EP3008226B1 - Procédé de traitement superficiel d'acier corten - Google Patents

Procédé de traitement superficiel d'acier corten Download PDF

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Publication number
EP3008226B1
EP3008226B1 EP14731592.3A EP14731592A EP3008226B1 EP 3008226 B1 EP3008226 B1 EP 3008226B1 EP 14731592 A EP14731592 A EP 14731592A EP 3008226 B1 EP3008226 B1 EP 3008226B1
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EP
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Prior art keywords
weight
corten
corten steel
proportion
sol
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EP14731592.3A
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German (de)
English (en)
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EP3008226A1 (fr
Inventor
Olaf Boehme
Siegfried Piesslinger-Schweiger
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Poligrat GmbH
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Poligrat GmbH
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • 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
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/086—Iron or steel solutions containing HF

Definitions

  • the present invention relates to a process for producing surface treated Corten steel comprising the steps of cleaning, activating, dyeing and sealing the surface.
  • the invention also relates to Corten steels produced by the method according to the invention.
  • Corten steels (eg, material No. 1.8946 ASTM A 242 and 1.8963 ASTM A 588 according to ASTM A 242) form on weathering on their surface a rust layer which is particularly dense at its base and prevents the continuation of corrosion, or at least slows down significantly , The surfaces then have a red-brown rust layer.
  • Corten steels are attractive for use in architecture e.g. as facade cladding. However, they have some disadvantages that hinder the low cost of large scale use so far.
  • the corrosion process on the surface does not come to a complete standstill, especially in an aggressive atmosphere, as is usually the case in cities and industrial areas.
  • the rust layer on Corten steels is then porous on its outer surface and mechanically unstable. It gives off rusty particles on contact or in running water, which can lead to rust marks on hands or clothing.
  • the subject of the present invention is a method as defined in the claims to control and selectively produce different color effects by means of a wet-chemical treatment of surfaces on Corten steels and to permanently protect the colored surfaces against further corrosion and alteration as well as contamination.
  • the invention also relates to a treated surface Corten steel containing a colorless, transparent, coating on a colored surface of the Corten steel, the surface treatment being carried out by a process according to the present invention.
  • the subject method involves treating the surface of Corten steel in 2 steps.
  • step (i) Corten steel is provided and a desired color is produced by wet-chemical treatment.
  • step (ii) consists of sealing the colored surface to permanently protect it from further corrosion and alteration and to impart water and dirt repellency to it.
  • Step (i) involves the provision of Corten steel as well as a treatment comprising the three stages of (1) cleaning, (2) activating and (3) dyeing.
  • Corten steel may comprise or consist of: iron as the main constituent (for example greater than 90% by weight or greater than 95% by weight), and one or more constituents selected from the group consisting of: carbon in one fraction from 0 to 0.16 wt .-%, chromium in an amount of 0.40 to 0.65 wt .-%, silicon in an amount of 0.30 to 0.50 wt .-%, manganese in a proportion of 0.80 to 1.25 wt%, phosphorus in an amount of 0 to 0.030 wt%, sulfur in an amount of 0 to 0.030 wt%, copper in a proportion of 0.10 to 0.40 Wt .-%, vanadium in an amount of 0.02 to 0.10 wt .-%, and nickel in an amount of 0 to 0.40 wt .-%.
  • the above percentages are based on the total mass of all components in Corten steel.
  • the Corten steel is made of iron in a proportion of at least 90% by weight, or at least 95% by weight, and the constituents: carbon in a proportion of 0 to 0.16% by weight, chromium in a content of 0 to 0.65 wt .-%, silicon in an amount of 0 to 0.50 wt .-%, manganese in an amount of 0 to 1.25 wt .-%, phosphorus in a proportion of 0 to 0.030 wt .-%, sulfur in an amount of 0 to 0.030 wt .-%, copper in a proportion of 0 to 0.40 wt .-%, vanadium in an amount of 0 to 0.10 wt .-%, and nickel in an amount of 0 to 0.40 wt .-%.
  • Corten steels are material Nos. 1.8946 and 1.8963 according to ASTM A 242 and A 588.
  • the Corten steel may be used as material / starting material, e.g. as steel sheet, or product, e.g. as part of a finished structure.
  • the Corten steel should not be treated or coated. However, the surface must be clean.
  • step (1) of step (i) is performed such that the cleaned surface of the Corten steel is metallically clean, free of grease and rust-free.
  • the cleaning in step (1) of step (i) may be carried out by first treating the surface of the Corten steel with an alkaline decoction (for example with AK 161 from Schlötter), followed by an intermediate rinsing with water, followed by a treatment with a Sparbeize (eg BESTA-S from POLIGRAT, Germany, containing sulfuric acid sulfamic acid, oxalic acid, inhibitors or a Sparbeize containing, for example, sulfuric acid, ortho-phosphoric acid, dimethyl sulfoxide and hexamethyltetramine), also followed by a rinsing treatment in city water / drinking water / tap water subjected becomes.
  • an alkaline decoction for example with AK 161 from Schlötter
  • a Sparbeize eg BESTA-S from POLIGRAT, Germany, containing sulfuric acid sulfamic acid, oxalic acid, inhibitors or a Sparbeize containing, for example, sulfuric acid,
  • step (2) in step (i) is to activate the cleaned surface (s) for subsequent dyeing.
  • the activation takes place by treatment of the cleaned surface with an aqueous activation solution (solution A) by dipping and / or spraying.
  • the treatment time at room temperature (20 ° C) may last, for example, 2 to 30 minutes, or 2 to 15 minutes, preferably 2 to 5 minutes.
  • the aqueous activating solution may be prepared using potable water / tap water by adding HF and oxidizing agent and one or more optional oxidizing agent stabilizers.
  • the aqueous activating solution based on the pKa value, contains no stronger acids than HF.
  • the aqueous activation solution contains HF as the only acid.
  • the aqueous activating solution consists of HF, oxidizing agent (s), optionally one or more stabilizers for the oxidizing agent (s), and drinking / service / tap water.
  • the aqueous activating solution may include fluoride ions, for example by using hydrogen fluoride, in an amount, based on the weight of the aqueous activating solution, of greater than 0 wt% and less than or equal to 3 wt%, or greater than 0.5 wt. % and less than or equal to 3% by weight, preferably greater than 0.5% by weight and less than or equal to 1% by weight.
  • a solution with such an amount of fluoride is not classified as toxic.
  • the active fluoride content is determined on the basis of the material removal of a sample sheet. Active fluoride content and material removal are linearly linked.
  • fluoride ions is derived from hydrogen fluoride added to the aqueous activating solution.
  • the fluoride ions may also be from other sources, for example, ammonium bifluoride, sodium bifluoride, and / or potassium bifluoride.
  • a suitable and preferred oxidizing agent is hydrogen peroxide.
  • Hydrogen peroxide can be used as an aqueous solution.
  • the amount of oxidizing agent can be selected by the person skilled in the art, depending on the oxidizing agent used, for example by carrying out simple test experiments.
  • the aqueous activation solution may, for example, the oxidizing agent (s), preferably hydrogen peroxide, in an amount of greater than 0 wt .-% and less than or equal to 30 wt .-%, or greater than 0 wt .-% and less than or equal to 20 wt. -%, preferably greater than 3 wt .-% and less than or equal to 20 wt .-%, or greater than 3 wt .-% and less than or equal to 10 wt .-%, contain.
  • the oxidizing agent (s) preferably hydrogen peroxide
  • the aqueous activating solution may in particular fluoride ions, for example of hydrogen fluoride, in an amount, based on the weight of the aqueous activating solution, of greater than 0.5 wt .-% and less than or equal to 3 wt .-%, preferably greater than 0.5 wt % and less than or equal to 1% by weight, and the oxidizing agent (s), preferably hydrogen peroxide, in an amount, based on the weight of the aqueous activating solution, of greater than 3% by weight and less than or equal to 20% by weight. %, contain.
  • fluoride ions for example of hydrogen fluoride
  • Suitable optional stabilizers for the oxidizing agent are, for example, mixtures of urea and one or more alkanediphosphonic acids, which are optionally substituted by one or more hydroxyl or amino groups, or salts thereof.
  • the hydrocarbon chain of the alkane diphosphonic acids preferably comprises 1, 2, 3 or 4 C atoms.
  • alkanediphosphonic acids are alkylenediphosphonic acids or amino- or hydroxy-substituted alkylidenediphosphonic acids.
  • a particularly suitable alkylidenediphosphonic acid is 1-hydroxyethane-1,1-diphosphonic acid.
  • Suitable stabilizers are also in EP 1 903 081 described.
  • the amount of stabilizer in the aqueous activating solution may be as in EP 1 903 081 be selected described.
  • a particularly high efficacy of this stabilizer has been observed when the weight ratio of urea to free alkane diphosphonic acids is in the range of 100: 1 to 20: 1. This weight ratio is preferably between 60: 1 and 35: 1, in particular about 50: 1.
  • the stabilizer serves to stabilize aqueous peroxide-containing solutions.
  • aqueous peroxide-containing solutions These are understood to mean primarily aqueous solutions containing hydrogen peroxide, but it is also possible to stabilize other peroxide-containing solutions in this manner, for example solutions which contain persulphuric acids and / or peroxycarboxylic acids, such as peracetic acid, or salts thereof. Chlorides / phosphates should not be present.
  • the concentration of a stabilized aqueous solution of hydrogen peroxide may be about 30 or 35%, but it may also be less, about 20%, 10% or 5%.
  • solution A may contain fluorides in an amount of at most 1% by weight, such as hydrofluoric acid 0.8%, and a strong oxidizing component such as hydrogen peroxide in an amount of about 5% by weight with a suitable stabilizer (eg according to EP1903081 (A2) from POLIGRAT).
  • fluorides in an amount of at most 1% by weight, such as hydrofluoric acid 0.8%
  • a strong oxidizing component such as hydrogen peroxide in an amount of about 5% by weight with a suitable stabilizer (eg according to EP1903081 (A2) from POLIGRAT).
  • the activation takes place by treatment of the cleaned surface in an aqueous solution (solution A) by dipping or spraying.
  • Solution A contains, for example, fluorides in an amount of at most 1% by weight HF and a strongly oxidizing component such as hydrogen peroxide in an amount of about 5% by weight with a suitable stabilizer (for example according to US Pat EP1903081 (A2) or product C600, C410 or C400 from POLIGRAT).
  • a suitable stabilizer for example according to US Pat EP1903081 (A2) or product C600, C410 or C400 from POLIGRAT.
  • city / drinking / utility / tap water refers to natural water with the minerals and trace elements commonly present.
  • the aqueous activating solution contains HF in an amount of 0.5% to 1% by weight, hydrogen peroxide in an amount of 2% to 10% by weight, and optionally one or more stabilizers.
  • an optional rinse step with water may be performed to partially or completely remove the aqueous activating solution. If the aqueous activation solution is not removed or only partially removed, this has an effect on the subsequent staining step. Depending on the desired color of the surface, the remaining amount of the aqueous activating solution can be adjusted. The less rinsed, the darker the color becomes.
  • step (i) the actual dyeing of the surfaces takes place.
  • step (3) of step (i) treating the activated surface in step (3) of step (i) with water, for example having a pH in the range of 6-8, over a period of, for example, 30 minutes to 15 hours, preferably 1 hour to 12 Hours to be performed.
  • water for example having a pH in the range of 6-8
  • the treatment with water can basically be done by spraying with water and by moisturizing.
  • the surface should not dry during treatment.
  • step (3) is thus carried out so that the surface does not dry completely during the treatment period.
  • a wet surface could be made by a simple handkerchief test, with the handkerchief appearing wet / wet after contact with the surface.
  • the surface to be treated can be covered for example in such a way, for example with plastic films, that the drying of the surface is at least slowed down.
  • the moisturization is carried out by lightly spraying or misting with water, similar to a spray irrigation in a greenhouse.
  • the amount of water can be chosen by the expert in this case so that the surface to be treated is kept completely and evenly moist, in particular to obtain a uniform color. ever more uniform and thinner the water film the more uniform the color achieved. Run-off water produces structured dyeings.
  • Variant 1 for the production of golden yellow, orange or light brown surfaces is
  • the surfaces are rinsed with water, for example, city water, and then, for example, lying, sloping or vertically standing by light spraying and moisturizing with water, such as city water, treated.
  • water for example, city water
  • different colors then appear on the surface of the Corten steel, for example after approx 1 hour: gold 3 hours: orange 12 hours: tan
  • the method may therefore be carried out, for example, such that the optional rinsing step with water is performed in step (2) of step (i) and the coloring of the activated surface in step (3) of step (i) by spraying and moisturizing the activated surface is carried out.
  • very little water is preferably used, for example 0.2-1 l / m 2 and h.
  • the method may therefore be carried out, for example, such that the optional rinsing step with water in step (2) of step (i) is not carried out and the dyeing of the activated surface in step (3) of step (i) using a little water, in particular only by moisturizing and not by rinsing, for example by spraying with water once and then moisturizing by covering the surface, or by continuous or interval-like light spraying with water, as described above, to minimize washing off of the activating solution.
  • Structured color effects such as streaks, are obtained by processing the surfaces in the first few minutes, for example 10 minutes after treatment in solution A, in a vertical or oblique position.
  • the original traces of the runoff of the water produce differently fine or coarse structures.
  • step (ii) After reaching the desired color, the surfaces are carefully dried and further treated in step (ii).
  • step (ii) the colored surfaces are sealed by means of a suitable colorless transparent coating, preferably a sol-gel coating / sol-gel lacquer (e.g., POLIANT or POLISEAL from POLIGRAT).
  • a suitable colorless transparent coating preferably a sol-gel coating / sol-gel lacquer (e.g., POLIANT or POLISEAL from POLIGRAT).
  • the sealing in step (ii) can thus be carried out, for example, using a sol-gel coating, wherein the sol-gel coating is baked on after application in order to achieve a glass-ceramic structure. It is, however possible to use other inorganic, transparent, dense and chemically resistant coatings capable of fully impregnating the paint layer.
  • sol-gel lacquer is first applied in the form of a liquid sol having colloidal particles suspended therein, which subsequently converts to a gel and eventually forms a solid, hard lacquer layer. So if the "application of the sol-gel varnish” or the “hardening of the sol-gel varnish” is mentioned, the expert knows in which state the sol-gel system is located.
  • the sol is a silica sol based on silanes which are dissolved in solvents, such as alcohol.
  • solvents such as alcohol.
  • these silica sols could also have one or more other sol-forming elements such as Al, Ti, Zr, Mg, Ca or Zn replacing Si atoms in the colloidal structures.
  • the hydrolyzable radicals OR ' are hydroxy, alkoxy and / or cycloalkoxy radicals. Suitable examples thereof include, for example, hydroxy, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, i-butoxy, t-butoxy, pentoxy, hexoxy, cyclopentyloxy, cyclohexyloxy, in particular Ethoxy, n-propoxy and isopropoxy are preferred.
  • the hydrolyzable radicals OR ' may be identical or different from one another.
  • the non-hydrolyzable radicals R " are alkyl and / or cycloalkyl radicals, suitable examples of which include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, cyclopentyl, cyclohexyl radicals, with particular preference being given to methyl, ethyl, n-propyl and isopropyl radicals
  • the nonhydrolyzable radicals R " may likewise be identical or different from one another.
  • a preferred sol-gel lacquer may be the starting materials TEOS (tetraethoxyorthosilane) and MTES (methyltriethoxysilane) and / or DMDES (dimethyldiethoxysilane).
  • the starting compounds are partially hydrolyzed to the corresponding hydroxy compounds (such as orthosilicic acid, trihydroxyalkylsilane, etc.), which can be promoted by the addition of a catalyst such as acid. Due to the high tendency for condensation of these hydroxy compounds, these can now condense with elimination of water to form smaller siloxane networks.
  • the sol already contains colloidal particles containing siloxane bonds. Siloxane bonds are bonds of the form ⁇ Si-O-Si ⁇ , where " ⁇ " symbolizes any three independent bonds with other elements, in particular OH, OR 'and R ", thereby forming a three-dimensional crosslinked structure arises in the colloidal particles.
  • OR 'and R have the same meaning as above.
  • the application of the sol-gel lacquer can be done in any way, such as by immersion, flooding, spraying or brushing. Preferably, however, it is done by spraying, since this allows precise control of the amount applied per unit area.
  • a sol-gel lacquer layer may have a layer thickness of up to about 6 ⁇ m, or from about 0.5 to 3 ⁇ m.
  • the viscosity of the sol-gel varnish can be adjusted by a person skilled in the art. It is known that the sol, with a correspondingly high dilution in its solvent, is sufficiently low-viscosity to penetrate into any pores of a surface which may be present.
  • Suitable solvents for the sol are water and especially alcohols such as methanol, ethanol, n-propanol or isopropanol, with ethanol and isopropanol being preferred because of their physical properties and the low toxicity of their vapors.
  • the applied sol is allowed to react to a gel.
  • This reaction converts the liquid sol into a solid gel layer, in which the colloidal particles of the sol crosslink with each other and with not yet hydrolyzed and condensed starting compounds by further hydrolysis and condensation. This can be done, for example, by evaporation of the alcoholic solvent during drying.
  • the sol-gel coatings are baked, forming a glass-ceramic structure that adheres firmly, resistant to aging and insensitive to environmental influences and permanently preserves the color effects.
  • the baking of the coating can be carried out by a person skilled in the art according to the usual procedure.
  • the gel-coated surfaces are subjected to thermal curing. This occurs at elevated temperatures, with the gel transforming into a colorless, transparent, glassy layer.
  • the silica sol constituents convert into an even more highly crosslinked silica which, depending on the composition of the underlying sol, may contain other constituents such as aluminum oxide, titanium oxide or zirconium oxide. These layers are hard, closed and resistant to many of the chemicals that a surface may come into contact under ordinary circumstances, and to temperatures up to about 500 ° C.
  • the coated surface is exposed in the subsequent curing of the gel temperatures of 160 ° C to 220 ° C.
  • This curing should be for a period of at least 10 minutes, preferably 20 to 45 minutes, for example 30 minutes.
  • the curing is preferably carried out at temperatures between 180 ° C and 210 ° C, for example at 200 ° C, but also temperatures below 180 ° C are suitable for this purpose.
  • the gel transforms into a hard, colorless and transparent, vitreous lacquer that tightly seals the surface, has no cracks and gives the surface high hardness and wear resistance.
  • the processes of gel formation and the curing of the gel can merge into one another, since, for example, gelation by drying and evaporation of the solvent can at least partly also take place at the beginning of the treatment for hardening. Also, such a method in which the processes of gelation and curing of the gel merge into one another, is encompassed by the invention.
  • cathodic curing can, for example, according to the patent application DE 21 26 129 respectively.
  • the invention also relates to a Corten steel with treated surface.
  • the present invention relates to a Corten steel having a colorless, transparent coating on a colored surface except for rusty brown of the Corten steel, the surface being treated by a method as described above, and the sealing in step (ii ) of this process, using a sol-gel coating, wherein the sol-gel coating is baked after application to obtain a glass-ceramic coating.
  • the Corten steel according to the invention differs structurally from known Corten steels, which is recognizable by the color and the properties, such as stability against corrosion.
  • a sheet of material no. 1.8963 in the dimensions 500x500x1.5 mm was degreased in an aqueous Abkochentfettung (AK 161 from Fa. Schlötter) at 60 ° C for a period of 10 minutes.
  • the surfaces were then rinsed twice with city water and then activated at room temperature (20 ° C) by immersion in an aqueous solution containing 0.8% HF-Gew and 5% -Gew hydrogen peroxide and with a stabilizer for the peroxide (product C600 from POLIGRAT ) for 4 minutes.
  • the surfaces were then rinsed once with city water and then laid down. In lying position, the surfaces were lightly sprayed kept moist with city water for 3 hours at room temperature. This resulted in an orange-colored surface.
  • the surface was dried and then spray-coated with the sol-gel POLIANT method by POLIGRAT and baked at 200 ° C. for 30 minutes.
  • the surface obtained was orange with an attractive stripe structure of lighter and darker shades with a metallic effect that reflected the light iridescent.
  • the surface was hydrophobic so that water blew off without leaving any wet traces.
  • Example 1 A sheet according to Example 1 was pretreated and activated as in Example 1. Subsequently, the sheet was lying without rinsing process and kept moist at room temperature by spraying with city water. After a period of 3 hours and a final rinse, the sheet had an olive green surface. The further treatment was carried out as in Example 1, wherein the metallic effect on the surface was slightly weaker compared to Example 1.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Claims (9)

  1. Procédé de traitement superficiel d'acier Corten, comprenant les étapes suivantes :
    (i) mise à disposition d'acier Corten et réalisation d'un traitement comprenant les opérations de :
    (1) nettoyage d'au moins une partie d'au moins une surface de l'acier Corten ;
    (2) activation d'au moins une partie de la surface nettoyée de l'acier Corten à l'opération (1) par mise en contact de la surface nettoyée avec une solution d'activation aqueuse, contenant des ions fluorure, un ou plusieurs agents d'oxydation et facultativement un ou plusieurs stabilisateurs pour le ou les agent(s) d'oxydation ; et
    (3) coloration d'au moins une partie de la surface activée de l'acier Corten à l'opération (2) par traitement de la surface activée avec de l'eau pendant une durée d'au moins 30 minutes et jusqu'à ce que la coloration souhaitée de la surface de l'acier Corten soit atteinte ; et
    (ii) scellement d'au moins une partie de la surface colorée au cours de l'opération (3) à l'étape (i) par application d'un revêtement incolore transparent, après quoi l'acier Corten traité en surface est obtenu.
  2. Procédé selon la revendication 1, dans lequel l'acier Corten comprend : du fer comme constituant principal, ainsi qu'un ou plusieurs constituants choisis dans le groupe constitué de : carbone dans une proportion de 0 à 0,16 % en poids, chrome dans une proportion de 0,40 à 0,65 % en poids, silicium dans une proportion de 0,30 à 0,50 % en poids, manganèse dans une proportion de 0,80 à 1,25 % en poids, phosphore dans une proportion de 0 à 0,030 % en poids, soufre dans une proportion de 0 à 0,030 % en poids, cuivre dans une proportion de 0,10 à 0,40 % en poids, vanadium dans une proportion de 0,02 à 0,10 % en poids et nickel dans une proportion de 0 à 0,40 % en poids.
  3. Procédé selon la revendication 1 ou 2, dans lequel l'opération de nettoyage (1) effectuée à l'étape (i) est réalisée de sorte que la surface nettoyée de l'acier Corten soit métalliquement propre, exempte de graisse et de rouille.
  4. Procédé selon l'une des revendications précédentes, dans lequel la solution d'activation aqueuse contient des ions fluorure dans une proportion supérieure à 0 % en poids et inférieure ou égale à 3 % en poids, et/ou la solution d'activation aqueuse contient le ou les agent(s) d'oxydation dans une proportion supérieure à 0 % en poids et inférieure ou égale à 20 % en poids.
  5. Procédé selon l'une des revendications précédentes, dans lequel le traitement de la surface activée au cours de l'opération (3) à l'étape (i) avec de l'eau est réalisé pendant une durée comprise entre 30 minutes et 15 heures jusqu'à ce que la couleur souhaitée de la surface soit obtenue.
  6. Procédé selon l'une des revendications précédentes, dans lequel une étape facultative de rinçage avec de l'eau est réalisée au cours de l'opération (2) à l'étape (i), et la coloration de la surface activée au cours de l'opération (3) à l'étape (i) est réalisée par aspersion et maintien humide de la surface activée.
  7. Procédé selon l'une des revendications précédentes, dans lequel l'étape de scellement (ii) est effectuée en utilisant un revêtement sol-gel, le revêtement sol-gel étant cuit après l'application pour obtenir une structure vitrocéramique.
  8. Procédé selon l'une des revendications précédentes, dans lequel au moins une partie de la quantité d'ions fluorure provient de fluorure d'hydrogène qui a été ajouté à la solution d'activation aqueuse.
  9. Acier Corten pourvu d'un revêtement incolore transparent sur une surface colorée - excepté en brun rouille - de l'acier Corten, la surface ayant été traitée moyennant un procédé selon l'une des revendications 1 à 6 ou 8, et l'étape de scellement (ii) effectuée au cours dudit procédé étant réalisée en utilisant un revêtement sol-gel, le revêtement sol-gel étant cuit après l'application pour obtenir un revêtement vitrocéramique.
EP14731592.3A 2013-06-14 2014-06-13 Procédé de traitement superficiel d'acier corten Not-in-force EP3008226B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013010080.1A DE102013010080A1 (de) 2013-06-14 2013-06-14 Verfahren zur Oberflächenbehandlung von Corten-Stahl
PCT/EP2014/062416 WO2014198917A1 (fr) 2013-06-14 2014-06-13 Procédé de traitement superficiel d'acier corten

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EP3008226A1 EP3008226A1 (fr) 2016-04-20
EP3008226B1 true EP3008226B1 (fr) 2017-08-02

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IT201700085414U1 (it) * 2017-07-26 2019-01-26 Nuova De Fi M S P A Sistema e filo di supporto
DE102018103052A1 (de) 2018-02-12 2019-08-14 Martin Piehler Verfahren zur Herstellung eines oberflächenbearbeiteten Metallobjekts
CN111534746B (zh) * 2020-04-30 2022-02-18 鞍钢股份有限公司 宽幅450MPa级热轧集装箱用耐候钢及其制造方法
CN111518998B (zh) * 2020-06-11 2022-02-15 攀钢集团西昌钢钒有限公司 一种高强耐酸彩涂板及其制备方法
CN114635141B (zh) * 2022-02-28 2023-10-27 武汉材保表面新材料有限公司 一种钢铁表面无磷转化膜的化学退膜液、制备方法及用途

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SI1903081T1 (sl) * 2006-09-19 2015-06-30 Poligrat Gmbh Stabilizator za kislinsko, kovinsko poliranje kadi
EP2145980A1 (fr) * 2008-07-07 2010-01-20 Poligrat Gmbh Surface d'acier noble coloré et procédé de coloration d'acier noble
DE102009038795A1 (de) * 2009-08-25 2011-05-05 Poligrat Gmbh Beizverfahren für Edelstahl
CN102925884B (zh) * 2012-11-29 2015-02-11 北京科技大学 加速耐候钢表面锈层稳定化的喷液预处理方法

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DE102013010080A1 (de) 2014-12-18
US20160177454A1 (en) 2016-06-23
EP3008226A1 (fr) 2016-04-20

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