EP1658390B1 - Procede de production d'un element constitutif en acier trempe - Google Patents

Procede de production d'un element constitutif en acier trempe Download PDF

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Publication number
EP1658390B1
EP1658390B1 EP04739755.9A EP04739755A EP1658390B1 EP 1658390 B1 EP1658390 B1 EP 1658390B1 EP 04739755 A EP04739755 A EP 04739755A EP 1658390 B1 EP1658390 B1 EP 1658390B1
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Prior art keywords
zinc
coating
corrosion protection
sheet
high oxygen
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German (de)
English (en)
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EP1658390A1 (fr
Inventor
Martin Fleischanderl
Siegfried Kolnberger
Josef Faderl
Gerald Landl
Anna Elisabeth Raab
Werner BRANDSTÄTTER
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Voestalpine Stahl GmbH
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Voestalpine Stahl GmbH
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Priority claimed from AT12022003A external-priority patent/AT412403B/de
Priority claimed from AT0120303A external-priority patent/AT412878B/de
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
    • C23C2/0224—Two or more thermal pretreatments
    • 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
    • C21D1/62—Quenching devices
    • C21D1/673—Quenching devices for die quenching
    • 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
    • B21D22/02—Stamping using rigid devices or tools
    • B21D22/04—Stamping using rigid devices or tools for dimpling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
    • B21J5/00—Methods for forging, hammering, or pressing; Special equipment or accessories therefor
    • 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
    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • C23C2/29—Cooling or quenching
    • 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
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36—Elongated material
    • C23C2/40—Plates; Strips
    • 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
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
    • 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
    • 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
    • C21D2221/00—Treating localised areas of an article
    • 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
    • C21D2251/00—Treating composite or clad material
    • C21D2251/02—Clad material
    • 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
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • 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
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/4998—Combined manufacture including applying or shaping of fluent material
    • Y10T29/49982—Coating
    • 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
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49995—Shaping one-piece blank by removing material
    • 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
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y10T428/12799—Next to Fe-base component [e.g., galvanized]
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal

Definitions

  • the invention relates to a method for producing a hardened steel component with cathodic corrosion protection, as well as a corrosion protection for steel sheets, as well as components made of steel sheets with the corrosion protection.
  • Low alloy steel sheets are not resistant to corrosion after being produced by suitable forming steps, either by hot rolling or cold rolling. This means that after a relatively short time and due to the humidity at the surface, oxidation occurs.
  • a corrosion protection layer is a layer produced on a metal or in the near-surface region of a metal, which consists of one or more layers. Multi-layer coatings are also referred to as corrosion protection systems.
  • Possible corrosion protection layers are, for example, organic coatings, inorganic coatings and metallic coatings.
  • the purpose of metallic corrosion protection layers is to transfer the properties of the support material to the steel surface for as long as possible. Accordingly, the choice of an effective metallic corrosion protection requires the knowledge of the corrosion-chemical relationships in the system steel / coating metal / attacking medium.
  • the coating metals can be electrochemically nobler or electrochemically less noble than steel.
  • the respective coating metal protects the steel only through the formation of protective layers.
  • barrier protection As soon as the surface of the coating metal has pores or was injured, a "local element" forms in the presence of moisture, in which the base partner is attacked by the metal to be protected.
  • the more noble coating metals include tin, nickel and copper.
  • Metallic protective layers are applied by various methods. Depending on the metal and process, the connection of the steel surface is chemical, physical or mechanical and ranges from alloy formation and diffusion to adhesion and mere mechanical clamping.
  • the metallic coatings are said to have similar technological and mechanical properties to steel as they do to steel, and to behave similarly to steel in terms of mechanical stress or plastic deformation. Accordingly, the coatings should not be damaged during forming and should not be affected by forming operations.
  • the metal to be protected is immersed in molten metal melts.
  • corresponding alloy layers are formed at the phase boundary steel-coating metal.
  • An example of this is the hot dip galvanizing.
  • Hot-dip galvanized products have high corrosion resistance, good weldability and formability, and their main applications are the construction, automotive and household appliance industries.
  • a coating of a zinc-iron alloy is known.
  • these products are subjected to a diffusion annealing at temperatures above the zinc melting point, usually between 480 ° C and 550 ° C after hot-dip galvanizing.
  • the zinc-iron alloy layers grow and absorb the overlying zinc layer. This process is called "galvannealing".
  • the zinc-iron alloy thus produced also has a high corrosion resistance, good weldability and formability.
  • Main applications are the automotive and home appliance industry.
  • other coatings of aluminum, aluminum-silicon, zinc-aluminum and aluminum-zinc-silicon can be produced by hot dipping.
  • electrodeposited metal coatings i. the electrolytic, so under current passage deposition of metallic coatings of electrolytes.
  • electrolytic coating is also possible with such metals, which can not be applied by hot dip process.
  • Conventional layer thicknesses in electrolytic coatings are usually between 2.5 and 10 microns, they are thus generally lower than hot-dip coatings.
  • Some metals, e.g. Zinc, also allow thick film coatings with electrolytic coating.
  • Electrolytically galvanized sheets are mainly used in the automotive industry, because of the high surface quality, these sheets are used above all in the outer skin area. They have good formability, weldability and storability as well as good paintable and matt surfaces.
  • the sheet is scaled on the surface by the heating, so that after forming and hardening the sheet surface must be cleaned, for example by sandblasting. Then the sheet is trimmed and, if necessary, necessary holes are punched.
  • the sheets have a very high hardness in the mechanical processing and therefore the processing is complicated and in particular a high tool wear exists.
  • the US 6,564,604 B2 The object of the invention is to provide steel sheets which are subsequently subjected to a heat treatment, and a method for producing parts by press-hardening these coated steel sheets. In this case, it should be ensured despite the increase in temperature that the steel sheet is not decarburized and the O-surface of the steel sheet is not oxidized before, during and after the hot pressing or heat treatment.
  • an alloyed intermetallic mixture should be applied to the surface before or after punching, which should provide protection against corrosion and decarburization and also can provide a lubricating function.
  • this document proposes to use a conventional, apparently electrolytically applied zinc layer, wherein this zinc layer is to convert with the steel substrate in a subsequent Austenit atmosphere the sheet substrate in a homogeneous Zn Fe Fe alloy layer.
  • This homogeneous layer structure is confirmed by microscopic images. Contrary to previous assumptions, this coating is said to have a mechanical resistance that prevents it from melting. In practice, however, such an effect does not show.
  • the use of zinc or zinc alloys is said to provide cathodic protection of the edges when Cuts are available.
  • the US 6,564,604 B2 For example, a coating consisting of 50% to 55% aluminum and 45% to 50% zinc with possibly small amounts of silicon is specified. Such a coating is not new in itself and known under the brand name Galvalume®. It is stated that the coating metals zinc and aluminum with iron should form a homogeneous zinc-aluminum-iron alloy coating. In the case of this coating, it is disadvantageous that sufficient cathodic corrosion protection is no longer achieved here, but the predominant barrier protection which is achieved with this is not sufficient when used in the press hardening process, since partial surface damage to the surface is unavoidable.
  • the method described in this document is unable to solve the problem that, in general, zinc-based cathodic corrosion coatings are not suitable for protecting steel sheets which are to be subjected to a heat treatment after coating and may also be subjected to a further shaping or forming step.
  • a method for producing a sheet metal component wherein the sheet on the surface should have an aluminum layer or an aluminum alloy layer.
  • a sheet provided with such coatings is to be subjected to a press hardening process, wherein possible coating alloys are mentioned Alloy with 9-10% silicon, 2-3.5% iron, balance aluminum with impurities and a second alloy with 2-4% iron and the balance aluminum with impurities.
  • Such coatings are known per se and correspond to the coating of a hot-dip aluminized steel sheet. In such a coating is disadvantageous in that only a so-called barrier protection is achieved. The moment that such a barrier layer is damaged or cracked in the Fe-Al layer, the base material, in this case the steel, is attacked and corroded. A cathodic protective effect is absent.
  • DE 10039375 A1 discloses a method for producing a corrosion protected steel sheet comprising the steps of: applying to a steel sheet a zinc coating by hot dipping in a zinc 5% aluminum melt, heating, alloying and curing (eg 950 ° C) in an atmosphere, wherein Oxide layer is formed on the surface and hot pressing of the coated steel sheet.
  • the DE 102 46 614 A1 proposes, therefore, to apply a coating as a metal or a metal alloy by means of a galvanic coating method in organic, non-aqueous solution, a particularly suitable and therefore preferred coating material being aluminum or an aluminum alloy.
  • a particularly suitable and therefore preferred coating material being aluminum or an aluminum alloy.
  • zinc or zinc alloys would be suitable.
  • Such a coated sheet can then be cold preformed and hot finished molded.
  • this method has the disadvantage that an aluminum coating, even if it was applied electrolytically, no longer offers corrosion protection in case of damage to the surface of the finished component, since the protective barrier has been broken.
  • an electrodeposited zinc coating it is disadvantageous that during heating for hot forming, the zinc is largely oxidized and no longer available for cathodic protection. Under a protective gas atmosphere, the zinc evaporates.
  • the object of the invention is to provide a method for producing a component from hardened steel sheet with an improved cathodic corrosion protection.
  • Another object is to provide a cathodic corrosion protection for steel sheets, which are subjected to forming and hardening.
  • the inventive method provides, on a hardenable steel sheet, a coating of a mixture consisting essentially of zinc and one or more oxygen-affine elements, such as magnesium, silicon, titanium, calcium, aluminum, boron and manganese with a content of 0.1 to 15
  • a coating of a mixture consisting essentially of zinc and one or more oxygen-affine elements, such as magnesium, silicon, titanium, calcium, aluminum, boron and manganese with a content of 0.1 to 15
  • Apply wt .-% of the oxygen affinity element and to heat the coated steel sheet at least partially with the access of oxygen to a temperature above the Austenitmaschinestemperatur the sheet metal alloy and before or subsequently reshape the sheet is cooled after sufficient heating and the cooling rate is measured in that hardening of the sheet metal alloy takes place.
  • a hardened component is obtained from a steel sheet having a good cathodic corrosion protection.
  • the corrosion protection according to the invention for steel sheets, which are first subjected to a heat treatment and then reformed and thereby hardened, is a cathodic corrosion protection which is essentially based on zinc.
  • a cathodic corrosion protection which is essentially based on zinc.
  • 0.1% to 15% of one or more oxygen-containing elements such as magnesium, silicon, titanium, calcium, aluminum, boron and manganese or any mixture or alloy thereof are added to the zinc forming the coating. It has been found that such small amounts of an oxygen affinity element as magnesium, silicon, titanium, calcium, aluminum, boron and manganese cause a surprising effect in this particular application.
  • At least Mg, Al, Ti, Si, Ca, B, Mn are suitable as oxygen-affine elements.
  • aluminum is mentioned below, this is representative of the other elements mentioned.
  • the application of the coating according to the invention on a steel sheet can be done, for example, by so-called hot-dip galvanizing, i. a hot dip coating is performed wherein a liquid mixture of zinc and the oxygen-affine element (s) is applied. Furthermore, it is possible to electrolytically apply the coating, i. to deposit the mixture of zinc and the oxygen-affine element (s) collectively on the sheet surface, or first to deposit a zinc layer and then to deposit on the zinc surface one or more oxygen-affine elements in succession or any mixture or alloy thereof, or by vapor deposition or other suitable method deposit.
  • hot-dip galvanizing i. a hot dip coating is performed wherein a liquid mixture of zinc and the oxygen-affine element (s) is applied.
  • electrolytically apply the coating i. to deposit the mixture of zinc and the oxygen-affine element (s) collectively on the sheet surface, or first to deposit a zinc layer and then to deposit on the zinc surface one or more oxygen-affine elements in succession or any mixture or alloy thereof, or
  • an oxygen-affine element in particular aluminum
  • an essentially of AL 2 O 3 or an oxide of the oxygen-affine element MgO, CaO, TiO, SiO 2 , B 2 O 3 , MnO
  • This very thin oxide layer protects the underlying Zn-containing corrosion protection layer from oxidation even at very high temperatures.
  • an approximately two-layer corrosion protection layer is formed, which consists of a cathodically highly effective layer, with a high proportion of zinc and a very thin oxidation protection layer of one or more oxides (AL 2 O 3 , MgO , CaO, TiO, SiO 2 , B 2 O 3 , MnO) to oxidation and Evaporation is protected.
  • a 2 O 3 , MgO , CaO, TiO, SiO 2 , B 2 O 3 , MnO oxides
  • the corrosion protection layer according to the invention for the press-hardening process also has such a high stability that a forming step following the austenitizing of the sheets does not destroy this layer. Even if microcracks occur on the cured component, however, the cathodic protection effect is at least significantly greater than the protective effect of the known corrosion protection layers for the press-hardening process.
  • a zinc alloy with a content of aluminum in weight percent of greater than 0.1 but less than 15%, in particular less than 10%, more preferably less than 5% on a Steel plate, in particular an alloyed steel sheet are applied, whereupon in a second step, parts of the coated sheet are machined and in particular cut out or punched out and heated on access of atmospheric oxygen to a temperature above the Austenitmaschinestemperatur the sheet metal alloy and then cooled at an increased speed.
  • a transformation of the cut out of the sheet metal part (the board) can be carried out before or after the heating of the sheet to the Austenitmaschinestemperatur.
  • the sheet when coating the sheet to the sheet surface or in the proximal region of the layer, a thin barrier phase of, in particular Fe 2 Al 5 -x Zn x is formed, which impedes the Fe-Zn diffusion in a liquid metal coating process, which takes place in particular at a temperature up to 690 ° C.
  • the sheet in the first process step, is formed with a zinc-metal coating with an addition of aluminum, which is effective only towards the sheet surface, as in the proximal region of the support an extremely thin barrier phase, which is effective against rapid growth of an iron-zinc compound phase, having.
  • the metal layer on the sheet is liquefied for the time being.
  • the oxygen-containing aluminum from the zinc reacts with atmospheric oxygen to form solid oxide, thereby causing a decrease in the aluminum metal concentration, which causes a steady diffusion of aluminum towards depletion, that is to the distal region.
  • This Tonerdeanreichtation, at the air exposed layer area now acts as oxidation protection for the layer metal and as Abdampfungssperre for the zinc.
  • the aluminum is withdrawn from the proximal blocking phase by continuous diffusion towards the distal region and is available there for the formation of the superficial Al 2 O 3 layer.
  • the formation of a sheet metal coating is achieved, which leaves a cathodically highly effective layer with a high zinc content.
  • Well suited is, for example, a zinc alloy with a content of aluminum in weight percent of greater than 0.2 but less than 4, preferably greater than 0.26 but less than 2.5 wt .-%.
  • the zinc alloy layer is applied to the sheet surface passing through a liquid metal bath at a temperature higher than 425 ° C, but lower than 690 ° C, especially at 440 ° C to 495 ° C, followed by cooling of the coated sheet, not only the proximal barrier phase can be effectively formed, or a very good diffusion inhibition can be observed in the region of the barrier layer, but it also takes place to improve the thermoforming properties of the sheet material.
  • An advantageous embodiment of the invention is given in a method in which a hot or cold rolled steel strip having a thickness of, for example, greater than 0.15 mm and a concentration range of at least one of the alloying elements within the limits in wt .-% carbon to 0.4, preferably 0.15 to 0.3 silicon until 19, preferably 0.11 to 1.5 manganese to 3.0, preferably 0.8 to 2.5 chrome to 1.5, preferably 0.1 to 0.9 molybdenum to 0, 9, preferably 0.1 to 0.5 nickel to 0, 9, titanium to 0.2 preferably 0.02 to 0.1 vanadium to 0.2 tungsten to 0.2, aluminum to 0.2, preferably 0.02 to 0.07 boron to 0.01, preferably 0.0005 to 0.005 sulfur Max. 0.01, preferably max. 0.008 phosphorus Max. 0.025, preferably max. 0.01 Rest iron and impurities is used.
  • the surface structure of the cathodic corrosion protection according to the invention is particularly favorable for a high adhesion of paints and varnishes.
  • the obtained samples were analyzed for optical and electrochemical differences.
  • Assessment criteria here were the appearance of the annealed steel sheets and the protection energy.
  • the protection energy is the measure for the electrochemical protection of the layer, determined by galvanostatic dissolution.
  • the electrochemical method of galvanostatic dissolution of the metallic surface coatings of a material allows to classify the mechanism of corrosion protection of the layer.
  • the potential-time behavior of a corrosion-protective layer is determined for a given constant current flow. For the measurements, a current density of 12.7 mA / cm 2 was specified.
  • the measuring arrangement is a three-electrode system.
  • the counterelectrode used was a platinum network, the reference electrode consisting of Ag / AgCl (3M).
  • the electrolyte consists of 100 g / l ZnSO 4 .5H 2 O and 200 g / l NaCl dissolved in deionized water.
  • the barrier protection is characterized by the fact that it separates the base material from the corrosive medium.
  • a hot-dip aluminized steel sheet is made by passing a steel sheet through a liquid aluminum bath. Annealing to 900 ° C produces an aluminum-iron surface layer due to the reaction of the steel with the aluminum coating. The corresponding annealed sheet shows a dark gray appearance, the surface is homogeneous and visually shows no defects.
  • a steel sheet was hot dip galvanized with an aluminum-zinc layer, the melt consisting of 55% aluminum, 44% zinc and about 1% silicon. After surface coating and subsequent annealing at 900 ° C, a gray-bluish surface appears without defects. A cross section is in FIG. 4 shown.
  • the annealed material is then subjected to galvanostatic dissolution.
  • the material shows a potential of about -0.92 V, which is necessary for the resolution, and is thus clearly below the steel potential.
  • This value is comparable to the potential needed to dissolve a hot dip galvanized coating prior to the annealing process.
  • this very zinc-rich phase ends after just about 350 seconds of measurement time. This is followed by a rapid increase to a potential that is now just below the steel potential lies.
  • the potential After breaking through this layer, the potential first drops to a value of about -0.54 V and then increases continuously to a value of about -0.35 V. Only then does it slowly sink to steel potential.
  • This material shows some cathodic corrosion protection due to the very negative potential at the beginning of the measurement, which is well below the steel potential, in addition to the barrier protection.
  • the part of the layer that provides cathodic protection against corrosion is used up after only about 350 seconds of measurement time.
  • the remaining layer can only offer a low cathodic corrosion protection, since the difference between the required potential for the layer dissolution and the steel potential now only less than 0.12 V. In a poorly conductive electrolyte, this part of the cathodic corrosion protection is no longer usable.
  • the potential-time diagram is in FIG. 5 shown.
  • a steel sheet is hot-dip galvanized with a melt consisting essentially of 95% zinc and 5% aluminum. After annealing, the sheet shows a silvery-gray surface with no defects.
  • FIG. 6 shows that the coating consists of a light phase and a dark phase, wherein the phases are Zn-Fe-Al-containing phases. The bright phases are more zinc-rich, the dark phases more iron-rich.
  • the galvanostatic dissolution shows a potential of about -0.7 V required for the resolution. This value is significantly below the potential of the steel. After a measuring time of approx. 1,000 seconds it turns a potential of about -0.6V. This potential is also clearly below the steel potential. After a measurement time of approximately 3,500 seconds, this part of the layer is used up and the necessary potential for dissolving the layer approaches the steel potential. This coating thus offers after the annealing in addition to the barrier protection a cathodic corrosion protection. The potential is up to a measuring time of 3,500 seconds at a value of ⁇ -0.6 V, so that a considerable cathodic protection is maintained over a long time, even if the sheet was fed to the austenitizing temperature.
  • the potential-time diagram is in FIG. 7 shown.
  • the sheet is passed through a melt or through a zinc bath, with a zinc content of 99.8% and an aluminum content of 0.2%.
  • Aluminum present in the zinc coating reacts with atmospheric oxygen during the calcination and forms a protective Al 2 O 3 skin. Through constant diffusion of the oxygen-affinity aluminum to the surface, this protective skin is maintained and expanded.
  • the sheet shows a silvery-gray surface without defects. From the originally about 15 microns thick zinc coating develops during the annealing due to diffusion, a about 20 to 25 microns thick layer, said layer ( FIG. 8 ) consists of a dark appearing phase with a composition Zn / Fe of about 30/70 and a bright area with the composition Zn / Fe of about 80/20.
  • the annealed material has a potential of approx. -0.75 V. After a measuring time of approx. 1,500 seconds, the potential required for the resolution increases to ⁇ -0.6 V. The phase lasts up to a measuring time of approx. 2,800 seconds. Then the required potential increases to steel potential. In this case too, in addition to barrier protection, there is cathodic corrosion protection. The potential is up to a measurement time of 2,800 seconds at a value of ⁇ -0.6 V. Thus, such a material has thus over a very long time a cathodic protection against corrosion.
  • the potential-time diagram is FIG. 9 refer to.
  • the sheet is heated to a temperature of about 500 ° C after exiting the metal strip from the molten zinc (about 450 ° C strip temperature).
  • the zinc layer is completely converted into Zn-Fe phases.
  • the zinc layer is thus wholly, i. converted to Zn-Fe phases to the surface.
  • This anticorrosive layer contains some aluminum in the zinc bath, of the order of about 0.13%.
  • a 1 mm thick steel sheet with said heat treated and fully converted coating is heated for 4 minutes and 30 seconds in a 900 ° C oven.
  • the result is a yellow-green surface.
  • the yellow-green surface indicates oxidation of the Zn-Fe phases during annealing.
  • An aluminum oxide protective layer is undetectable. The reason for the absence of an aluminum oxide protective layer can be explained by the fact that in the Annealing treatment due to solid Zn-Fe phases, aluminum can not migrate to the surface so rapidly and protect the Zn-Fe coating from oxidation. When heating this material at temperatures around 500 ° C is still no liquid zinc-rich phase, because this forms only at higher temperatures of 782 ° C. If 782 ° C are reached, thermodynamically there is a liquid zinc-rich phase in which the aluminum is freely available. Nevertheless, the surface layer is not protected against oxidation.
  • the corrosion protection layer is already partially oxidized before and it can no longer form opaque alumina skin.
  • the layer is wavy rugged in cross section and consists of Zn and Zn Fe oxides ( FIG. 11 ).
  • the surface of the said material is much larger due to the highly crystalline acicular surface formation of the surface, which could also be disadvantageous for the formation of a covering and thicker aluminum oxide protective layer.
  • the said non-inventive coating forms in the initial state, ie not in the thermally treated state, a brittle layer which is provided with numerous cracks, both transversely and longitudinally to the coating. ( FIG. 10 in comparison to the aforementioned inventive example (left in the picture)).
  • a sheet, as in the aforementioned example, is heat-treated immediately after hot-dip galvanizing at about 490 ° C to 550 ° C with the zinc layer only partially converted to Zn-Fe phases.
  • the process is carried out in such a way that the phase transformation is only partially carried out and therefore not yet converted zinc with aluminum on the surface is present and thus free aluminum as oxidation protection for the zinc layer is available.
  • a 1 mm thick steel sheet is rapidly inductively heated to 900 ° C with the inventive heat-treated and only partially converted into Zn-Fe phase coating.
  • the result is a surface that is gray and without defects.
  • a SEM / EDX examination of the cross section shows an approximately 20 microns thick surface layer, wherein from the originally about 15 microns thick zinc coating of the coating has formed in the inductive annealing due to diffusion, an about 20 microns Zn-Fe layer, said layer with the typical for the invention two-phase structure a "leopard pattern" shows, with a dark phase in the image with a composition Zn / Fe of about 30/70 and bright areas with the composition Zn / Fe of about 80/20. In addition, individual areas with zinc contents ⁇ 90% zinc are present. On the surface a protective layer of alumina is detectable.
  • a sheet is electrolytically galvanized by electrochemical deposition of zinc on steel. During annealing, the diffusion of the steel and the zinc layer creates a thin Zn-Fe layer. Most of the zinc oxidizes to zinc oxide, which appears green by the simultaneous formation of iron oxides. The surface shows a green appearance with local scale marks where the zinc oxide layer does not adhere to the steel.
  • a REM / EDX examination ( FIG. 15 ) of the sample sheet in transverse section confirms that a large part of the coating consists of zinc-iron-oxide deposits.
  • the potential required for the current flow is included about +1 V and thus well above the steel potential.
  • the potential fluctuates between +0.8 and -0.1 V, but is above the steel potential throughout the entire dissolution of the coating. It follows that the corrosion protection of a annealed, electrolytically galvanized sheet is a pure barrier protection, but which is less efficient than with fumed sheet, since the potential is lower at the beginning of the measurement with electrolytically coated sheet than with hot-dip aluminized sheet.
  • the potential required for the dissolution lies above the steel potential throughout the entire dissolution. Thus, even with a annealed, electrolytically coated metal sheet there is no cathodic corrosion protection at any time.
  • the potential-time diagram is FIG. 16 refer to.
  • the potential is fundamentally above steel potential, but varies in detail depending on the experiment under identical experimental conditions.
  • a sheet is made by electroplating zinc and nickel on the steel surface.
  • the weight ratio of zinc to nickel in the anticorrosion layer is about 90/10.
  • the deposited layer thickness is 5 ⁇ m.
  • the sheet is annealed with the coating for 4 minutes and 30 seconds at 900 ° C in the presence of atmospheric oxygen.
  • the diffusion of the steel and the zinc layer creates a thin diffusion layer of zinc, nickel and iron.
  • most of the zinc oxidizes again to zinc oxide.
  • the surface shows a scaled, green appearance with small local flaking to which the oxide layer does not adhere to the steel.
  • FIG. 17 A SEM / EDX examination of a cross section ( FIG. 17 ) shows that the majority of the coating has been oxidized and is therefore not available for cathodic corrosion protection.
  • the potential required for the resolution of the layer is 1.5 V, far above the steel potential. After approx. 250 seconds it sinks to approx. 0.04 V and oscillates between + 0.25 V. After approx. 1.700 seconds measuring time, it finally settles to a value of - 0.27 V and remains until the end of the Measurement at this value.
  • the potential required for the resolution of the layer is well above the steel potential throughout the entire measurement time. Consequently, this coating has a pure barrier protection after annealing, without any cathodic corrosion protection (Figure 18).
  • Example 4 steel sheet with a layer thickness of 15 microns was placed for 4 min 30 s in a 900 ° C hot air blast furnace, then rapidly cooled between two 5 cm thick steel plates and the surface with a GDOES measurement analyzed.
  • FIGS. 25 and 26 the GDOES analyzes of the coated sheet according to Example 4 are shown before and after the annealing. Before hardening ( Fig. 25 ) is reached after about 15 microns, the transition zinc layer steel, after curing, the layer is about 23 microns thick.
  • the cathodic corrosion protection is negligible with a voltage difference of 100 mV to the steel potential in poorly conducting electrolytes.
  • a smaller difference to the steel potential is in principle still a cathodic corrosion protection, if a current flow is detected when using a steel electrode, but this is negligible for practical aspects, since the corrosive medium must conduct very well, so this contribution to the cathodic corrosion protection can be used.
  • the area between the potential curve at the galvanostatic dissolution and the specified threshold value of 100 mV was set below the steel potential ( FIG. 20 ). Only the area below the threshold is taken into account. The overlying surface contributes negligibly little or not at all to the cathodic corrosion protection and is therefore not included in the evaluation.
  • the area thus obtained is multiplied by the current density, the protection energy per unit area with which the base material can be actively protected against corrosion. The greater this energy, the better the cathodic corrosion protection.
  • FIG. 21 the calculated protective energies per unit area are compared. While a sheet with the known aluminum-zinc layer of 55% aluminum and 44% zinc, as it is also known from the prior art, only a protection energy per unit area of about 1.8 J / cm 2 , which is Protection energy per unit area in accordance with the invention coated sheets 5.6 J / cm 2 and 5.9 J / cm 2 .
  • cathodic corrosion protection in the context of the invention, it is subsequently specified that coatings of 15 ⁇ m thickness are used and the illustrated process and experimental conditions at least a cathodic corrosion protection energy of 4 J / cm 2 is present.
  • a zinc layer which has been deposited electrolytically on the steel sheet surface is not in itself capable of providing a corrosion protection according to the invention, even after a heating step above the austenitizing temperature.
  • the invention can also be achieved with an electrodeposited coating.
  • the zinc can be deposited simultaneously with the oxygen-affine elements or elements in an electrolysis step on the sheet surface simultaneously, so that on the sheet surface, a coating with a homogeneous structure is formed containing both zinc and the oxygen-affine or the elements.
  • a coating behaves like a coating of the same composition applied to the sheet surface in the hot-dip galvanizing process.
  • a first electrolysis step only zinc is deposited on the sheet surface and in a second electrolysis step, the oxygen-affine element (s) is deposited on the zinc layer.
  • the second coating of the oxygen-affine elements may be significantly thinner than the zinc coating.
  • the outer layer located on the zinc layer oxidizes from the oxygen-affine element (s) and protects the underlying zinc with an oxide skin.
  • the oxygen affinity element or elements are selected so that they do not evaporate from the zinc layer or are oxidized in a manner that does not leave a protective oxide skin.
  • first a zinc layer is deposited electrolytically and then a layer of the oxygen-affine element (s) is applied by vapor deposition or other suitable non-electrolytic coating methods.

Claims (39)

  1. Procédé pour produire un composant en acier trempé avec une protection anticorrosion cathodique, dans lequel :
    a) dans un processus de revêtement continu, on applique un revêtement sur une tôle en alliage d'acier capable d'être trempé, et
    b) le revêtement est essentiellement constitué de zinc, et
    c) le revêtement contient en outre un ou plusieurs éléments présentant une affinité à l'oxygène, dans une quantité totale de 0,1 % en poids jusqu'à 15 % en poids, par référence à la totalité de revêtement, et
    d) la tôle d'acier revêtue est amenée ensuite au moins sur des zones partielles et avec apport d'oxygène atmosphérique jusqu'à une température d'austénitisation nécessaire pour la trempe, et est chauffée jusqu'à une modification de structure nécessaire pour la trempe,
    e) on forme sur le revêtement une peau de surface en un oxyde du ou des élément(s) présentant une affinité à l'oxygène, et
    f) la tôle est déformée avant ou après le chauffage,
    g) après un échauffement suffisant, la tôle est refroidie et la vitesse de refroidissement est choisie de telle façon que l'on obtient une trempe de l'alliage de la tôle, et
    h) on utilise dans le mélange à titre d'éléments présentant une affinité à l'oxygène du magnésium et/ou du silicium et/ou du titane et/ou du calcium et/ou de l'aluminium et/ou du manganèse et/ou du bore, et
    i) le mélange de revêtement est sélectionné de telle façon que la couche forme pendant le chauffage une peau superficielle en oxyde formée d'oxyde(s) du ou des éléments présentant une affinité à l'oxygène, et le revêtement forme au moins deux phases, de manière à former une phase riche en zinc et une phase riche en fer.
  2. Procédé selon la revendication 1, caractérisé en ce que le revêtement est appliqué selon une procédure de plongée dans un bain en fusion, dans laquelle on utilise un mélange formé essentiellement de zinc avec le ou les éléments présentant une affinité à l'oxygène.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'on utilise 0,2 % en poids à 5 % en poids des éléments présentant une affinité à l'oxygène.
  4. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'on utilise 0,26 % en poids jusqu'à 2,5 % en poids des éléments présentant une affinité à l'oxygène.
  5. Procédé selon l'une des revendications précédentes, caractérisé en ce que la phase riche en fer présente un rapport zinc/fer au maximum de 0,95 (Zn/Fe ≤ 0,95), de préférence de 0,20 à 0,80 (Zn/Fe = 0,20 à 0,80) et la phase riche en zinc présent un rapport zinc/fer d'au moins 2,0 (Zn/Fo ≥2,0), de préférence de 2,3 à 19,0 (Zn/Fe = 2,3 à 19,0).
  6. Procédé selon l'une des revendications précédentes, caractérisé en ce que la phase riche en fer possède un rapport zinc/fer d'environ 30:70, et la phase riche en zinc est réalisée avec un rapport zinc/fer d'environ 80:20.
  7. Procédé selon l'une des revendications précédentes, caractérisée en ce que la couche contient en outre des zones individuelles avec des parts de zinc > 90 %.
  8. Procédé selon l'une des revendications précédentes, caractérisé en ce que le revêtement est réalisé de telle façon que, pour l'épaisseur de départ de 15 µm après le processus de trempe, il développe un effet de protection cathodique d'au moins 4 J/cm2.
  9. Procédé selon l'une des revendications précédentes, caractérisé en ce que le revêtement avec le mélange de zinc et du ou des éléments présentant une affinité à l'oxygène, a lieu à la traversée d'un bain de métal liquide à une température de 425° C à 690° C, avec un refroidissement successif de la tôle revêtue.
  10. Procédé selon l'une des revendications précédentes, caractérisé en ce que le revêtement avec le mélange de zinc et des éléments présentant une affinité à l'oxygène a lieu à la traversée d'un bain de métal liquide à une température de 440° C à 495° C, avec un refroidissement successif de la tôle revêtue.
  11. Procédé selon l'une des revendications précédentes, caractérisé en ce que la tôle est chauffée par induction.
  12. Procédé selon l'une des revendications précédentes, caractérisé en ce que la tôle est chauffée par induction dans l'outil.
  13. Procédé selon l'une des revendications précédentes, caractérisé en ce que la tôle est chauffée dans un four à rayonnement.
  14. Procédé selon l'une des revendications précédentes, caractérisé en ce que le refroidissement a lieu dans l'outil de mise en forme.
  15. Procédé selon l'une des revendications précédentes, caractérisé en ce que le refroidissement est exécuté lors de la mise en forme au moyen d'outils de mise en forme refroidis.
  16. Procédé selon l'une des revendications précédentes, caractérisé en ce que le refroidissement a lieu après la mise en forme dans l'outil de mise en forme.
  17. Procédé selon l'une des revendications précédentes, caractérisé en ce que le refroidissement a lieu dans un outil de trempe et de moulage, dans lequel la tôle mise en forme est posée après le chauffage, et dans lequel on établit une coopération de formes entre la tôle déformée et les outils de trempe et de moulage refroidis présentant une forme correspondante.
  18. Procédé selon l'une des revendications précédentes, caractérisé en ce que le chauffage et le refroidissement a lieu dans l'outil de trempe et de moulage, et le chauffage a lieu par induction et le moule est refroidi après le chauffage inductif.
  19. Procédé selon l'une des revendications précédentes, caractérisé en ce que la mise en forme et la trempe du composant un lieu avec un appareil de mise en forme par laminage, dans lequel la tôle revêtue est chauffée au moins partiellement à la température d'austénitisation et est mise en forme par laminage avant, pendant et/ou après et, à la suite de la mise en forme par laminage elle est refroidie à une vitesse de refroidissement qui provoque une trempe de l'alliage de la tôle.
  20. Procédé de production d'un composant en acier trempé avec une protection anticorrosion cathodique, dans lequel :
    a) dans un processus de revêtement continu, on applique un revêtement sur une tôle en alliage d'acier capable d'être trempé, et
    b) le revêtement est essentiellement constitué de zinc, et
    c) le revêtement contient en outre un ou plusieurs éléments présentant une affinité à l'oxygène, dans une quantité totale de 0,1 % en poids jusqu'à 15 % en poids, par référence à la totalité de revêtement, et
    d) la tôle d'acier revêtue est amenée ensuite au moins sur des zones partielles et avec apport d'oxygène atmosphérique jusqu'à une température d'austénitisation nécessaire pour la trempe, et est chauffée jusqu'à une modification de structure nécessaire pour la trempe,
    e) on forme sur le revêtement une peau de surface en un oxyde du ou des élément(s) présentant une affinité à l'oxygène, et
    f) la tôle est déformée avant ou après le chauffage,
    g) après un échauffement suffisant, la tôle est refroidie et la vitesse de refroidissement est choisie de telle façon que l'on obtient une trempe de l'alliage de la tôle, et
    h) on utilise dans le mélange à titre d'éléments présentant une affinité à l'oxygène du magnésium et/ou du silicium et/ou du titane et/ou du calcium et/ou de l'aluminium et/ou du manganèse et/ou du bore, et
    i) le mélange de revêtement est sélectionné de telle façon que la couche forme pendant le chauffage une peau superficielle en oxyde formée d'oxyde(s) du ou des éléments présentant une affinité à l'oxygène, et le revêtement forme au moins deux phases, de manière à former une phase riche en zinc et une phase riche en fer, et
    j) le revêtement est appliqué par voie électronique.
  21. Procédé selon la revendication 20, caractérisé en ce que lors du revêtement électrolytique, on dépose tout d'abord une couche de zinc et on dépose à la suite en une seconde passe sur la couche de zinc déposée le ou les éléments présentant une affinité à l'oxygène.
  22. Procédé selon la revendication 20 ou 21, caractérisé en ce que l'on dépose tout d'abord une couche de zinc par voie électrolytique sur la surface de la tôle, et l'on applique ensuite sur la surface du zinc un revêtement du ou des éléments présentant une affinité à l'oxygène.
  23. Procédé selon l'une des revendications 20 à 22, caractérisé en ce que le ou les éléments présentant une affinité à l'oxygène sont appliqués par vaporisation pour par d'autres procédures appropriées.
  24. Procédé selon l'une des revendications 20 à 23, caractérisé en ce que l'on utilise 0,26 % en poids à 2,5 % en poids des éléments présentant une affinité à l'oxygène.
  25. Couche de protection anticorrosion sur des tôles d'acier qui sont soumises à une étape de trempe, dans laquelle la couche de protection anticorrosion est soumise après l'application sur la tôle d'acier à un traitement thermique sous apport d'oxygène, dans laquelle le revêtement est essentiellement constitué de zinc et contient en outre un ou plusieurs éléments présentant une affinité à l'oxygène dans une quantité totale de 0,1 % en poids à 15,0 % en poids par référence à la totalité de revêtement, ladite couche de protection anticorrosion possédant en surface une peau d'oxyde formée des oxydes du ou des éléments présentant une affinité à l'oxygène, et le revêtement forme au moins deux phases, c'est-à-dire une phase riche en zinc et une phase riche en fer.
  26. Couche de protection anticorrosion sur des tôles d'acier qui sont soumises à une étape de trempe, dans laquelle la couche de protection anticorrosion est soumise après l'application sur la tôle d'acier à un traitement thermique sous apport d'oxygène, dans laquelle le revêtement est essentiellement constitué de zinc et contient en outre un ou plusieurs éléments présentant une affinité à l'oxygène dans une quantité totale de 0,1 % en poids à 15,0 % en poids par référence à la totalité de revêtement, ladite couche de protection anticorrosion possédant en surface une peau d'oxyde formée des oxydes du ou des éléments présentant une affinité à l'oxygène et le revêtement forme au moins deux phases, à savoir une phase riche en zinc et une phase riche en fer, ladite couche de protection anticorrosion étant une couche de protection anticorrosion appliquée par un procédé de déposition électrolytique dans lequel la couche de protection anticorrosion a été formée par déposition électrolytique essentiellement de zinc et simultanément d'un ou plusieurs éléments présentant une affinité à l'oxygène, ou dans lequel la couche de protection anticorrosion a été formée tout d'abord par déposition électrolytique essentiellement de zinc et par vaporisation successive ou application avec d'autres procédures appropriées d'un ou plusieurs éléments présentant une affinité à l'oxygène.
  27. Couche de protection anticorrosion selon la revendication 25 ou 26, caractérisée en ce que la couche de protection anticorrosion contient dans le mélange à titre d'éléments présentant une affinité à l'oxygène du magnésium et/ou du silicium et/ou du titane et/ou du calcium et/ou de l'aluminium et/ou du bore et/ou du manganèse.
  28. Couche de protection anticorrosion selon la revendication 25 ou 27, caractérisée en ce que la couche de protection anticorrosion est une couche de protection anticorrosion appliquée par une procédure de plongée dans un bain en fusion.
  29. Couche de protection anticorrosion selon l'une des revendications 25 à 28, caractérisée en ce que le revêtement est constitué d'un mélange composé essentiellement de zinc et le mélange contient en outre un ou plusieurs éléments présentant une affinité à l'oxygène.
  30. Couche de protection anticorrosion selon l'une des revendications 25 à 29, caractérisée en ce que les éléments présentant une affinité à l'oxygène sont contenus dans une quantité totale de 0,1 à 15,0 % en poids par référence à la totalité du revêtement.
  31. Couche de protection anticorrosion selon l'une des revendications 25 à 30, caractérisée en ce que lesdits éléments présentant une affinité à l'oxygène sont contenus dans une quantité totale de 0,02 à 0,5 % en poids par référence à la totalité du revêtement.
  32. Couche de protection des corrosions selon l'une des revendications 25 à 31, caractérisée en ce que les éléments présentant une affinité à l'oxygène sont contenus dans une quantité totale de 0,6 à 2,5 % en poids par référence à la totalité du revêtement.
  33. Couche de protection anticorrosion selon l'une des revendications 25 à 32, caractérisée en ce qu'elle contient essentiellement de l'aluminium à titre d'éléments présentant une affinité à l'oxygène.
  34. Couche de protection anticorrosion selon l'une des revendications 25 à 32, caractérisée en ce que la phase riche en fer présente un rapport zinc/fer au maximum de 0,95 (Zn/Fe ≤ 0,95), de préférence de 0,20 à 0,80 (Zn/Fe = 0,20 à 0,80) et la phase riche en zinc présent un rapport zinc/fer d'au moins 2,0 (Zn/Fe ≥ 2,0), de préférence de 2,3 à 19,0 (Zn/Fe = 2,3 à 19,0).
  35. Couche de protection anticorrosion selon l'une des revendications 25 à 34, caractérisée en ce que la phase riche en fer possède un rapport zinc/fer d'environ 30:70, et la phase riche en zinc présente un rapport zinc/fer d'environ 80:20.
  36. Couche de protection anticorrosion selon l'une des revendications 25 à 35, caractérisée en ce que la couche de protection anticorrosion contient en outre des zones individuelles avec des parts de zinc ≥ 90 % en poids.
  37. Couche de protection anticorrosion selon l'une des revendications 25 à 36, caractérisée en ce que la couche de protection anticorrosion possède, pour une épaisseur de départ de 15 µm, une énergie de protection cathodique d'au moins 4 J/cm2.
  38. Composant en acier trempé avec protection anticorrosion cathodique réalisé à partir d'un ruban d'acier laminé à chaud ou à froid avec une épaisseur ≥ 0,15 mm, dans lequel la trempe a été obtenue par chauffage à une température d'austénitisation nécessaire pour la trempe et jusqu'à une modification de structure nécessaire pour la trempe, et par un refroidissement exécuté après le chauffage suffisant, dans lequel la vitesse de refroidissement est choisie de telle façon que l'on obtient une trempe de l'alliage de la tôle, dans lequel un revêtement constitué essentiellement de zinc est présent sur la surface, le revêtement contenant un ou plusieurs éléments présentant une affinité à l'oxygène dans une quantité totale de 0,1 % en poids à 15 % en poids, le refroidissement étant obtenu lors de la mise en forme au moyen d'outils de mise en forme refroidis, en particulier composant en tôle trempée obtenu avec un procédé selon l'une des revendications 1 à 24 et présentant une couche de protection anticorrosion selon l'une des revendications 25 à 37.
  39. Composant en acier trempé selon la revendication 38, caractérisé en ce que le composant est réalisé avec des éléments d'alliage dans des plages de concentration présentant les limites suivantes, en pourcentage en poids : carbone jusqu'à 0,4 de préférence 0,15 à 0,3 silicium jusqu'à 1,9 de préférence 0,11 à 1,5 manganèse jusqu'à 3,0 de préférence 0,8 à 2,5 chrome jusqu'à 1,5 de préférence 0,1 à 0,9 molybdène jusqu'à 0,9 de préférence 0,1 à 0,5 nickel jusqu'à 0,9, titane jusqu'à 0,2 de préférence 0,02 à 0,1 vanadium jusqu'à 0,2 tungstène jusqu'à 0,2 aluminium jusqu'à 0,2 de préférence 0,02 à 0,07 bore jusqu'à 0,01 de préférence 0,0005 à 0,005 soufre maximum 0,41 de préférence maximum 0,008 phosphore maximum 0,0 25 de préférence maximum 0,01
    le reste étant du fer et des impuretés.
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AT12022003A AT412403B (de) 2003-07-29 2003-07-29 Korrosionsgeschütztes stahlblech
AT0120303A AT412878B (de) 2003-07-29 2003-07-29 Korrosionsgeschütztes stahlblechteil mit hoher festigkeit
PCT/EP2004/006251 WO2005021822A1 (fr) 2003-07-29 2004-06-09 Procede de production d'un element constitutif en acier trempe

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DE102022107131A1 (de) 2022-03-25 2023-09-28 Voestalpine Metal Forming Gmbh Verfahren und Vorrichtung zum Erzeugen gehärteter Stahlblechbauteile

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ES2350931T3 (es) 2011-01-28
US7938949B2 (en) 2011-05-10
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US20070000117A1 (en) 2007-01-04
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US20070271978A1 (en) 2007-11-29
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US8181331B2 (en) 2012-05-22
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US20110045316A1 (en) 2011-02-24
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US7832242B2 (en) 2010-11-16
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