EP2802682B1 - Verwendung einer lösung mit sulfationen zur verringerung des schwärzens oder anlaufens eines metallbleches während der lagerung und mit einer solchen lösung behandeltes metallblech - Google Patents

Verwendung einer lösung mit sulfationen zur verringerung des schwärzens oder anlaufens eines metallbleches während der lagerung und mit einer solchen lösung behandeltes metallblech Download PDF

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EP2802682B1
EP2802682B1 EP12705147.2A EP12705147A EP2802682B1 EP 2802682 B1 EP2802682 B1 EP 2802682B1 EP 12705147 A EP12705147 A EP 12705147A EP 2802682 B1 EP2802682 B1 EP 2802682B1
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Prior art keywords
zinc
coating
use according
ions
treatment solution
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EP12705147.2A
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English (en)
French (fr)
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EP2802682A1 (de
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Daniel Chaleix
Christian Allely
Maxime Monnoyer
Pascale FELTIN
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ArcelorMittal SA
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ArcelorMittal SA
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Priority to HUE12705147A priority Critical patent/HUE051070T2/hu
Priority to PL12705147T priority patent/PL2802682T3/pl
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    • 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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical 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
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
    • 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
    • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/53—Treatment of zinc 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
    • 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
    • C23C22/68—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 solutions with pH between 6 and 8
    • 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
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/1266—O, S, or organic compound in metal component

Definitions

  • the present invention relates to a sheet comprising a steel substrate coated on at least one of its faces with a coating comprising zinc and magnesium.
  • Such sheets are more particularly intended for the manufacture of parts for the automobile, without however being limited thereto.
  • Coatings comprising essentially zinc are traditionally used for their good protection against corrosion, whether in the automotive sector or in construction, for example. However, these coatings cause weldability problems and are now in competition with coatings comprising zinc and magnesium.
  • magnesium clearly increases the resistance to perforating corrosion of these coatings, which can make it possible to reduce their thickness and therefore improve their weldability or even to maintain the coating thickness and increase the guarantee of protection against corrosion over time.
  • the improvement in corrosion resistance is such that it is now possible to reduce or even eliminate the use of secondary protective measures such as the use of waxes or sealants in places most susceptible to damage. 'be corroded.
  • the coils of sheets with such surface coatings can sometimes stay in storage sheds for several months and must not see this surface deteriorate by the appearance of surface corrosion, before being put into storage. form by the end user.
  • no initiation of corrosion must appear whatever the storage environment, even in the event of exposure to the sun and / or to a humid or even saline environment.
  • Standard galvanized products that is to say those whose coatings mainly comprise zinc, are also subject to these stresses and are coated with a protective oil which is generally sufficient.
  • the present inventors have observed that, in the event of dewetting of the protective oil, the coatings comprising zinc and magnesium exhibit, during storage, a slight surface oxidation which modifies the interaction of light with the surface and which therefore modifies its visual appearance.
  • He is known to WO2005 / 071140 to use an aqueous treatment solution containing sulphate ions at a concentration greater than or equal to 0.01 mol / l on a galvanized steel sheet in order to reduce the degradation of the coating during the forming of the sheet.
  • the invention relates to a use according to claim 1.
  • Sheet 1 of the figure 1 comprises a substrate 3 made of steel, preferably hot rolled and then cold rolled, and is for example coiled so as to be able to be used subsequently as a body part for the automobile.
  • the invention is not however limited to this field and can find a use for any steel part whatever its end use.
  • the sheet 1 will then be unwound from the coil then cut and shaped to constitute a part.
  • the substrate 3 is covered on one side 5 by a coating 7.
  • a coating 7 can be present on both sides of the substrate 3.
  • the coating 7 comprises at least one layer 9 based on zinc.
  • Layer 9 preferably comprises 0.1 to 20% by weight of magnesium.
  • This layer 9 generally has a thickness less than or equal to 20 ⁇ m and aims to protect the substrate 3 against perforating corrosion, in a conventional manner. It will be observed that the relative thicknesses of the substrate 3 and of the various layers covering it have not been observed on the figure 1 in order to facilitate representation.
  • Layer 9 comprises at least 0.1% by weight of magnesium because no effect of protection against perforating corrosion is visible below.
  • layer 9 contains at least 0.5%, preferably at least 2% by weight of magnesium.
  • the magnesium content is limited to 20% by weight in the layer 9 because it has been observed that a greater proportion would lead to too rapid consumption of the coating 7 and therefore paradoxically degraded anticorrosion performance.
  • Layer 9 can in particular be obtained by a vacuum deposition process, such as magnetron sputtering, or vacuum evaporation by Joule effect, by induction or under an electron beam.
  • a vacuum deposition process such as magnetron sputtering, or vacuum evaporation by Joule effect, by induction or under an electron beam.
  • layer 9 generally only comprises zinc and magnesium, other elements, such as aluminum or silicon, however, being able to be added, if necessary, to improve other characteristics of layer 9 such as its ductility or its adhesion to the substrate 3.
  • the layer 9 only comprises zinc and magnesium, it is particularly preferred that the layer 9 comprises between 14 and 18% by weight of magnesium, and better that it mainly corresponds to the intermetallic compound of formula Zn 2 Mg, comprising approximately 16% by weight of magnesium, which exhibits particularly good puncture corrosion resistance properties.
  • the coating 7 may comprise a layer 11 of zinc between the layer 9 and the face 5 of the substrate 3. This layer 11 may have been obtained for example by a vacuum deposition or electrodeposition process.
  • the layer 9 comprises zinc, magnesium and aluminum
  • the layer 9 comprises between 0.1 and 10% by weight of magnesium and between 0.1 and 20% by weight of aluminum. More preferably, layer 9 comprises between 2 and 4% by weight of magnesium and between 2 and 6% by weight of aluminum, and it is therefore close to the composition of the ternary zinc / aluminum / magnesium eutectic.
  • the layer 9 can be obtained by a hot dip coating process in a molten zinc bath containing magnesium up to a content of 10% by weight and aluminum up to a content of 20. % in weight.
  • the bath can also contain up to 0.3% by weight of optional addition elements such as Si, Sb, Pb, Ti, Ca, Mn, Sn, La, Ce, Cr, Ni, Zr or Bi.
  • the bath may finally contain residual elements originating from the feed ingots or resulting from the passage of the substrate 3 through the bath.
  • the coating 7 is covered with a layer 13 of temporary protection.
  • Layer 13 was obtained for example by application to coating 7, optionally after degreasing, of an aqueous treatment solution containing SO 4 2- sulfate ions at a concentration greater than or equal to 0.01 mol / l.
  • the layer 13 thus formed is based on zinc hydroxysulphate and zinc sulphate. It is both sufficiently thick and adherent.
  • the aqueous treatment solution is applied in a conventional manner, for example by dipping, by sprinkling or by coating.
  • the aqueous treatment solution also contains Zn 2+ ions at a concentration greater than or equal to 0.01 mol / l, which make it possible to obtain a more homogeneous deposit.
  • the aqueous treatment solution is prepared by dissolving zinc sulfate in pure water.
  • zinc sulfate heptahydrate ZnSO 4 , 7 H 2 O
  • the concentration of Zn 2+ ions is then equal to that of SO 4 2- anions.
  • the pH of the aqueous treatment solution preferably corresponds to the natural pH of the solution, without addition of base or acid.
  • the value of this pH is generally between 5 and 7.
  • the aqueous treatment solution is applied to the coating 7, under conditions of temperature, of contact time with the coating 7, of concentration of SO 4 2- ions and of Zn 2+ ions adjusted so that the layer 13 contains an amount of sulfur greater than or equal to 0.5 mg / m 2 .
  • the contact time of the aqueous treatment solution with the coating 7 is between 2 seconds and 2 minutes, and the temperature of the aqueous treatment solution is between 20 and 60 ° C.
  • the aqueous treatment solution used contains between 20 and 160 g / l of zinc sulfate heptahydrate, corresponding to a concentration of Zn 2+ ions and a concentration of SO 4 2- ions of between 0.07 and 0.55 mol / l.
  • the rate of deposition was little influenced by the value of the concentration.
  • the aqueous treatment solution is applied under conditions of temperature, of contact time with the coating 7, and of concentrations of SO 4 2- ions and of Zn 2+ ions adjusted to form a layer 13 having a quantity of sulfur. between 3.7 and 27 mg / m 2 .
  • the aqueous treatment solution contains an agent which oxidizes zinc, such as hydrogen peroxide.
  • This oxidizing agent can have a very marked accelerating effect of hydroxysulfation and sulfation at low concentration. It was found that the addition of only 0.03%, i.e. 8.10 -3 mol / liter of hydrogen peroxide, or 2.10 -4 mole / liter of potassium permanganate in the solution made it possible to (approximately) double the speed of deposit. It was observed, on the contrary, that concentrations 100 times higher no longer made it possible to obtain this improvement in the deposition rate.
  • the deposited layer 13 is adherent.
  • the drying is adjusted to remove residual liquid water from the deposit.
  • the sheet 1 is preferably rinsed so as to remove the soluble part of the deposit obtained.
  • the absence of rinsing and the obtaining of a deposit which is partially soluble in water which results therefrom is not very detrimental to the reduction in the degradation of the coating 7 during the subsequent shaping of the sheet 1, as long as that the deposit obtained does indeed include a layer 13 insoluble in water.
  • the aqueous treatment solution comprises a concentration of SO 4 2- ions greater than or equal to 0.01 mol / l and is applied under anodic polarization, and the pH of the aqueous solution of treatment is greater than or equal to 12, and less than 13.
  • the pH of the solution is less than 12, no adherent hydroxysulphates are formed on the surface to be treated. If the pH of the solution is greater than or equal to 13, the hydroxysulfate re-dissolves and / or decomposes into zinc hydroxides.
  • the sodium sulfate concentration is less than 1.42 g / l in the solution, little hydroxysulfate formation is observed on the surface.
  • This concentration is equivalent to 0.01 mol / l of SO 4 2- and, more generally, it is therefore important that the concentration of SO 4 2- ions is greater than or equal to 0.01 mol / l, and preferably greater or equal to 0.07 mol / l.
  • the concentration of sulfate ions is preferably less than or equal to 1 mole / liter.
  • concentrations greater than 142 g / l, for example 180 g / l at concentrations greater than 142 g / l, for example 180 g / l, a decrease in the yield of formation of the layer 13 is observed.
  • the total amount of hydroxysulfates and sulfates deposited should be greater than or equal to 0.5 mg / m 2 and less than or equal to 30 mg / m 2 in sulfur equivalent, preferably between 3.5 and 27 mg / m 2 in sulfur equivalent.
  • the charge density applied is preferably between 10 and 100 C / dm 2 of surface to be treated.
  • the layer 13 based on zinc hydroxysulfate and zinc sulfate under a high polarization current density, in particular greater than 20 A / dm 2 and, for example 200 A. / dm 2 .
  • a titanium cathode As a counter electrode, a titanium cathode can be used.
  • the temperature of the aqueous treatment solution is generally between 20 ° C and 60 ° C.
  • the procedure is carried out at a temperature greater than or equal to 40 ° C., so as to increase the conductivity of the solution and to reduce the ohmic losses.
  • the treated surface is rinsed thoroughly with demineralized water. This rinsing step makes it possible to remove the alkaline reagents on the surface of the deposit, which would cause corrosion problems.
  • This lubrication can be ensured by applying a film of oil (not shown) with a weight of less than 2 g / m 2 on layer 13.
  • a layer 13 makes it possible to improve the resistance to blackening in the case of a coating 7 comprising zinc. and magnesium, and improve the tarnish resistance in cases where the coating 7 includes zinc, magnesium and aluminum. This increased resistance is particularly useful in the absence of an oil film, for example following a dewetting of an oil film applied to the coating 7.
  • This increase in resistance to blackening and tarnishing is mainly due to the formation of a conversion layer based on zinc hydroxysulfate Zn 4 SO 4 (OH) 6 .
  • the presence of magnesium in coating 7 helps to stabilize the zinc hydroxysulphate layer over time and therefore to prevent its transformation into zinc carbonate under the effect of the CO 2 contained. in the air.
  • Zinc carbonates are indeed recognized to have a less protective power (less barrier) than zinc hydroxysulphates.
  • the proportion of altered surface is determined by visual inspection of an operator.
  • the figure 2A shows the visual appearance of a ZEMg test piece without a layer 13 after Quaker 6130 oiling as described above.
  • This test piece exhibits significant blackening making it unsuitable for use by French automobile manufacturers.
  • the ZEMg test pieces with layer 13 ( figures 2B to 2D ) and after oiling Quaker 6130 as described above still meet the requirements of French car manufacturers at the end of the test.
  • a ZnMg Full PVD test piece without layer 13 ( Fig. 3E ) after Fuchs oiling as described above does not meet the requirements of German car manufacturers, unlike a ZnMg Full PVD test tube with layer 13 ( Figure 3F ) after Fuchs oiling as described above.
  • the coating 7 only comprises a layer 9 of approximately 10 ⁇ m in thickness and comprising approximately 3% by weight of magnesium, approximately 3.7% by weight of aluminum, the remainder being zinc and the inevitable impurities.
  • the substrate 3 is then a cold rolled steel for deep drawing. These test pieces will be referred to as ZnMgAI hereafter.
  • the temporary protection of the ZnMgAI test pieces was evaluated via an aging test in natural exposure under shelter according to the VDA 230-213 standard (test duration 12 weeks). It has in fact been observed that the humidotherm test did not make it possible to reproduce the tarnishing phenomenon observed under natural storage conditions.
  • the ZnMgAI specimens were tested in the oiled state (Quaker 6130 film with a weight of approximately 1 g / m 2 ) and unoiled, with and without layer 13. For comparison, the same tests were carried out on specimens. from a standard galvanized sheet with a 10 ⁇ m thick zinc coating and a cold rolled steel substrate for deep drawing. These latter specimens will be referred to hereinafter as GI.
  • the evolution of the tarnish during the test was monitored using a colorimeter measuring the difference in luminance (measurement of ⁇ L *).
  • corresponding to the appearance of tarnish was set to 2.
  • the level of tarnishing reached by the ZnMgAI test pieces with layer 13 is equivalent to that of the oiled GI test pieces.

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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)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Laminated Bodies (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Prevention Of Electric Corrosion (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Claims (14)

  1. Anwendung einer wässrigen Behandlungslösung, die Sulfationen SO4 2- in einer Konzentration größer oder gleich 0,01 mol/l aufweist, zum Behandeln eines Blechs (1), das ein Stahlsubstrat (3) aufweist, das auf mindestens einer seiner Oberflächen (5) mit einer Beschichtung (7) beschichtet ist, die mindestens Zink und Magnesium aufweist, zum Reduzieren der Schwärzung oder der Trübung des Blechs (1) während seiner Lagerung in Abwesenheit von Öl für temporären Schutz.
  2. Anwendung gemäß Anspruch 1, wobei die Beschichtung (7) mindestens Zink, Magnesium und Aluminium aufweist.
  3. Anwendung gemäß Anspruch 1 oder 2, wobei der pH-Wert der wässrigen Behandlungslösung zwischen einschließlich 5 und 7 liegt.
  4. Anwendung gemäß einem der Ansprüche 1 bis 3, wobei die wässrige Behandlungslösung ferner Zn2+-Ionen in einer Konzentration größer oder gleich 0,01 mol/l aufweist.
  5. Anwendung gemäß Anspruch 4, wobei die Konzentration an Zn2+-Ionen und die Konzentration an SO4 2--Ionen zwischen einschließlich 0,07 und 0,55 mol/l in der wässrigen Behandlungslösung beträgt.
  6. Anwendung gemäß Anspruch 5, wobei die wässrige Behandlungslösung bei Bedingungen bezüglich der Temperatur, der Kontaktzeit mit der Beschichtung (7), der Konzentration an SO4 2--Ionen und an Zn2+-Ionen auf die Beschichtung (7) angewendet wird, die derart angepasst sind, dass eine temporäre Schutzschicht (13) basierend auf Zinkhydroxysulfat und Zinksulfat gebildet wird, deren Schwefelgehalt größer oder gleich 0,5 mg/m2 und kleiner oder gleich 30 mg/m2 ist.
  7. Anwendung gemäß Anspruch 6, wobei die wässrige Behandlungslösung bei Bedingungen bezüglich der Temperatur, der Kontaktzeit mit der Beschichtung (7), der Konzentration an SO4 2--Ionen und an Zn2+-Ionen auf die Beschichtung (7) angewendet wird, die derart angepasst sind, dass eine temporäre Schutzschicht (13) basierend auf Zinkhydroxysulfat und Zinksulfat gebildet wird, die einen Schwefelgehalt zwischen einschließlich 3,7 und 27 mg/m2 aufweist.
  8. Anwendung gemäß einem der Ansprüche 1 bis 7, wobei nach Anwenden der wässrigen Behandlungslösung auf die Beschichtung (7) das Blech (1) getrocknet wird, nachdem es gegebenenfalls gespült wurde.
  9. Anwendung gemäß Anspruch 1 oder 2, wobei die wässrige Behandlungslösung unter Anodenpolarisationsspannung angewendet wird, und der pH-Wert der wässrigen Behandlungslösung größer oder gleich 12 und kleiner als 13 ist.
  10. Anwendung gemäß Anspruch 9, wobei die Konzentration an SO4 2-Ionen größer als 0,07 mol/l ist.
  11. Anwendung gemäß Anspruch 9 oder 10, wobei die Dichte an elektrischen Ladungen, die sich während der Behandlung durch die Beschichtung (7) hindurch bewegen, zum Bilden einer temporären Schutzschicht (13) basierend auf Zinkhydroxysulfat und Zinksulfat, deren Schwefelgehalt größer oder gleich 0,5 mg/m2 und kleiner oder gleich 30 mg/m2 beträgt, angepasst wird.
  12. Anwendung gemäß Anspruch 11, wobei die Dichte an elektrischen Ladungen zum Bilden einer temporären Schutzschicht (13) basierend auf Zinkhydroxysulfat und Zinksulfat, deren Schwefelgehalt zwischen einschließlich 3,7 und 27 mg/m2 beträgt, angepasst wird.
  13. Anwendung gemäß einem der Ansprüche 9 bis 12, wobei die Stromdichte der angelegten Polarisationsspannung während der Behandlung größer als 20 A/dm2 ist.
  14. Anwendung gemäß einem der Ansprüche 9 bis 13, wobei das Blech (1) nach der Anwendung der wässrigen Behandlungslösung auf die Beschichtung (7) gespült wird.
EP12705147.2A 2012-01-10 2012-01-10 Verwendung einer lösung mit sulfationen zur verringerung des schwärzens oder anlaufens eines metallbleches während der lagerung und mit einer solchen lösung behandeltes metallblech Active EP2802682B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
HUE12705147A HUE051070T2 (hu) 2012-01-10 2012-01-10 Szulfátionokat tartalmazó oldat alkalmazása fémlemez feketedésének vagy elfénytelenedésének csökkentésére annak tárolása során, és ilyen oldattal kezelt fémlemez
PL12705147T PL2802682T3 (pl) 2012-01-10 2012-01-10 Zastosowanie roztworu zawierającego jony siarczanowe w celu zmniejszenia czernienia lub matowienia blachy podczas jej przechowywania oraz blacha traktowana takim roztworem

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/FR2012/000013 WO2013104835A1 (fr) 2012-01-10 2012-01-10 Utilisation d'une solution contenant des ions sulfates pour reduire le noircissement ou le ternissement d'une tole lors de son stockage et tole traitee par une telle solution.

Publications (2)

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EP2802682A1 EP2802682A1 (de) 2014-11-19
EP2802682B1 true EP2802682B1 (de) 2020-09-23

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EP12705147.2A Active EP2802682B1 (de) 2012-01-10 2012-01-10 Verwendung einer lösung mit sulfationen zur verringerung des schwärzens oder anlaufens eines metallbleches während der lagerung und mit einer solchen lösung behandeltes metallblech

Country Status (16)

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US (2) US10704157B2 (de)
EP (1) EP2802682B1 (de)
JP (1) JP6280049B2 (de)
KR (3) KR20140119729A (de)
CN (2) CN104040027A (de)
BR (1) BR112014016471B1 (de)
CA (1) CA2863497C (de)
ES (1) ES2828473T3 (de)
HU (1) HUE051070T2 (de)
MA (1) MA35743B1 (de)
MX (1) MX2014008455A (de)
PL (1) PL2802682T3 (de)
RU (1) RU2581943C2 (de)
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EP2995674B1 (de) * 2014-09-11 2020-07-15 thyssenkrupp AG Verwendung eines Sulfats sowie Verfahren zum Herstellen eines Stahlbauteils durch Umformen in einer Umformmaschine
JP6629979B2 (ja) * 2016-01-19 2020-01-15 ティッセンクルップ スチール ヨーロッパ アクチェンゲゼルシャフトＴｈｙｓｓｅｎＫｒｕｐｐ Ｓｔｅｅｌ Ｅｕｒｏｐｅ ＡＧ Ｚｎコーティングおよびこのコーティングに堆積されたトライボロジー活性層を有する鋼製品を製造する方法、およびこの方法に従って製造された鋼製品
WO2019073273A1 (en) * 2017-10-12 2019-04-18 Arcelormittal PROCESS FOR PROCESSING METAL SHEET AND METAL SHEET TREATED WITH THIS METHOD
WO2019073274A1 (en) * 2017-10-12 2019-04-18 Arcelormittal PROCESS FOR PROCESSING METAL SHEET AND METAL SHEET TREATED USING THE SAME
WO2021074672A1 (en) * 2019-10-16 2021-04-22 Arcelormittal Metal sheet treatment method and metal sheet treated with this method

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BR112014016471B1 (pt) 2021-07-06
KR102258538B1 (ko) 2021-05-31
PL2802682T3 (pl) 2021-04-19
HUE051070T2 (hu) 2021-01-28
RU2581943C2 (ru) 2016-04-20
KR20190060018A (ko) 2019-05-31
EP2802682A1 (de) 2014-11-19
US20200318252A1 (en) 2020-10-08
BR112014016471A2 (pt) 2017-06-13
CN109440097A (zh) 2019-03-08
KR20160128440A (ko) 2016-11-07
CA2863497A1 (fr) 2013-07-18
CN104040027A (zh) 2014-09-10
UA111876C2 (uk) 2016-06-24
ZA201404502B (en) 2015-09-30
JP2015504977A (ja) 2015-02-16
MX2014008455A (es) 2015-04-08
JP6280049B2 (ja) 2018-02-14
KR20140119729A (ko) 2014-10-10
CA2863497C (fr) 2016-09-06
WO2013104835A1 (fr) 2013-07-18
ES2828473T3 (es) 2021-05-26
RU2014132696A (ru) 2016-03-10
US20150093594A1 (en) 2015-04-02
US10704157B2 (en) 2020-07-07
MA35743B1 (fr) 2014-12-01
BR112014016471A8 (pt) 2017-07-04

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