EP2802682A1 - Use of a solution containing sulphate ions for reducing the blackening or tarnishing of a metal sheet during the storage thereof and metal sheet treated with such a solution - Google Patents

Use of a solution containing sulphate ions for reducing the blackening or tarnishing of a metal sheet during the storage thereof and metal sheet treated with such a solution

Info

Publication number
EP2802682A1
EP2802682A1 EP12705147.2A EP12705147A EP2802682A1 EP 2802682 A1 EP2802682 A1 EP 2802682A1 EP 12705147 A EP12705147 A EP 12705147A EP 2802682 A1 EP2802682 A1 EP 2802682A1
Authority
EP
European Patent Office
Prior art keywords
coating
zinc
equal
use according
treatment solution
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.)
Granted
Application number
EP12705147.2A
Other languages
German (de)
French (fr)
Other versions
EP2802682B1 (en
Inventor
Daniel Chaleix
Christian Allely
Maxime Monnoyer
Pascale FELTIN
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.)
ArcelorMittal SA
Original Assignee
ArcelorMittal Investigacion y Desarrollo SL
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 ArcelorMittal Investigacion y Desarrollo SL filed Critical ArcelorMittal Investigacion y Desarrollo SL
Priority to HUE12705147A priority Critical patent/HUE051070T2/en
Priority to PL12705147T priority patent/PL2802682T3/en
Publication of EP2802682A1 publication Critical patent/EP2802682A1/en
Application granted granted Critical
Publication of EP2802682B1 publication Critical patent/EP2802682B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • 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
    • 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
    • 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 being limited thereto.
  • Coatings essentially comprising 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 competing with coatings comprising zinc and magnesium.
  • magnesium significantly increases the resistance to perforating corrosion of these coatings, which can reduce their thickness and thus improve their weldability or 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 at the places most likely to to be corroded.
  • sheet metal coils with such surface coatings can sometimes remain in storage sheds for several months and must not see this surface deteriorate by the appearance of surface corrosion, before being put into service. form by the end user.
  • no corrosion primer should appear regardless of the storage environment, even in the event of exposure to the sun and / or a wet or salty environment.
  • Standard galvanized products that is to say whose coatings essentially comprise zinc, are also subject to these stresses and are coated with a protective oil which is generally sufficient.
  • coatings comprising zinc and magnesium exhibit during storage a slight surface oxidation which modifies the interaction of light with the surface and which modifies its visual aspect. Indeed, we then observe the appearance of black spots for coatings comprising zinc and magnesium, this phenomenon being referred to as blackening.
  • blackening For coatings that include zinc, magnesium, and aluminum, the entire surface that is no longer covered with oil tarnishes. This is called tarnishing.
  • a temporary protection oil is quite restrictive because, on the one hand, the oil tends to dirty the working environment and the tools used to cut and shape the coils of sheet metal and on the other hand, a degreasing is often necessary in a subsequent step of manufacturing the parts from these coils.
  • the invention firstly relates to a use according to claim 1.
  • the invention also has for its second object a sheet according to claim 15.
  • the sheet according to the invention may also comprise the features of claims 16 to 18, taken separately or in combination.
  • FIG. 1 is a diagrammatic sectional view illustrating the structure of a sheet according to the invention
  • FIGS. 2A to 2D and 3A to 3F are snapshots illustrating the results of humidity-humidification tests carried out on various specimens of sheets treated according to the invention or untreated,
  • FIGS. 4 to 6 show curves illustrating the results of aging tests in natural exposure under shelter carried out on various test pieces of sheet treated according to the invention or untreated.
  • the sheet 1 of FIG. 1 comprises a substrate 3 made of steel, preferably hot-rolled then cold-rolled, and is for example wound so as to be able to be used later as a bodywork part for the automobile.
  • the invention is not limited to this area and can find a job for any steel piece regardless of its end use.
  • the sheet 1 will then be unwound from the coil and cut and shaped to form a part.
  • the substrate 3 is covered on one side 5 by a coating 7.
  • a coating 7 may be present on both sides of the substrate 3.
  • the coating 7 comprises at least one layer 9 based on zinc.
  • the layer 9 preferably comprises from 0.1 to 20% by weight of magnesium.
  • This layer 9 generally has a thickness less than or equal to 20 ⁇ 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 the different layers covering it have not been respected in FIG. 1 in order to facilitate the representation.
  • the layer 9 comprises at least 0.1% by weight of magnesium because no protective effect against perforating corrosion is visible below.
  • the 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 larger proportion would lead to a too rapid consumption of the coating 7 and thus paradoxically degraded anticorrosive performance.
  • the layer 9 can in particular be obtained by a vacuum deposition method such as magnetron sputtering, or vacuum evaporation by Joule effect, induction or under an electron beam ⁇
  • the layer 9 generally only comprises zinc and magnesium, other elements, such as aluminum or silicon, may however be added, if necessary, to improve other characteristics of the layer 9 such as ductility or substrate adhesion 3.
  • the layer 9 comprises only zinc and magnesium, it is particularly preferred that the layer 9 comprises between 14 and 18% by weight of magnesium, and better that it corresponds mainly to the intermetallic compound of formula Zn 2 Mg, comprising approximately 16% by weight of magnesium, which exhibits particularly good perforating 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 electroplating process.
  • magnesium can simply be deposited under vacuum on zinc previously deposited by electrodeposition on the substrate 3 and then carry out a heat treatment to combine the deposited magnesium and zinc and thus constitute the layer 9 comprising zinc and magnesium overlying the layer 11 comprising zinc.
  • 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, the layer 9 comprises between 2 and 4% by weight of magnesium and between 2 and 6% by weight of aluminum, and is therefore close to the composition of the ternary zinc / aluminum / magnesium eutectic.
  • the layer 9 can be obtained by a hot dipping coating process in a molten zinc bath containing magnesium up to a content of 10% by weight and aluminum to a content of 20%. % in weight.
  • the bath may 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 from the ingots or resulting from the passage of the substrate 3 in the bath.
  • the coating 7 is covered with a layer 13 of temporary protection.
  • the layer 13 was obtained for example by application to the coating 7, optionally after degreasing, of an aqueous treatment solution containing sulphate ions S0 4 2 - at a concentration greater than or equal to 0.01 mol / l. 13 thus formed is based on zinc hydroxysulfate and zinc sulphate and is at the same time sufficiently thick and adherent.
  • the aqueous treatment solution is applied conventionally, for example by dipping, by spraying or by coating.
  • the aqueous treatment solution additionally 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 deposition.
  • the aqueous solution of treatment by dissolution of zinc sulphate in pure water is prepared.
  • zinc sulfate heptahydrate ZnSO 4, 7H 2 O
  • the concentration of ions Zn 2+ is then equal to that of the anions S0 4 2 ⁇
  • 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, time of contact with the coating 7, concentration of S0 4 2 " ions and 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 used aqueous treatment solution contains between 20 and 160 g / l of zinc sulfate heptahydrate, corresponding to an ion concentration of Zn 2+ ions and a concentration of S0 4 2 "of between 0.07 and 0.55 Indeed, it has been found that, in this concentration range, the deposition rate was little influenced by the value of the concentration.
  • the aqueous treatment solution is applied under conditions of temperature, time of contact with the coating 7, and concentrations of S0 4 2 " ions and 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 oxidizing agent for zinc, such as hydrogen peroxide.
  • This oxidizing agent can have a very marked hydroxysulfation and sulphation accelerator effect at low concentration. It has been found that the addition of only 0.03%, ie 8.10 -3 mol / l of hydrogen peroxide, or 2.10 -4 mol / l of potassium permanganate in the solution allowed to double (approximately) the speed of deposit. It has been found, on the contrary, that concentrations 100 times higher no longer made it possible to obtain this improvement in the deposition rate.
  • the layer 13 deposited is adherent. Drying is adjusted to remove residual liquid water from the deposit.
  • the sheet 1 is preferably rinsed so as to eliminate the soluble part of the deposit obtained.
  • the absence of rinsing and the obtaining of a partially water-soluble deposit resulting therefrom are not very detrimental to the reduction of the degradation of the coating 7 during the subsequent shaping of the sheet 1, the moment that the deposit obtained comprises a layer 13 insoluble in water.
  • the aqueous treatment solution comprises an ion concentration S0 4 2 "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 hydroxysu adhering adhesives are formed on the surface to be treated. If the pH of the solution is greater than or equal to 13, the hydroxysulfate is redissolved and / or decomposed into zinc hydroxides.
  • the sodium sulfate concentration is less than 1.42 g / l in the solution, little formation of hydroxysulfates is observed on the surface.
  • This concentration is equivalent to 0.01 mol / l of S0 4 2 " and, more generally, it is therefore important for the concentration of S0 4 2" ions to be greater than or equal to 0.01 mol / l, and preferably greater than or equal to 0.01 mol / l. or equal to 0.07 mol / l.
  • the concentration of sulphate ions is preferably less than or equal to 1 mol / 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 formation yield of the layer 13 is observed.
  • the total amount of hydroxysulfates and sulphates deposited should be greater than or equal to 0.5 mg / m 2 and not more than 30 mg / m 2 in sulfur equivalent, preferably between 3.5 and 27 mg / m 2 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 sulphate should be deposited under a high polarization current density, especially greater than 20 A / dm 2 and, for example, 200 A / dm 2 .
  • the temperature of the aqueous treatment solution is generally between 20 ° C and 60 ° C. Preferably, a temperature greater than or equal to 40 ° C. is used, so as to increase the conductivity of the solution and to reduce the ohmic losses.
  • the treated surface is thoroughly rinsed with demineralised water. This rinsing step removes alkaline reagents on the surface of the deposit, which would cause corrosion problems.
  • the layer 13 of the sheet 1 may be optionally lubricated. This lubrication can be ensured by applying an oil film (not shown) with a weight of less than 2 g / m 2 on the 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 to improve the tarnish resistance in cases where the coating 7 comprises zinc, magnesium, and aluminum. This increased resistance is particularly useful in the absence of an oil film, for example following dewetting of an oil film applied to the coating 7.
  • This increase in the resistance to blackening and tarnishing is mainly due to the formation of a conversion layer based on zinc hydroxysulfate Zn 4 S0 4 (OH) 6 .
  • the reactions involved in applying the aqueous treatment solution to the coating 7 are:
  • the presence of magnesium in the coating 7 contributes to stabilizing the zinc hydroxysulfate layer over time and thus preventing its conversion into zinc carbonate under the effect of the C0 2 content in the air.
  • Zinc carbonates are indeed known to have a less protective (less barrier) power than zinc hydroxysulfates.
  • Test pieces are cut into two types of sheet 1, namely:
  • sheets 1, the coating 7 of which comprises a layer 1 1 of zinc 5.5 ⁇ m in thickness and a layer 9 of 3.5 ⁇ m in thickness, the layer 9 comprising approximately 84% by weight of zinc and 16% by weight of magnesium.
  • a layer of 7.5 ⁇ of zinc was first deposited by electroplating and a layer of 1.5 ⁇ of magnesium by vacuum deposition and the sheet was subjected to a heat treatment to combine the magnesium and zinc.
  • These specimens will be designated ZEMg thereafter; and sheets 1, the coating 7 of which comprises a 4 ⁇ m thick layer of zinc deposited by vacuum deposition and a layer 9 of 3.5 ⁇ deposited by vacuum deposition and comprising approximately 80% by weight of zinc and % by weight of magnesium.
  • ZnMg Full PVD thereafter.
  • the substrate 3 of ZEMg and ZnMgFullPVD specimens is a cold rolled steel for deep drawing.
  • test pieces were coated with a layer 13 having a weight of between 17 and 20 mg / m 2 of sulfur.
  • the application conditions for forming the layer 13 were as follows:
  • Drying by carrying the specimens to a temperature between 70 and 80 ° C.
  • test pieces are subjected to aging cycles of 24 hours in a humidotherm, that is to say an enclosure with controlled atmosphere and temperature. These cycles simulate the corrosion conditions of a sheet metal coil or sheet metal sheet during storage.
  • a humidotherm that is to say an enclosure with controlled atmosphere and temperature.
  • the proportion of altered surface is determined by visual inspection of an operator.
  • Figure 2A shows the visual appearance of a ZEMg test tube without Layer 3 after Quaker 6130 oiling as described above.
  • This test tube has a significant darkening making it unfit for use by French car manufacturers.
  • the ZEMg test pieces with layer 13 FIGGS. 2B to 2D
  • the ZEMg test pieces with layer 13 FIGS. 2B to 2D
  • FIGS. 3A to 3D allowing to show the visual aspects, at the end of the test, of ZnMg Full PVD specimens, without layer 13 (FIG 3A) and with layer 13 (FIG 3B to 3D), after oiling Quaker 6130 tel as described above.
  • the presence of the layer 13 can meet the requirements of French car manufacturers.
  • a ZnMg Full PVD test tube without a 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 such as described above.
  • the coating 7 comprises only 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 balance being zinc and the unavoidable impurities.
  • the substrate 3 is then a cold rolled steel for deep drawing. These specimens will be designated ZnMgAI thereafter.
  • the ZnMgAI test pieces were tested in the oiled state (Quaker 6130 film with a weight of about 1 g / m 2 ) and not oiled, with and without a layer 13. By comparison, the same tests were carried out on specimens from a standard galvanized sheet with a zinc coating 10 ⁇ thick and a cold-rolled steel substrate for deep drawing. These last test pieces will be designated Gl thereafter.
  • the monitoring of the evolution of tarnishing during the test was carried out via a colorimeter measuring the luminance difference (measurement of AL * ).
  • corresponding to the appearance of tarnishing was set at 2.
  • the level of tarnishing achieved by the ZnMgAI test specimens with layer 13 is equivalent to that of the oiled Gl specimens.

Abstract

The invention relates mainly to the use of an aqueous treatment solution containing sulphate ions SO4 2- at a concentration of greater than or equal to 0.01 mol/l, for treating a metal sheet comprising a steel substrate coated on at least one of its faces with a coating comprising at least zinc and magnesium, in order to reduce the blackening or tarnishing of the metal sheet during the storage thereof. The invention also relates to the metal sheet treated with such a solution.

Description

UTILISATION D'UNE SOLUTION CONTENANT DES IONS SULFATES POUR REDUIRE LE NOIRCISSEMENT OU LE TERNISSEMENT D'UNE TOLE LORS DE SON STOCKAGE ET TOLE USE OF A SOLUTION CONTAINING SULFATE IONS TO REDUCE THE BLINDING OR LENGTH OF A SHEET DURING ITS STORAGE AND SHEET
TRAITEE PAR UNE TELLE SOLUTION  TREATED BY SUCH A SOLUTION
La présente invention est relative à une tôle comprenant un substrat en acier revêtu sur au moins une de ses faces par un revêtement comprenant du zinc et du magnésium. 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.
De telles tôles sont plus particulièrement destinées à la fabrication de pièces pour l'automobile, sans pour autant y être limitées.  Such sheets are more particularly intended for the manufacture of parts for the automobile, without being limited thereto.
Les revêtements comprenant essentiellement du zinc sont traditionnellement utilisés pour leur bonne protection contre la corrosion, que ce soit dans le secteur automobile ou dans la construction, par exemple. Cependant, ces revêtements entraînent des problèmes de soudabilité et sont à présent concurrencés par les revêtements comprenant du zinc et du magnésium.  Coatings essentially comprising 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 competing with coatings comprising zinc and magnesium.
En effet, l'ajout de magnésium augmente nettement la résistance à la corrosion perforante de ces revêtements, ce qui peut permettre de réduire leur épaisseur et donc d'améliorer leur aptitude au soudage ou bien encore de maintenir l'épaisseur de revêtement et d'augmenter la garantie de protection contre la corrosion dans le temps.  Indeed, the addition of magnesium significantly increases the resistance to perforating corrosion of these coatings, which can reduce their thickness and thus improve their weldability or to maintain the coating thickness and increase the guarantee of protection against corrosion over time.
En outre, l'amélioration de la résistance à la corrosion est telle qu'il est à présent possible de réduire voire de supprimer l'utilisation de mesures de protection secondaires telles que l'utilisation de cires ou de mastics aux endroits les plus susceptibles d'être corrodés.  In addition, 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 at the places most likely to to be corroded.
Cependant, les bobines de tôles avec de tels revêtements en surface peuvent parfois séjourner dans des hangars de stockage pendant plusieurs mois et ne doivent pas voir cette surface s'altérer par l'apparition d'une corrosion de surface, avant d'être mises en forme par l'utilisateur final. En particulier, aucune amorce de corrosion ne doit apparaître quel que soit l'environnement de stockage, même en cas d'exposition au soleil et/ou à un environnement humide voire salin.  However, sheet metal coils with such surface coatings can sometimes remain in storage sheds for several months and must not see this surface deteriorate by the appearance of surface corrosion, before being put into service. form by the end user. In particular, no corrosion primer should appear regardless of the storage environment, even in the event of exposure to the sun and / or a wet or salty environment.
Les produits galvanisés standards, c'est-à-dire dont les revêtements comprennent essentiellement du zinc, sont aussi soumis à ces contraintes et sont enduits d'une huile de protection qui est généralement suffisante.  Standard galvanized products, that is to say whose coatings essentially comprise zinc, are also subject to these stresses and are coated with a protective oil which is generally sufficient.
Or, les présents inventeurs ont constaté que, en cas de démouillage de l'huile de protection, les revêtements comprenant du zinc et du magnésium présentent au cours du stockage une légère oxydation de surface qui modifie l'interaction de la lumière avec la surface et qui modifie de ce fait son aspect visuel. En effet, on observe alors l'apparition de points noirs pour les revêtements comprenant du zinc et du magnésium, ce phénomène étant désigné sous le terme de noircissement. Pour les revêtements comprenant du zinc, du magnésium et de l'aluminium, l'ensemble de la surface qui n'est plus recouvert d'huile se ternit. On parle alors de ternissement. However, the present inventors have found that, in the case of dewetting of the protective oil, coatings comprising zinc and magnesium exhibit during storage a slight surface oxidation which modifies the interaction of light with the surface and which modifies its visual aspect. Indeed, we then observe the appearance of black spots for coatings comprising zinc and magnesium, this phenomenon being referred to as blackening. For coatings that include zinc, magnesium, and aluminum, the entire surface that is no longer covered with oil tarnishes. This is called tarnishing.
Par ailleurs, le recours à une huile de protection temporaire est assez contraignant car, d'une part, l'huile tend à salir l'environnement de travail et les outils utilisés pour découper et mettre en forme les bobines de tôles et, d'autre part, un dégraissage est souvent nécessaire dans une étape ultérieure de fabrication des pièces issues de ces bobines.  Furthermore, the use of a temporary protection oil is quite restrictive because, on the one hand, the oil tends to dirty the working environment and the tools used to cut and shape the coils of sheet metal and on the other hand, a degreasing is often necessary in a subsequent step of manufacturing the parts from these coils.
Il existe donc un besoin pour développer un système de protection temporaire pour de tels revêtements, notamment vis-à-vis des phénomènes de noircissement et de ternissement, système qui soit efficace même en l'absence d'huile de protection temporaire.  There is therefore a need to develop a temporary protection system for such coatings, in particular vis-à-vis blackening phenomena and tarnishing system that is effective even in the absence of temporary protection oil.
A cet effet, l'invention a pour premier objet une utilisation selon la revendication 1. For this purpose, the invention firstly relates to a use according to claim 1.
L'utilisation selon l'invention peut également comprendre les caractéristiques des revendications 2 à 14, prises isolément ou en combinaison. The use according to the invention may also comprise the features of claims 2 to 14, taken alone or in combination.
L'invention a également pour deuxième objet une tôle selon la revendication 15. La tôle selon l'invention peut également comprendre les caractéristiques des revendications 16 à 18, prises isolément ou en combinaison.  The invention also has for its second object a sheet according to claim 15. The sheet according to the invention may also comprise the features of claims 16 to 18, taken separately or in combination.
D'autres caractéristiques et avantages de l'invention apparaîtront à la lecture de la description qui va suivre, donnée uniquement à titre d'exemple non limitatif.  Other characteristics and advantages of the invention will appear on reading the description which follows, given solely by way of non-limiting example.
L'invention va à présent être illustrée par des exemples donnés à titre indicatif, et non limitatif, et en référence aux figures annexées sur lesquelles :  The invention will now be illustrated by examples given for information only, and not limiting, and with reference to the appended figures in which:
- la figure 1 est une vue schématique en coupe illustrant la structure d'une tôle selon l'invention,  FIG. 1 is a diagrammatic sectional view illustrating the structure of a sheet according to the invention,
- les figures 2A à 2D et 3A à 3F sont des clichés illustrant les résultats de tests de corrosion en humidotherme effectués sur différentes éprouvettes de tôles traitées selon l'invention ou non traitées,  FIGS. 2A to 2D and 3A to 3F are snapshots illustrating the results of humidity-humidification tests carried out on various specimens of sheets treated according to the invention or untreated,
- les figures 4 à 6 présentent des courbes illustrant les résultats de tests de vieillissement en exposition naturelle sous abri effectués sur différentes éprouvettes de tôle traitées selon l'invention ou non traitées.  FIGS. 4 to 6 show curves illustrating the results of aging tests in natural exposure under shelter carried out on various test pieces of sheet treated according to the invention or untreated.
La tôle 1 de la figure 1 comprend un substrat 3 en acier, de préférence laminé à chaud puis laminé à froid, et est par exemple bobinée pour pouvoir être utilisée ultérieurement en tant que pièce de carrosserie pour l'automobile. L'invention n'est pas pour autant limitée à ce domaine et peut trouver un emploi pour toute pièce en acier quel que soit son usage final. The sheet 1 of FIG. 1 comprises a substrate 3 made of steel, preferably hot-rolled then cold-rolled, and is for example wound so as to be able to be used later as a bodywork part for the automobile. The invention is not limited to this area and can find a job for any steel piece regardless of its end use.
Dans cet exemple, la tôle 1 sera alors dévidée de la bobine puis découpée et mise en forme pour constituer une pièce.  In this example, the sheet 1 will then be unwound from the coil and cut and shaped to form a part.
Le substrat 3 est recouvert sur une face 5 par un revêtement 7. Dans certaines variantes, un tel revêtement 7 peut être présent sur les deux faces du substrat 3.  The substrate 3 is covered on one side 5 by a coating 7. In some variants, such a coating 7 may be present on both sides of the substrate 3.
Le revêtement 7 comprend au moins une couche 9 à base de zinc. La couche 9 comprend de préférence de 0,1 à 20% en poids de magnésium.  The coating 7 comprises at least one layer 9 based on zinc. The layer 9 preferably comprises from 0.1 to 20% by weight of magnesium.
Cette couche 9 présente généralement une épaisseur inférieure ou égale à 20 μιη et vise à protéger le substrat 3 contre la corrosion perforante, de façon classique. On observera que les épaisseurs relatives du substrat 3 et des différentes couches le recouvrant n'ont pas été respectées sur la figure 1 afin de faciliter la représentation.  This layer 9 generally has a thickness less than or equal to 20 μιη 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 the different layers covering it have not been respected in FIG. 1 in order to facilitate the representation.
La couche 9 comprend au moins 0,1% en poids de magnésium car aucun effet de protection contre la corrosion perforante n'est visible en deçà.  The layer 9 comprises at least 0.1% by weight of magnesium because no protective effect against perforating corrosion is visible below.
Dans un mode de réalisation préféré, la couche 9 contient au moins 0,5%, de préférence au moins 2% en poids de magnésium.  In a preferred embodiment, the layer 9 contains at least 0.5%, preferably at least 2% by weight of magnesium.
On limite la teneur du magnésium à 20% en poids dans la couche 9 car il a été observé qu'une proportion plus importante entraînerait une consommation trop rapide du revêtement 7 et donc des performances anticorrosion paradoxalement dégradées.  The magnesium content is limited to 20% by weight in the layer 9 because it has been observed that a larger proportion would lead to a too rapid consumption of the coating 7 and thus paradoxically degraded anticorrosive performance.
La couche 9 peut notamment être obtenue par un procédé de dépôt sous vide, tel que le sputtering magnétron, ou l'évaporation sous vide par effet joule, par induction ou sous faisceau d'électrons^ The layer 9 can in particular be obtained by a vacuum deposition method such as magnetron sputtering, or vacuum evaporation by Joule effect, induction or under an electron beam ^
Dans ce cas, la couche 9 ne comprend généralement que du zinc et du magnésium, d'autres éléments, tels que l'aluminium ou le silicium pouvant cependant être ajoutés, si nécessaire, pour améliorer d'autres caractéristiques de la couche 9 telles que sa ductilité ou son adhésion au substrat 3.  In this case, the layer 9 generally only comprises zinc and magnesium, other elements, such as aluminum or silicon, may however be added, if necessary, to improve other characteristics of the layer 9 such as ductility or substrate adhesion 3.
Lorsque la couche 9 ne comprend que du zinc et du magnésium, on préfère en particulier que la couche 9 comprenne entre 14 et 18% en poids de magnésium, et mieux qu'elle corresponde majoritairement au composé intermétallique de formule Zn2Mg, comportant environ 16% en poids de magnésium, qui présente des propriétés de résistance à la corrosion perforante particulièrement bonnes. When the layer 9 comprises only zinc and magnesium, it is particularly preferred that the layer 9 comprises between 14 and 18% by weight of magnesium, and better that it corresponds mainly to the intermetallic compound of formula Zn 2 Mg, comprising approximately 16% by weight of magnesium, which exhibits particularly good perforating corrosion resistance properties.
Dans certaines variantes, le revêtement 7 peut comprendre une couche 11 de zinc entre la couche 9 et la face 5 du substrat 3. Cette couche 11 peut avoir été obtenue par exemple par un procédé de dépôt sous vide ou d'électrodéposition.  In some embodiments, 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 electroplating process.
Dans cette dernière hypothèse, on peut simplement déposer sous vide du magnésium sur du zinc préalablement déposé par électrodéposition sur le substrat 3 et réaliser ensuite un traitement thermique pour allier le magnésium et le zinc déposés et ainsi constituer la couche 9 comprenant du zinc et du magnésium surmontant la couche 11 comprenant du zinc. In the latter case, magnesium can simply be deposited under vacuum on zinc previously deposited by electrodeposition on the substrate 3 and then carry out a heat treatment to combine the deposited magnesium and zinc and thus constitute the layer 9 comprising zinc and magnesium overlying the layer 11 comprising zinc.
Lorsque la couche 9 comprend du zinc, du magnésium et de l'aluminium, on préfère en particulier que la couche 9 comprenne entre 0.1 et 10% en poids de magnésium et entre 0.1 et 20% en poids d'aluminium. De préférence encore, la couche 9 comprend entre 2 et 4% en poids de magnésium et entre 2 et 6% en poids d'aluminium, et elle est donc proche de la composition de l'eutectique ternaire zinc/aluminium/magnésium.  When the layer 9 comprises zinc, magnesium and aluminum, it is particularly preferred that 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, the layer 9 comprises between 2 and 4% by weight of magnesium and between 2 and 6% by weight of aluminum, and is therefore close to the composition of the ternary zinc / aluminum / magnesium eutectic.
Dans ce cas, la couche 9 peut être obtenue par un procédé de revêtement au trempé à chaud dans un bain de zinc fondu contenant du magnésium jusqu'à une teneur de 10% en poids et de l'aluminium jusqu'à une teneur de 20% en poids. Le bain peut également contenir jusqu'à 0,3% en poids d'éléments optionnels d'addition tels que Si, Sb, Pb, Ti, Ca, Mn, Sn, La, Ce, Cr, Ni, Zr ou Bi.  In this case, the layer 9 can be obtained by a hot dipping coating process in a molten zinc bath containing magnesium up to a content of 10% by weight and aluminum to a content of 20%. % in weight. The bath may 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.
Ces différents éléments peuvent permettre, entre autres, d'améliorer la ductilité ou l'adhésion de la couche 9 sur le substrat 3. L'homme du métier qui connaît leurs effets sur les caractéristiques de la couche 9 saura les employer en fonction du but complémentaire recherché. Le bain peut enfin contenir des éléments résiduels provenant des lingots d'alimentation ou résultant du passage du substrat 3 dans le bain.  These various elements may make it possible, inter alia, to improve the ductility or the adhesion of the layer 9 to the substrate 3. The skilled person who knows their effects on the characteristics of the layer 9 will be able to use them according to the purpose complementary research. The bath may finally contain residual elements from the ingots or resulting from the passage of the substrate 3 in the bath.
Le revêtement 7 est recouvert d'une couche 13 de protection temporaire.  The coating 7 is covered with a layer 13 of temporary protection.
La couche 13 a été obtenue par exemple par application sur le revêtement 7, éventuellement après dégraissage, d'une solution aqueuse de traitement contenant des ions sulfates S04 2" à une concentration supérieure ou égale à 0,01 mol/l. La couche 13 ainsi formée est à base d'hydroxysulfate de zinc et de sulfate de zinc. Elle est à la fois suffisamment épaisse et adhérente. The layer 13 was obtained for example by application to the coating 7, optionally after degreasing, of an aqueous treatment solution containing sulphate ions S0 4 2 - at a concentration greater than or equal to 0.01 mol / l. 13 thus formed is based on zinc hydroxysulfate and zinc sulphate and is at the same time sufficiently thick and adherent.
On ne parvient pas à former une telle couche 13 lorsque la concentration en S04 2~ est inférieure à 0,01 mol/l, mais on constate aussi qu'une concentration trop élevée n'améliore pas sensiblement la vitesse de dépôt et peut même la diminuer légèrement. It is not possible to form such a layer 13 when the concentration of S0 4 2 ~ is less than 0.01 mol / l, but it is also found that a too high concentration does not appreciably improve the rate of deposition and may even reduce it slightly.
La solution aqueuse de traitement s'applique de manière classique, par exemple au trempé, par aspersion ou par enduction.  The aqueous treatment solution is applied conventionally, for example by dipping, by spraying or by coating.
Dans un mode de réalisation préféré, la solution aqueuse de traitement contient en outre des ions Zn2+ à une concentration supérieure ou égale à 0,01 mol/l, lesquels permettent d'obtenir un dépôt plus homogène. In a preferred embodiment, the aqueous treatment solution additionally 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 deposition.
On prépare par exemple la solution aqueuse de traitement par dissolution de sulfate de zinc dans de l'eau pure. On utilise par exemple du sulfate de zinc heptahydraté (ZnS04, 7 H2O). La concentration en ions Zn2+ est alors égale à celle des anions S04 2\ Le pH de la solution aqueuse de traitement correspond de préférence au pH naturel de la solution, sans addition de base ni d'acide. La valeur de ce pH est généralement comprise entre 5 et 7. For example, the aqueous solution of treatment by dissolution of zinc sulphate in pure water is prepared. For example, zinc sulfate heptahydrate (ZnSO 4, 7H 2 O) is used. The concentration of ions Zn 2+ is then equal to that of the anions S0 4 2 \ 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.
De préférence, on applique la solution aqueuse de traitement sur le revêtement 7, dans des conditions de température, de temps de contact avec le revêtement 7, de concentration en ions S04 2" et en ions Zn2+ ajustés pour que la couche 13 contienne une quantité en soufre supérieure ou égale à 0,5 mg/m2. Preferably, the aqueous treatment solution is applied to the coating 7, under conditions of temperature, time of contact with the coating 7, concentration of S0 4 2 " ions and Zn 2+ ions adjusted so that the layer 13 contains an amount of sulfur greater than or equal to 0.5 mg / m 2 .
Ainsi, le temps de contact de la solution aqueuse de traitement avec le revêtement 7 est compris entre 2 secondes et 2 minutes, et la température de la solution aqueuse de traitement est comprise entre 20 et 60°C.  Thus, 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.
De préférence, la solution aqueuse de traitement utilisée contient entre 20 et 160 g/l de sulfate de zinc heptahydraté, correspondant à une concentration en ions Zn2+ et une concentration en ions S04 2" comprises entre 0,07 et 0,55 mol/l. En effet, il a été constaté que, dans ce domaine de concentrations, la vitesse de dépôt était peu influencée par la valeur de la concentration. Preferably, the used aqueous treatment solution contains between 20 and 160 g / l of zinc sulfate heptahydrate, corresponding to an ion concentration of Zn 2+ ions and a concentration of S0 4 2 "of between 0.07 and 0.55 Indeed, it has been found that, in this concentration range, the deposition rate was little influenced by the value of the concentration.
Avantageusement, la solution aqueuse de traitement est appliquée dans des conditions de température, de temps de contact avec le revêtement 7, et de concentrations en ions S04 2" et en ions Zn2+ ajustées pour former une couche 13 présentant une quantité de soufre comprise entre 3,7 et 27 mg/m2. Advantageously, the aqueous treatment solution is applied under conditions of temperature, time of contact with the coating 7, and concentrations of S0 4 2 " ions and Zn 2+ ions adjusted to form a layer 13 having a quantity of sulfur between 3.7 and 27 mg / m 2 .
Selon une variante de l'invention, la solution aqueuse de traitement contient un agent oxydant du zinc, comme l'eau oxygénée. Cet agent oxydant peut avoir un effet accélérateur d'hydroxysulfatation et de sulfatation très marqué à faible concentration. On a constaté que l'addition de seulement 0,03%, soit 8.10"3 mol/litre d'eau oxygénée, ou de 2.10"4 mole/litre de permanganate de potassium dans la solution permettait de doubler (approximativement) la vitesse de dépôt. On a constaté, au contraire, que des concentrations 100 fois supérieures ne permettaient plus d'obtenir cette amélioration de la vitesse de dépôt. According to a variant of the invention, the aqueous treatment solution contains an oxidizing agent for zinc, such as hydrogen peroxide. This oxidizing agent can have a very marked hydroxysulfation and sulphation accelerator effect at low concentration. It has been found that the addition of only 0.03%, ie 8.10 -3 mol / l of hydrogen peroxide, or 2.10 -4 mol / l of potassium permanganate in the solution allowed to double (approximately) the speed of deposit. It has been found, on the contrary, that concentrations 100 times higher no longer made it possible to obtain this improvement in the deposition rate.
Après application de la solution aqueuse de traitement et avant séchage, la couche 13 déposée est adhérente. Le séchage est ajusté pour éliminer l'eau liquide résiduelle du dépôt.  After application of the aqueous treatment solution and before drying, the layer 13 deposited is adherent. Drying is adjusted to remove residual liquid water from the deposit.
Entre l'étape d'application et l'étape de séchage, on rince de préférence la tôle 1 de manière à éliminer la partie soluble du dépôt obtenu. L'absence de rinçage et l'obtention d'un dépôt partiellement solubilisable à l'eau qui en résulte ne sont pas très préjudiciables à la réduction de la dégradation du revêtement 7 lors de la mise en forme ultérieure de la tôle 1 , du moment que le dépôt obtenu comprend bien une couche 13 insoluble à l'eau. Selon un autre mode de réalisation de l'invention, la solution aqueuse de traitement comprend une concentration en ions S04 2" supérieure ou égale à 0,01 mol/l et est appliquée sous polarisation anodique, et le pH de la solution aqueuse de traitement est supérieur ou égal à 12, et inférieur à 13. Between the application step and the drying step, the sheet 1 is preferably rinsed so as to eliminate the soluble part of the deposit obtained. The absence of rinsing and the obtaining of a partially water-soluble deposit resulting therefrom are not very detrimental to the reduction of the degradation of the coating 7 during the subsequent shaping of the sheet 1, the moment that the deposit obtained comprises a layer 13 insoluble in water. According to another embodiment of the invention, the aqueous treatment solution comprises an ion concentration S0 4 2 "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.
Si le pH de la solution est inférieur à 12, on ne forme pas d'hydroxysu liâtes adhérents sur la surface à traiter. Si le pH de la solution est supérieur ou égal à 13, l'hydroxysulfate se re-dissout et/ou se décompose en hydroxydes de zinc.  If the pH of the solution is less than 12, no hydroxysu adhering adhesives are formed on the surface to be treated. If the pH of the solution is greater than or equal to 13, the hydroxysulfate is redissolved and / or decomposed into zinc hydroxides.
Lorsqu'on utilise du sulfate de sodium dans la solution aqueuse de traitement, si la concentration en sulfate de sodium est inférieure à 1 ,42 g/l dans la solution, on observe peu de formation d'hydroxysulfates sur la surface. Cette concentration équivaut à 0,01 mol/l de S04 2" et, de façon plus générale, il importe donc que la concentration en ions S04 2" soit supérieure ou égale à 0,01 mol/l, et de préférence supérieure ou égale à 0,07 mol/l. When sodium sulfate is used in the aqueous treatment solution, if the sodium sulfate concentration is less than 1.42 g / l in the solution, little formation of hydroxysulfates is observed on the surface. This concentration is equivalent to 0.01 mol / l of S0 4 2 " and, more generally, it is therefore important for the concentration of S0 4 2" ions to be greater than or equal to 0.01 mol / l, and preferably greater than or equal to 0.01 mol / l. or equal to 0.07 mol / l.
En outre, la concentration en ions sulfates est préférentiellement inférieure ou égale à 1 mole/litre. Dans le cas de l'utilisation de sulfate de sodium, à des concentrations supérieures à 142 g/l, par exemple 180 g/l, on observe une diminution du rendement de formation de la couche 13.  In addition, the concentration of sulphate ions is preferably less than or equal to 1 mol / liter. In the case of the use of sodium sulphate, at concentrations greater than 142 g / l, for example 180 g / l, a decrease in the formation yield of the layer 13 is observed.
De préférence, il convient que la quantité totale d'hydroxysulfates et de sulfates déposée soit- supérieure ou égale à 0,5 mg/m2 et inférieure ou égale à 30 mg/m2 en équivalent soufre, de préférence comprise entre 3,5 et 27 mg/m2 en équivalent soufre. Preferably, the total amount of hydroxysulfates and sulphates deposited should be greater than or equal to 0.5 mg / m 2 and not more than 30 mg / m 2 in sulfur equivalent, preferably between 3.5 and 27 mg / m 2 sulfur equivalent.
De préférence, la densité de charge appliquée est de préférence comprise entre 10 et 100 C/dm2 de surface à traiter. Preferably, the charge density applied is preferably between 10 and 100 C / dm 2 of surface to be treated.
De préférence, il convient d'effectuer le dépôt de la couche 13 à base d'hydroxysulfate de zinc et de sulfate de zinc sous une densité de courant de polarisation élevée, notamment supérieure à 20 A/dm2 et, par exemple de 200 A/dm2. Preferably, the layer 13 based on zinc hydroxysulfate and zinc sulphate should be deposited under a high polarization current density, especially greater than 20 A / dm 2 and, for example, 200 A / dm 2 .
Comme contre-électrode, on peut utiliser une cathode en titane.  As a counter-electrode, it is possible to use a titanium cathode.
La température de la solution aqueuse de traitement est généralement comprise entre 20°C et 60°C. De préférence, on procède à une température supérieure ou égale à 40°C, de manière à augmenter la conductivité de la solution et à diminuer les pertes ohmiques.  The temperature of the aqueous treatment solution is generally between 20 ° C and 60 ° C. Preferably, a temperature greater than or equal to 40 ° C. is used, so as to increase the conductivity of the solution and to reduce the ohmic losses.
Après formation de la couche 13 selon cet autre mode de réalisation, on rince abondamment la surface traitée à l'eau déminéralisée. Cette étape de rinçage permet d'éliminer les réactifs alcalins à la surface du dépôt, qui causeraient des problèmes de corrosion.  After formation of the layer 13 according to this other embodiment, the treated surface is thoroughly rinsed with demineralised water. This rinsing step removes alkaline reagents on the surface of the deposit, which would cause corrosion problems.
Après réalisation de la couche 13 selon l'une des méthodes décrites ci-dessus, on peut éventuellement lubrifier la couche 13 de la tôle 1. Cette lubrification peut être assurée en appliquant un film d'huile (non-représenté) avec un poids inférieur à 2 g/m2 sur la couche 13. After producing the layer 13 according to one of the methods described above, the layer 13 of the sheet 1 may be optionally lubricated. This lubrication can be ensured by applying an oil film (not shown) with a weight of less than 2 g / m 2 on the layer 13.
Comme on le verra dans les exemples ci-dessous, réalisés à titre indicatif et non limitatif, les inventeurs ont montré que la présence d'une couche 13 permettait d'améliorer la résistance au noircissement dans le cas d'un revêtement 7 comprenant du zinc et du magnésium, et d'améliorer la résistance au ternissement dans les cas où le revêtement 7 comprend du zinc, du magnésium et de l'aluminium. Cette résistance accrue est particulièrement utile en cas d'absence de film d'huile, par exemple suite à un démouillage d'un film d'huile appliqué sur le revêtement 7.  As will be seen in the examples below, which are provided for information only and are not limiting, the inventors have shown that the presence of a layer 13 makes it possible to improve the resistance to blackening in the case of a coating 7 comprising zinc. and magnesium, and to improve the tarnish resistance in cases where the coating 7 comprises zinc, magnesium, and aluminum. This increased resistance is particularly useful in the absence of an oil film, for example following dewetting of an oil film applied to the coating 7.
Cette augmentation de la résistance au noircissement et au ternissement est due essentiellement à la formation d'une couche de conversion à base d'hydroxysulfate de zinc Zn4S04(OH)6. This increase in the resistance to blackening and tarnishing is mainly due to the formation of a conversion layer based on zinc hydroxysulfate Zn 4 S0 4 (OH) 6 .
Les réactions mises en jeu lors de l'application de la solution aqueuse de traitement sur le revêtement 7 sont:  The reactions involved in applying the aqueous treatment solution to the coating 7 are:
1. Attaque acide du zinc métal (solution de S04 2" à pH compris entre 5 et 7), qui aboutit à la formation d'ions Zn2+ et à l'alcalinisation du milieu : Zn + 2H20 -> Zn2+ + 20H" + H2 1. Acid attack of zinc metal (solution of S0 4 2 " at pH between 5 and 7), which results in the formation of Zn 2+ ions and the alkalization of the medium: Zn + 2H 2 0 -> Zn 2+ + 20H " + H 2
2. Précipitation d'hydroxysulfate de zinc sous l'effet de l'accumulation d'ions Zn2+ et OH" dans la solution de sulfate : 4 Zn2+ + S04 2" + 6 OH" -> Zn4S04(OH)6. 2. Precipitation of zinc hydroxysulfate under the effect of the accumulation of Zn 2+ and OH " ions in the sulphate solution: 4 Zn 2+ + S0 4 2" + 6 OH " -> Zn 4 S0 4 (OH) 6 .
Par rapport à un revêtement ne comprenant que du zinc, la présence du magnésium dans le revêtement 7 contribue à stabiliser dans le temps la couche d'hydroxysulfate de zinc et donc à empêcher sa transformation en carbonate de zinc sous l'effet du C02 contenu dans l'air. Les carbonates de zinc sont en effet reconnus pour avoir un pouvoir moins protecteur (moins barrière) que les hydroxysulfates de zinc. With respect to a coating comprising only zinc, the presence of magnesium in the coating 7 contributes to stabilizing the zinc hydroxysulfate layer over time and thus preventing its conversion into zinc carbonate under the effect of the C0 2 content in the air. Zinc carbonates are indeed known to have a less protective (less barrier) power than zinc hydroxysulfates.
Résistance au noircissement : Blackness resistance:
On découpe des éprouvettes dans deux types de tôles 1 , à savoir : Test pieces are cut into two types of sheet 1, namely:
- des tôles 1 dont le revêtement 7 comprend une couche 1 1 de zinc de 5,5 μιη d'épaisseur et une couche 9 de 3,5 im d'épaisseur, la couche 9 comprenant environ 84% en poids de zinc et 16% en poids de magnésium. Pour réaliser ces couches, on a tout d'abord déposé une couche de 7,5 μπι de zinc par électrodéposition et une couche de 1 ,5 μηη de magnésium par dépôt sous vide et on a soumis la tôle à un traitement thermique pour allier le magnésium et le zinc. Ces éprouvettes seront désignées ZEMg par la suite; et - des tôles 1 dont le revêtement 7 comprend une couche 11 de zinc de 4 μπι d'épaisseur déposée par dépôt sous vide et une couche 9 de 3,5 μιτι déposée par dépôt sous vide et comprenant environ 80% en poids de zinc et 20% en poids de magnésium. Ces éprouvettes seront désignées ZnMg Full PVD par la suite. sheets 1, the coating 7 of which comprises a layer 1 1 of zinc 5.5 μm in thickness and a layer 9 of 3.5 μm in thickness, the layer 9 comprising approximately 84% by weight of zinc and 16% by weight of magnesium. To produce these layers, a layer of 7.5 μπι of zinc was first deposited by electroplating and a layer of 1.5 μηη of magnesium by vacuum deposition and the sheet was subjected to a heat treatment to combine the magnesium and zinc. These specimens will be designated ZEMg thereafter; and sheets 1, the coating 7 of which comprises a 4 μm thick layer of zinc deposited by vacuum deposition and a layer 9 of 3.5 μιτι deposited by vacuum deposition and comprising approximately 80% by weight of zinc and % by weight of magnesium. These specimens will be designated ZnMg Full PVD thereafter.
Le substrat 3 des éprouvettes ZEMg et ZnMgFullPVD est un acier laminé à froid pour emboutissage profond.  The substrate 3 of ZEMg and ZnMgFullPVD specimens is a cold rolled steel for deep drawing.
Certaines des éprouvettes ont été revêtues par une couche 13 ayant un poids compris entre 17 à 20 mg/m2 de soufre. Some of the test pieces were coated with a layer 13 having a weight of between 17 and 20 mg / m 2 of sulfur.
Les conditions d'application pour former la couche 13 étaient les suivantes : The application conditions for forming the layer 13 were as follows:
-Mode d'application = Spin Coater à une vitesse de 700 tr/min pendant 15 secondes,  -Mode of application = Spin Coater at a speed of 700 rpm for 15 seconds,
-Concentration de la solution = 40 g/l de sulfate de zinc heptahydraté  -Concentration of the solution = 40 g / l of zinc sulphate heptahydrate
-pH de la solution = 5  -pH of the solution = 5
-Température de la solution = ambiante,  -Temperature of the solution = ambient,
-Séchage = en portant les éprouvettes jusqu'à une température comprise entre 70 et 80°C.  Drying = by carrying the specimens to a temperature between 70 and 80 ° C.
La protection temporaire des éprouvettes a été évaluée par un test en humidotherme selon la norme DIN EN ISO 6270-2 après application des huiles de protection suivantes sur les couches 13 :  The temporary protection of the specimens was evaluated by a humidity test according to DIN EN ISO 6270-2 after the application of the following protective oils to the layers 13:
- Quaker (marque déposée) 6130 : poids du film d'huile environ 1 g/m2, et - Quaker (registered trademark) 6130: weight of the oil film about 1 g / m 2 , and
- Fuchs (marque déposée) 4107 S : poids du film d'huile environ 1.2 g/m2. - Fuchs (registered trademark) 4107 S: weight of the oil film about 1.2 g / m 2 .
Dans un test en humidotherme selon la norme DIN EN ISO 6270-2, on soumet les éprouvettes a des cycles de vieillissement de 24 heures dans un humidotherme, c'est-à- dire une enceinte à atmosphère et à température contrôlées. Ces cycles simulent les conditions de corrosion d'une bobine de tôle ou d'une tôle découpée en feuille pendant son stockage. Chaque cycle comprend :  In a humidothermal test according to DIN EN ISO 6270-2, the test pieces are subjected to aging cycles of 24 hours in a humidotherm, that is to say an enclosure with controlled atmosphere and temperature. These cycles simulate the corrosion conditions of a sheet metal coil or sheet metal sheet during storage. Each cycle includes:
- une première phase de 8 heures à 40°C ± 3°C et à environ 98% d'humidité relative, suivie  a first phase of 8 hours at 40 ° C. ± 3 ° C. and at about 98% relative humidity, followed by
- d'une seconde phase de 16 heures à 21 °C ± 3°C et à moins de 98% d'humidité relative.  a second phase of 16 hours at 21 ° C. ± 3 ° C. and less than 98% relative humidity.
A l'issue de ces cycles, moins de 10% de la surface des éprouvettes doit être visuellement altérée:  At the end of these cycles, less than 10% of the test specimen surface must be visually impaired:
- après 10 cycles avec 1 g/m2 d'huile Quaker 6130 pour les constructeurs automobiles français, - après 15 cycles avec 1.2 g/m2 d'huile Fuchs 4107 S pour les constructeurs automobiles allemands. - after 10 cycles with 1 g / m 2 of Quaker 6130 oil for French car manufacturers, - after 15 cycles with 1.2 g / m 2 of Fuchs 4107 S oil for German car manufacturers.
La proportion de surface altérée est déterminée par inspection visuelle d'un opérateur.  The proportion of altered surface is determined by visual inspection of an operator.
La figure 2A montre l'aspect visuel d'une éprouvette ZEMg sans couche 3 après huilage Quaker 6130 tel que décrit ci-dessus. Cette éprouvette présente un noircissement important la rendant impropre à un usage par des constructeurs automobiles français. Au contraire, les éprouvettes ZEMg avec couche 13 (figures 2B à 2D) et après huilage Quaker 6130 tel que décrit ci-dessus satisfont toujours aux exigences des constructeurs automobiles français à l'issue du test.  Figure 2A shows the visual appearance of a ZEMg test tube without Layer 3 after Quaker 6130 oiling as described above. This test tube has a significant darkening making it unfit for use by French car manufacturers. On the contrary, the ZEMg test pieces with layer 13 (FIGS. 2B to 2D) and after Quaker 6130 oiling as described above still meet the requirements of the French car manufacturers at the end of the test.
Les figures 3A à 3D permettant montrent les aspects visuels, à l'issue du test, d'éprouvettes ZnMg Full PVD, sans couche 13 (Fig. 3A) et avec couche 13 (Fig. 3B à 3D), après huilage Quaker 6130 tel que décrit ci-dessus. Comme on le voit sur ces figures, la présence de la couche 13 permet de satisfaire aux exigences des constructeurs automobiles français.  FIGS. 3A to 3D allowing to show the visual aspects, at the end of the test, of ZnMg Full PVD specimens, without layer 13 (FIG 3A) and with layer 13 (FIG 3B to 3D), after oiling Quaker 6130 tel as described above. As seen in these figures, the presence of the layer 13 can meet the requirements of French car manufacturers.
Une éprouvette ZnMg Full PVD sans couche 13 (Fig. 3E) après huilage Fuchs tel que décrit ci-dessus ne satisfait pas aux exigences des constructeurs automobiles allemands, contrairement à une éprouvette ZnMg Full PVD avec couche 13 (Figure 3F) après huilage Fuchs tel que décrit ci-dessus.  A ZnMg Full PVD test tube without a 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 such as described above.
Les résultats du test en humidotherme ont été confirmés par des mesures de résistance de polarisation réalisées à partir d'essais d'impédancemétrie et de courbe de polarisation dans une solution de chlorure de sodium à 5% à pH 7.  The results of the humidothermal test were confirmed by polarization resistance measurements made from impedance and polarization tests in a 5% sodium chloride solution at pH 7.
Ces mesures montrent que les éprouvettes ZnMg Full PVD sans couche 13 présentent une résistance de polarisation comprise entre 160Ω et 380Ω. Avec une couche 13, cette résistance augmente à des valeurs comprises entre 840Ω et 1200Ω, confirmant ainsi le pouvoir protecteur de la couche 13.  These measurements show that ZnMg Full PVD test specimens without layer 13 have a polarization resistance of between 160Ω and 380Ω. With a layer 13, this resistance increases to values between 840Ω and 1200Ω, thus confirming the protective power of the layer 13.
L'ensemble des résultats obtenus sur les éprouvettes ZnMg Full PVD montre que les couches 13 permettent de réduire le noircissement de tôles 1 à revêtement 7 comprenant du zinc et du magnésium. Cet effet est indépendant de la diminution du démouillage que les couches 13 permettent d'obtenir, comme décrit dans la demande WO-2005/071 140. Ainsi, on peut utiliser un revêtement "7 avec une couche 13 sans huilage, tout en conservant une bonne protection temporaire. Résistance au ternissement : The set of results obtained on the ZnMg Full PVD test pieces shows that the layers 13 make it possible to reduce the blackening of coated metal sheets 1 comprising zinc and magnesium. This effect is independent of the decrease in dewetting that the layers 13 make it possible to obtain, as described in the application WO-2005/071 140. Thus, it is possible to use a coating 7 with a layer 13 without oiling, while retaining a good temporary protection. Tarnish resistance:
Une seule configuration de tôles 1 a été étudiée dans ce cas. Le revêtement 7 comprend uniquement une couche 9 d'environ 10 pm d'épaisseur et comprenant environ 3% en poids de magnésium, environ 3.7% en poids d'aluminium, le reste étant du zinc et les impuretés inévitables. Le substrat 3 est alors un acier laminé à froid pour emboutissage profond. Ces éprouvettes seront désignées ZnMgAI par la suite. Only one sheet configuration 1 has been studied in this case. The coating 7 comprises only a layer 9 of approximately 10 μm in thickness and comprising approximately 3% by weight of magnesium, approximately 3.7% by weight of aluminum, the balance being zinc and the unavoidable impurities. The substrate 3 is then a cold rolled steel for deep drawing. These specimens will be designated ZnMgAI thereafter.
Deux approvisionnements différents correspondant à cette configuration ont été testés et ils seront désignés par les références AR 2596 et AR 2598 par la suite.  Two different supplies corresponding to this configuration have been tested and they will be designated by references AR 2596 and AR 2598 thereafter.
La protection temporaire des éprouvettes ZnMgAI a été évaluée via un test de vieillissement en exposition naturelle sous abri selon la norme VDA 230-213 (durée du test 12 semaines). Il a en effet été constaté que le test en humidotherme ne permettait pas de reproduire le phénomène de ternissement observé dans des conditions naturelles de stockage.  Temporary protection of ZnMgAI specimens was evaluated via a natural exposure aging test under shelter in accordance with the VDA 230-213 standard (12 week test duration). It has indeed been found that the test in humidotherm did not reproduce the phenomenon of tarnishing observed in natural storage conditions.
Les éprouvettes ZnMgAI ont été testées à l'état huilé (film de Quaker 6130 avec un poids d'environ 1g/m2) et non huilé, avec et sans couche 13. A titre comparatif, les mêmes tests ont été menés sur des éprouvettes issues d'une tôle galvanisée standard avec un revêtement de zinc de 10 μηι d'épaisseur et un substrat d'acier laminé à froid pour emboutissage profond. Ces dernières éprouvettes seront désignées Gl par la suite. The ZnMgAI test pieces were tested in the oiled state (Quaker 6130 film with a weight of about 1 g / m 2 ) and not oiled, with and without a layer 13. By comparison, the same tests were carried out on specimens from a standard galvanized sheet with a zinc coating 10 μηι thick and a cold-rolled steel substrate for deep drawing. These last test pieces will be designated Gl thereafter.
Le suivi de l'évolution du ternissement au cours du test a été réalisé via un colorimètre mesurant l'écart de luminance (mesure du AL*). La valeur seuil de | AL* | correspondant à l'apparition du ternissement a été fixée à 2. The monitoring of the evolution of tarnishing during the test was carried out via a colorimeter measuring the luminance difference (measurement of AL * ). The threshold value of | AL * | corresponding to the appearance of tarnishing was set at 2.
Les résultats obtenus pour les éprouvettes Gl, ZnMgAI AR 2596 et ZnMgAI AR 2598 sont représentés respectivement sur les figures 4 à 6 où le temps, en semaines, est porté en abscisse et l'évolution de AL* est portée en ordonnées.  The results obtained for the specimens Gl, ZnMgAI AR 2596 and ZnMgAI AR 2598 are represented respectively in FIGS. 4 to 6, where the time in weeks is plotted on the abscissa and the evolution of AL * is plotted on the ordinate.
Les différentes courbes sont repérées par les symboles suivants sur chacune des figures 4 à 6 :  The different curves are marked by the following symbols in each of FIGS. 4 to 6:
• : éprouvettes sans couche 13 ni huilage,  •: specimens without layer 13 or oiling,
x : éprouvettes sans couche 13 mais huilées avec un film d'huile Quaker 6130 d'un poids d'environ 1 g/m2, x: test pieces without layer 13 but oiled with a Quaker 6130 oil film weighing approximately 1 g / m 2 ,
■ : éprouvettes avec couche 13 et huilées avec un film d'huile Quaker 6130 d'un poids d'environ 1 g/m2, ■: specimens with layer 13 and oiled with a Quaker 6130 oil film weighing approximately 1 g / m 2 ,
♦ : éprouvettes avec couche 13 sans huilage.  ♦: specimens with layer 13 without oiling.
Ces résultats montrent l'intérêt des couches 13 pour la protection temporaire contre le ternissement de revêtements 7 comprenant du zinc, du magnésium et de l'aluminium, puisque l'ensemble des éprouvettes avec une couche 13 présentent une cinétique de ternissement ralentie par rapport aux éprouvettes sans couche 13, que ce soit avec ou sans huilage, et ce même pour les éprouvettes Gl. These results show the advantage of the layers 13 for the temporary protection against the tarnishing of coatings 7 comprising zinc, magnesium and aluminum, since the set of specimens with a layer 13 exhibit a slowed stain kinetics compared to the test pieces without layer 13, whether with or without oiling, and this even for the specimens G1.
Après 12 semaines, le niveau de ternissement atteint par les éprouvettes ZnMgAI avec couche 13 est équivalent à celui des éprouvettes Gl huilées.  After 12 weeks, the level of tarnishing achieved by the ZnMgAI test specimens with layer 13 is equivalent to that of the oiled Gl specimens.

Claims

REVENDICATIONS
1. Utilisation d'une solution aqueuse de traitement contenant des ions sulfates S04 2" à une concentration supérieure ou égale à 0,01 mol/l, pour traiter une tôle (1) comprenant un substrat (3) en acier revêtu sur au moins une de ses faces (5) d'un revêtement (7) comprenant au moins du zinc et du magnésium, en vue de réduire le noircissement ou le ternissement de la tôle (1 ) lors de son stockage. 1. Use of an aqueous treatment solution containing sulphate ions S0 4 2 " at a concentration greater than or equal to 0.01 mol / l, for treating a sheet (1) comprising a substrate (3) coated steel on at least one of its faces (5) of a coating (7) comprising at least zinc and magnesium, in order to reduce the blackening or tarnishing of the sheet (1) during storage.
2. Utilisation selon la revendication 1 , dans laquelle le revêtement (7) comprend au moins du zinc, du magnésium et de l'aluminium.  2. Use according to claim 1, wherein the coating (7) comprises at least zinc, magnesium and aluminum.
3. Utilisation selon la revendication 1 ou 2, dans laquelle le pH de la solution aqueuse de traitement est compris entre 5 et 7.  3. Use according to claim 1 or 2, wherein the pH of the aqueous treatment solution is between 5 and 7.
4. Utilisation selon l'une quelconque des revendications 1 à 3, dans laquelle la solution aqueuse de traitement contient en outre des ions Zn2+ à une concentration supérieure ou égale à 0,01 mol/l. 4. Use according to any one of claims 1 to 3, wherein the aqueous treatment solution further contains Zn 2+ ions at a concentration greater than or equal to 0.01 mol / l.
5. Utilisation selon la revendication 4, dans laquelle la concentration en ions Zn2+ et la concentration en ions S04 2" sont comprises entre 0,07 et 0,55 mol/l dans la solution aqueuse de traitement. 5. Use according to claim 4, wherein the concentration of Zn 2+ ions and the ion concentration S0 4 2 "are between 0.07 and 0.55 mol / l in the aqueous treatment solution.
6. Utilisation selon la revendication 5, dans laquelle la solution aqueuse de traitement est appliquée sur le revêtement (7) dans des conditions de température, de temps de contact avec le revêtement (7), de concentration en ions S04 2" et en ions Zn2+ ajustés pour former une couche de protection temporaire (13) à base d'hydroxysulfate de zinc et de sulfate de zinc dont la quantité en soufre est supérieure ou égale à 0,5 mg/m2 et inférieure ou égale à 30mg/m2. The use according to claim 5, wherein the aqueous treatment solution is applied to the coating (7) under conditions of temperature, coating contact time (7), SO 4 2- ion concentration and Zn 2+ ions adjusted to form a temporary protective layer (13) based on zinc hydroxysulfate and zinc sulphate whose sulfur content is greater than or equal to 0.5 mg / m 2 and less than or equal to 30 mg / m 2 .
7. Utilisation selon la revendication 6, dans laquelle la solution aqueuse de traitement est appliquée sur le revêtement (7) dans des conditions de température, de temps de contact avec le revêtement (7), de concentrations en ions S04 2" et en ions Zn2+ ajustées pour former une couche de protection temporaire (13) à base d'hydroxysulfate de zinc et de sulfate de zinc présentant une quantité en soufre comprise entre 3,7 et 27 mg/m2. The use according to claim 6, wherein the aqueous treatment solution is applied to the coating (7) under conditions of temperature, coating contact time (7), SO 4 2 - ion concentrations and Zn 2+ ions adjusted to form a temporary protective layer (13) based on zinc hydroxysulfate and zinc sulphate having a sulfur content of between 3.7 and 27 mg / m 2 .
8. Utilisation selon l'une quelconque des revendications 1 à 7, dans laquelle, après l'application de la solution aqueuse de traitement sur le revêtement (7), la tôle (1) est séchée, après avoir été éventuellement rincée. 8. Use according to any one of claims 1 to 7, wherein, after the application of the aqueous treatment solution on the coating (7), the sheet (1) is dried, after being optionally rinsed.
9. Utilisation selon la revendication 1 ou 2, dans laquelle la solution aqueuse de traitement est appliquée sous polarisation anodique, et le pH de la solution aqueuse de traitement est supérieur ou égal à 12, et inférieur à 13. 9. Use according to claim 1 or 2, wherein the aqueous treatment solution is applied under anodic polarization, and the pH of the aqueous treatment solution is greater than or equal to 12, and less than 13.
10. Utilisation selon la revendication 9, dans laquelle la concentration en ion S04 2" est supérieure à 0,07 mol/l. 10. Use according to claim 9, wherein the ion concentration S0 4 2 "is more than 0.07 mol / l.
11. Utilisation selon la revendication 9 ou 10, dans laquelle la densité de charges électriques circulant pendant le traitement au travers du revêtement (7), est ajustée pour former une couche de protection temporaire (13) à base d'hydroxysulfate de zinc et de sulfate de zinc dont la quantité en soufre est supérieure ou égale à 0,5 mg/m2 et inférieure ou égale à 30 mg/m2. Use according to claim 9 or 10, wherein the density of electrical charges flowing during treatment through the coating (7) is adjusted to form a temporary protective layer (13) based on zinc hydroxysulfate and zinc sulphate with a sulfur content greater than or equal to 0.5 mg / m 2 and less than or equal to 30 mg / m 2 .
12. Utilisation selon la revendication 11 , dans laquelle la densité de charges électriques est ajustée pour former une couche de protection temporaire (13) à base d'hydroxysulfate de zinc et de sulfate de zinc dont la quantité en soufre est comprise entre 3,7 et 27 mg/m2. 12. Use according to claim 11, wherein the density of electrical charges is adjusted to form a temporary protective layer (13) based on zinc hydroxysulfate and zinc sulphate whose sulfur content is between 3.7 and 27 mg / m 2 .
13. Utilisation selon l'une quelconque des revendications 9 à 12, dans laquelle la densité de courant de polarisation appliquée pendant le traitement est supérieure à 20 A/dm2.Use according to any one of claims 9 to 12, wherein the bias current density applied during the treatment is greater than 20 A / dm 2 .
14. Utilisation selon l'une quelconque des revendications 9 à 13, dans laquelle, après l'application de la solution aqueuse de traitement sur le revêtement (7), la tôle (1) est rincée. 14. Use according to any one of claims 9 to 13, wherein, after the application of the aqueous treatment solution on the coating (7), the sheet (1) is rinsed.
15. Tôle (1) comprenant un substrat (3) en acier, un revêtement (7) recouvrant au moins une face (5) du substrat (3), le revêtement (7) comprenant du zinc, du magnésium et de l'aluminium, la tôle (1) comprenant en outre une couche de protection temporaire (13) à base d'hydroxysulfate de zinc et de sulfate de zinc dont la quantité en soufre est supérieure ou égale à 0,5 mg/m2 et inférieure ou égale à 30 mg/m2, ladite couche de protection temporaire (13) surmontant le revêtement (7). 15. Sheet (1) comprising a substrate (3) of steel, a coating (7) covering at least one face (5) of the substrate (3), the coating (7) comprising zinc, magnesium and aluminum , the sheet (1) further comprising a temporary protective layer (13) based on zinc hydroxysulfate and zinc sulphate whose sulfur content is greater than or equal to 0.5 mg / m 2 and less than or equal to at 30 mg / m 2 , said temporary protective layer (13) surmounting the coating (7).
16. Tôle selon la revendication 15, dans laquelle la couche de protection temporaire (13) a une quantité en soufre supérieure ou égale à 3,7 mg/m2 et inférieure ou égale à 27 mg/m2. 16. Sheet according to claim 15, wherein the temporary protective layer (13) has a sulfur content greater than or equal to 3.7 mg / m 2 and less than or equal to 27 mg / m 2 .
17. Tôle selon la revendication 15 ou 16, dans laquelle le revêtement (7) comprend entre 0,1 et 10% en poids de magnésium et entre 0,1 et 20% en poids d'aluminium.  17. Sheet according to claim 15 or 16, wherein the coating (7) comprises between 0.1 and 10% by weight of magnesium and between 0.1 and 20% by weight of aluminum.
18. Tôle selon l'une quelconque des revendications 15 à 17, dans laquelle le revêtement (7) comprend entre 2 et 4% en poids de magnésium et entre 2 et 6% en poids d'aluminium.  18. Sheet according to any one of claims 15 to 17, wherein the coating (7) comprises between 2 and 4% by weight of magnesium and between 2 and 6% by weight of aluminum.
EP12705147.2A 2012-01-10 2012-01-10 Use of a solution containing sulphate ions for reducing the blackening or tarnishing of a metal sheet during the storage thereof and metal sheet treated with such a solution Active EP2802682B1 (en)

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CN111133123A (en) * 2017-10-12 2020-05-08 安赛乐米塔尔公司 Method for treating metal plate and metal plate treated by the method
CN111133123B (en) * 2017-10-12 2021-12-03 安赛乐米塔尔公司 Method for treating metal plate and metal plate treated by the method

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US20200318252A1 (en) 2020-10-08
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WO2013104835A1 (en) 2013-07-18
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JP6280049B2 (en) 2018-02-14
PL2802682T3 (en) 2021-04-19

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