 2022-05-18
US20230279574A1 (en) 2023-09-07

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