EP1699947A1 - Hydroxysulfate surface treatment - Google Patents

Hydroxysulfate surface treatment

Info

Publication number
EP1699947A1
EP1699947A1 EP04816380A EP04816380A EP1699947A1 EP 1699947 A1 EP1699947 A1 EP 1699947A1 EP 04816380 A EP04816380 A EP 04816380A EP 04816380 A EP04816380 A EP 04816380A EP 1699947 A1 EP1699947 A1 EP 1699947A1
Authority
EP
European Patent Office
Prior art keywords
zinc
sheet
treatment solution
use according
ions
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04816380A
Other languages
German (de)
French (fr)
Inventor
Alain Bello
Eric Jacqueson
Claude Arnoux
Jacques Petitjean
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 France SA
Original Assignee
Arcelor France SA
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 Arcelor France SA filed Critical Arcelor France SA
Priority to EP12000368A priority Critical patent/EP2450470A1/en
Publication of EP1699947A1 publication Critical patent/EP1699947A1/en
Withdrawn legal-status Critical Current

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
    • C23C22/68—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
    • B21D22/20—Deep-drawing
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/06—Electrolytic coating other than with metals with inorganic materials by anodic processes

Definitions

  • the present invention relates to the use of a treatment solution for treating the surface of a steel sheet coated with a metallic coating based on zinc or its alloys. It also relates to a method of lubricating such a coated sheet.
  • Steel sheets coated with zinc or its alloys are commonly used in the automotive field and in industry in general, because they have excellent resistance to corrosion.
  • these galvanized steel sheets present a certain number of difficulties when they are shaped, for example by stamping, to manufacture parts.
  • a film of lubricating oil is applied to their surface which facilitates shaping.
  • the very high friction exerted by the shaping tools on the surface of the sheet metal causes, on the surface of the sheet metal, powder or particles based on zinc or its alloys generated by degradation of the coating.
  • the accumulation and / or agglomeration of these particles or of this powder in the shaping tools can cause damage to the formed parts, by the formation of spikes and / or necks.
  • the sheet due to the high coefficient of friction which characterizes the sliding of a galvanized surface in contact with the surface of a forming tool, the sheet may break if there is insufficient sliding of the sheet in the grip of the formatting tool.
  • the present invention therefore aims to provide a treatment solution which, applied to the surface of a steel sheet coated with a metallic layer based on zinc or its alloys, makes it possible to reduce the degradation of the zinc-plated surface. of this sheet during its shaping, to reduce the quantity of lubricating oil to deposit on the sheet before its shaping, and to improve the temporary protection against corrosion of the sheet.
  • the subject of the invention is the use of an aqueous treatment solution containing sulphate ions SO 4 2 " at a concentration greater than or equal to 0.01 mol / l, for treating the surface of a sheet of steel coated on at least one of its faces with a metallic coating based on zinc or its alloys, in order to reduce the formation of powder or metallic particles based on zinc or its alloys generated by degradation of the coating during the shaping of said sheet.
  • metallic coating based on zinc alloy means a zinc coating comprising one or more alloying elements, such as, for example and without limitation, iron, aluminum, silicon, magnesium, and nickel. According to the invention, the use of a steel sheet coated with an almost pure zinc coating is preferred.
  • the treatment solution is applied in a conventional manner, for example by dipping, by sprinkling or by coating, both on electro-galvanized sheets and on galvanized sheets.
  • 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 treatment solution is prepared, for example, by dissolving zinc sulfate in pure water; for example, zinc sulphate heptahydrate (ZnSO4, 7 H2O) is used; the concentration of Zn 2+ ions is then equal to that of the SO 4 2 7 anions.
  • the pH of the treatment solution preferably corresponds to the natural pH of the solution, without the addition of base or acid; the value of this pH is generally between 5 and 7.
  • concentration of SO4 2 " ions and Zn 2+ ions adjusted to form a layer based on zinc hydroxysulfate and zinc sulphate with a sulfur quantity greater than or equal to 0.5 mg / m 2.
  • the contact time of the treatment solution with the galvanized surface is between 2 seconds and 2 minutes, and the temperature of the treatment solution is between 20 and 60 ° C.
  • the solution of treatment 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 between 0.07 and 0.55 mol / l. Indeed, it was found that, in this concentration range, the deposition rate was little influenced by the value of the concentration.
  • the treatment solution is applied under conditions of temperature, time of contact with the galvanized surface, and concentrations of SO4 2 " ions and of Zn 2+ ions adjusted to form a layer based on hydroxysulphate and sulphate having a quantity of sulfur of between 3.7 and 27 mg / m 2.
  • the treatment solution contains an oxidizing agent for zinc, such as hydrogen peroxide.
  • This oxidizing agent can have an accelerating effect on hydroxysulfation and very marked sulfation at low concentration. It has been found that the addition of only 0.03% , that is to say 8.10 "3 mol / liter of hydrogen peroxide, or of 2.10 " 4 mole / liter of potassium permanganate in the solution made it possible to double (approximately) the rate of deposition. It was found, on the contrary, that concentrations 100 times higher no longer allowed this improvement in the deposition rate to be obtained.
  • the layer deposited on the sheet is adherent;
  • the drying is adjusted to remove the residual liquid water between the application step and the drying step, the sheet is preferably rinsed so as to remove the soluble part of the deposit obtained; the absence of rinsing and obtaining a deposit which is partially soluble in water which results therefrom are not very detrimental to the reduction of the degradation of the zinc-plated coating during the shaping of the sheet, as long as the deposit obtained includes a layer based on zinc hydroxysulfate and zinc sulfate insoluble in water in contact with the sheet.
  • the aqueous treatment solution comprising a concentration of SO 2 " ions greater than or equal to 0.01 mol / l is applied under anodic polarization, and the pH of the treatment solution is higher or equal to 12, and less than 13. If the pH of the solution is less than 12, no adherent hydroxysulfates are formed on the surface to be treated. If the pH of the solution is greater than or equal to 13, the hydroxysulfate redissolves and / or decomposes into zinc hydroxides.
  • the concentration of SO 4 2 " ions be greater than or equal to 0.01 moles per liter, and preferably greater than or equal to 0.07 mol / l.
  • the ion concentration sulfates is preferably less than or equal to 1 mole / liter; in the case of the use of sodium sulfate, at concentrations greater than 142 g / l (equivalent to 1 mole SO 4 2 " / liter), for example 180 g / l, there is a decrease in the yield of formation of the layer based on zinc hydroxysulfate and zinc sulfate.
  • the total amount of hydroxysulphates and sulphates 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 zinc necessary for the formation of the deposit based on zinc hydroxysulphate and zinc sulphate comes from the anodic dissolution of zinc under the effect of the polarization of the zinc-plated surface. It is therefore appropriate that the density of electrical charges, circulating during the treatment through the surface of the sheet, be adjusted so as to form a layer based on zinc hydroxysulfate and on zinc sulfate with a higher sulfur content.
  • the charge density applied is preferably between 10 and 100 C / dm 2 of surface to be treated. If the charge density exceeds 100 C / dm 2 , it can be seen that the quantity of sulfur deposited on the surface no longer increases and even decreases. Thanks to the anodic polarization of the zinc-plated surface to be treated, there is a rapid dissolution of the zinc in the immediate vicinity of the zinc-plated surface, which promotes the precipitation of zinc salts on this surface. Thus, to carry out this treatment as productively as possible with a satisfactory faradic yield, it is advisable to deposit the layer based on zinc hydroxysulfate and zinc sulfate under a high bias current density, in particular greater than 20
  • the deposition efficiency is very low and the amount of sulfur in the deposited layer does not make it possible to obtain a significant reduction in the degradation of the zinc coating of the sheet. during its shaping.
  • a titanium cathode can be used as a counter electrode.
  • the temperature of the treatment solution is generally between 20 ° C and 60 ° C. Preferably, the temperature is greater than or equal to 40 ° C., so as to increase the conductivity of the solution and to reduce the ohmic losses.
  • the speed of circulation of the solution on the surface of the sheet does not, here, have a decisive effect on the treatment according to the invention.
  • the treated surface is thoroughly rinsed with demineralized water. This rinsing step is important to remove alkaline reagents from the surface of the deposit, which would cause corrosion problems.
  • the invention also relates to a method of lubricating a steel sheet coated with a layer consisting of a metallic coating based on zinc or its alloys, and in which: - said sheet is coated with a layer upper based on zinc hydroxysulphate and zinc sulphate, said upper layer having been obtained by the use of a treatment solution according to the invention, then - a film of lubricating oil is applied to the upper layer with a grammage of less than 1 g / m 2 .
  • the film of lubricating oil is applied with a grammage preferably less than 0.9 g / m 2 , and more preferably between 0.2 and 0.5 g / m 2 , because these grammages are sufficient to obtain excellent protection temporary against corrosion and avoid any risk of pollution of workshops and shaping tools.
  • the subject of the invention is the use of an aqueous treatment solution comprising sulphate ions at a concentration greater than or equal to 0.01 mol / l, to improve the temporary protection against corrosion of a sheet of steel coated with a metallic layer based on zinc or its alloys.
  • this aqueous treatment solution to the steel sheet is carried out according to the embodiments described in the paragraphs concerning the use of an aqueous treatment solution containing sulphate ions to treat a galvanized steel sheet. to reduce the degradation of the zinc coating during its shaping.
  • an aqueous treatment solution containing sulphate ions to treat a galvanized steel sheet. to reduce the degradation of the zinc coating during its shaping.
  • the inventors have shown that temporary protection against corrosion of a galvanized steel sheet first treated with a treatment solution according to the invention, then coated with a film of oil was much superior to that of a galvanized steel sheet not previously treated.
  • An aqueous treatment solution was prepared in accordance with the invention, prepared with 125 g / l zinc sulfate heptahydrate ZnS ⁇ 4 , 7 H 2 O. This treatment solution was then applied to part of the test pieces by spraying the solution treatment, at a temperature of 40 ° C. After a contact time of the solution with the sheet of 3 to 4 s, the treated sheet is wrung and then dried. Then was applied to the layer based on zinc hydroxysulphate and zinc sulphate formed on the surface of the test pieces of galvanized steel sheet, a film of lubricating oil which may be either QUAKER 6130 oil (from Quaker company), i.e.
  • FUCHS 4107S oil (from Fuchs company), with a grammage of 1.5 g / m 2 .
  • Another part of the test pieces which had not been previously treated with the treatment solution according to the invention was oiled either with QUAKER 6130 oil or with FUCHS 4107S oil also with a grammage of 1.5 g / m 2 .
  • the two series of test pieces were then subjected to a deformation test controlled by means of a press comprising a punch, a matrix and a blank holder, recreating in the laboratory the stresses undergone by the sheet during the stamping operation, in particular in the matrix radii and / or in the retaining rods which equip the stamping tools. Different clamping forces of the blank holder were applied to the test pieces tested.
  • test pieces of the two series were weighed before the oiling operation, then at the end of the test after oil removal, using a balance accurate to 0.0001 grams.
  • the difference in measured mass was reduced to a loss of mass per square meter, taking into account the surface affected by friction during the simulation of the stamping of the test piece, identical for each of the test pieces.
  • the press was wiped so as to identify the powder or particles of zinc coating lost by the test piece in the press.
  • Table 1 The results of loss of mass of the test pieces after stamping, as well as the identification of the powder and / or of the zinc particles resulting from the coating are grouped in Table 1.
  • test pieces Part of these test pieces is treated with a treatment solution according to the invention, under the same conditions as those indicated in Example 1, so as to form a layer based on zinc hydroxysulfate and zinc sulfate. Then a film of lubricating oil (QUAKER 6130 oil) is applied to this layer with quantities of between 0.25 and 2.5 g / m 2 . Another part of the test pieces was oiled in the same way as above, but was not previously treated with the treatment solution according to the invention. Then the friction characterization of each of the test pieces is carried out using a tribology test apparatus, in the following manner: The test apparatus is a plane-plane tribometer known in itself.
  • the test pieces to be tested are clamped according to a clamping force Fs between two high-speed steel plates providing a bearing (or sliding) surface on the test pieces.
  • the coefficient of friction N is measured, while moving the test piece relative to the pads over a total stroke D of 180 mm and at the speed of 10 mm / Fs by gradually increasing the clamping force Fs.
  • test pieces Part of these test pieces is treated with a treatment solution according to the invention, under the same conditions as those indicated in Example 1, so as to form a layer based on zinc hydroxysulfate and zinc sulfate. Then a film of lubricating oil (QUAKER 6130 oil) is applied to this layer with grammages between 0.25 and 1.0 g / m 2 . Another part of the test pieces was oiled in the same way as above, but was not previously treated with the treatment solution according to the invention.
  • the lubricating oils applied to steel sheets coated with a zinc-based metal layer guarantee protection against corrosion during the period of time between the manufacture of the sheets and their implementation, for example by stamping.
  • test specimens are placed in a climatic chamber corresponding to the DIN 50017 standard, which simulates the corrosion conditions of an outer coil of sheet metal coil or of a sheet metal cut into sheets during storage.
  • the test pieces are individually hung vertically.
  • the test result, shown in table 3 is obtained by recording the number of successive cycles before the corrosion traces appear on the test piece.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Coating With Molten Metal (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

The aim of the invention is the use of an sulphate ions-containing solution for treating the surface of a galvanised steel sheet in order to reduce a coating degradation during the chapping thereof and to improve the temporary protecting said sheet against corrosion. A method for lubricating said coated sheet is also disclosed.

Description

Traitement de surface par hydroxysulfate Surface treatment with hydroxysulfate
La présente invention concerne l'utilisation d'une solution de traitement pour traiter la surface d'une tôle d'acier revêtue d'un revêtement métallique à base de zinc ou de ses alliages. Elle concerne également un procédé de lubrification d'une telle tôle revêtue. Les tôles d'acier revêtues de zinc ou de ses alliages sont couramment utilisées dans le domaine automobile et de l'industrie en général, car elles présentent une excellente résistance à la corrosion. Cependant, ces tôles d'acier zinguées présentent un certain nombre de difficultés lorsque qu'on les met en forme, par exemple par emboutissage, pour fabriquer des pièces. Habituellement afin de conférer aux tôles d'aciers zinguées de meilleures propriétés tribologiques, on applique sur leur surface un film d'huile de lubrification qui facilite la mise en forme. Cependant, malgré l'application d'un film d'huile de lubrification adapté, les frottements très importants exercés par les outils de mise en forme sur la surface de la tôle provoquent, à la surface de la tôle, de la poudre ou des particules à base de zinc ou de ses alliages générées par la dégradation du revêtement. L'accumulation et/ou l'agglomération de ces particules ou de cette poudre dans les outils de mise en forme peuvent provoquer l'endommagement des pièces formées, par formation de picots et/ou de strictions. En outre, en raison du coefficient de frottement élevé qui caractérise le glissement d'une surface zinguée en contact avec la surface d'un outil de mise en forme, la tôle risque de se rompre en cas de glissement insuffisant de la tôle dans l'emprise de l'outil de mise en forme. Ces ruptures peuvent apparaître, même en appliquant à la surface de la tôle un film d'huile avec un grammage suffisant, soit supérieur à 1 g/m2, car il n'est pas possible de conserver à la surface de la tôle une répartition homogène du film d'huile. Ceci est du au phénomène de démouillage qui correspond à la présence de zones présentant un déficit d'huile. Cependant, le fait de déposer à la surface de la tôle un film d'huile relativement épais pose des problèmes de pollution des ateliers et des outils d'emboutissage, et impose l'utilisation de quantités importantes de produits dégraissants pour nettoyer la tôle ainsi que des moyens importants pour traiter les effluents issus du nettoyage. Par ailleurs, les déficits d'huile dans certaines zones du film d'huile dus au phénomène de démouillage, sont également responsables d'une moindre protection temporaire contre la corrosion de la tôle d'acier lors de son stockage. La présente invention a donc pour but de proposer une solution de traitement qui, appliquée à la surface d'une tôle d'acier revêtue d'une couche métallique à base de zinc ou de ses alliages, permette de réduire la dégradation de la surface zinguée de cette tôle lors de sa mise en forme, de réduire la quantité d'huile de lubrification à déposer sur la tôle avant sa mise en forme, et d'améliorer la protection temporaire contre la corrosion de la tôle. A cet effet, l'invention a pour objet l'utilisation d'une solution aqueuse de traitement contenant des ions sulfates SO4 2" à une concentration supérieure ou égale à 0,01 mol/l, pour traiter la surface d'une tôle d'acier revêtue sur au moins une de ses faces, d'un revêtement métallique à base de zinc ou de ses alliages, en vue de réduire la formation de poudre ou de particules métalliques à base de zinc ou de ses alliages générées par la dégradation du revêtement lors de la mise en forme de ladite tôle. On entend par revêtement métallique à base d'alliage de zinc, un revêtement de zinc comprenant un ou plusieurs éléments d'alliage, comme par exemple et à titre non limitatif, le fer, l'aluminium, le silicium, le magnésium, et le nickel. Selon l'invention, on préfère l'utilisation d'une tôle d'acier revêtue d'un revêtement de zinc quasiment pur. Lorsque l'on traite la surface d'une tôle d'acier revêtue par un revêtement métallique à base de zinc ou de ses alliages, au moyen d'une solution de traitement aqueuse conforme à l'invention, il se forme à la surface de la tôle une couche à base d'hydroxysulfate de zinc et de sulfate de zinc à la fois suffisamment épaisse et adhérente. En revanche, on ne parvient pas à former une telle couche lorsque la concentration en SO4 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. Dans un premier mode de réalisation de l'invention, la solution de traitement s'applique de manière classique, par exemple au trempé, par aspersion ou par enduction, aussi bien sur des tôles electrozinguees que sur des tôles galvanisées au trempé. 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. On prépare par exemple la solution 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 SO4 27 Le pH de la solution 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. Pour réduire au maximum, la formation de poudre ou de particules de zinc ou de ses alliages issus de la dégradation du revêtement de la tôle lors de sa mise en forme, on applique la solution de traitement à la surface de la tôle dans des conditions de température, de temps de contact avec la surface zinguée, de concentration en ions SO42" et en ions Zn2+ ajustés pour former une couche 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. En effet, lorsque la quantité en soufre est inférieure à 0,5 mg/m2, l'amélioration de la dégradation du revêtement est moins sensible. Ainsi, le temps de contact de la solution de traitement avec la surface zinguée est compris entre 2 secondes et 2 minutes, et la température de la solution de traitement est comprise entre 20 et 60°C. De préférence, la solution 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 SO4 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. Avantageusement, la solution de traitement est appliquée dans des conditions de température, de temps de contact avec la surface zinguée, et de concentrations en ions SO42" et en ions Zn2+ ajustées pour former une couche à base d'hydroxysulfate et de sulfate présentant une quantité de soufre comprise entre 3,7 et 27 mg/m2. Selon une variante de l'invention, la solution 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. Après application de la solution de traitement et avant séchage, la couche déposée sur la tôle est adhérente; Le séchage est ajusté pour éliminer l'eau liquide résiduelle du dépôt. Entre l'étape d'application et l'étape de séchage, on rince de préférence la tôle 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 zingué lors de la mise en forme de la tôle, du moment que le dépôt obtenu comprend bien une couche à base d'hydroxysulfate de zinc et de sulfate de zinc insoluble à l'eau au contact de la tôle. Selon un second mode de réalisation de l'invention, la solution aqueuse de traitement comprenant une concentration en ions SO 2" supérieure ou égale à 0,01 mol/l est appliquée sous polarisation anodique, et le pH de la solution de traitement est supérieur ou égal à 12, et inférieur à 13. Si le pH de la solution est inférieur à 12, on ne forme pas d'hydroxysulfates 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. Lorsqu'on utilise du sulfate de sodium dans la solution de traitement, si la concentration en sulfate de sodium est inférieure à 1 ,4 g/l dans la solution, on observe peu de formation d'hydroxysulfates sur la surface ; de façon plus générale, il importe donc que la concentration en ions SO4 2" soit supérieure ou égale à 0,01 moles par litre, et de préférence supérieure ou égale à 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 (équivalent à 1 mole SO4 2" /litre), par exemple 180 g/l, on observe une diminution du rendement de formation de la couche à base d'hydroxysulfate de zinc et de sulfate de zinc. On a constaté que la réduction de la dégradation du revêtement zingué de la tôle lors de sa mise en forme n'était obtenue que si l'épaisseur de la couche à base d'hydroxysulfate de zinc et de sulfate de zinc déposée correspondait à plus de 0,5 mg/m2 en équivalent soufre, de préférence au moins 3,5 mg/m2 en équivalent soufre. On a constaté à l'inverse que la réduction de la dégradation du revêtement zingué diminuait si la quantité de soufre dans la couche à base d'hydroxysulfate de zinc et de sulfate de zinc déposée dépassait largement 30 mg/m2, du fait, semble-t-il, de la dégradation de l'adhérence de cette couche. Ainsi, pour obtenir une réduction de la détérioration du revêtement zingué significative, 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. Le zinc nécessaire à la formation du dépôt à base d'hydroxysulfate de zinc et de sulfate de zinc provient de la dissolution anodique du zinc sous l'effet de la polarisation de la surface zinguée. Il convient donc que la densité de charges électriques, circulant pendant le traitement au travers de la surface de la tôle, soit ajustée de manière à former une couche à base d'hydroxysulfate de zinc et de sulfate de zinc dont le quantité en soufre est supérieure ou égale à 0,5 mg/m2. Ainsi, de préférence, la densité de charge appliquée est de préférence comprise entre 10 et 100 C/dm2 de surface à traiter. Si la densité de charge dépasse 100 C/dm2, on constate que la quantité de soufre déposée sur la surface n'augmente plus et même diminue. Grâce à la polarisation anodique de la surface zinguée à traiter, on assiste à une dissolution rapide du zinc à proximité immédiate de la surface zinguée, ce qui favorise la précipitation de sels de zinc sur cette surface. Ainsi, pour réaliser ce traitement de manière aussi productive que possible avec un rendement faradique satisfaisant, il convient d'effectuer le dépôt de la couche à base d'hydroxysulfate de zinc et de sulfate de zinc sous une densité de courant de polarisation élevée, notamment supérieure à 20The present invention relates to the use of a treatment solution for treating the surface of a steel sheet coated with a metallic coating based on zinc or its alloys. It also relates to a method of lubricating such a coated sheet. Steel sheets coated with zinc or its alloys are commonly used in the automotive field and in industry in general, because they have excellent resistance to corrosion. However, these galvanized steel sheets present a certain number of difficulties when they are shaped, for example by stamping, to manufacture parts. Usually in order to give the galvanized steel sheets better tribological properties, a film of lubricating oil is applied to their surface which facilitates shaping. However, despite the application of a suitable lubricating oil film, the very high friction exerted by the shaping tools on the surface of the sheet metal causes, on the surface of the sheet metal, powder or particles based on zinc or its alloys generated by degradation of the coating. The accumulation and / or agglomeration of these particles or of this powder in the shaping tools can cause damage to the formed parts, by the formation of spikes and / or necks. In addition, due to the high coefficient of friction which characterizes the sliding of a galvanized surface in contact with the surface of a forming tool, the sheet may break if there is insufficient sliding of the sheet in the grip of the formatting tool. These ruptures can appear, even by applying to the surface of the sheet a film of oil with a sufficient grammage, that is to say greater than 1 g / m 2 , because it is not possible to keep a distribution on the sheet surface homogeneous oil film. This is due to the dewetting phenomenon which corresponds to the presence of areas with an oil deficit. However, the fact of depositing on the surface of the sheet a relatively thick film of oil poses problems of pollution of workshops and stamping tools, and requires the use of large quantities of products. degreasers to clean the sheet as well as important means to treat the effluents from cleaning. Furthermore, the oil deficits in certain zones of the oil film due to the dewetting phenomenon, are also responsible for less temporary protection against corrosion of the steel sheet during its storage. The present invention therefore aims to provide a treatment solution which, applied to the surface of a steel sheet coated with a metallic layer based on zinc or its alloys, makes it possible to reduce the degradation of the zinc-plated surface. of this sheet during its shaping, to reduce the quantity of lubricating oil to deposit on the sheet before its shaping, and to improve the temporary protection against corrosion of the sheet. To this end, the subject of the invention is the use of an aqueous treatment solution containing sulphate ions SO 4 2 " at a concentration greater than or equal to 0.01 mol / l, for treating the surface of a sheet of steel coated on at least one of its faces with a metallic coating based on zinc or its alloys, in order to reduce the formation of powder or metallic particles based on zinc or its alloys generated by degradation of the coating during the shaping of said sheet. The term “metallic coating based on zinc alloy” means a zinc coating comprising one or more alloying elements, such as, for example and without limitation, iron, aluminum, silicon, magnesium, and nickel. According to the invention, the use of a steel sheet coated with an almost pure zinc coating is preferred. a steel sheet coated with a metallic coating based on zinc or its alloys, by means of an aqueous treatment solution according to the invention, a layer based on zinc hydroxysulfate and zinc sulfate is formed on the surface of the sheet which is both sufficiently thick and adherent. On the other hand, it does not succeed in forming such a layer when the SO 4 2 " concentration is less than 0.01 mol / l, but it is also found that a too high concentration does not appreciably improve the deposition rate and may even decrease it slightly. In a first embodiment of the invention, the treatment solution is applied in a conventional manner, for example by dipping, by sprinkling or by coating, both on electro-galvanized sheets and on galvanized sheets. In a preferred embodiment, 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 treatment solution is prepared, for example, by dissolving zinc sulfate in pure water; for example, zinc sulphate heptahydrate (ZnSO4, 7 H2O) is used; the concentration of Zn 2+ ions is then equal to that of the SO 4 2 7 anions. The pH of the treatment solution preferably corresponds to the natural pH of the solution, without the addition of base or acid; the value of this pH is generally between 5 and 7. To reduce as much as possible, the formation of powder or particles of zinc or its alloys resulting from the degradation of the coating of the sheet during its shaping, the treatment solution on the surface of the sheet under conditions of temperature, contact time with the galvanized surface, concentration of SO4 2 " ions and Zn 2+ ions adjusted to form a layer based on zinc hydroxysulfate and zinc sulphate with a sulfur quantity greater than or equal to 0.5 mg / m 2. Indeed, when the sulfur quantity is less than 0.5 mg / m 2 , the improvement in the degradation of the coating is less sensitive. Thus, the contact time of the treatment solution with the galvanized surface is between 2 seconds and 2 minutes, and the temperature of the treatment solution is between 20 and 60 ° C. Preferably, the solution of treatment 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 between 0.07 and 0.55 mol / l. Indeed, it was found that, in this concentration range, the deposition rate was little influenced by the value of the concentration. Advantageously, the treatment solution is applied under conditions of temperature, time of contact with the galvanized surface, and concentrations of SO4 2 " ions and of Zn 2+ ions adjusted to form a layer based on hydroxysulphate and sulphate having a quantity of sulfur of between 3.7 and 27 mg / m 2. According to a variant of the invention, the treatment solution contains an oxidizing agent for zinc, such as hydrogen peroxide. This oxidizing agent can have an accelerating effect on hydroxysulfation and very marked sulfation at low concentration. It has been found that the addition of only 0.03% , that is to say 8.10 "3 mol / liter of hydrogen peroxide, or of 2.10 " 4 mole / liter of potassium permanganate in the solution made it possible to double (approximately) the rate of deposition. It was found, on the contrary, that concentrations 100 times higher no longer allowed this improvement in the deposition rate to be obtained. After application of the treatment solution and before drying, the layer deposited on the sheet is adherent; The drying is adjusted to remove the residual liquid water between the application step and the drying step, the sheet is preferably rinsed so as to remove the soluble part of the deposit obtained; the absence of rinsing and obtaining a deposit which is partially soluble in water which results therefrom are not very detrimental to the reduction of the degradation of the zinc-plated coating during the shaping of the sheet, as long as the deposit obtained includes a layer based on zinc hydroxysulfate and zinc sulfate insoluble in water in contact with the sheet. According to a second embodiment of the invention, the aqueous treatment solution comprising a concentration of SO 2 " ions greater than or equal to 0.01 mol / l is applied under anodic polarization, and the pH of the treatment solution is higher or equal to 12, and less than 13. If the pH of the solution is less than 12, no adherent hydroxysulfates are formed on the surface to be treated. If the pH of the solution is greater than or equal to 13, the hydroxysulfate redissolves and / or decomposes into zinc hydroxides. When sodium sulphate is used in the treatment solution, if the sodium sulphate concentration is less than 1.4 g / l in the solution, little formation of hydroxysulphates is observed on the surface; more generally, it is therefore important that the concentration of SO 4 2 " ions be greater than or equal to 0.01 moles per liter, and preferably greater than or equal to 0.07 mol / l. Furthermore, the ion concentration sulfates is preferably less than or equal to 1 mole / liter; in the case of the use of sodium sulfate, at concentrations greater than 142 g / l (equivalent to 1 mole SO 4 2 " / liter), for example 180 g / l, there is a decrease in the yield of formation of the layer based on zinc hydroxysulfate and zinc sulfate. It has been found that the reduction in the degradation of the galvanized coating of the sheet during its shaping was only obtained if the thickness of the layer based on zinc hydroxysulfate and on deposited zinc sulfate corresponded to more than 0.5 mg / m 2 in sulfur equivalent, preferably at least 3.5 mg / m 2 in sulfur equivalent. Conversely, it has been observed that the reduction in the degradation of the zinc-plated coating decreases if the quantity of sulfur in the layer based on zinc hydroxysulphate and zinc sulphate deposited largely exceeds 30 mg / m 2 , therefore, seems it, degradation of the adhesion of this layer. Thus, to obtain a significant reduction in the deterioration of the galvanized coating, the total amount of hydroxysulphates and sulphates 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 zinc necessary for the formation of the deposit based on zinc hydroxysulphate and zinc sulphate comes from the anodic dissolution of zinc under the effect of the polarization of the zinc-plated surface. It is therefore appropriate that the density of electrical charges, circulating during the treatment through the surface of the sheet, be adjusted so as to form a layer based on zinc hydroxysulfate and on zinc sulfate with a higher sulfur content. or equal to 0.5 mg / m 2 . Thus, preferably, the charge density applied is preferably between 10 and 100 C / dm 2 of surface to be treated. If the charge density exceeds 100 C / dm 2 , it can be seen that the quantity of sulfur deposited on the surface no longer increases and even decreases. Thanks to the anodic polarization of the zinc-plated surface to be treated, there is a rapid dissolution of the zinc in the immediate vicinity of the zinc-plated surface, which promotes the precipitation of zinc salts on this surface. Thus, to carry out this treatment as productively as possible with a satisfactory faradic yield, it is advisable to deposit the layer based on zinc hydroxysulfate and zinc sulfate under a high bias current density, in particular greater than 20
A dm2 et, par exemple de 200 A/dm2. Pour une densité de courant inférieure ou égale à 20 A/dm2, le rendement de dépôt est très faible et la quantité en soufre dans la couche déposée ne permet pas d'obtenir une réduction significative de la dégradation du revêtement de zinc de la tôle lors de sa mise en forme. Comme contre-électrode, on peut utiliser une cathode en titane. La température de la solution 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. La vitesse de circulation de la solution à la surface de la tôle n'a pas, ici, d'incidence déterminante sur le traitement selon l'invention. Après formation de la couche à base d'hydroxysulfate et de sulfate sur la surface, on rince abondamment la surface traitée à l'eau déminéralisée. Cette étape de rinçage est importante pour éliminer les réactifs alcalins à la surface du dépôt, qui causeraient des problèmes de corrosion.At dm 2 and, for example 200 A / dm 2 . For a current density less than or equal to 20 A / dm 2 , the deposition efficiency is very low and the amount of sulfur in the deposited layer does not make it possible to obtain a significant reduction in the degradation of the zinc coating of the sheet. during its shaping. As a counter electrode, a titanium cathode can be used. The temperature of the treatment solution is generally between 20 ° C and 60 ° C. Preferably, the temperature is greater than or equal to 40 ° C., so as to increase the conductivity of the solution and to reduce the ohmic losses. The speed of circulation of the solution on the surface of the sheet does not, here, have a decisive effect on the treatment according to the invention. After formation of the hydroxysulfate and sulfate base layer on the surface, the treated surface is thoroughly rinsed with demineralized water. This rinsing step is important to remove alkaline reagents from the surface of the deposit, which would cause corrosion problems.
L'invention a également pour objet un procédé de lubrification d'une tôle d'acier revêtue d'une couche constituée par un revêtement métallique à base de zinc ou de ses alliages, et dans lequel : - on revêt ladite tôle d'une couche supérieure à base d'hydroxysulfate de zinc et de sulfate de zinc, ladite couche supérieure ayant été obtenue par l'utilisation d'une solution de traitement selon l'invention, puis - on applique un film d'huile de lubrification sur la couche supérieure avec un grammage inférieur à 1 g/m2. On applique le film d'huile lubrifiante avec un grammage de préférence inférieur à 0,9 g/m2, et plus préférentiellement compris entre 0,2 et 0,5 g/m2, car ces grammages sont suffisants pour obtenir une excellente protection temporaire contre la corrosion et éviter tout risque de pollution des ateliers et des outils de mise en forme. Enfin, l'invention a pour objet l'utilisation d'une solution aqueuse de traitement comprenant des ions sulfates à une concentration supérieure ou égale à 0,01 mol/l, pour améliorer la protection temporaire contre la corrosion d'une tôle d'acier revêtue d'une couche métallique à base de zinc ou de ses alliages. L'application de cette solution aqueuse de traitement sur la tôle d'acier est réalisée selon les modes de réalisation décrits dans les paragraphes concernant l'utilisation d'une solution aqueuse de traitement contenant des ions sulfates pour traiter une tôle d'acier zinguée en vue de réduire la dégradation du revêtement de zinc lors de sa mise en forme. A cet effet, on se reportera aux paragraphes y relatifs. Comme on le verra dans les exemples illustrant l'invention, les inventeurs ont montré que la protection temporaire contre la corrosion d'une tôle d'acier zinguée d'abord traitée par une solution de traitement conforme à l'invention, puis revêtue d'un film d'huile était très supérieure, à celle d'une tôle d'acier zinguée non préalablement traitée.The invention also relates to a method of lubricating a steel sheet coated with a layer consisting of a metallic coating based on zinc or its alloys, and in which: - said sheet is coated with a layer upper based on zinc hydroxysulphate and zinc sulphate, said upper layer having been obtained by the use of a treatment solution according to the invention, then - a film of lubricating oil is applied to the upper layer with a grammage of less than 1 g / m 2 . The film of lubricating oil is applied with a grammage preferably less than 0.9 g / m 2 , and more preferably between 0.2 and 0.5 g / m 2 , because these grammages are sufficient to obtain excellent protection temporary against corrosion and avoid any risk of pollution of workshops and shaping tools. Finally, the subject of the invention is the use of an aqueous treatment solution comprising sulphate ions at a concentration greater than or equal to 0.01 mol / l, to improve the temporary protection against corrosion of a sheet of steel coated with a metallic layer based on zinc or its alloys. The application of this aqueous treatment solution to the steel sheet is carried out according to the embodiments described in the paragraphs concerning the use of an aqueous treatment solution containing sulphate ions to treat a galvanized steel sheet. to reduce the degradation of the zinc coating during its shaping. To this end, reference is made to the relevant paragraphs. As will be seen in the examples illustrating the invention, the inventors have shown that temporary protection against corrosion of a galvanized steel sheet first treated with a treatment solution according to the invention, then coated with a film of oil was much superior to that of a galvanized steel sheet not previously treated.
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 : - la figure 1 , en référence à l'exemple 2, illustre les résultats des tests de frottement effectués sur différentes éprouvettes de tôle traitées selon l'invention ou non traitées, - la figure 2, en référence à l'exemple 3, illustre les résultats des tests de corrosion en humidotherme effectués sur différentes éprouvettes de tôle traitées selon l'invention ou non traitées. 1. Réduction de la formation de poudre ou de particules de revêtement lors de l'emboutissage d'une tôle zinguée On découpe des éprouvettes dans une tôle d'acier, de nuance dite "acier calmé à l'aluminium" de qualité ES, d'épaisseur 0,7 mm, revêtue sur chacune de ses faces par un revêtement de zinc réalisé au trempé à chaud dans un bain de zinc. On a préparé une solution aqueuse de traitement conforme à l'invention, préparée avec 125 g/l sulfate de zinc heptahydraté ZnSθ4,7 H2O. On a ensuite appliqué cette solution de traitement sur une partie des éprouvettes par aspersion de la solution de traitement, à une température de 40°C. Après un temps de contact de la solution avec la tôle de 3 à 4 s, la tôle traitée est essorée puis séchée. Puis on a appliqué sur la couche à base d'hydroxysulfate de zinc et de sulfate de zinc formée à la surface des éprouvettes de tôle d'acier zingué, un film d'huile de lubrification pouvant être soit l'huile QUAKER 6130 (de la société Quaker), soit l'huile FUCHS 4107S (de la société Fuchs), avec un grammage de 1 ,5 g/m2. Une autre partie des éprouvettes n'ayant pas été traitée préalablement avec la solution de traitement conforme à l'invention, a été huilée soit avec l'huile QUAKER 6130, soit avec l'huile FUCHS 4107S également avec un grammage de 1 ,5 g/m2. Les deux séries d'éprouvettes ont ensuite subi un test de déformation contrôlé au moyen d'une presse comprenant un poinçon, une matrice et un serre-flan, recréant en laboratoire les contraintes subies par la tôle lors de l'opération d'emboutissage, notamment dans les rayons de matrice et/ou dans les joncs de retenue qui équipent les outils d'emboutissage. Différentes forces de serrage du serre-flan ont été appliquées sur les éprouvettes testées. Chacune des éprouvettes des deux séries a été pesée avant l'opération d'huilage, puis en fin de test après déshuilage, au moyen d'une balance précise à 0,0001 gramme. La différence de masse mesurée a été ramenée à une perte de masse au mètre carré, en prenant en compte la surface affectée par le frottement lors de la simulation de l'emboutissage de l'éprouvette, identique pour chacune des éprouvettes. Par ailleurs, après avoir mis en forme une éprouvette et avant de mettre en forme l'éprouvette suivante, la presse a été essuyée de manière à identifier la poudre ou les particules de revêtement de zinc perdues par l'éprouvette dans la presse. Les résultats de perte de masse des éprouvettes après emboutissage, ainsi que l'identification de la poudre et/ou des particules de zinc issues du revêtement sont regroupés dans le tableau 1. L'identification des particules et/ou de la poudre est cotée de la manière suivante selon une échelle allant de 1 à 4, avec : cotation 1 : très peu de particules ou de poudre, cotation 2 : peu de particules ou de poudre, cotation 3 : beaucoup de particules ou de poudre, et cotation 4 : niveau très élevé de particules ou de poudre. Tableau 1 : résultats des essaisThe invention will now be illustrated by examples given for information, and not limitation, and with reference to the appended figures in which: - Figure 1, with reference to example 2, illustrates the results of the friction tests carried out on different sheet metal samples treated according to the invention or not treated, - Figure 2, with reference to Example 3, illustrates the results of the corrosion tests in humidotherm carried out on different sheet metal samples treated according to the invention or untreated. 1. Reduction of the formation of powder or coating particles during the stamping of a galvanized sheet. Test pieces are cut from a steel sheet, of grade known as "aluminum calm steel" of ES quality, d 0.7 mm thick, coated on each of its faces with a zinc coating made by hot dipping in a zinc bath. An aqueous treatment solution was prepared in accordance with the invention, prepared with 125 g / l zinc sulfate heptahydrate ZnSθ 4 , 7 H 2 O. This treatment solution was then applied to part of the test pieces by spraying the solution treatment, at a temperature of 40 ° C. After a contact time of the solution with the sheet of 3 to 4 s, the treated sheet is wrung and then dried. Then was applied to the layer based on zinc hydroxysulphate and zinc sulphate formed on the surface of the test pieces of galvanized steel sheet, a film of lubricating oil which may be either QUAKER 6130 oil (from Quaker company), i.e. FUCHS 4107S oil (from Fuchs company), with a grammage of 1.5 g / m 2 . Another part of the test pieces which had not been previously treated with the treatment solution according to the invention was oiled either with QUAKER 6130 oil or with FUCHS 4107S oil also with a grammage of 1.5 g / m 2 . The two series of test pieces were then subjected to a deformation test controlled by means of a press comprising a punch, a matrix and a blank holder, recreating in the laboratory the stresses undergone by the sheet during the stamping operation, in particular in the matrix radii and / or in the retaining rods which equip the stamping tools. Different clamping forces of the blank holder were applied to the test pieces tested. Each of the test pieces of the two series was weighed before the oiling operation, then at the end of the test after oil removal, using a balance accurate to 0.0001 grams. The difference in measured mass was reduced to a loss of mass per square meter, taking into account the surface affected by friction during the simulation of the stamping of the test piece, identical for each of the test pieces. Furthermore, after having shaped a test piece and before shaping the next test piece, the press was wiped so as to identify the powder or particles of zinc coating lost by the test piece in the press. The results of loss of mass of the test pieces after stamping, as well as the identification of the powder and / or of the zinc particles resulting from the coating are grouped in Table 1. The identification of the particles and / or of the powder is listed as the following way on a scale from 1 to 4, with: rating 1: very few particles or powder, rating 2: few particles or powder, rating 3: lots of particles or powder, and rating 4: level very high particles or powder. Table 1: test results
Les pertes de masse mesurées ainsi que les quantités de poudre et particules observées lors de l'essuyage des outils montrent que la perte de matière du revêtement de zinc, due au passage de la tôle d'acier zinguée sur le poinçon, est significativement diminuée lorsque la tôle a été traitée avec la solution de traitement conforme à l'invention préalablement à son huilage. 2. Diminution de l'effet du démouillage, effet sur le comportement tribologigue - Test de frottement On découpe des éprouvettes de 1 cm2 dans une tôle d'acier, de nuance dite "acier calmé à l'aluminium" de qualité ES, d'épaisseur 0,7 mm, revêtue sur chacune de ses faces par un revêtement de zinc réalisé au trempé à chaud dans un bain de zinc. On traite une partie de ces éprouvettes avec une solution de traitement conforme à l'invention, dans les mêmes conditions que celles indiquées dans l'exemple 1 , de manière à former une couche à base d'hydroxysulfate de zinc et de sulfate de zinc. Puis on applique sur cette couche un film d'huile de lubrification (huile QUAKER 6130) avec des quantités comprises entre 0,25 et 2,5 g/m2. Une autre partie des éprouvettes a été huilée de la même façon que précédemment, mais n'a pas été traitée au préalable par la solution de traitement conforme à l'invention. Puis on procède à la caractérisation en frottement de chacune des éprouvettes en utilisant un appareil de test de tribologie, de la manière suivante : L'appareil de test est un tribomètre plan-plan connu en lui-même. Les éprouvettes à tester sont serrées selon une force de serrage Fs entre deux plaquettes en acier rapide offrant une surface d'appui (ou de glissement) sur les éprouvettes. On mesure le coefficient de frottement N, tout en déplaçant l'éprouvette par rapport aux plaquettes sur une course D totale de 180 mm et à la vitesse de 10 mm/Fs en augmentant progressivement la force de serrage Fs. On peut alors tracer une courbe d'évolution du coefficient de friction en fonction de la force de serrage Fs, avec un grammage d'huile de lubrification donné (voir figure 1). Les différentes courbes sont repérées par les symboles suivants : + : tôle traitée selon l'invention, puis revêtue d'un film d'huile QUAKER 6130 de 0,25 g/m2/face x : tôle traitée selon l'invention, puis revêtue d'un film d'huile QUAKER 6130 de 1 ,0 g/m2/face • : tôle traitée selon l'invention, puis revêtue d'un film d'huile QUAKER 6130 de 2,5 g/m2/face M : tôle non traitée revêtue d'un film d'huile QUAKER 6130 de 0,25 g/m2/face À : tôle non traitée revêtue d'un film d'huile QUAKER 6130 de 1 ,0 g/m2/faceThe mass losses measured as well as the quantities of powder and particles observed during the wiping of the tools show that the loss of material of the zinc coating, due to the passage of the galvanized steel sheet on the punch, is significantly reduced when the sheet was treated with the treatment solution according to the invention before it was oiled. 2. Decrease in the effect of dewetting, effect on tribological behavior - Friction test Test pieces of 1 cm 2 are cut from a sheet of steel, of grade called "aluminum-calmed steel" of ES quality, d 0.7 mm thick, coated on each of its faces with a zinc coating made by hot dipping in a zinc bath. Part of these test pieces is treated with a treatment solution according to the invention, under the same conditions as those indicated in Example 1, so as to form a layer based on zinc hydroxysulfate and zinc sulfate. Then a film of lubricating oil (QUAKER 6130 oil) is applied to this layer with quantities of between 0.25 and 2.5 g / m 2 . Another part of the test pieces was oiled in the same way as above, but was not previously treated with the treatment solution according to the invention. Then the friction characterization of each of the test pieces is carried out using a tribology test apparatus, in the following manner: The test apparatus is a plane-plane tribometer known in itself. The test pieces to be tested are clamped according to a clamping force Fs between two high-speed steel plates providing a bearing (or sliding) surface on the test pieces. The coefficient of friction N is measured, while moving the test piece relative to the pads over a total stroke D of 180 mm and at the speed of 10 mm / Fs by gradually increasing the clamping force Fs. We can then draw a curve of evolution of the friction coefficient as a function of the clamping force Fs, with a given grammage of lubricating oil (see Figure 1). The different curves are identified by the following symbols: +: sheet treated according to the invention, then coated with a QUAKER 6130 oil film of 0.25 g / m 2 / side x: sheet treated according to the invention, then coated with a QUAKER 6130 oil film of 1.0 g / m 2 / side •: sheet treated according to the invention, then coated with a QUAKER 6130 oil film of 2.5 g / m 2 / side M: untreated sheet coated with a QUAKER 6130 oil film of 0.25 g / m 2 / face TO: untreated sheet coated with a film of QUAKER 6130 oil of 1.0 g / m 2 / face
* : tôle non traitée revêtue d'un film d'huile QUAKER 6130 de 2,5 g/m /face Sur le tableau 2, on a fait figurer, pour chacune des éprouvettes testées, une valeur moyenne du coefficient de frottement pour une force de serrage Fs donnée. Tableau 2*: untreated sheet coated with a QUAKER 6130 oil film of 2.5 g / m / side In Table 2, an average value of the coefficient of friction for a force has been shown for each of the test pieces tested of tightening Fs given. Table 2
Les résultats obtenus montrent qu'une diminution du grammage d'huile entraîne une augmentation importante du coefficient de frottement en absence d'application de la solution de traitement conforme à l'invention préalablement à l'application du film d'huile. En revanche lorsque la solution de traitement conforme à l'invention a été appliquée sur la tôle zinguée préalablement à l'application du film d'huile de lubrification, les coefficients de frottement obtenus sont très faibles, même avec des grammages d'huile inférieurs à 0,5 g/m2. 3. Diminution de l'effet du démouillage, effet sur la protection temporaire contre la corrosion On découpe des éprouvettes dans une tôle d'acier, de nuance dite "acier calmé à l'aluminium" de qualité ES, d'épaisseur 0,7 mm, revêtue sur chacune de ses faces par un revêtement de zinc réalisé au trempé à chaud dans un bain de zinc. On traite une partie de ces éprouvettes avec une solution de traitement conforme à l'invention, dans les mêmes conditions que celles indiquées dans l'exemple 1 , de manière à former une couche à base d'hydroxysulfate de zinc et de sulfate de zinc. Puis on applique sur cette couche un film d'huile de lubrification (huile QUAKER 6130) avec des grammages compris entre 0,25 et 1 ,0 g/m2. Une autre partie des éprouvettes a été huilée de la même façon que précédemment, mais n'a pas été traitée au préalable par la solution de traitement conforme à l'invention. Les huiles de lubrification appliquées sur les tôles d'acier revêtues d'une couche métallique à base de zinc garantissent une protection contre la corrosion pendant le laps de temps compris entre la fabrication des tôles et leur mise en oeuvre par exemple par emboutissage. La conformité du produit livré sur ce point est vérifiée au travers des résultats d'un test de corrosion humidotherme accéléré. A cet effet les éprouvettes à tester sont placées dans une enceinte climatique correspondant à la norme DIN 50017, ce qui simule les conditions de corrosion d'une spire extérieure de bobine de tôle ou d'une tôle découpée en feuille pendant le stockage. Le détail du cycle (un cycle = 24 heures) en humidotherme est décrit ci-dessous : - 8 h à 40°C et 95-100% de RH (humidité relative) - 16 h à 20°C et 75% de RH. Les éprouvettes sont suspendues individuellement verticalement. Le résultat du test, figurant dans le tableau 3, s'obtient en relevant le nombre de cycles successifs avant qu'apparaissent les traces de corrosion sur l'éprouvette. On peut alors tracer une courbe d'évolution du pourcentage de rouille blanche en fonction du nombre de cycles pour chacune des éprouvettes testées (cf figure 2). Les différentes courbes sont repérées par les symboles suivants : + : tôle traitée selon l'invention, puis revêtue d'un film d'huile QUAKER 6130 de 0,25 g/m2/face * : tôle traitée selon l'invention, puis revêtue d'un film d'huile QUAKER 6130 de 0,5 g/m2/face À : tôle traitée selon l'invention, puis revêtue d'un film d'huile QUAKER 6130 de 1 ,0 g/m2/face * : tôle non traitée revêtue d'un film d'huile QUAKER 6130 de 0,25 g/m2/face M : tôle non traitée revêtue d'un film d'huile QUAKER 6130 de 0,5 g/m2/face • : tôle non traitée revêtue d'un film d'huile QUAKER 6130 de 1 ,0 g/m2/faceThe results obtained show that a reduction in the grammage of oil leads to a significant increase in the coefficient of friction in the absence of application of the treatment solution according to the invention before the application of the oil film. On the other hand, when the treatment solution according to the invention has been applied to the galvanized sheet prior to the application of the lubricating oil film, the friction coefficients obtained are very low, even with oil weights lower than 0.5 g / m 2 . 3. Decrease in the effect of dewetting, effect on temporary protection against corrosion. Test specimens are cut from a sheet of steel, grade called "aluminum calm steel" of ES quality, thickness 0.7. mm, coated on each of its faces with a zinc coating made by hot dipping in a zinc bath. Part of these test pieces is treated with a treatment solution according to the invention, under the same conditions as those indicated in Example 1, so as to form a layer based on zinc hydroxysulfate and zinc sulfate. Then a film of lubricating oil (QUAKER 6130 oil) is applied to this layer with grammages between 0.25 and 1.0 g / m 2 . Another part of the test pieces was oiled in the same way as above, but was not previously treated with the treatment solution according to the invention. The lubricating oils applied to steel sheets coated with a zinc-based metal layer guarantee protection against corrosion during the period of time between the manufacture of the sheets and their implementation, for example by stamping. The conformity of the product delivered on this point is verified through the results of an accelerated humidothermal corrosion test. To this end, the test specimens are placed in a climatic chamber corresponding to the DIN 50017 standard, which simulates the corrosion conditions of an outer coil of sheet metal coil or of a sheet metal cut into sheets during storage. The detail of the cycle (one cycle = 24 hours) in humidotherm is described below: - 8 h at 40 ° C and 95-100% RH (relative humidity) - 16 h at 20 ° C and 75% RH. The test pieces are individually hung vertically. The test result, shown in table 3, is obtained by recording the number of successive cycles before the corrosion traces appear on the test piece. We can then draw an evolution curve for the percentage of white rust as a function of the number of cycles for each of the test pieces tested (see Figure 2). The different curves are identified by the following symbols: +: sheet treated according to the invention, then coated with a QUAKER 6130 oil film of 0.25 g / m 2 / side *: sheet treated according to the invention, then coated with a QUAKER 6130 oil film of 0.5 g / m 2 / side A: sheet treated according to the invention, then coated with a QUAKER 6130 oil film of 1.0 g / m 2 / side *: untreated sheet coated with a QUAKER 6130 oil film of 0.25 g / m 2 / side M: untreated sheet coated with a QUAKER 6130 oil film of 0.5 g / m 2 / side •: untreated sheet coated with a film of QUAKER 6130 oil of 1.0 g / m 2 / side
Tableau 3Table 3
Il a été constaté qu'il était possible d'améliorer de façon très significative la protection temporaire contre la corrosion des tôles d'acier zinguées sur laquelle une solution de traitement conforme à l'invention a été appliquée avant l'application du film d'huile de lubrification, et cela même lorsque le grammage d'huile est inférieur à 1 g/m2. It was found that it was possible to significantly improve the temporary protection against corrosion of galvanized steel sheets to which a treatment solution according to the invention was applied before the application of the film. lubricating oil, even when the grammage of oil is less than 1 g / m 2 .

Claims

REVENDICATIONS
1. Utilisation d'une solution aqueuse de traitement contenant des ions sulfates SO4 2" à une concentration supérieure ou égale à 0,01 mol/l, pour traiter la surface d'une tôle d'acier revêtue sur au moins une de ses faces, d'un revêtement métallique à base de zinc ou de ses alliages, en vue de réduire la formation de poudre ou de particules métalliques à base de zinc ou de ses alliages générées par la dégradation du revêtement lors de la mise en forme de ladite tôle.1. Use of an aqueous treatment solution containing sulphate ions SO 4 2 " at a concentration greater than or equal to 0.01 mol / l, for treating the surface of a steel sheet coated on at least one of its sides of a metallic coating based on zinc or its alloys, in order to reduce the formation of powder or metallic particles based on zinc or its alloys generated by the degradation of the coating during the shaping of said coating sheet.
2. Utilisation selon la revendication 1 , dans laquelle la solution aqueuse de traitement contient en outre des ions zinc Zn2+ à une concentration supérieure ou égale à 0,01 mol/l,2. Use according to claim 1, in which the aqueous treatment solution also contains zinc ions Zn 2+ at a concentration greater than or equal to 0.01 mol / l,
3. Utilisation selon l'une des revendications 1 ou 2, dans laquelle la solution de traitement est appliquée à la surface de la tôle dans des conditions de température, de temps de contact avec la surface zinguée, de concentration en ions SO4 2" et en ions Zn2+ ajustés pour former une couche 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. 3. Use according to one of claims 1 or 2, in which the treatment solution is applied to the surface of the sheet under conditions of temperature, time of contact with the galvanized surface, concentration of SO 4 2 ions " and in Zn 2+ ions adjusted to form a layer based on zinc hydroxysulfate and zinc sulfate, the sulfur quantity of which is greater than or equal to 0.5 mg / m 2 .
4. Utilisation selon l'une quelconque des revendications 1 à 3, dans laquelle la concentration en ions Zn2+ et la concentration en ions SO4 2" sont comprises entre 0,07 et 0,55 mol/l. 4. Use according to any one of claims 1 to 3, in which the concentration of Zn 2+ ions and the concentration of SO 4 2 " ions are between 0.07 and 0.55 mol / l.
5. Utilisation selon l'une quelconque des revendications 1 à 4, dans laquelle le pH de la solution de traitement est compris entre 5 et 7. 5. Use according to any one of claims 1 to 4, in which the pH of the treatment solution is between 5 and 7.
6. Utilisation selon l'une quelconque des revendications 1 à 5, dans laquelle la solution de traitement est appliquée dans des conditions de température, de temps de contact avec la surface zinguée, de concentrations en ions SO4 2" et en ions Zn2+ ajustées pour former une couche d'hydroxysulfate et de sulfate présentant une quantité en soufre comprise entre 3,7 et 27 mg/m2.6. Use according to any one of claims 1 to 5, in which the treatment solution is applied under conditions of temperature, contact time with the galvanized surface, concentrations of SO 4 2 " ions and Zn 2 ions. + adjusted to form a layer of hydroxysulphate and sulphate having a quantity of sulfur of between 3.7 and 27 mg / m 2 .
7. Utilisation selon l'une quelconque des revendications 1 à 6, dans laquelle, après l'application de la solution de traitement sur la tôle, ladite tôle est séchée, après avoir été éventuellement rincée pour éliminer la partie soluble de la couche d'hydroxysulfate et de sulfate.7. Use according to any one of claims 1 to 6, in which, after the application of the treatment solution to the sheet, said sheet is dried, after being optionally rinsed to remove the soluble part of the hydroxysulfate and sulfate layer.
8. Utilisation selon la revendication 1 , dans laquelle la solution de traitement est appliquée sous polarisation anodique, et le pH de la solution de traitement est supérieur ou égal à 12, et inférieur à 13.8. Use according to claim 1, in which the treatment solution is applied under anodic polarization, and the pH of the treatment solution is greater than or equal to 12, and less than 13.
9. Utilisation selon la revendication 8, dans laquelle la densité de charges électriques, circulant pendant le traitement au travers de la surface de la tôle, est ajustée pour former une couche à base d'hydroxysulfate de zinc et de sulfate de zinc dont la quantité en soufre est supérieure ou égale à 0,5 mg/m2.9. Use according to claim 8, in which the density of electric charges, circulating during the treatment through the surface of the sheet, is adjusted to form a layer based on zinc hydroxysulfate and zinc sulfate, the quantity of which sulfur is greater than or equal to 0.5 mg / m 2 .
10. Utilisation selon l'une des revendications 8 ou 9, dans laquelle la concentration en ion SO4 2" est supérieure à 0,07 mol/l.10. Use according to one of claims 8 or 9, in which the concentration of SO 4 2 " ion is greater than 0.07 mol / l.
11. Utilisation selon l'une quelconque des revendications 8 à 10, dans laquelle, dans laquelle la densité de charges électriques est ajustée pour former une couche à base d'hydroxysulfate de zinc et de sulfate de zinc dont la quantité en soufre est comprise entre 3,7 et 27 mg/m2.11. Use according to any one of claims 8 to 10, in which in which the density of electrical charges is adjusted to form a layer based on zinc hydroxysulfate and zinc sulfate, the amount of sulfur of which is between 3.7 and 27 mg / m 2 .
12. Utilisation selon l'une quelconque des revendications 8 à 11 , dans laquelle la densité de courant de polarisation appliquée pendant le traitement est supérieure à 20 A/dm2. 12. Use according to any one of claims 8 to 11, in which the bias current density applied during the treatment is greater than 20 A / dm 2 .
13. Utilisation selon l'une quelconque des revendications 8 à 12, dans laquelle, après l'application de la solution de traitement sur la tôle, ladite tôle est rincée.13. Use according to any one of claims 8 to 12, wherein, after the application of the treatment solution on the sheet, said sheet is rinsed.
14. Procédé de lubrification d'une tôle d'acier revêtue d'une couche constituée par un revêtement métallique à base de zinc ou de ses alliages, et dans lequel : - on revêt ladite tôle d'une couche supérieure à base d'hydroxysulfate de zinc et de sulfate de zinc, ladite couche supérieure ayant été obtenue par l'utilisation d'une solution de traitement telle que définie dans l'une quelconque des revendications 1 à 13, puis - on applique un film d'huile de lubrification sur la couche supérieure avec un grammage inférieur à 1 g/m2.14. A method of lubricating a steel sheet coated with a layer consisting of a metallic coating based on zinc or its alloys, and in which: - said sheet is coated with an upper layer based on hydroxysulfate of zinc and zinc sulfate, said upper layer having been obtained by the use of a treatment solution as defined in any one of claims 1 to 13, then - a film of lubricating oil is applied to the upper layer with a grammage of less than 1 g / m 2 .
15. Procédé selon la revendication 14, caractérisé en ce que le grammage du film d'huile est inférieur à 0,9 g/m2. 15. The method of claim 14, characterized in that the grammage of the oil film is less than 0.9 g / m 2 .
16. Procédé selon la revendication 15, caractérisé en ce que le grammage du film d'huile est compris entre 0,2 et 0,5 g /m2.16. Method according to claim 15, characterized in that the grammage of the oil film is between 0.2 and 0.5 g / m 2 .
17. Utilisation d'une solution aqueuse de traitement contenant des ions sulfates SO4 2" à une concentration supérieure ou égale à 0,01 mol/l, pour traiter la surface d'une tôle d'acier revêtue sur au moins une de ses faces, d'un revêtement métallique à base de zinc ou de ses alliages, en vue d'améliorer la protection temporaire contre la corrosion de ladite tôle. 17. Use of an aqueous treatment solution containing sulphate ions SO 4 2 " at a concentration greater than or equal to 0.01 mol / l, for treating the surface of a steel sheet coated on at least one of its faces, of a metallic coating based on zinc or its alloys, in order to improve the temporary protection against corrosion of said sheet.
EP04816380A 2003-12-24 2004-12-14 Hydroxysulfate surface treatment Withdrawn EP1699947A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10287665B2 (en) 2014-06-27 2019-05-14 Henkel Ag & Co. Kgaa Dry lubricant for zinc coated steel

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5239570B2 (en) * 2007-09-04 2013-07-17 Ｊｆｅスチール株式会社 Galvanized steel sheet
JP5354165B2 (en) * 2008-01-30 2013-11-27 Ｊｆｅスチール株式会社 Method for producing galvanized steel sheet
KR20110073573A (en) * 2008-12-16 2011-06-29 제이에프이 스틸 가부시키가이샤 Galvanized steel sheet and method for manufacturing the same
JP5396921B2 (en) * 2009-03-06 2014-01-22 Ｊｆｅスチール株式会社 Zinc-coated steel sheet that prevents molten metal from adhering to the surface
JP4883240B1 (en) 2010-08-04 2012-02-22 Ｊｆｅスチール株式会社 Steel sheet for hot press and method for producing hot press member using the same
JP5884151B2 (en) 2010-11-25 2016-03-15 Ｊｆｅスチール株式会社 Steel sheet for hot press and method for producing hot press member using the same
CN104040027A (en) 2012-01-10 2014-09-10 安赛乐米塔尔研发有限公司 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
KR101678511B1 (en) 2012-03-07 2016-11-22 제이에프이 스틸 가부시키가이샤 Steel sheet for hot press-forming, method for manufacturing the same, and method for producing hot press-formed parts using the same
WO2013160566A1 (en) * 2012-04-25 2013-10-31 Arcelormittal Investigacion Y Desarrollo, S.L. Method for producing a metal sheet having oiled zn-al-mg coatings, and corresponding metal sheet
JP5928247B2 (en) * 2012-08-27 2016-06-01 Ｊｆｅスチール株式会社 Cold rolled steel sheet and method for producing the same
DE102012109855B4 (en) * 2012-10-16 2015-07-23 Thyssenkrupp Steel Europe Ag Process for producing a metal corrosion protection coated steel product
ES2734456T3 (en) 2013-09-19 2019-12-10 Fuchs Petrolub Se Inorganic functional layer on hot dipped galvanized steel to aid shaping
EP2995674B1 (en) * 2014-09-11 2020-07-15 thyssenkrupp AG Use of a sulfate and a process for the production of a steel component by forming in a machine
CN108473664B (en) 2016-01-13 2021-03-09 Sika技术股份公司 One-component, heat-curable epoxy adhesive with improved adhesion
US11078573B2 (en) 2016-01-19 2021-08-03 Thyssenkrupp Ag Method for producing a steel product with a Zn coating and a tribologically active layer deposited on the coating, and a steel product produced according to said method
CN110546303A (en) 2017-03-30 2019-12-06 塔塔钢铁艾默伊登有限责任公司 aqueous acidic composition for treating metal surfaces, treatment method using such a composition and use of the treated metal surfaces
WO2019073273A1 (en) * 2017-10-12 2019-04-18 Arcelormittal Metal sheet treatment method and metal sheet treated with this method
WO2019073274A1 (en) 2017-10-12 2019-04-18 Arcelormittal Metal sheet treatment method and metal sheet treated with this method
EP3643759B1 (en) 2018-10-26 2022-03-23 Henkel AG & Co. KGaA Polycarboxylate coated steel strip and its use for deep drawing
EP3898860A1 (en) 2018-12-19 2021-10-27 Henkel AG & Co. KGaA Forming coating agent, steel strip coated with said agent, and use thereof in the production of components by forming

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005021823A1 (en) * 2003-08-29 2005-03-10 Jfe Steel Corporation Hot dip zinc plated steel sheet and method for production thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6528182B1 (en) * 1998-09-15 2003-03-04 Sollac Zinc coated steel plates coated with a pre-lubricating hydroxysulphate layer and methods for obtaining same
FR2803855B1 (en) * 2000-01-13 2002-05-31 Usinor PROCESS FOR OXALATING THE ZINC-PLATED SURFACE OF A SHEET
JP2001329352A (en) * 2000-05-19 2001-11-27 Sumitomo Metal Ind Ltd Galvannealed steel sheet excellent in slidability
CA2411879A1 (en) * 2001-05-28 2002-12-04 Yoichi Tobiyama Alloy galvanized steel plate having excellent slidability
JP3582511B2 (en) * 2001-10-23 2004-10-27 住友金属工業株式会社 Surface-treated steel for hot press forming and its manufacturing method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005021823A1 (en) * 2003-08-29 2005-03-10 Jfe Steel Corporation Hot dip zinc plated steel sheet and method for production thereof
EP1666624A1 (en) * 2003-08-29 2006-06-07 JFE Steel Corporation Hot dip zinc plated steel sheet and method for production thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10287665B2 (en) 2014-06-27 2019-05-14 Henkel Ag & Co. Kgaa Dry lubricant for zinc coated steel

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