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EP4029973A2 - Procédé de fabrication d'une tôle d'acier revêtue de manière électrolytique - Google Patents

Procédé de fabrication d'une tôle d'acier revêtue de manière électrolytique Download PDF

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Publication number
EP4029973A2
EP4029973A2 EP22150305.5A EP22150305A EP4029973A2 EP 4029973 A2 EP4029973 A2 EP 4029973A2 EP 22150305 A EP22150305 A EP 22150305A EP 4029973 A2 EP4029973 A2 EP 4029973A2
Authority
EP
European Patent Office
Prior art keywords
steel sheet
coated steel
target temperature
heat treatment
holding time
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
Application number
EP22150305.5A
Other languages
German (de)
English (en)
Other versions
EP4029973A3 (fr
Inventor
Oliver Moll
Franz Hinte
Frank Panter
André Samusch
Marc Blumenau
Jörg STEINEBRUNNER
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 EP4029973A2 publication Critical patent/EP4029973A2/fr
Publication of EP4029973A3 publication Critical patent/EP4029973A3/fr
Pending legal-status Critical Current

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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
    • 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
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
    • 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
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/22—Servicing or operating apparatus or multistep processes

Definitions

  • the invention relates to a method for producing an electrolytically coated steel sheet, the method comprising the following steps: - providing a steel sheet; - Electrolytic coating of the steel sheet.
  • Coated steel sheets are formed into components in vehicle construction, which are usually fed to a painting process after shaping, often cathodic dip painting (KTL), which after dip painting requires heat treatment between 160 and 180°C for approx. 20 minutes to bake the paint is downstream.
  • KTL cathodic dip painting
  • Painted components formed from electrolytically coated sheet steel have been found to have scratches on the paintwork, which are presumably caused by outgassing as a result of the temperature effect in the painting process and, as a result, the surface defects and the qualitatively unacceptable appearance mean that the affected components have to be scrapped or costly to rework would lead. There is therefore a need for optimization with regard to the electrolytically coated steel sheets.
  • the invention is therefore based on the object of providing a method for producing an electrolytically coated steel sheet, with which the aforementioned disadvantages can be essentially avoided or at least significantly reduced.
  • the method for producing an electrolytically coated steel sheet comprises: providing a steel sheet; Electrolytic plating of the steel sheet, additionally the step that after the electrolytic plating, the plated steel sheet undergoes a heat treatment, wherein the plated steel sheet is heated to a target temperature between 60°C and 400°C and for a holding time between 0.10s and 300s target temperature is maintained.
  • the electrolytically coated steel sheet is subjected to a heat treatment, so that the heat treatment, if present, recombines gaseous hydrogen in the steel sheet and can thus generate a high pressure, which allows the gas to pass through and thus escape through the closed electrolytically applied coating allows.
  • other gaseous and/or liquid components that are present and embedded in the steel sheet can also escape or be expelled as a result of the heat treatment.
  • These gaseous and/or liquid components were incorporated into the steel/base material or its near-surface structure during the preliminary stages of sheet steel production, e.g. during a pickling or annealing process. This effectively causes outgassing, which can no longer lead to paint irritation or surface defects in the painted state in the later painting process.
  • the heat treatment according to the invention therefore does not correspond to the heat treatment in the painting process.
  • electrolytic coating primarily means the deposition of a coating of zinc (ZE) or a zinc alloy, for example zinc-nickel, which can optionally be optimized with an organic top layer in the form of phosphating and/or chromating.
  • ZE zinc
  • zinc alloy for example zinc-nickel
  • Steel sheet is to be understood as a hot- or cold-rolled steel sheet which, in the planar undeformed state, can be provided in sheet form as a steel sheet blank or in strip form as a steel strip.
  • a cold-rolled and, in particular, recrystallization-annealed steel strip is preferably provided as the steel sheet.
  • the thickness of the steel sheet can be between 0.3 and 4 mm.
  • the thickness is in particular at least 0.4 mm, preferably at least 0.5 mm and is in particular limited to a maximum of 3.5 mm, preferably to a maximum of 3 mm.
  • the thickness of the electrolytic coating can be between 1.5 ⁇ m and 15 ⁇ m (per side).
  • the electrolytic coating of steel sheets, in particular steel strips, is state of the art.
  • the steel sheets can be electrolytically coated on one or both sides, depending on the requirements.
  • Zinc-based coatings are preferably used, which ensure a certain degree of cathodic corrosion protection for the steel sheet.
  • Such coatings are also known in the art under the designation "ZE” (zinc electrolytic) or "EG” (electrogalvanized) in English-speaking countries.
  • the steel sheets coated with ZE are also called “steel sheet” in professional circles. This includes all conceivable compositions of carbon steels which can be coated electrolytically and are preferably used in vehicle construction. This can include soft steels for cold forming according to DIN EN 10152, e.g. B.
  • high and higher strength steels for cold forming according to DIN EN 10268 e.g. B. high-strength IF steels such as HC180Y and higher, e.g. B. isotropic steels such as HC2201 and higher, e.g. B. Bake-hardening steels such as HC180B and higher, e.g. B. micro-alloyed steels such as HC260LA and higher; or multi-phase steels for cold forming according to DIN 10338, on the one hand cold-rolled, e.g. B. Dual phase steels such as HCT450X and higher, e.g. B. retained austenite steels such as HCT690T and higher, e.g. B.
  • complex-phase steels such as HCT600C and higher, or on the other hot-rolled, z.
  • Complex phase steels such as HDT760C and/or CP-W1000, e.g. g. martensite phase steels such as HDT1180G1, see also https://ucpcdn.thyssenkrupp.com/ legacy/UCPthyssenkruppBAMXProcessingEurope/assets.fi les/downloads/tkmpe electrolytically galvanized thin sheet de 20190807.pdf. This enumeration of the possible sheet steel grades and the associated composition of the carbon steels is not intended to be conclusive.
  • the selection of the target temperature and the selection of the holding time must be adapted to the composition (carbon steel) of the steel sheet in particular, so that aging processes in particular are essentially avoided during heat treatment .
  • the target temperature/holding time to be set optimally for the steel sheet used and in particular taking into account the available system technology can be verified either by "trial and error" tests or alternatively or additionally can also be set using specialist knowledge.
  • the target temperature and holding time are to be selected according to the invention in such a way that outgassing/diffusion takes place effectively, the mechanical properties of the steel/base material but not be changed. Furthermore, the target temperature and the holding time are to be selected in particular in such a way that preferably no alloying of the coating with the steel/base material can take place.
  • the target temperature is at least 80° C., in particular at least 100° C., preferably at least 130° C., preferably at least 150° C. and at most 350° C., in particular at most 300° C., preferably at most 280° C., preferably maximum 250 °C.
  • the holding time is at least 0.50 s, in particular at least 1.0 s, preferably at least 1.50 s, preferably at least 2.0 s and at most 200 s, in particular at most 100 s, preferably at most 50 s, preferably at most 30 s, more preferably at most 20 s.
  • the heating to the target temperature can be carried out inductively, in a continuous furnace or by means of radiation sources, depending on the existing system concept and/or installation space.
  • the heating is preferably carried out inductively, for example by means of inductors, which can set a heat pulse in a targeted manner or can be controlled accordingly in order to heat the coated steel sheet relatively quickly.
  • inductive heating heating rates of at least 20 K/s, in particular at least 50 K/s, preferably at least 80 K/s, can be achieved, as a result of which the installation space can be selected to be relatively small, preferably when the heat treatment is considered inline in the process direction, is carried out after the electrolytic plating.
  • the heat treatment is preferably carried out inline as a post-treatment of a continuous electrolytic coating of steel strips.
  • the target temperature can be maintained, for example, within an enclosure through which the heated, coated steel sheet is passed. Holding can thus preferably take place in a continuous furnace.
  • the coated steel sheet is moved in the process direction during the heating, with the coated steel sheet being homogeneously heated transversely to the process direction.
  • Homogeneous heating viewed transversely to the process direction means that over the (entire) width of the coated steel sheet, if possible, no and only small temperature differences/differences are permitted during the heat treatment in order to ensure essentially "full-surface” outgassing over the entire surface of the coated steel sheet .
  • the coated steel sheet is actively cooled after the holding time.
  • Active cooling means that the still warm coated steel sheet is cooled in a targeted manner with suitable means, for example with known and common means that can bring about cooling, for example with a cooling rate of at least 5 K/s, in particular of at least 10 K/s, preferably at least 20 K/s.
  • suitable means for example with known and common means that can bring about cooling, for example with a cooling rate of at least 5 K/s, in particular of at least 10 K/s, preferably at least 20 K/s.
  • the steel sheet is heat-treated inline after the electrolytic coating, it may be that the steel sheet should be cooled to a maximum temperature of 120 °C, in particular a maximum of 100 °C, in order to avoid other components in the process chain that are in contact with the still warm sheet steel, not to be thermally stressed.
  • a steel sheet (1) has been provided in the form of a steel strip, which has been conventionally electrolytically coated or electrolytically galvanized in the opposite direction of the process, not shown, and in the process direction (P) a heat treatment (10th ) is supplied.
  • the electrolytic coated steel sheet (1) may be further phosphated and/or chromated before or after the heat treatment of the present invention.
  • a phosphating and/or chromating to increase the paint adhesion and/or the corrosion resistance is not relevant for the implementation of the heat treatment according to the invention and is therefore not discussed further here.
  • the coated steel sheet (1) undergoes a heat treatment (10) after the electrolytic coating Example inline in process direction (P) after electrolytic coating.
  • the coated steel sheet (1) is heated to a target temperature (T z ) of between 60° C. and 400° C. and held at the target temperature (Tz) for a holding time (tH) of between 0.10 s and 300 s.
  • the heating (11) to the target temperature (Tz) is preferably carried out inductively, since the coated steel sheet (1) moved and coated in the process direction (P) is targeted and rapid, in particular by arranging an inductor (not shown) above and/or below the coated steel sheet (1).
  • a homogeneous heating (11) transverse to the process direction (P) and thus over the (entire) width of the steel sheet (1) can also be ensured.
  • a continuous furnace or a radiation source, not shown, can also be considered for the heating (11).
  • active cooling (13) can take place so that the still warm coated steel sheet (1) cannot have any negative thermal influences on the downstream components inline in the process chain. Active cooling (13) allows the temperature of the coated steel sheet (1) undergoing the heat treatment (10) to be reduced to a maximum of 120° C., for example. After the heat treatment (10) according to the invention, the coated steel sheet (1) can be subjected to further processing steps.
  • FIG 1 a sketched temperature profile of an electrolytically coated steel sheet (1) heat-treated according to the invention in a time (t)-temperature (T) diagram.
  • the temperature profile can be specified or defined individually and depending on the composition of the steel sheet as well as the existing system concept.
  • the heat treatment can also take place offline.
  • the deposited coating may have a more columnar or plate-like crystal structure.
  • the method according to the invention is shown in tests to be independent of the morphology of the coating. Even in the case of a plate-shaped crystal structure with the associated lower porosity, which in particular does not favor outgassing, the task of the invention can still be achieved when the heat treatment is carried out according to the invention.
  • Tests were carried out on electrolytically galvanized steel sheets (1).
  • two steel strips were provided as steel sheet (1), each an identical cold-rolled bake-hardening steel with a thickness of 0.8 mm, which were electrolytically galvanized on both sides with the same parameters with a thickness of 5 ⁇ m per side.
  • the first steel sheet was further processed conventionally as a reference.
  • the second steel sheet (1) was inline, analogous to the outlined figure 1 , fed after the electrolytic coating of a heat treatment (10).
  • the heating (11) took place on both sides via an inductor arranged across the width above and below the steel sheet (1), which in each case applied the second steel sheet (1) at a heating rate of 200 K/s and to a target temperature (Tz) of 220 °C warmed up.
  • the holding time (tH) was 4.50 s at 220°C and the holding was done in a continuous furnace (12) to maintain the target temperature (T z ) of 220°C.
  • the hot coated steel sheet (1) Downstream of the holding zone (12) in the process direction (P), the hot coated steel sheet (1) was actively cooled using a water spray (13) and the hot coated steel sheet (1) was cooled to 70 °C at a cooling rate of 120 K/ s cooled down so that it could be further processed without thermally negatively influencing the other components in the process chain.
  • the number of faults caused by outgassing in the KTL process in the reference samples based on 600 cm 2 was determined as follows for all samples: over 5000 holes and over 100 pustules.
  • the defect pattern in the samples from the second steel sheet (1) based on 600 cm 2 was determined as follows for all samples: under 50 holes and under 15 pustules.
  • the features described can all be combined with one another as far as technically possible.
  • the invention does not have to be carried out inline on a steel strip, but rather it can also be carried out on sheet-like steel sheet blanks before these are further processed. It has also been shown within the scope of the invention that the heat treatment does not necessarily have to include outgassing/effusion of the entire steel/base material. On the other hand, it is sufficient to expel the gaseous and/or liquid components in a near-surface area, for example up to 20 ⁇ m, of the steel/base material, which typically also contains the inclusions from the preliminary stages of sheet steel production, in order to meet the requirements.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Laminated Bodies (AREA)
EP22150305.5A 2021-01-13 2022-01-05 Procédé de fabrication d'une tôle d'acier revêtue de manière électrolytique Pending EP4029973A3 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102021200229.3A DE102021200229A1 (de) 2021-01-13 2021-01-13 Verfahren zur Herstellung eines elektrolytisch beschichteten Stahlblechs

Publications (2)

Publication Number Publication Date
EP4029973A2 true EP4029973A2 (fr) 2022-07-20
EP4029973A3 EP4029973A3 (fr) 2022-09-28

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Application Number Title Priority Date Filing Date
EP22150305.5A Pending EP4029973A3 (fr) 2021-01-13 2022-01-05 Procédé de fabrication d'une tôle d'acier revêtue de manière électrolytique

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EP (1) EP4029973A3 (fr)
DE (1) DE102021200229A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4508601A (en) * 1982-09-07 1985-04-02 Toyo Kohan Co., Ltd. Process for producing a thin tin and zinc plated steel sheet

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2157319A (en) * 1984-04-13 1985-10-23 Toyo Kohan Co Ltd Tin free steel and its production
DE10257737B3 (de) 2002-12-10 2004-02-26 Thyssenkrupp Stahl Ag Verfahren zur elektrolytischen Magnesium-Abscheidung auf verzinktem Blech
DE102008004728A1 (de) * 2008-01-16 2009-07-23 Henkel Ag & Co. Kgaa Phosphatiertes Stahlblech sowie Verfahren zur Herstellung eines solchen Blechs
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
DE102013010025A1 (de) * 2013-06-17 2014-12-18 Muhr Und Bender Kg Verfahren zum Herstellen eines Erzeugnisses aus flexibel gewalztem Bandmaterial
DE102015113878B4 (de) 2015-08-21 2023-03-16 Thyssenkrupp Ag Verfahren zur thermischen Behandlung eines mit einer Konversionsschicht beschichteten Schwarzblechs

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4508601A (en) * 1982-09-07 1985-04-02 Toyo Kohan Co., Ltd. Process for producing a thin tin and zinc plated steel sheet

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Publication number Publication date
DE102021200229A1 (de) 2022-07-14
EP4029973A3 (fr) 2022-09-28

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