EP2290133B1 - Procédé de fabrication d'un composant en acier revêtu d'une coiffe métallique protégeant de la corrosion et composant en acier - Google Patents

Procédé de fabrication d'un composant en acier revêtu d'une coiffe métallique protégeant de la corrosion et composant en acier Download PDF

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Publication number
EP2290133B1
EP2290133B1 EP09168605A EP09168605A EP2290133B1 EP 2290133 B1 EP2290133 B1 EP 2290133B1 EP 09168605 A EP09168605 A EP 09168605A EP 09168605 A EP09168605 A EP 09168605A EP 2290133 B1 EP2290133 B1 EP 2290133B1
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EP
European Patent Office
Prior art keywords
steel
coating
steel component
znni
forming
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.)
Revoked
Application number
EP09168605A
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German (de)
English (en)
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EP2290133A1 (fr
Inventor
Dr.-Ing. Patrik Kuhn
Manfred Meurer
Dipl.-Ing. Jens Kondratiuk
Dr.-Ing. Wilhelm Warnecke
Dipl.-Ing. Werner Schüler
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ThyssenKrupp Steel Europe AG
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ThyssenKrupp Steel Europe AG
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Application filed by ThyssenKrupp Steel Europe AG filed Critical ThyssenKrupp Steel Europe AG
Priority to AT09168605T priority Critical patent/ATE554190T1/de
Priority to ES09168605T priority patent/ES2384135T3/es
Priority to PT09168605T priority patent/PT2290133E/pt
Priority to EP09168605A priority patent/EP2290133B1/fr
Priority to PL09168605T priority patent/PL2290133T3/pl
Priority to KR1020117026993A priority patent/KR101674625B1/ko
Priority to JP2012525942A priority patent/JP5650222B2/ja
Priority to PL10706201T priority patent/PL2414562T3/pl
Priority to PCT/EP2010/052326 priority patent/WO2011023418A1/fr
Priority to RU2012111247/02A priority patent/RU2496887C1/ru
Priority to PT107062010T priority patent/PT2414562E/pt
Priority to ES10706201T priority patent/ES2400221T3/es
Priority to CN201080037681.9A priority patent/CN102625863B/zh
Priority to MX2011011932A priority patent/MX2011011932A/es
Priority to US13/266,941 priority patent/US9284655B2/en
Priority to EP10706201A priority patent/EP2414562B1/fr
Priority to CA2758629A priority patent/CA2758629C/fr
Priority to AU2010288814A priority patent/AU2010288814B2/en
Priority to BRPI1015352A priority patent/BRPI1015352A2/pt
Publication of EP2290133A1 publication Critical patent/EP2290133A1/fr
Priority to ZA2011/07674A priority patent/ZA201107674B/en
Publication of EP2290133B1 publication Critical patent/EP2290133B1/fr
Application granted granted Critical
Priority to US15/046,884 priority patent/US10053752B2/en
Revoked legal-status Critical Current
Anticipated expiration legal-status Critical

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • 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.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • 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.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12951—Fe-base component
    • Y10T428/12958—Next to Fe-base component

Definitions

  • the invention relates to a method of producing a steel component provided with a metallic corrosion protective coating by forming a mild steel Mn steel product which is provided with a ZnNi alloy coating prior to forming the steel component.
  • a typical example of a steel suitable for hot press hardening is known as "22MnB5" and found in steel key 2004 under material number 1.5528.
  • manganese-containing steels are generally not resistant to wet corrosion and are difficult to passivate.
  • This compared to lower alloyed steels when exposed to elevated chloride ion concentrations great tendency to locally limited, but intense corrosion makes the use of the material group of high-alloy steel sheets belonging steels straight in the body construction difficult.
  • manganese-containing steels tend to surface corrosion, which also limits the spectrum of their usability.
  • a steel sheet is first provided with a zinc coating and then heated before the hot deformation such that adjusts an intermetallic compound in the heating of the flat steel product by a transformation of the coating on the steel sheet. This is to protect the steel sheet against corrosion and decarburization and take over a lubricating function during the hot forming in the pressing tool.
  • EP 1 630 244 A1 A proposal on how to produce zinc coatings on steel strips, to which an organic coating can be applied particularly well, is in EP 1 630 244 A1 described. Accordingly, an up to 20 wt .-% Fe containing Zn layer is applied, for example, electrolytically or using another known coating method on the steel sheet to be processed. Subsequently, the thus coated steel sheet from room temperature Heated to 850-950 ° C and thermoformed at 700-950 ° C. Particularly suitable for the production of the Zn layer while the electrolytic deposition is mentioned.
  • the Zn layer may also be formed as an alloy layer according to the known method.
  • alloy components of this layer are in the EP 1 630 244 A1 Mn, Ni, Cr, Co, Mg, Sn and Pb, and also mentioned Be, B, Si, P, S, Ti, V, W, Mo, Sb, Cd, Nb, Cu and Sr as additional alloying components.
  • the present on him 1-50 microns thick Zn coating comprises an iron-zinc solid solution phase and has a zinc oxide layer whose thickness is limited on average to at most 2 microns.
  • either the annealing condition when heating to the temperature required for the hot press forming is selected so that at best a controlled oxide formation occurs, or after hot forming the oxide layer present on the obtained steel component is or particle-removing process at least partially removed so far that the according to the EP 1 630 244 A1 maximum thickness of the oxide layer is maintained.
  • this known procedure also requires complex measures in order to ensure, on the one hand, the desired anticorrosive effect of the Zn coating and, on the other hand, the required good coatability and lacquer adhesion in the case of coating taking place after thermoforming.
  • the results of a systematic study of the properties of zinc alloy coatings on a steel sheet consisting of a hardenable steel are in the WO 2005/021822 A1 contain.
  • the coating consisted essentially of zinc and additionally contained one or more oxygen-affine elements in a total amount of 0.1-15 wt .-% based on the total coating.
  • the oxygen-affine elements are specifically named Mg, Al, Ti, Si, Ca, B and Mn.
  • the steel sheet coated in this way was then brought to a temperature necessary for hardening under the admission of atmospheric oxygen. In this heat treatment, a superficial oxide layer of the oxygen-affine element (s) formed.
  • the ZnNi coating thus obtained was a pure barrier protection without cathodic corrosion protection effect. Its surface showed a verdallert, green appearance with small local flaking to which the oxide layer does not adhere to the steel. These errors are in accordance with the WO 2005/021822 due to the fact that the coating itself did not contain a sufficiently oxygen-affine element.
  • the object underlying the invention was to specify a method which is easy to carry out in practice and which makes it possible to produce a steel component with comparatively little effort, which is provided with a metallic coating which adheres well and reliably protects against corrosion.
  • a corresponding procured steel component should be specified.
  • this object has been achieved according to a first variant of the invention in that in the production of a steel component, the method steps indicated in claim 1 are passed.
  • the first variant of the method according to the invention comprises the shaping of the steel component in the so-called "direct” method, while the second method variant involves the shaping of the steel component in the so-called “indirect” method.
  • the solution according to the invention of the abovementioned object is that such a component has the features specified in claim 13.
  • Advantageous variants of the steel component according to the invention are specified in the claims related back to claim 13 and explained below.
  • a flat steel product ie a steel strip or steel sheet
  • a flat steel product is first of all made of a 0.3 to 3 wt .-% manganese-containing, higher-strength and hardenable steel material is produced. This has a yield strength of 150-1100 MPa and a tensile strength of 300-1200 MPa.
  • this steel material may be a high strength MnB steel of known composition. Accordingly, in addition to iron and unavoidable impurities (in% by weight), the steel processed according to the invention may contain 0.2-0.5% C, 0.5-3.0% Mn, 0.002-0.004% B, and optionally one or more elements of Group "Si, Cr, Al, Ti" contained in the following contents: 0.1-0.3% Si, 0.1-0.5% Cr, 0.02-0.05% Al, 0.025-0.04 % Ti.
  • the inventive method is suitable for the production of steel components both from conventionally only hot rolled hot strip or sheet as well as from conventionally cold rolled steel strip or sheet.
  • this coating comprises an electrolytically applied to the steel substrate, one-phase consisting of ⁇ -ZnNi phase zinc-nickel alloy coating.
  • This ZnNi alloy coating alone can form the corrosion coating or be supplemented by further protective layers applied to it.
  • the ⁇ -zinc-nickel phase of the resting on the steel substrate ZnNi alloy coating is already realized by the electrolytic coating. That is, unlike coating processes in which an alloy layer forms only as a result of heating to the temperature required for the subsequent hot forming and curing and the resulting diffusion processes, according to the invention is an alloy layer of certain composition and prior to heating on the steel flat product Structure composed of zinc and nickel.
  • the proportions of Zn and Ni and the deposition conditions during the production of the ZnNi alloy layer are selected so that the ZnNi alloy layer is formed as a single-phase coating of Ni5Zn21 phase with a cubic lattice structure.
  • this ⁇ -ZnNi phase layer is deposited in an electrolyte deposition not in the stoichiometric composition, but at nickel contents in the range of 7-15%, with at Ni contents of up to 13 wt. %, in particular from 9 to 11% by weight, give particularly good properties of the coating.
  • a particular advantage of the electrolytic coating according to the invention of the flat steel product with a ZnNi alloy layer of exactly predetermined composition and structure is also that the coating produced therefrom has a matt, rough surface which has a lower reflectivity than those typically produced in the course of known hot-press molding processes Zn-coatings.
  • steel flat products coated in accordance with the invention have an increased heat absorption capacity, so that the subsequent heating to the respective board or component temperature can take place more quickly and with less expenditure of energy. The thus made shorter furnace lay times and energy savings make the inventive method particularly economical.
  • a steel plate is then formed. This can be divided in a conventional manner of the respective steel strip or steel sheet. It is also conceivable, however, that the flat steel product in the coating already has the shape required for the subsequent shaping of the component, that is to say corresponds to the printed circuit board.
  • the steel component is first at least preformed from the blank and only then is the heating carried out to a component temperature of at least 800 ° C.
  • the coating produced according to the invention always consists of cubic intermetallic phases both in the undeformed flat steel product and in the finished steel component: in the starting state in the flat steel product of ⁇ -ZnNi coated according to the invention and after the heating and hot working of the finished steel component made of ⁇ -ZnNi and ⁇ -ZnFe.
  • the inventively heated to a temperature of at least 800 ° C board is formed to the steel component.
  • This can be done, for example, that the board is conveyed immediately after the heating to the mold used in each case. On the way to the mold, it is inevitable that the board will cool down, such that in the case of such hot forming following heating, the temperature of the board as it enters the mold is usually lower than the board temperature at the exit of the furnace.
  • the steel plate is formed in a conventional manner to the steel component.
  • the steel component obtained can be cooled, starting from the respective temperature, at a cooling rate sufficient for the formation of tempering or hardening structure in its steel substrate. This process can be carried out particularly economically in the thermoforming tool itself.
  • the method of the invention is due to the insensitivity of coated in accordance with the invention steel flat product against cracks in the steel substrate and abrasion especially for one-stage hot press molding, in which a hot forming and cooling of the steel component by utilizing the heat of the previously carried out heating to the board temperature in one go be done in a tool.
  • the steel component is formed from this circuit board.
  • the forming of the steel component is typically carried out in a cold forming process, in which one or more cold forming operations are performed.
  • the degree of cold forming can be so high that the steel component obtained is substantially completely finished.
  • This finish forming can be combined with the hardening process by carrying out the hardening as a form hardening in a suitable molding tool.
  • the steel component is placed in a finished final shape imaging tool and cooled sufficiently quickly for the formation of the desired hardness or tempering.
  • the form hardening thus enables a particularly good dimensional stability of the steel component.
  • the shape change during mold hardening is usually low.
  • the Mn content of the inventively processed steel substrate of 0.3 to 3 wt .-%, in particular 0.5 to 3 wt .-%, comes in combination with the invention produced on the steel flat product one-phase television series ⁇ -ZnNi alloy coating of particular importance to.
  • the Mn present in the steel substrate contributes significantly to the good adhesion of the zinc-nickel alloy coating in the steel component produced according to the invention.
  • the anticorrosive coating applied according to the invention contains less than 0.1% by weight of manganese in each case. During the subsequent heating to the board or component temperature, diffusion of the manganese present in the steel substrate then begins in the direction of the free surface of the anticorrosive coating applied according to the invention.
  • the Mn atoms diffusing into the ZnNi alloy layer upon heating cause an intensive coupling of the coating to the steel substrate.
  • Mn reaches a substantial part of the surface of the corrosion protection coating produced according to the invention and is deposited there in metallic and / or oxidic form.
  • the thickness of the Mn-containing layer present in this way on the coating produced according to the invention - hereinafter referred to simply as "Mn oxide layer" for the sake of simplicity - is typically 0.1-5 ⁇ m.
  • the positive effects of the Mn oxide layer are particularly safe when their thickness is at least 0.2 .mu.m, in particular at least 0.5 ⁇ m.
  • the Mn content of the anticorrosive coating is in this near-surface, adjacent to the surface Mn-containing layer at 1-18 wt .-%, in particular 4-7 wt .-%.
  • the pronounced Mn oxide layer present on the coating produced in accordance with the invention ensures particularly good adhesion of organic coatings applied to the anticorrosive coating.
  • the procedure according to the invention is therefore particularly suitable for the production of parts for vehicle bodies, which are provided with a coating after their shaping.
  • a practice-oriented embodiment of the method variants according to the invention provides that the oxide layer obtained in the process according to the invention selectively remains on the anticorrosive coating, since this oxide layer not only a particularly good coatability, but because of their comparatively high conductivity beyond a total good weldability inventively produced and procured Steel components guaranteed.
  • Using steels with a Mn content of less than 0.3% by weight results in a yellowish-appearance coating, indicating that a coating consisting primarily of ZnO is present on the coating Oxide layer is present.
  • the coating thus obtained shows after the thermoforming, similar to that in the WO 2005/012822 reported trial, local flaking and tindering.
  • a coating produced according to the invention on a steel containing at least 0.3% by weight of Mn has a brownish surface which is free from tearing and flaking.
  • the ZnNi coating deposited on the flat steel product according to the invention is applied in practice with a thickness of 0.5-20 ⁇ m.
  • a particularly good protective effect of the ZnNi coating produced according to the invention arises in this case if it is deposited more than 2 ⁇ m thick on the flat steel product.
  • Typical thicknesses of a coating produced according to the invention are in the range from 2 to 20 ⁇ m, in particular from 5 to 10 ⁇ m.
  • a further optimized protection of the steel component according to the invention against corrosion can be achieved by the anticorrosive coating comprising, in addition to the ZnNi alloy coating applied to the flat steel product, a Zn layer which is likewise applied to the ZnNi layer before the heating step. It is then on the prepared for further processing to the component according to the invention flat steel product before heating to the respective board or component temperature before at least a two-layer anticorrosive coating whose first layer of the inventively embodied ZnNi alloy layer and its second layer of the formed thereon, consisting only of zinc Zn layer is formed.
  • the additionally applied, typically 2.5-12.5 ⁇ m thick Zn layer is present in the finished steel component according to the invention as a Zn-rich layer into which Mn and Fe of the steel substrate and Ni from the ZnNi layer can be alloyed.
  • Zn partially reacts to form Zn oxide and forms with the Mn from the base material the Mn-containing layer lying on the anticorrosive coating produced according to the invention.
  • the application of an additional Zn layer of the anti-corrosion coating before heating for the hot forming thus leads to a further improvement of the cathodic corrosion protection.
  • the additional Zn layer of the anticorrosive coating can be deposited as well as the previously applied ZnNi layer electrolytically. This can be done, for example, in a continuous pass through, multi-stage device for electrolytic Coating in the first stages of ZnNi alloy coating on the respective steel substrate and in the steps passed through the Zn layer are deposited on the ZnNi layer.
  • a steel member according to the present invention is made by hot press molding and has a steel substrate made of a 0.3-3 wt% manganese-containing steel substrate and an anticorrosive coating thereon comprising an electrodeposited ZnNi alloy plating composed of ⁇ -ZnNi and ⁇ -ZnFe, and having on its free surface a Mn-containing layer in which Mn is present in metallic or oxidic form.
  • the anticorrosive coating in the manner already described above can comprise a Zn layer resting on the ZnNi layer, the Mn-containing layer also being present on the anticorrosive coating in this case as well.
  • a hood annealed cold strip is alkaline degreased and additionally degreased electrolytically.
  • the degreasing bath at a concentration of 15 g / l contains a commercial cleaner available under the name "Ridoline C72" containing more than 25% sodium hydroxide, 1-5% of a fatty alcohol ether and 5-10% of an ethoxylated, propoxylated and methylated C12- 18 alcohol.
  • the bath temperature is 65 ° C.
  • the residence time in the spray degreasing is 5 s. This is followed by a brush cleaning.
  • the strip is electrolytically degreased at a residence time of 3 s with anodic and cathodic polarity and a current density of 15 A / dm second
  • a multi-stage sink with demineralized water at room temperature with brush insert The residence time in the sink is 3 s.
  • a hydrochloric acid (20 g / l, temperature 35-38 ° C) is passed through with a residence time of 11 s.
  • the plate is transferred after passing through a squeezing in the electrolysis cell.
  • the coating according to the invention of the steel strip or sheet is explained below with reference to the embodiments in detail.
  • the steel flat product emerging from the electrolytic coating line can be rinsed in several stages with water and demineralized water at room temperature.
  • the total residence time in the sink is 17 s. Subsequently, the flat steel product then passes through a drying section.
  • Hot strip (pickled) of grade 22MnB5 (1.5528) is alkaline degreased and degreased electrolytically.
  • the tape undergoes a brush cleaning in alkaline spray degreasing.
  • the degreasing bath contains, at a concentration of 20 g / l, a commercial cleaner available under the name "Ridoline 1893" which contains 5-10% sodium hydroxide and 10-20% potassium hydroxide.
  • the bath temperature is 75 ° C.
  • the residence time in the spray degreasing is 2 s.
  • the sheet After a five-stage cascade rinse with demineralized water, the sheet is transferred after passing through a squeezing into the electrolysis cell and there, as described in the following with reference to the embodiments, provided in accordance with the invention with a corrosion protection coating.
  • the steel flat product coated according to the invention After emerging from the plant for electrolytic coating, the steel flat product coated according to the invention is then rinsed in three stages with demineralized water at 50.degree. The sample then passes through a drying section with circulating air dryer, the air temperature being more than 100 ° C.
  • Bonnet annealed cold strip of grade 22MnB5 (1.5528) is alkaline degreased and degreased electrolytically.
  • the degreasing bath at a concentration of 20 g / l contains a cleaner containing 1-5% C12-18 fatty alcohol polyethylene glycol butyl ether and 0.5-2% potassium hydroxide.
  • the bath temperature is 75 ° C.
  • the residence time in the horizontal spray rinse is 12 s. This is followed by a double brush cleaning.
  • In the course of the strip is electrolytically degreased at a residence time of 9 s with anodic and cathodic polarity and a current density of 10 A / dm second This is followed by a multi-stage sink with demineralized water at room temperature with brush insert.
  • the residence time is 3 s. in the Subsequently, a hydrochloric acid (100 g / l, room temperature) is passed through with a residence time of 27 s. After a combined brushing and Spritzfrischementigan Fe the sheet is transferred after passing through a squeezing in the electrolytic cell. Therein, the electrolytic deposition of the anticorrosive coating according to the invention takes place as explained below with reference to the exemplary embodiments. Subsequent to the electrolytic coating, the steel flat product coated in accordance with the invention is then rinsed in two stages with water and demineralized water at 40.degree. Total residence time 18 s. Afterwards, the sample passes through a drying section with circulation fan with a recirculation air temperature of 75 ° C.
  • Optimal work results arise when the board or component temperature in a conventional manner maximum 920 ° C, in particular 830-905 ° C, is. This applies in particular if the shaping of the steel component is carried out as hot forming following the heating to the board or component temperature such that the heated board ("direct” method) or the heated steel component (“indirect” method) Acceptance of a certain temperature loss is placed in each subsequently used mold.
  • the final thermoforming can be carried out particularly reliably when the board or component temperature is 850 - 880 ° C.
  • the heating to the board or component temperature can be done in a conventional manner in a continuous flow in a continuous furnace. Typical annealing times are in the range of 3 to 15 minutes. Alternatively, however, it is also possible to carry out the heating by means of an inductively or conductively operating heating device. This allows a particularly rapid and accurate heating to the respective predetermined temperature.
  • samples A-V2 Cold rolled and recrystallized annealed as well as temper rolled strip samples A-V2 - hereafter referred to simply as "Samples A-V2" for simplicity - have been provided with a zinc nickel alloy layer in a continuous pass electrogalvanizing line.
  • a sample "Z” has been hot-dip coated for comparison.
  • Samples A-Q and Z each contained Mn contents of more than 0.3 wt%, while the Mn contents of Samples V1, V2 were below the threshold of 0.3 wt%.
  • the respective sample A - V2 was subjected in a 60 ° C warm alkaline cleaning bath at a residence time of 6 s spray cleaning with brush insert.
  • sample Z has been conventionally hot-dip galvanized.
  • Table 2 lists, in addition to the Mn contents of the respective samples A-V2, the properties of the ZnNi coatings which have been electrodeposited under these conditions. It can be seen that in variants A-H and N-P a single-phase ⁇ -ZnNi coating according to the invention has been obtained whereas in variants I - K ⁇ -Zn, i. elemental zinc, and ⁇ -ZnNi coexistent.
  • the Ni content of the sample Q was too high, so that this too was not considered to be in accordance with the invention.
  • the samples V1 and V2 have been produced on a steel with a too low Mn content. Therefore, these samples are also not according to the invention, although they had a ⁇ -ZnNi coating according to the invention.
  • the boards 1 to 41 are then heated to the specified in Table 3 board temperature "T-furnace” over a glow time “t-annealed” and hot-press-formed in a conventional hot press tool single stage to each steel component and cooled so quickly that in the steel substrate hardness structure established.
  • the steel components formed from the boards 1 to 36 and 41 were then subjected to a salt spray test according to DIN EN ISO 9227. If corrosion of the base metal has been detected after 72h or 144h, the column “Base metal corrosion 72h” and “Base metal corrosion 144h” of Table 3 is noted.
  • GDOS Low Discharge Optical Emission Spectrometry
  • Fig. 1 the typical result of the GDOS measurement of the corrosion protection coating of a steel component produced and obtained in accordance with the invention is shown.
  • the contents of Mn (short dashed line), O (dotted line), Zn (long dashed line), Fe (dash-dotted line) and Ni (solid line) are plotted over the layer thickness of the coating. It turns out that there is a high concentration of Mn on the surface of the coating, which has diffused from the steel substrate through the coating on its surface where it is oxidized with the ambient oxygen.
  • the Mn content is significantly lower and only increases again in the steel substrate. This is particularly clear on the basis of Fig. 2 ,
  • the Ni content of the coating is essentially constant over its entire thickness.
  • a recrystallized cold strip is initially electrolytically with a, as in the above-described inventive samples single-phase ⁇ -ZnNi phase ZnNi alloy coating has been coated.
  • the layer thickness of the ⁇ -ZnNi alloy coating was 7 ⁇ m at a Ni content of 10%.
  • a 5 ⁇ m thick pure zinc Zn layer was also electrolytically applied to this ZnNi alloy coating.

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Claims (19)

  1. Procédé de fabrication d'un composant en acier, pourvu d'un revêtement métallique de protection contre la corrosion, lequel procédé comprend les étapes suivantes :
    a) mise à disposition d'un produit plat en acier, fabriqué à partir d'acier, qui, contenant 0,3 à 3 % en poids de manganèse, présente une limite d'étirage de 150 à 1100 MPa et une résistance à la traction de 300 à 1200 MPa ;
    b) recouvrement du produit plat en acier avec un revêtement de protection contre la corrosion comprenant un alliage ZnNi, qui, déposé par électrolyte sur le produit plat en acier et consistant en une phase unique de γ-ZnNi, contient, outre du zinc et des impuretés inévitables, 7 à 15 % en poids de nickel ;
    c) chauffage d'un flan, formé à partir d'un produit plat en acier, à une température de flan d'au moins 800 °C ;
    d) formage, dans un moule, du composant en acier à partir du flan ;
    e) refroidissement du composant en acier par refroidissement à partir d'une température, à laquelle le composant en acier se trouve dans un état approprié à la réalisation d'une structure de trempe ou de revenu, avec un taux de refroidissement suffisant pour la réalisation de la structure de trempe ou de revenu.
  2. Procédé de fabrication d'un composant en acier, pourvu d'un revêtement métallique, de protection contre la corrosion, lequel procédé comprend les étapes suivantes :
    a) mise à disposition d'un produit plat en acier, fabriqué à partir d'acier, qui, contenant 0,3 à 3 % en poids de manganèse, présente une limite d'étirage de 150 à 1100 MPa et une résistance à la traction de 300 à 1200 MPa ;
    b) recouvrement du produit plat en acier avec un revêtement de protection contre la corrosion comprenant un alliage ZnNi, qui, déposé par électrolyte sur le produit plat en acier et consistant en une phase unique de γ-ZnNi, contient, outre du zinc et des impuretés inévitables, 7 à 15 % en poids de nickel ;
    c) chauffage d'un flan, formé à partir d'un produit plat en acier, à une température de flan d'au moins 800 °C ;
    d) formage, dans un moule, du composant en acier à partir du flan ;
    e) durcissement du composant en acier par refroidissement à partir d'une température, à laquelle le composant en acier se trouve dans un état approprié à la réalisation d'une structure de trempe ou de revenu, avec un taux de refroidissement suffisant pour la réalisation de la structure de trempe ou de revenu.
  3. Procédé selon la revendication 2, caractérisé en ce que le formage du composant en acier (étape c) est effectué en tant que préformage et que le composant en acier est complètement formé après le chauffage (étape d).
  4. Procédé selon l'une des revendications précédentes, caractérisé en ce que le revêtement en alliage ZnNi, qui recouvre le composant en acier terminé, consiste en γ-ZnNi et Γ-ZnFe.
  5. Procédé selon l'une des revendications précédentes, caractérisé en ce que, le composant en acier étant fini, une couche contenant du Mn, dans laquelle le Mn présente une forme métallique ou oxydée, est présente sur le revêtement de protection contre la corrosion.
  6. Procédé selon la revendication 5, caractérisé en ce que la couche contenant du Mn présente une épaisseur de 0,1 à 5 µm.
  7. Procédé selon revendication 5 ou 6, caractérisé en ce que la teneur en Mn de la couche contenant du Mn est de 0,1 à 18 % en poids.
  8. Procédé selon l'une des revendications précédentes, caractérisé en ce que la couche de protection contre la corrosion comprend, avant le formage du composant en acier, une couche de Zn supplémentaire, qui est appliquée, également avant le formage du composant en acier, sur le revêtement en alliage ZnNi.
  9. Procédé selon la revendication 8, caractérisé en ce que la couche de Zn présente une épaisseur de 2,5 à 12,5 µm.
  10. Procédé selon l'une des revendications 8 ou 9, caractérisé en ce que le revêtement de protection contre la corrosion du composant en acier fini comprend une couche riche en Zn, qui est posée sur le revêtement en alliage contenant du nickel.
  11. Procédé selon l'une des revendications précédentes, caractérisé en ce que le formage du composant en acier est effectué en tant que formage à chaud et que le formage et le refroidissement du composant en acier sont effectués, en une étape, dans un moule de formage à chaud.
  12. Procédé selon l'une des revendications 1 à 11, caractérisé en ce que le formage du composant en acier et le durcissement sont effectués l'un après l'autre, en deux étapes séparées.
  13. Composant en acier avec un substrat en acier, qui consiste en acier contenant 0,3 à 3 % en poids de manganèse, et avec un revêtement de protection contre la corrosion, appliqué sur le substrat en acier, lequel composant comprend un revêtement en alliage ZnNi
  14. Composant en acier selon la revendication 13, caractérisé en ce que le revêtement en alliage ZnNi présente une épaisseur, qui est supérieure à 2 µm.
  15. Composant en acier selon l'une des revendications 13 ou 14, caractérisé en ce que le revêtement en alliage ZnNi contient 1 à 15 % en poids de Ni.
  16. Composant en acier selon l'une des revendications 13 à 15, caractérisé en ce que la teneur en Mn de la couche contenant du Mn est de 1 à 18 % en poids.
  17. Composant en acier selon l'une des revendications 13 à 16, caractérisé en ce que l'épaisseur de la couche contenant du Mn est de 0,1 à 5 µm.
  18. Composant en acier selon l'une des revendications 13 à 17, caractérisé en ce que le revêtement de protection contre la corrosion comprend une couche riche en zinc, qui est placée sur le revêtement en alliage ZnNi.
  19. Composant en acier selon l'une des revendications 13 à 18, caractérisé en ce que, sur la couche contenant du Mn, est appliqué un revêtement organique.
EP09168605A 2009-08-25 2009-08-25 Procédé de fabrication d'un composant en acier revêtu d'une coiffe métallique protégeant de la corrosion et composant en acier Revoked EP2290133B1 (fr)

Priority Applications (21)

Application Number Priority Date Filing Date Title
AT09168605T ATE554190T1 (de) 2009-08-25 2009-08-25 Verfahren zum herstellen eines mit einem metallischen, vor korrosion schützenden überzug versehenen stahlbauteils und stahlbauteil
ES09168605T ES2384135T3 (es) 2009-08-25 2009-08-25 Procedimiento para fabricar un componente de acero provisto de un recubrimiento metálico de protección contra la corrosión y componente de acero
PT09168605T PT2290133E (pt) 2009-08-25 2009-08-25 Método para a produção de um componente de aço com um revestimento metálico anti-corrosão e um componente de aço
EP09168605A EP2290133B1 (fr) 2009-08-25 2009-08-25 Procédé de fabrication d'un composant en acier revêtu d'une coiffe métallique protégeant de la corrosion et composant en acier
PL09168605T PL2290133T3 (pl) 2009-08-25 2009-08-25 Sposób wytwarzania elementu stalowego z antykorozyjną powłoką metalową i element stalowy
CN201080037681.9A CN102625863B (zh) 2009-08-25 2010-02-24 设有金属的防腐镀层的钢部件的制造方法和钢部件
CA2758629A CA2758629C (fr) 2009-08-25 2010-02-24 Element de construction en acier pourvu d'un depot anticorrosion, et son procede de fabrication
PL10706201T PL2414562T3 (pl) 2009-08-25 2010-02-24 Sposób wytwarzania elementu stalowego zaopatrzonego w powłokę metaliczną zabezpieczającą przed korozją oraz element stalowy
PCT/EP2010/052326 WO2011023418A1 (fr) 2009-08-25 2010-02-24 Élément de construction en acier pourvu d'un dépôt anticorrosion, et son procédé de fabrication
RU2012111247/02A RU2496887C1 (ru) 2009-08-25 2010-02-24 Способ получения стального компонента с металлическим покрытием, обеспечивающим защиту от коррозии, и стальной компонент
PT107062010T PT2414562E (pt) 2009-08-25 2010-02-24 Método de produção de um componente de aço provido de um revestimento metálico que oferece proteção contra a corrosão, e um componente de aço
ES10706201T ES2400221T3 (es) 2009-08-25 2010-02-24 Procedimiento de fabricación un componente de acero provisto de un revestimiento metálico que proporciona protección contra la corrosión y un componente de acero
KR1020117026993A KR101674625B1 (ko) 2009-08-25 2010-02-24 내식성 금속 코팅을 구비한 강 부품 제조 방법 및 강 부품
MX2011011932A MX2011011932A (es) 2009-08-25 2010-02-24 Procedimiento de produccion de un componente de acero provisto de un revestimiento metalico que le da proteccion frente a corrosion, y un componente de acero.
US13/266,941 US9284655B2 (en) 2009-08-25 2010-02-24 Method of producing a steel component provided with a metallic coating giving protection against corrosion
EP10706201A EP2414562B1 (fr) 2009-08-25 2010-02-24 Élément de construction en acier pourvu d'un dépôt anticorrosion, et son procédé de fabrication
JP2012525942A JP5650222B2 (ja) 2009-08-25 2010-02-24 腐食に対する保護を与える金属コーティングが施された鋼部材を製造する方法、および鋼部材
AU2010288814A AU2010288814B2 (en) 2009-08-25 2010-02-24 Method for producing a steel component provided with a metal coating protecting against corrosion and steel component
BRPI1015352A BRPI1015352A2 (pt) 2009-08-25 2010-02-24 método de produção de um componente de aço provido de um revestimento metálico que dá proteção contra a corrosão, e um componente de aço
ZA2011/07674A ZA201107674B (en) 2009-08-25 2011-10-19 Method for producing a steel component provided with a metal coating protecting against corrosion and steel component
US15/046,884 US10053752B2 (en) 2009-08-25 2016-02-18 Steel component provided with a metallic coating giving protection against corrosion

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EP09168605A EP2290133B1 (fr) 2009-08-25 2009-08-25 Procédé de fabrication d'un composant en acier revêtu d'une coiffe métallique protégeant de la corrosion et composant en acier

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EP10706201A Revoked EP2414562B1 (fr) 2009-08-25 2010-02-24 Élément de construction en acier pourvu d'un dépôt anticorrosion, et son procédé de fabrication

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EP (2) EP2290133B1 (fr)
JP (1) JP5650222B2 (fr)
KR (1) KR101674625B1 (fr)
CN (1) CN102625863B (fr)
AT (1) ATE554190T1 (fr)
AU (1) AU2010288814B2 (fr)
BR (1) BRPI1015352A2 (fr)
CA (1) CA2758629C (fr)
ES (2) ES2384135T3 (fr)
MX (1) MX2011011932A (fr)
PL (2) PL2290133T3 (fr)
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US10053752B2 (en) 2018-08-21
US20160160322A1 (en) 2016-06-09
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US9284655B2 (en) 2016-03-15
ES2384135T3 (es) 2012-06-29
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JP5650222B2 (ja) 2015-01-07
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CN102625863A (zh) 2012-08-01
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BRPI1015352A2 (pt) 2016-05-10
EP2290133A1 (fr) 2011-03-02
US20120164472A1 (en) 2012-06-28
WO2011023418A1 (fr) 2011-03-03
EP2414562A1 (fr) 2012-02-08
PT2290133E (pt) 2012-06-19
ATE554190T1 (de) 2012-05-15
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KR20120054563A (ko) 2012-05-30
EP2414562B1 (fr) 2013-01-16

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