EP3559319A1 - Surface grisâtre aux fins d'un chauffage raccourci - Google Patents

Surface grisâtre aux fins d'un chauffage raccourci

Info

Publication number
EP3559319A1
EP3559319A1 EP17828671.2A EP17828671A EP3559319A1 EP 3559319 A1 EP3559319 A1 EP 3559319A1 EP 17828671 A EP17828671 A EP 17828671A EP 3559319 A1 EP3559319 A1 EP 3559319A1
Authority
EP
European Patent Office
Prior art keywords
protective coating
steel substrate
modified
stage
range
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.)
Withdrawn
Application number
EP17828671.2A
Other languages
German (de)
English (en)
Inventor
Maria KÖYER
Sascha Sikora
Florian Rollbusch
Thomas Wälte
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
ThyssenKrupp AG
Original Assignee
ThyssenKrupp Steel Europe AG
ThyssenKrupp 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, ThyssenKrupp AG filed Critical ThyssenKrupp Steel Europe AG
Publication of EP3559319A1 publication Critical patent/EP3559319A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/62—Quenching devices
    • C21D1/673—Quenching devices for die quenching
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/30—Acidic compositions for etching other metallic material
    • 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
    • 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
    • C25D5/08—Electroplating with moving electrolyte e.g. jet electroplating
    • 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
    • C25D5/50—After-treatment of electroplated surfaces by heat-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
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • 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
    • 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
    • C25D7/0642—Anodes

Definitions

  • the present invention relates to a method for producing a steel substrate having a modified Zn protective coating and to the steel substrate produced by the method according to the invention, which is provided for forming into a component by hot press molding. Furthermore, the present invention relates to a method for producing a component made of a modified Zn protective coating steel substrate. Moreover, the present invention relates to the use of the steel substrate according to the invention for producing a component.
  • steel blanks which have been cut in advance by a cold or hot rolled steel strip are heated to a deformation temperature generally above the austenitizing temperature of the respective steel and placed in a mold of a forming press in the heated state.
  • the steel plate on the one hand receives the desired shape and, on the other hand, undergoes rapid cooling due to the contact with the cool tool, so that a hardened structure is produced in the component.
  • a steel substrate is first provided for producing a steel substrate with a modified Zn protective coating.
  • the steel substrate is a steel strip, a steel sheet or a board obtained therefrom.
  • the steel is a hot-press hardenable steel known as "22MnB5.”
  • the application of a zinc protective coating is by electrolysis.An electrolytic process can be used to uniformly thin and very pure zinc layers
  • a layer thickness of the Zn protective coating is preferably in the range from 2 to 30 ⁇ m, more preferably in the range from 1 to 10 ⁇ m, preferably a thickness of the zinc protective coating is ensured. most preferably applied in the range of 1.5 to 4.5 ⁇ .
  • the electrolytic galvanizing is preferably carried out as a continuous coil coating process.
  • the surface of the Zn protective coating steel substrate is modified by means of an acidic solution, so that a provided with a modified Zn protective coating steel substrate is obtained.
  • the surface structure of the resulting steel component is generated inline next to the coating process and thus does not have to be laboriously produced in a further step, for example in the form of an additional layer.
  • the steel substrate for applying the Zn protective coating is passed through a plurality of electrolysis cells, each electrolysis cell consisting of at least two anode half cells.
  • the anode half cells can be aligned in such a way that the steel substrate is fed horizontally and / or vertically to it and passes through it.
  • an electrolyte flow of 200 to 600 L / min and a belt speed of 20 to 100 m / min are set to apply the Zn protective coating.
  • a belt speed of 40 to 60 m / min is set.
  • the Zn protective coating is applied at a temperature in the range of 40 to 60 ° C and at a pH in the range of 0.7 to 2.5. More preferably, the Zn protective coating is applied at a temperature in the range of 45 to 55 ° C and at a pH in the range of 0.7 to 2.5. In another preferred variant, the Zn protective coating is applied at a temperature in the range from 40 to 60 ° C. and at a pH in the range from 1.2 to 1.3. Most preferably, the Zn protective coating is applied at a temperature in the range of 45 to 55 ° C and at a pH in the range of 1.2 to 1.3.
  • the Zn protective coating is applied on one or two sides.
  • an electrolyte flow rate of 200 to 600 L / min, more preferably 300 to 500 L / min, most preferably 300 to 350 L / min.
  • two different electrolyte flows are set.
  • an electrolyte flow of 300 to 500 L / min, more preferably 300 to 400 L / min is set above the continuous steel substrate, and below the continuous steel substrate, an electrolyte flow of 600 to 400 L / min, more preferably 400 to 500 rpm.
  • the electrolytic coating is carried out in such a way that the zinc coating is applied with different layer thicknesses per steel substrate side. In addition to the possibility of performing the coating on one or two sides, this allows a needs-based adjustment of the zinc coating.
  • the steel substrate provided with a Zn protective coating is first passed through a first stage containing a first acidic solution and then through a second stage containing a second acidic solution.
  • the pH in the second stage is smaller by a factor of 0.5 to 0.7 than in the first stage. More preferably, the second stage pH is 0.7-0.9.
  • the modification in the second stage is carried out at a temperature in the range of 15 to 40 ° C, more preferably in the range of 15 to 25 ° C.
  • At least one of the electrolysis cells is ambivalent.
  • this electrolysis cell preferably in the first half-cell arranged in the strip running direction, a coating process takes place in accordance with the process parameters mentioned for the coating process.
  • the galvanized surface is modified.
  • the ambivalent electrolysis cell is arranged in the strip running direction as the last electrolytic cell in the continuous electrolysis apparatus.
  • the continuous electrolysis apparatus may contain one or more further ambivalent electrolysis cells.
  • the modification preferably takes place in that the second half cell is de-energized.
  • the galvanized steel substrate is exposed to an acidic environment so that the steel substrate provided with the Zn protective coating is modified.
  • a smaller electrolyte flow rate is set for this half cell.
  • the electrolyte flow rate in the second half-cell of the ambivalent electrolysis cell is preferably reduced by a factor of 0.1 to 0.15 in relation to the electrolyte flow rate of the remaining half-cells preceding in the strip running direction.
  • the entire electrolytic cell or even several whole electrolytic cell can be used to modify the surface.
  • the first stage preferably the last half cell in the strip running direction
  • the second stage preferably an acid washing stage, arranged in the strip running direction.
  • the steel substrate according to the invention provided with a modified Zn protective coating can, if it is designed as a steel strip, then be wound into coils and transported for further processing. The further process steps required for producing a component from the steel substrate according to the invention can be carried out spatially and temporally separately.
  • the present invention relates to a steel substrate having a modified Zn protective coating prepared by the method of the invention.
  • the steel substrate provided with a modified Zn protective coating produced by the process according to the invention has a surface roughness R t in the range from 20 to 60 ⁇ m, more preferably from 30 to 40 ⁇ m.
  • the present invention relates to a method for producing a component from a modified Zn-protective coated steel substrate, comprising the following steps: providing the modified Zn protective cover according to the invention steel substrate,
  • Forming the steel substrate in a forming tool to form a component Forming the steel substrate in a forming tool to form a component.
  • the improved heat radiation absorption of the modified Zn protective coating provided steel substrate has also surprisingly been found that the heating of the steel substrate to the first temperature range is faster, so that a higher throughput in hot working is possible.
  • the steel substrate provided with the modified Zn protective coating is heated to a temperature range of 850 to 900 ° C, more preferably to a temperature range of 870 to 890 ° C.
  • the steel substrate provided with a modified Zn protective coating is converted to the desired component by so-called direct hot forming
  • the invention provided with a modified Zn protective coating steel substrate is first cold formed, heated in a next step to the Austenitmaschinestemperatur and then transferred ge state by rapid cooling in the temper or hardened state.
  • the steel substrate provided with the modified Zn protective coating is heated to the austenitizing temperature and briefly cooled before the subsequent hot working.
  • the present invention also relates to the use of the modified Zn protective coating according to the invention steel substrate for the production of a component, in particular a body part for a motor vehicle.
  • Figure 1 is a SEM image of the surface of a provided with a zinc protective coating
  • Figure 2 is an SEM photograph of the surface of a manganese-boron steel substrate provided with a modified zinc protective coating
  • Figure 3 is a graph showing the heating curves of a zinc-coated protective over a manganese-boron steel substrate provided with a modified zinc protective coating.
  • FIG. 1 shows a SEM image of a surface of an electrolytically galvanized manganese-boron steel substrate.
  • the 5000x magnification shows a surface structure with elongated, smooth terraced gradations.
  • the determination of the surface roughness by means of white light interferometry gave an R r value of 26 ⁇ .
  • FIG. 2 shows a SEM image of a modified surface of an electrolytically galvanized manganese-boron steel substrate.
  • the 5000x magnification in comparison to FIG. 1, shows a diffuse surface structure with several larger depressions (represented by the dark regions).
  • the determination of the surface roughness by means of the white light interferometry gave an R r value of 38 ⁇ .
  • Figure 3 shows the heating curves of a manganese-boron steel substrate sample having an electrolytically galvanized (unmodified) surface versus a modified electrolytically galvanized surface.
  • the modified surface surprisingly shows a shorter heating time compared to an unmodified surface.
  • 120 s are required instead of 150 s, which results in a time saving of approx. 20% corresponds.
  • Example 1 An annealed cold strip (steel flat product) grade 22MnB5 (1.5528) pretreated for electrolysis was fed to a continuous electrolysis apparatus.
  • the continuous electrolyzer comprises 20 horizontally oriented half-cells, each of the 20 half-cells again having an anode above and below the passing flat steel product. Furthermore, each of the 20 half cells has an electrolyte inlet arranged above and below the continuous flat steel product, through which the electrolyte is supplied to the half cell.
  • the following operating parameters were set for the coating according to the invention. For half cells 1 to 19:
  • Electrolyte flow rate 300 - 500 L / min top
  • Electrolyte flow rate 300 - 500 L / min top
  • the steel flat product emerging from the continuous electrolysis apparatus was then fed in accordance with the invention to an acid washing stage arranged directly on the last half cell.
  • the following operating parameters were set for the coating according to the invention:
  • the provided with a modified 4 ⁇ thick Zn protective coating steel substrate was rinsed with water at a temperature in the range of 15 to 40 ° C and fed to a drying section.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

L'invention concerne un procédé servant à fabriquer un substrat en acier comprenant un revêtement de protection de Zn modifié. Le procédé comprend les étapes qui suivent consistant : - à fournir un substrat en acier ; - à appliquer un revêtement de protection de Zn au moyen d'une électrolyse de manière à obtenir un substrat en acier pourvu d'un revêtement de protection de Zn ; - à modifier la surface au moyen d'un solution contenant un acide de manière à obtenir un substrat en acier pourvu d'un revêtement de protection de Zn modifié.
EP17828671.2A 2016-12-20 2017-12-13 Surface grisâtre aux fins d'un chauffage raccourci Withdrawn EP3559319A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102016225681.5A DE102016225681A1 (de) 2016-12-20 2016-12-20 Vergraute Oberfläche zum Zwecke einer verkürzten Aufheizung
PCT/EP2017/082532 WO2018114498A1 (fr) 2016-12-20 2017-12-13 Surface grisâtre aux fins d'un chauffage raccourci

Publications (1)

Publication Number Publication Date
EP3559319A1 true EP3559319A1 (fr) 2019-10-30

Family

ID=60954996

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17828671.2A Withdrawn EP3559319A1 (fr) 2016-12-20 2017-12-13 Surface grisâtre aux fins d'un chauffage raccourci

Country Status (4)

Country Link
EP (1) EP3559319A1 (fr)
CN (1) CN109661482A (fr)
DE (1) DE102016225681A1 (fr)
WO (1) WO2018114498A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022091480A1 (fr) * 2020-10-28 2022-05-05 Ｊｆｅスチール株式会社 Élément pressé à chaud et tôle d'acier pour pressage à chaud, et procédé de fabrication pour élément pressé à chaud

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5617438B2 (fr) * 1972-02-12 1981-04-22
JPS63307297A (ja) * 1987-06-09 1988-12-14 Sumitomo Metal Ind Ltd 自動車用防錆鋼板の製造方法
US5015341A (en) * 1988-08-05 1991-05-14 Armco Steel Company, L.P. Induction galvannealed electroplated steel strip
EP2096193B1 (fr) * 2008-02-21 2013-04-03 Atotech Deutschland GmbH Procédé de préparation de pièces linéaires ou complexes, résistantes à la corrosion plaquées en zinc et en zinc-nickel
ES2384135T3 (es) * 2009-08-25 2012-06-29 Thyssenkrupp Steel Europe Ag Procedimiento para fabricar un componente de acero provisto de un recubrimiento metálico de protección contra la corrosión y componente de acero
DE102011001140A1 (de) * 2011-03-08 2012-09-13 Thyssenkrupp Steel Europe Ag Stahlflachprodukt, Verfahren zum Herstellen eines Stahlflachprodukts und Verfahren zum Herstellen eines Bauteils
EP2848715B1 (fr) * 2013-09-13 2018-10-31 ThyssenKrupp Steel Europe AG Procédé de fabrication d'un composant en acier revêtu d'une coiffe métallique protégeant de la corrosion
JP6211908B2 (ja) * 2013-12-02 2017-10-11 トヨタ自動車株式会社 ホットスタンプ成形品の製造方法
CA2961508C (fr) * 2014-09-18 2024-04-09 Modumetal, Inc. Procede et appareil d'application en continu de revetements metalliques nanostratifies

Also Published As

Publication number Publication date
CN109661482A (zh) 2019-04-19
WO2018114498A1 (fr) 2018-06-28
DE102016225681A1 (de) 2018-06-21

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