EP3008226B1 - Method for the surface treatment of corten steel - Google Patents
Method for the surface treatment of corten steel Download PDFInfo
- 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
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- corten
- corten steel
- proportion
- sol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Not-in-force
Links
- 229910000870 Weathering steel Inorganic materials 0.000 title claims description 66
- 238000000034 method Methods 0.000 title claims description 30
- 238000004381 surface treatment Methods 0.000 title claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 230000003213 activating effect Effects 0.000 claims description 29
- 238000000576 coating method Methods 0.000 claims description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 17
- 239000007800 oxidant agent Substances 0.000 claims description 17
- -1 fluoride ions Chemical class 0.000 claims description 14
- 239000003381 stabilizer Substances 0.000 claims description 14
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 12
- 238000005507 spraying Methods 0.000 claims description 12
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 11
- 238000007789 sealing Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002241 glass-ceramic Substances 0.000 claims description 5
- 238000004040 coloring Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
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- 239000000126 substance Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 240000007817 Olea europaea Species 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
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- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
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- 239000007787 solid Substances 0.000 description 2
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- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- OBRBQQWIWWPOPM-UHFFFAOYSA-N NS(O)(=O)=O.OS(O)(=O)=O Chemical compound NS(O)(=O)=O.OS(O)(=O)=O OBRBQQWIWWPOPM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
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- 125000000217 alkyl group Chemical group 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
-
- 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
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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
- 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
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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
- 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.
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von oberflächenbehandeltem Corten-Stahl, umfassend die Schritte des Reinigens, Aktivierens, Färbens und Versiegelns der Oberfläche. Die Erfindung betrifft zudem Corten-Stähle, hergestellt durch das erfindungsgemäße Verfahren.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-Stähle (z.B. Werkstoff Nr. 1.8946 ASTM A 242 und 1.8963 ASTM A 588 gemäß ASTM A 242) bilden bei Bewitterung auf ihrer Oberfläche eine Rostschicht aus, die an ihrer Basis besonders dicht ist und den Weitergang der Korrosion verhindert, oder zumindest deutlich verlangsamt. Die Oberflächen weisen dann eine rotbraune Rostschicht auf.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.
Wegen der relativ guten Korrosionsbeständigkeit gepaart mit günstigen Beschaffungskosten sind Corten-Stähle attraktiv für eine Verwendung in der Architektur z.B. als Fassadenverkleidungen. Sie weisen aber einige Nachteile auf, die den günstigen Kosten einer Verwendung in großem Umfang bisher entgegenstehen.Because of the relatively good corrosion resistance coupled with low cost of procurement, 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.
Der Korrosionsprozess an der Oberfläche kommt speziell in aggressiver Atmosphäre, wie sie in Städten und Industriegebieten meist vorliegt, nicht vollständig zum Stillstand. Die Rostschicht auf Corten-Stählen ist dann an ihrer äußeren Oberfläche porös und mechanisch nicht stabil. Sie gibt bei Berührung oder in ablaufendes Wasser Rostpartikel ab, die zu Rostflecken an Händen oder Kleidung führen können.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.
Aus der Literatur sind zahlreiche Versuche bekannt, die Rostschicht auf Corten-Stählen durch Aufbringen von Lackschichten oder durch Imprägnieren mit Wachsen zu stabilisieren. Alle diese Versuche schlugen fehl, weil Lackschichten auf dem instabilen Untergrund nicht haften, sondern abblättern und Wachse selbst nicht dauerhaft wetterbeständig sind.From the literature numerous attempts are known to stabilize the rust layer on Corten steels by applying paint layers or by impregnation with waxes. All of these attempts failed because paint layers do not adhere to the unstable surface, but peel off and waxes themselves are not permanently weatherproof.
Ein weiterer Nachteil liegt darin, dass eine farbliche Gestaltung außer Rostbraun nicht möglich ist. Die optische Wertigkeit solcher Oberflächen ist nicht sehr hoch und die Möglichkeit architektonische Akzente über Farbgebung zu erzielen ist deutlich eingeschränkt.Another disadvantage is that a color design is not possible except rust brown. The visual value of such surfaces is not very high and the opportunity to achieve architectural accents on color is clearly limited.
Ein wesentlicher Nachteil bei der Verwendung von Corten-Stahl in der Architektur besteht darin, dass sich die Patina erst langsam nachträglich bildet und es Jahre dauern kann, bis der endgültige Zustand erreicht ist und das Gebäude das gewünschte Aussehen zeigt.A major drawback to the use of Corten steel in architecture is that the patina forms slowly and subsequently, and it can take years to reach the final state and the building looks the way it should.
Es gibt eine Reihe von Rezepturen zur Vorbehandlung neuen Corten-Stahls, um auf schnellem Weg eine Rostschicht mit einem Aussehen zu erzeugen, das dem Endzustand ähnlich ist. Diese Rezepturen basieren meist auf wässrigen Lösungen mit sehr korrosiven Säuregemischen, die im wesentlichen Salzsäure enthalten und daneben eine Reihe anderer Säuren wie Schwefelsäure oder Salpetersäure. Der wesentliche Nachteil diese Vorbehandlungen besteht darin, dass die erzielten Rostschichten nicht denen aus der natürlichen Alterung entsprechen und Reste der korrosiven Medien aus der Vorbehandlung enthalten können, die wegen der Porosität der Schichten nicht rückstandsfrei ausgespült werden konnten. Die Folge ist, dass diese Substanzen, wie zum Beispiel Chloride, Korrosion fördern und das Verlangsamen der späteren Korrosion mit der Bildung einer schützenden Patina behindern können.There are a number of formulations for pretreating new Corten steel to quickly create a rust layer with an appearance similar to the final state. These formulations are mostly based on aqueous solutions with very corrosive acid mixtures, which contain essentially hydrochloric acid and next to a number of other acids such as sulfuric acid or nitric acid. The main disadvantage of these pretreatments is that the rust layers achieved do not correspond to those from natural aging and may contain residues of the corrosive media from the pretreatment, which could not be flushed out without leaving any residue owing to the porosity of the layers. The result is that these substances, such as chlorides, promote corrosion and can hinder the slowing down of subsequent corrosion with the formation of a protective patina.
Es besteht erhebliches Interesse in der Architektur kostengünstige Corten-Stähle einsetzen zu können, deren Oberflächen außer in tristem Rostbraun auch in anderen Farben gestaltet werden können, die stabil gegen Witterung und Abrieb sind und die keine Rostflecke verursachen. Diesen Anforderungen entspricht die vorliegende Erfindung. Es ist daher eine Aufgabe der vorliegenden Erfindung neue Corten-Stähle sowie Verfahren zu deren Herstellung bereitzustellen, wobei diese Corten-Stähle oben genannte Vorteile aufweisen und/oder oben genannte Nachteile überwinden.There is considerable interest in the architecture to use cost-effective Corten steels whose surfaces except in dull rust brown can be designed in other colors that are stable to weathering and abrasion and that do not cause rust marks. These requirements correspond to the present invention. It is therefore an object of the present invention to provide new Corten steels and processes for their production, which Corten steels have the above-mentioned advantages and / or overcome the above-mentioned disadvantages.
Der Gegenstand der vorliegenden Erfindung ist ein Verfahren, wie in den Ansprüchen definiert, um mittels einer nasschemische Behandlung von Oberflächen auf Corten-Stählen kontrolliert und gezielt unterschiedliche Farbeffekte zu erzeugen und die gefärbten Oberflächen dauerhaft vor weiterer Korrosion und Veränderung sowie Verschmutzung zu schützen.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.
Die vorliegende Erfindung betrifft somit ein Verfahren zur Herstellung von oberflächenbehandeltem Corten-Stahl, umfassend die Schritte:
- Schritt (i): Bereitstellen von Corten-Stahl und Durchführen einer Behandlung, umfassend oder bestehend aus den Stufen:
- Stufe (1): Reinigen von zumindest einem Teil von mindestens einer Oberfläche des Corten-Stahls;
- Stufe (2): Aktivieren von zumindest einem Teil der gereinigten Oberfläche des Corten-Stahls aus Stufe (1) durch in Kontakt bringen der gereinigten Oberfläche mit einer wässrigen Aktivierungslösung, enthaltend Fluoridionen, ein oder mehrere Oxidationsmittel und optional ein oder mehrere Stabilisatoren für das/die Oxidationsmittel, gefolgt von einem optionalen Spülschritt mit Wasser, um zumindest einen Teil der wässrigen Aktivierungslösung von der aktivierten Oberfläche zu entfernen; und
- Stufe (3): Färben von zumindest einem Teil der aktivierten Oberfläche des Corten-Stahls aus Stufe (2) durch Behandeln der aktivierten Oberfläche mit Wasser für eine Zeitdauer von mindestens 30 Minuten und solange, bis die gewünschte Färbung der Oberfläche des Corten-Stahls erreicht ist; Durchführen eines optionalen Spülschritts mit Wasser, falls noch wässrige Aktivierungslösung auf der gefärbten Oberfläche vorhanden ist; und Durchführen eines Trocknungsschrittes; und
- Schritt (ii): Versiegeln von zumindest einem Teil der gefärbten Oberfläche aus Stufe (3) von Schritt (i) durch Aufbringen einer farblosen, transparenten Beschichtung, woraufhin der oberflächenbehandelte Corten-Stahl erhalten wird.
- Step (i): providing Corten steel and performing a treatment comprising or consisting of the steps:
- Stage (1): cleaning at least part of at least one surface of the Corten steel;
- Step (2): activating at least a portion of the cleaned surface of the Corten steel of step (1) by contacting the cleaned surface with an aqueous activating solution containing fluoride ions, one or more oxidizing agents, and optionally one or more stabilizers for the / the oxidizing agents followed by an optional rinsing step with water to remove at least a portion of the aqueous activating solution from the activated surface; and
- Step (3): Dyeing at least part of the activated surface of the Corten steel of step (2) by treating the activated surface with water for a period of at least 30 minutes and until the desired coloration reaches the surface of the Corten steel is; Carrying out an optional rinsing step with water if there is still aqueous activating solution present on the colored surface; and performing a drying step; and
- Step (ii): sealing at least part of the colored surface of step (3) of step (i) by applying a colorless, transparent coating, whereupon the surface treated Corten steel is obtained.
Die Erfindung betrifft auch einen Corten-Stahl mit behandelter Oberfläche, enthaltend eine farblose, transparente, Beschichtung auf einer gefärbten Oberfläche des Corten-Stahls, wobei die Oberflächenbehandlung nach einem Verfahren gemäß der vorliegenden Erfindung durchgeführt wird.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.
Das gegenständliche Verfahren beinhaltet eine Behandlung der Oberfläche von Corten-Stahl in 2 Schritten. In Schritt (i) wird Corten-Stahl bereitgestellt und durch nasschemische Behandlung eine gewünschte Farbe erzeugt. Schritt (ii) besteht aus der Versiegelung der gefärbten Oberfläche, um sie dauerhaft vor weiterer Korrosion und Veränderung zu schützen und ihr wasser- und schmutzabweisende Eigenschaften zu verleihen.The subject method involves treating the surface of Corten steel in 2 steps. In 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.
Die vorliegende Erfindung betrifft somit ein Verfahren zur Herstellung von oberflächenbehandeltem Corten-Stahl, umfassend oder bestehend aus den Schritten:
- (i) Bereitstellen von Corten-Stahl und Durchführen einer Behandlung, umfassend oder bestehend aus den Stufen:
- (1) Reinigen von zumindest einem Teil von mindestens einer Oberfläche des Corten-Stahls;
- (2) Aktivieren von zumindest einem Teil der gereinigten Oberfläche des Corten-Stahls aus Stufe (1) durch in Kontakt bringen der gereinigten Oberfläche mit einer wässrigen Aktivierungslösung, enthaltend Fluoridionen, beispielsweise stammen die Fluoridionen aus Flußsäure, Ammoniumbiflourid, Natriumbifluorid, Kaliumbifluorid, insbesondere aus Fluorwasserstoff (HF), ein oder mehrere Oxidationsmittel und optional ein oder mehrere Stabilisatoren für das/die Oxidationsmittel, gefolgt von einem optionalen Spülschritt mit Wasser, um zumindest einen Teil der wässrigen Aktivierungslösung von der aktivierten Oberfläche zu entfernen; wenn keine Glättung der Oberfläche erfolgen muss, kann auch HCl, H2SO4 oder FeCl3 eingesetzt werden, und
- (3) Färben von zumindest einem Teil der aktivierten Oberfläche des Corten-Stahls aus Stufe (2) durch Behandeln der aktivierten Oberfläche mit Wasser für eine Zeitdauer von mindestens 30 Minuten und solange, bis die gewünschte Färbung der Oberfläche des Corten-Stahls erreicht ist; Durchführen eines optionalen Spülschritts mit Wasser, falls noch wässrige Aktivierungslösung auf der gefärbten Oberfläche vorhanden ist; und Durchführen eines Trocknungsschrittes; und
- (ii) Versiegeln von zumindest einem Teil der gefärbten Oberfläche aus Stufe (3) von Schritt (i) durch Aufbringen einer farblosen, transparenten Beschichtung, woraufhin der oberflächenbehandelte Corten-Stahl erhalten wird.
- (i) providing Corten steel and performing a treatment comprising or consisting of the stages:
- (1) cleaning at least part of at least one surface of the Corten steel;
- (2) activating at least a portion of the cleaned surface of the Corten steel of step (1) by contacting the cleaned surface with an aqueous activating solution containing fluoride ions, for example, the fluoride ions are derived from hydrofluoric acid, ammonium biflouride, sodium bifluoride, potassium bifluoride, in particular Hydrogen fluoride (HF), one or more oxidants, and optionally one or more oxidizer stabilizers, followed by an optional water rinse step to remove at least a portion of the aqueous activating solution from the activated surface; if no smoothing of the surface must take place, HCl, H 2 SO 4 or FeCl 3 can also be used, and
- (3) dyeing at least a portion of the activated surface of the Corten steel of step (2) by treating the activated surface with water for a period of time for at least 30 minutes and until the desired coloration of the surface of the Corten steel is achieved; Carrying out an optional rinsing step with water if there is still aqueous activating solution present on the colored surface; and performing a drying step; and
- (ii) sealing at least part of the colored surface of step (3) of step (i) by applying a colorless, transparent coating, whereupon the surface treated Corten steel is obtained.
Schritt (i) umfasst die Bereitstellung von Corten-Stahl, sowie eine Behandlung umfassend die drei Stufen (1) Reinigen, (2) Aktivieren und (3) Färben.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.
Zunächst wird Corten-Stahl bereitgestellt. Beispielsweise kann ein Corten-Stahl gemäß Richtanalyse umfassen oder bestehen aus: Eisen als Hauptbestandteil (beispielsweise größer 90 Gew.-% oder größer 95 Gew.-%), sowie ein oder mehrere Bestandteile, ausgewählt aus der Gruppe bestehend aus: Kohlenstoff in einem Anteil von 0 bis 0,16 Gew.-%, Chrom in einem Anteil von 0,40 bis 0,65 Gew.-%, Silizium in einem Anteil von 0,30 bis 0,50 Gew.-%, Mangan in einem Anteil von 0,80 bis 1,25 Gew.-%, Phosphor in einem Anteil von 0 bis 0,030 Gew.-%, Schwefel in einem Anteil von 0 bis 0,030 Gew.-%, Kupfer in einem Anteil von 0,10 bis 0,40 Gew.-%, Vanadium in einem Anteil von 0,02 bis 0,10 Gew.-%, und Nickel in einem Anteil von 0 bis 0,40 Gew.-%. Die vorstehenden Prozentangaben beziehen sich auf die Gesamtmasse aller Bestandteile im Corten-Stahl.First, Corten steel is provided. For example, a 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.
In einer Ausführungsform besteht der Corten-Stahl aus Eisen in einem Anteil von mindestens 90 Gew.-%, oder mindestens 95 Gew.-%, sowie den Bestandteilen: Kohlenstoff in einem Anteil von 0 bis 0,16 Gew.-%, Chrom in einem Anteil von 0 bis 0,65 Gew.-%, Silizium in einem Anteil von 0 bis 0,50 Gew.-%, Mangan in einem Anteil von 0 bis 1,25 Gew.-%, Phosphor in einem Anteil von 0 bis 0,030 Gew.-%, Schwefel in einem Anteil von 0 bis 0,030 Gew.-%, Kupfer in einem Anteil von 0 bis 0,40 Gew.-%, Vanadium in einem Anteil von 0 bis 0,10 Gew.-%, und Nickel in einem Anteil von 0 bis 0,40 Gew.-%.In one embodiment, 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 .-%.
Beispiele für Corten-Stähle sind der Werkstoff Nr. 1.8946 und 1.8963 gemäß ASTM A 242 und A 588.Examples of Corten steels are material Nos. 1.8946 and 1.8963 according to ASTM A 242 and A 588.
Der Corten-Stahl kann als Werkstoff/Ausgangsmaterial, z.B. als Stahlblech, oder Produkt, z.B. als Bestandteil eines fertigen Bauwerks, vorliegen. Der Corten-Stahl sollte nicht behandelt oder beschichtet sein. Allerdings muss die Oberfläche sauber sein.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.
Der bereitgestellte Corten-Stahl wird dann gereinigt. Das Reinigen in Stufe (1) von Schritt (i) erfolgt derart, dass die gereinigte Oberfläche des Corten-Stahls metallisch sauber, fettfrei und rostfrei ist.The supplied Corten steel is then cleaned. The cleaning in 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.
Das Reinigen in Stufe (1) von Schritt (i) kann derart erfolgen, dass die Oberfläche des Corten-Stahls zuerst einer alkalischen Abkochentfettung (beispielsweise mit AK 161 der Firma Schlötter), anschließend einer Zwischenspülung der Oberfläche mit Wasser, gefolgt von einer Behandlung mit einer Sparbeize (z.B. BESTA-S von der Firma POLIGRAT, Deutschland, enthaltend Schwefelsäure Amidosulfonsäure, Oxalsäure, Inhibitoren oder einer Sparbeize enthaltend beispielsweise Schwefelsäure, ortho-Phosphorsäure, Dimethylsulfoxid und Hexamethyltetramin), ebenfalls gefolgt von einer Spülbehandlung in Stadtwasser/Trinkwasser/Leitungswasser, unterzogen wird.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.
Die zweite Stufe, Stufe (2) in Schritt (i), dient zum Aktivieren der gereinigten Oberfläche bzw. den gereinigte Oberflächen für das nachfolgende Färben. Das Aktivieren erfolgt durch eine Behandlung der gereinigten Oberfläche mit einer wässrigen Aktivierungslösung (Lösung A) durch Tauchen und/oder Besprühen. Die Behandlungszeit bei Raumtemperatur (20°C) kann beispielsweise 2 bis 30 Minuten, oder 2 bis 15 Minuten, bevorzugt 2 bis 5 Minuten dauern.The second step, 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.
Die wässrige Aktivierungslösung kann unter Verwendung von Trink-/Brauch-/Leitungswasser hergestellt werden, indem HF und Oxidationsmittel sowie ein oder mehrere optionale Stabilisatoren für das Oxidationsmittel zugesetzt werden. Bevorzugt enthält die wässrige Aktivierungslösung, bezogen auf den pKa Wert, keine stärkeren Säuren als HF. Bevorzugt enthält die wässrige Aktivierungslösung HF als einzige Säure.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. Preferably, the aqueous activating solution, based on the pKa value, contains no stronger acids than HF. Preferably, the aqueous activation solution contains HF as the only acid.
Bevorzugt besteht die wässrige Aktivierungslösung aus HF, Oxidationsmittel(n), optional ein oder mehrere Stabilisatoren für das/die Oxidationsmittel, und Trink-/Brauch-/Leitungswasser.Preferably, 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.
Die wässrige Aktivierungslösung kann Fluoridionen, beispielsweise durch Verwendung von Fluorwasserstoff, in einer Menge, bezogen auf das Gewicht der wässrigen Aktivierungslösung, von größer als 0 Gew.-% und kleiner oder gleich 3 Gew.-%, oder größer als 0,5 Gew.-% und kleiner oder gleich 3 Gew.-%, bevorzugt größer als 0,5 Gew.-% und kleiner oder gleich 1 Gew.-%, enthalten. Vorteilhafterweise wird eine Lösung mit einer derartigen Menge an Fluorid nicht als giftig eingestuft. Der aktive Fluoridanteil wird anhand des Materialabtrages eines Probebleches bestimmt. Aktiver Fluoridgehalt und Materialabtrag sind linear verknüpft.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. Advantageously, 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.
Bevorzugt stammt zumindest ein Teil der Menge oder auch die gesamte Menge an Fluoridionen aus Fluorwasserstoff, der der wässrigen Aktivierungslösung zugesetzt wurde. Die Fluoridionen können auch aus anderen Quellen stammen, beispielsweise Ammoniumbifluorid, Natriumbifluorid, und/oder Kaliumbifluorid.Preferably, at least a portion of the amount, or even the total amount, of 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.
Ein geeignetes und bevorzugtes Oxidationsmittel ist Wasserstoffperoxid. Wasserstoffperoxid kann als wässrige Lösung eingesetzt werden. Die Menge an Oxidationsmittel kann in Abhängigkeit des eingesetzten Oxidationsmittels vom Fachmann gewählt werden, beispielsweise indem einfache Testversuche durchgeführt werden.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.
Die wässrige Aktivierungslösung kann beispielsweise das/die Oxidationsmittel, bevorzugt Wasserstoffperoxid, in einer Menge von größer als 0 Gew.-% und kleiner oder gleich 30 Gew.-%, oder von größer als 0 Gew.-% und kleiner oder gleich 20 Gew.-%, bevorzugt größer als 3 Gew.-% und kleiner oder gleich 20 Gew.-%, oder größer als 3 Gew.-% und kleiner oder gleich 10 Gew.-%, enthalten.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.
Die wässrige Aktivierungslösung kann insbesondere Fluoridionen, beispielsweise aus Fluorwasserstoff, in einer Menge, bezogen auf das Gewicht der wässrigen Aktivierungslösung, von größer als 0,5 Gew.-% und kleiner oder gleich 3 Gew.-%, bevorzugt größer als 0,5 Gew.-% und kleiner oder gleich 1 Gew.-%, und das/die Oxidationsmittel, bevorzugt Wasserstoffperoxid, in einer Menge, bezogen auf das Gewicht der wässrigen Aktivierungslösung, von größer als 3 Gew.-% und kleiner oder gleich 20 Gew.-%, enthalten.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.
Geeignete optionale Stabilisatoren für das Oxidationsmittel sind beispielsweise Gemische aus Harnstoff und einer oder mehreren Alkandiphosphonsäuren, die gegebenenfalls mit einer oder mehreren Hydroxyl- oder Aminogruppen substituiert sind, bzw. deren Salze. Die Kohlenwasserstoffkette der Alkandiphosphonsäuren umfasst bevorzugt 1, 2, 3 oder 4 C-Atome. Beispiele solcher Alkandiphosphonsäuren sind Alkylendiphosphonsäuren oder amino- bzw. hydroxy-substituierte Alkylidendiphosphonsäuren. Eine besonders geeignete Alkylidendiphosphonsäure ist 1-Hydroxyethan-1,1-diphosphonsäure. Geeignete Stabilisatoren sind auch in
Die Menge an Stabilisatoren in der wässrigen Aktivierungslösung kann wie in
Der Stabilisator dient der Stabilisierung von wässrigen peroxidhaltigen Lösungen. Darunter werden in erster Linie wässrige Wasserstoffperoxid-haltige Lösungen verstanden, es können aber auch andere peroxidhaltige Lösungen auf diese Weise stabilisiert werden, etwa Lösungen, die Perschwefelsäuren und/oder Peroxycarbonsäuren, wie etwa Peressigsäure, bzw. deren Salze enthalten. Chloride/ Phosphate sollten nicht vorhanden sein.The stabilizer serves to stabilize 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.
Die Konzentration einer stabilisierten wässrigen Lösung von Wasserstoffperoxid kann dabei etwa 30 oder 35% betragen, sie kann aber auch geringer sein, etwa 20%, 10% oder 5%.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%.
Beispielsweise kann Lösung A Fluoride in einer Menge von maximal 1 Gew.-% enthalten, so wie Flußsäure 0,8%, und eine stark oxidierende Komponente, wie z.B. Wasserstoffperoxid, in einer Menge von ca. 5 Gew.-% mit einem geeigneten Stabilisator (z.B. gemäß
Beispielsweise erfolgt das Aktivieren durch eine Behandlung der gereinigten Oberfläche in einer wässrigen Lösung (Lösung A) durch Tauchen oder Besprühen. Lösung A enthält beispielsweise Fluoride in einer Menge von maximal 1 Gew.-% HF und eine stark oxidierende Komponente wie z.B. Wasserstoffperoxid in einer Menge von ca. 5% Gew.-% mit einem geeigneten Stabilisator (z.B. gemäß
Der Begriff "Stadt-/Trink-/Brauch-/Leitungswasser" wie hier verwendet, betrifft natürliches Wasser mit den üblicherweise enthaltenen Mineralstoffen und Spurenelementen.The term "city / drinking / utility / tap water" as used herein refers to natural water with the minerals and trace elements commonly present.
In einer Ausführungsform enthält die wässrige Aktivierungslösung HF in einer Menge von 0,5 Gew.-% bis 1 Gew.-%, Wasserstoffperoxid in einer Menge von 2 Gew.-% bis 10 Gew.-% und optional ein oder mehrere Stabilisatoren.In one embodiment, 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.
Nach der Aktvierung der Oberfläche kann ein optionaler Spülschritt mit Wasser durchgeführt werden, um die wässrige Aktivierungslösung teilweise oder vollständig zu entfernen. Wird die wässrige Aktivierungslösung nicht oder nur teilweise entfernt, so hat dies Auswirkungen auf den nachfolgenden Färbeschritt. Je nach gewünschter Farbe der Oberfläche kann die verbleibende Menge der wässrigen Aktivierungslösung eingestellt werden. Je weniger gespült wird, desto dunkler wird die Farbe.After surface activation, 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.
In der dritten Stufe von Schritt (i) erfolgt das eigentliche Färben der Oberflächen.In the third step of step (i) the actual dyeing of the surfaces takes place.
Hierbei kann das Behandeln der aktivierten Oberfläche in Stufe (3) von Schritt (i) mit Wasser, beispielsweise mit einem pH-Wert in dem Bereich von 6-8, über einen Zeitraum von beispielsweise 30 Minuten bis 15 Stunden, bevorzugt 1 Stunde bis 12 Stunden, durchgeführt werden.Herein, 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.
Das Behandeln mit Wasser kann grundsätzlich durch Besprühen mit Wasser und durch Feuchthalten erfolgen. Die Oberfläche soll während der Behandlung zwischendurch nicht trocknen. Bevorzugt wird Stufe (3) somit so durchgeführt, dass die Oberfläche während der Behandlungsdauer nicht vollständig trocknet. Eine feuchte Oberfläche könnte beispielsweise durch einen einfachen Test mit einem Taschentuch durchgeführt werden, wobei das Taschentuch nach Kontakt mit der Oberfläche feucht/nass erscheint. Beim Feuchthalten kann die zu behandelnde Oberfläche beispielsweise derart abgedeckt werden, beispielsweise mit Kunststofffolien, dass das Trocknen der Oberfläche zumindest verlangsamt wird. Bevorzug erfolgt das Feuchthalten durch leichtes Besprühen bzw. Vernebeln mit Wasser, ähnlich einer Sprühbewässerung in einem Gewächshaus. Die Wassermenge kann vom Fachmann hierbei so gewählt werden, dass die zu behandelnde Fläche vollständig und gleichmäßig feucht gehalten wird, insbesondere um einen gleichmäßigen Farbton zu erhalten. Je gleichmäßiger und dünner der Wasserfilm desto gleichmäßiger wird die erzielte Farbe. Ablaufendes Wasser erzeugt strukturierte Färbungen.The treatment with water can basically be done by spraying with water and by moisturizing. The surface should not dry during treatment. Preferably, step (3) is thus carried out so that the surface does not dry completely during the treatment period. For example, a wet surface could be made by a simple handkerchief test, with the handkerchief appearing wet / wet after contact with the surface. When moisturizing, 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. Preferably, 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.
Es kann Stadt-/Trink-/Brauch-/Leitungswasser verwendet werden, beispielsweise Münchner Trinkwasser.It can be used city / drinking / utility / tap water, such as Munich drinking water.
Grundsätzlich gibt es zwei Varianten für die Färbung der Oberflächen abhängig von der gewünschten Farbe.Basically, there are two variants for the coloring of the surfaces depending on the desired color.
Nach der Behandlung in Lösung A werden die Oberflächen mit Wasser, beispielsweise Stadtwasser, abgespült und anschließend beispielsweise liegend, schräg stehend oder senkrecht stehend durch leichtes Besprühen und Feuchthalten mit Wasser, beispielsweise Stadtwasser, behandelt. Je nach Dauer der Behandlung entstehen dann auf der Oberfläche des Corten-Stahls unterschiedliche Farben und zwar beispielsweise nach zirka
Das Verfahren kann daher beispielsweise so durchgeführt werden, dass der optionale Spülschritt mit Wasser in Stufe (2) von Schritt (i) durchgeführt wird und das Färben der aktivierten Oberfläche in Stufe (3) von Schritt (i) durch Besprühen und Feuchthalten der aktivierten Oberfläche durchgeführt wird. Hierbei wird bevorzugt sehr wenig Wasser verwendet, beispielsweise 0,2 - 1 l/m2 und h.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. In this case, very little water is preferably used, for example 0.2-1 l / m 2 and h.
Nach der Behandlung in Lösung A werden die Oberflächen, z.B. Bleche, ohne Spülen mit Wasser beispielsweise in horizontaler, schräger oder vertikaler Lage für die Dauer von beispielsweise 1 bis 2 Minuten mit Wasser, beispielsweise Stadtwasser, besprüht und anschließend nur feucht gehalten. Je nach Dauer der Behandlung entstehen auf der Oberfläche des Corten-Stahls folgende Farben beispielsweise nach etwa zirka
- 3 Stunden: Olivgrün
- 12 Stunden: Dunkelbraun
- 3 hours: olive green
- 12 hours: Dark brown
Das Verfahren kann daher beispielsweise so durchgeführt werden, dass der optionale Spülschritt mit Wasser in Stufe (2) von Schritt (i) nicht durchgeführt wird und das Färben der aktivierten Oberfläche in Stufe (3) von Schritt (i) unter Verwendung von wenig Wasser, insbesondere nur durch Feuchthalten und nicht durch Spülen, erfolgt, beispielsweise durch einmaliges Besprühen mit Wasser und anschließendem Feuchthalten durch Abdecken der Oberfläche, oder durch kontinuierliches oder intervallartiges leichtes Besprühen mit Wasser, wie oben beschrieben, um ein Abwaschen der Aktivierungslösung gering zu halten.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.
Strukturierte Farbeffekte, beispielsweise Streifen, erhält man, indem man die Oberflächen in den ersten Minuten, beispielsweise 10 Minuten nach der Behandlung in Lösung A, in senkrechter oder schräger Position bearbeitet. Abhängig von der Steilheit der Oberflächen bei der Bearbeitung und der Intensität mit der die Oberflächen berieselt oder besprüht werden, entstehen aus den ursprünglichen Ablaufspuren des Wassers unterschiedlich feine oder grobe Strukturen.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. Depending on the steepness of the surfaces during the processing and the intensity with which the surfaces are sprinkled or sprayed, the original traces of the runoff of the water produce differently fine or coarse structures.
Nach dem Erreichen der gewünschten Farbe werden die Oberflächen sorgfältig getrocknet und weiter behandelt in Schritt (ii).After reaching the desired color, the surfaces are carefully dried and further treated in step (ii).
In Schritt (ii) werden die farbigen Oberflächen mittels einer geeigneten, farblos transparenten Beschichtung, bevorzugt einer Sol-Gel-Beschichtung/Sol-Gel-Lack (z.B. POLIANT oder POLISEAL von POLIGRAT), versiegelt.In 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).
Das Versiegeln in Schritt (ii) kann somit beispielsweise unter Verwendung einer Sol-Gel-Beschichtung erfolgen, wobei die Sol-Gel-Beschichtung nach dem Aufbringen eingebrannt wird, um eine glaskeramische Struktur zu erzielen. Es ist jedoch auch möglich, andere anorganische, transparente, dichte und chemisch beständige Beschichtungen zu verwenden, die in der Lage sind die Farbschicht vollständig zu imprägnieren.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.
Es versteht sich für den Fachmann, dass der bevorzugte Sol-Gel-Lack zunächst in Form eines flüssigen Sols mit darin schwebenden kolloidalen Partikeln aufgebracht wird, das sich anschließend in ein Gel umwandelt und schließlich eine feste, harte Lackschicht bildet. Wenn also vom "Auftragen des Sol-Gel-Lacks" bzw. dem "Härten des Sol-Gel-Lacks" die Rede ist, weiß der Fachmann, in welchem Zustand sich das Sol-Gel-System dabei befindet.It will be understood by those skilled in the art that the preferred 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.
Vorzugsweise handelt es sich bei dem Sol um ein Kieselsol, basierend auf Silanen, die in Lösemittel, etwa Alkohol, gelöst werden. Wahlweise könne diese Kieselsole auch ein oder mehrere weitere Sol-bildende Elemente wie etwa Al, Ti, Zr, Mg, Ca oder Zn aufweisen, die Si-Atome in den kolloidalen Strukturen ersetzen.Preferably, the sol is a silica sol based on silanes which are dissolved in solvents, such as alcohol. Optionally, 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.
Die Ausgangsverbindungen zur Bildung der Sole und schließlich des Sol-Gel-Lacks sind hydrolysierbare Silane der Formel SiR4, wobei die 4 Reste R 2-4 hydrolysierbare Reste OR' und 0-2 nicht-hydrolysierbare Reste R" umfassen. Diese Ausgangs-Silane können also auch als Si(OR')4-nR"n mit n = 0,1 oder 2 dargestellt werden. Wenn zusätzliche Sol-bildende Elemente, wie sie eben beschrieben wurden, eingesetzt werden, sind entsprechende Verbindungen gemäß den Wertigkeiten der Elemente als Ausgangsverbindungen zu wählen, etwa AlR3, usw.The starting compounds for the formation of the sols and finally of the sol-gel lacquer are hydrolyzable silanes of the formula SiR 4 , where the 4 radicals R 2-4 comprise hydrolyzable radicals OR 'and 0-2 comprise non-hydrolyzable radicals R "These starting silanes Thus, they can also be represented as Si (OR ') 4-n R " n with n = 0,1 or 2. If additional sol-forming elements as just described are used, appropriate compounds should be selected according to the valences of the elements as starting compounds, such as AlR 3 , etc.
Die hydrolysierbaren Reste OR' sind Hydroxy-, Alkoxy- und/oder Cycloalkoxyreste. Geeignete Beispiele hierfür umfassen etwa Hydroxy-, Methoxy-, Ethoxy-, n-Propoxy-, Isopropoxy-, n-Butoxy-, i-Butoxy-, t-Butoxy-, Pentoxy-, Hexoxy-, Cyclopentyloxy-, Cyclohexyloxyreste, wobei insbesondere Ethoxy-, n-Propoxy- und Isopropoxyreste bevorzugt werden. Die hydrolysierbaren Reste OR' können gleich oder verschieden voneinander sein.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.
Die nicht-hydrolysierbaren Reste R", so sie vorhanden sind, sind Alkyl- und/oder Cycloalkylreste. Geeignete Beispiele hierfür umfassen etwa Methyl-, Ethyl-, n-Propyl-, Isopropyl-, n-Butyl-, i-Butyl-, t-Butyl-, Pentyl-, Hexyl-, Cyclopentyl-, Cyclohexylreste, wobei insbesondere Methyl-, Ethyl-, n-Propyl- und Isopropylreste bevorzugt werden. Die nicht-hydrolysierbaren Reste R" können ebenfalls gleich oder verschieden voneinander sein.The non-hydrolyzable radicals R ", if present, 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.
Die Ausgangsverbindungen der Sole können aus einer einzigen Art von Silan bestehen, häufig werden sie aber Gemische aus mehreren Silanen (und gegebenenfalls zusätzlichen Sol-bildenden Ausgangsverbindungen anderer Elemente) umfassen. Bevorzugt ist, dass zumindest eine der Komponenten der Ausgangsverbindungen ein Silan der Formel Si(OR')4-nR"n mit n = 0 ist, also Si(OR')4. Beispielsweise kann ein bevorzugter Sol-Gel-Lack die Ausgangsmaterialien TEOS (Tetraethoxyorthosilan) und MTES (Methyltriethoxysilan) und/oder DMDES (Dimethyldiethoxysilan) umfassen.The brine starting compounds may consist of a single type of silane, but often they will comprise mixtures of several silanes (and optionally additional sol-forming starting compounds of other elements). It is preferred that at least one of the components of the starting compounds is a silane of the formula Si (OR ') 4-n R " n where n = 0, ie Si (OR') 4 For example, a preferred sol-gel lacquer may be the starting materials TEOS (tetraethoxyorthosilane) and MTES (methyltriethoxysilane) and / or DMDES (dimethyldiethoxysilane).
Daneben können natürlich auch andere, auf dem Gebiet der Sol-Gel-Systeme übliche Zusatzstoffe eingesetzt werden, beispielsweise zusätzliche Netzwerkbildner, wie etwa Acryloxypropyltrimethoxysilan bzw. Methacryloxypropyltrimethoxysilan, die für weitere organische Vernetzungen sorgen können, insbesondere wenn ein nicht unerheblicher Teil der Ausgangsverbindungen sogenannte netzwerkwandelnde Verbindungen der Formel Si(OR')4-nR"n mit n = 1 oder 2 sind.In addition, it is of course also possible to use other additives customary in the field of sol-gel systems, for example additional network formers, such as acryloxypropyltrimethoxysilane or methacryloxypropyltrimethoxysilane, which can provide further organic crosslinks, especially if a not inconsiderable proportion of the starting compounds are so-called network-converting compounds of the formula Si (OR ') 4-n R " n where n = 1 or 2.
Im Sol sind die Ausgangsverbindungen zum Teil zu den entsprechenden Hydroxyverbindungen (etwa Orthokieselsäure, Trihydroxyalkylsilan, usw.) hydrolysiert, was durch die Zugabe eines Katalysators, etwa von Säure, begünstigt werden kann. Aufgrund der hohen Neigung zur Kondensation dieser Hydroxyverbindungen können diese nun unter Abspaltung von Wasser zu kleineren Siloxannetzwerken kondensieren. In dem Sol liegen bereits kolloidale Partikel vor, die Siloxan-Bindungen enthalten. Siloxan-Bindungen sind Bindungen der Form ≡Si-O-Si≡, wobei "≡" drei voneinander unabhängige beliebige Bindungen mit anderen Elementen, insbesondere mit OH, OR' und R", symbolisiert, wodurch eine dreidimensionale vernetzte Struktur in den kolloidalen Partikeln entsteht. Dabei haben OR' und R" dieselbe Bedeutung wie oben.In the sol, 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. Here, OR 'and R "have the same meaning as above.
Das Auftragen des Sol-Gel-Lacks kann dabei auf jede beliebige Art und Weise erfolgen, etwa durch Eintauchen, Fluten, Aufsprühen oder Aufstreichen. Vorzugsweise erfolgt er jedoch durch Aufsprühen, da dies eine genaue Kontrolle der pro Flächeneinheit aufgebrachten Menge ermöglicht.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.
Dabei kann die Menge nach Bedarf eingestellt werden. Beispielsweise kann ein Sol-Gel-Lackschicht eine Schichtdicke von bis zu etwa 6 µm aufweisen, oder von etwa 0,5 bis 3 µm.The amount can be adjusted as needed. For example, a sol-gel lacquer layer may have a layer thickness of up to about 6 μm, or from about 0.5 to 3 μm.
Die Viskosität des Sol-Gel-Lacks kann vom Fachmann eingestellt werden. Es ist bekannt, dass das Sol bei entsprechend hoher Verdünnung in seinem Lösemittel ausreichend dünnflüssig ist, um in die eventuell vorhandenen Poren einer Oberfläche einzudringen.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.
Geeignete Lösemittel für das Sol sind Wasser und vor allem Alkohole wie Methanol, Ethanol, n-Propanol oder Isopropanol, wobei Ethanol und Isopropanol aufgrund ihrer physikalischen Eigenschaften und der geringen Toxizität ihrer Dämpfe bevorzugt werden.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.
Daraufhin lässt man das aufgetragene Sol zu einem Gel reagieren. Diese Reaktion überführt das flüssige Sol in eine feste Gelschicht, in der sich die kolloidalen Partikel des Sols durch weitere Hydrolyse und Kondensation miteinander und mit noch nicht hydrolysierten und kondensierten Ausgangsverbindungen vernetzen. Dies kann beispielsweise durch Verdunsten des alkoholischen Lösemittels beim Trocknen geschehen.Then 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.
Nach dem Trocknen der Oberflächen werden die Sol-Gel-Beschichtungen eingebrannt, wodurch eine glaskeramische Struktur bildet, die fest haftet, alterungsbeständig und unempfindlich gegen Umwelteinflüsse ist und die Farbeffekte dauerhaft konserviert. Das Einbrennen der Beschichtung kann vom Fachmann nach üblicher Vorgehensweise durchgeführt werden.After drying the surfaces, 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.
Beispielsweise werden die mit dem Gel beschichteten Oberflächen einer thermischen Härtung unterzogen. Dies geschieht bei erhöhten Temperaturen, wobei sich das Gel in eine farblose, transparente, glasartige Schicht umwandelt. Die Kieselsol-Bestandteile wandeln sich dabei in ein noch stärker vernetztes Siliziumdioxid um, das je nach Zusammensetzung des zugrundeliegenden Sols weitere Bestandteile wie etwa Aluminiumoxid, Titanoxid oder Zirkoniumoxid enthalten kann. Diese Schichten sind hart, geschlossen und beständig gegen viele der Chemikalien, mit denen eine Oberfläche unter gewöhnlichen Umständen in Berührung kommen kann, sowie gegen Temperaturen bis etwa 500°C.For example, 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.
Gemäß einer bevorzugten Ausführungsform wird die beschichtete Oberfläche bei der anschließenden Härtung des Gels Temperaturen von 160 °C bis 220°C ausgesetzt. Diese Härtung sollte für eine Dauer von mindestens 10 Minuten, vorzugsweise 20 bis 45 Minuten, beispielsweise 30 Minuten lang erfolgen. Die Härtung wird vorzugsweise bei Temperaturen zwischen 180°C und 210°C, beispielsweise bei 200°C, durchgeführt, aber auch Temperaturen unterhalb von 180°C eignen sich hierfür. Dabei wandelt sich das Gel in einen harten, farblosen und transparenten, glasartigen Lack um, der die Oberfläche dicht versiegelt, seinerseits keine Risse aufweist und der Oberfläche eine hohe Härte und Verschleißbeständigkeit verleiht.According to a preferred embodiment, 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.
Die Prozesse der Gelbildung und der Härtung des Gels können dabei ineinander übergehen, da etwa eine Gelbildung durch Trocknen und Verdunsten des Lösemittels zumindest teilweise auch noch zu Beginn der Behandlung zur Härtung erfolgen kann. Auch ein solches Verfahren, bei dem die Prozesse der Gelbildung und der Härtung des Gels ineinander übergehen, ist von der Erfindung umfasst.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.
Es können jedoch auch andere herkömmliche Härtungsverfahren, insbesondere eine kathodische Härtung, durchgeführt werden. Die kathodische Härtung kann dabei beispielsweise gemäß der Patentanmeldung
Die Erfindung betrifft auch einen Corten-Stahl mit behandelter Oberfläche.The invention also relates to a Corten steel with treated surface.
Aus dem Dokument
Die vorliegende Erfindung betrifft dem gegenüber ein Corten-Stahl mit einer farblosen, transparenten Beschichtung auf einer gefärbten Oberfläche - ausgenommen Rostbraun - des Corten-Stahls, wobei die Oberfläche nach einem, wie vorstehend, beschriebenem Verfahren behandelt wurde, und das Versiegeln in Schritt (ii) dieses Verfahrens, unter Verwendung einer Sol-Gel-Beschichtung erfolgt, wobei die Sol-Gel-Beschichtung nach dem Aufbringen eingebrannt wird, um eine glaskeramische Beschichtung zu erzielen. Der erfindungsgemäße Corten-Stahl unterscheidet sich strukturell von bekannten Corten-Stählen, was an der Farbe und den Eigenschaften, wie Stabilität gegen Korrosion, erkennbar ist.On the other hand, 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.
Ein Blech aus Werkstoff-Nr. 1.8963 in den Abmessungen 500x500x1,5 mm wurde in einer wässrigen Abkochentfettung (AK 161 von Fa. Schlötter) bei 60°C für die Dauer von 10 Minuten entfettet.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.
Anschließend wurden die Oberflächen zweimal mit Stadtwasser gespült und dann in einer Sparbeize (BESTA-S von der Firma POLIGRAT, Deutschland) bei 60°C für die Dauer von 2 Minuten entrostet.Subsequently, the surfaces were rinsed twice with city water and then de-rusted in a Sparbeize (BESTA-S from POLIGRAT, Germany) at 60 ° C for a period of 2 minutes.
Die Oberflächen wurden anschließend zweimal mit Stadtwasser gespült und dann bei Raumtemperatur (20 °C) aktiviert durch Tauchen in einer wässrigen Lösung mit 0,8% HF-Gew und 5%-Gew Wasserstoffperoxid sowie mit einem Stabilisator für das Peroxid (Produkt C600 von POLIGRAT) für die Dauer von 4 Minuten.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.
Die Oberflächen wurden anschließend einmal mit Stadtwasser gespült und dann hingelegt. In liegender Stellung wurden die Oberflächen durch leichtes Besprühen mit Stadtwasser für die Dauer von 3 Stunden bei Raumtemperatur feucht gehalten. Dabei entstand eine orangenfarbige Oberfläche.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.
Die Oberfläche wurde getrocknet und anschließend mit dem Sol-Gel-Verfahren POLIANT von der Firma POLIGRAT im Sprühverfahren beschichtet und für die Dauer von 30 Minuten bei 200°C eingebrannt.The surface was dried and then spray-coated with the sol-gel POLIANT method by POLIGRAT and baked at 200 ° C. for 30 minutes.
Die erzielte Oberfläche war orangefarbig mit einer attraktiven Streifenstruktur aus helleren und dunkleren Farbtönen mit Metalliceffekt, die das Licht irisierend reflektierte. Die Oberfläche war hydrophob, sodass Wasser abperlte ohne feuchte Spuren zu hinterlassen.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.
Ein Blech, entsprechend dem Beispiel 1, wurde wie in Beispiel 1 vorbehandelt und aktiviert. Anschließend wurde das Blech ohne Spülprozess liegend und bei Raumtemperatur mittels Besprühen mit Stadtwasser feucht gehalten. Nach einer Dauer von 3 Stunden und einem abschließenden Spülen wies das Blech eine olivgrüne Oberfläche auf. Die weitere Behandlung erfolgte wie in Beispiel 1, wobei der Metalliceffekt auf der Oberfläche im Vergleich zu Beispiel 1 etwas schwächer ausgeprägt war.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.
Claims (9)
- A method for the surface treatment of Corten steel, comprising the steps:(i) providing Corten steel and carrying out a treatment comprising the stages:(1) cleaning at least a portion of at least one surface of the Corten steel;(2) activating at least a portion of the cleaned surface of the Corten steel from stage (1) by bringing the cleaned surface into contact with an aqueous activating solution containing fluoride ions, one or more oxidizing agents, and optionally one or more stabilizers for the oxidizing agent(s); and(3) colouring at least a portion of the activated surface of the Corten steel from stage (2) by treating the activated surface with water for a period of at least 30 minutes and until the desired coloration of the surface of the Corten steel is achieved; and(ii) sealing at least a portion of the coloured surface from stage (3) of step (i) by applying a colourless, transparent coating, as the result of which the surface-treated Corten steel is obtained.
- The method according to Claim 1, wherein the Corten steel comprises: iron as the main component, as well as one or more components selected from the group consisting of: carbon in a proportion of 0 to 0.16% by weight, chromium in a proportion of 0.40 to 0.65% by weight, silicon in a proportion of 0.30 to 0.50% by weight, manganese in a proportion of 0.80 to 1.25% by weight, phosphorus in a proportion of 0 to 0.030% by weight, sulfur in a proportion of 0 to 0.030% by weight, copper in a proportion of 0.10 to 0.40% by weight, vanadium in a proportion of 0.02 to 0.10% by weight, and nickel in a proportion of 0 to 0.40% by weight.
- The method according to Claim 1 or 2, wherein the cleaning in stage (1) of step (i) takes place in such a way that the cleaned surface of the Corten steel is metallically clean, free of grease, and free of rust.
- The method according to a preceding claim, wherein the aqueous activating solution contains fluoride ions in a quantity of greater than 0% by weight and less than or equal to 3% by weight, and/or the aqueous activating solution contains the oxidizing agent(s) in a quantity of greater than 0% by weight and less than or equal to 20% by weight.
- The method according to a preceding claim, wherein the treatment of the activated surface in stage (3) of step (i) is carried out with water over a period of between 30 minutes and 15 hours, up to the desired colour of the surface.
- The method according to a preceding claim, wherein an optional rinsing step with water in stage (2) of step (i) is carried out, and the colouring of the activated surface in stage (3) of step (i) is carried out by spraying and keeping the activated surface moist.
- The method according to a preceding claim, wherein the sealing in step (ii) takes place using a sol-gel coating, the sol-gel coating being burned in after the application in order to achieve a glass ceramic structure.
- The method according to a preceding claim, wherein at least a portion of the amount of fluoride ions originates from hydrogen fluoride, which has been added to the aqueous activating solution.
- A Corten steel having a colourless, transparent coating on a coloured surface, with the exception of rust brown, of the Corten steel, wherein the surface has been treated by a method according to one of Claims 1-6 or 8, and the sealing in step (ii) of this method takes place using a sol-gel coating, the sol-gel coating being burned in after the application in order to achieve a glass ceramic coating.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102013010080.1A DE102013010080A1 (en) | 2013-06-14 | 2013-06-14 | Process for the surface treatment of Corten steel |
| PCT/EP2014/062416 WO2014198917A1 (en) | 2013-06-14 | 2014-06-13 | Method for the surface treatment of corten steel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP3008226A1 EP3008226A1 (en) | 2016-04-20 |
| EP3008226B1 true EP3008226B1 (en) | 2017-08-02 |
Family
ID=50979746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP14731592.3A Not-in-force EP3008226B1 (en) | 2013-06-14 | 2014-06-13 | Method for the surface treatment of corten steel |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20160177454A1 (en) |
| EP (1) | EP3008226B1 (en) |
| DE (1) | DE102013010080A1 (en) |
| WO (1) | WO2014198917A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT201700085414U1 (en) * | 2017-07-26 | 2019-01-26 | Nuova De Fi M S P A | SYSTEM AND SUPPORT WIRE |
| DE102018103052A1 (en) | 2018-02-12 | 2019-08-14 | Martin Piehler | Method for producing a surface-treated metal object |
| CN111534746B (en) * | 2020-04-30 | 2022-02-18 | 鞍钢股份有限公司 | Weather-resistant steel for wide 450 MPa-grade hot-rolled container and manufacturing method thereof |
| CN111518998B (en) * | 2020-06-11 | 2022-02-15 | 攀钢集团西昌钢钒有限公司 | High-strength acid-resistant color-coated sheet and preparation method thereof |
| CN114635141B (en) * | 2022-02-28 | 2023-10-27 | 武汉材保表面新材料有限公司 | Chemical film stripping liquid for non-phosphate conversion film on steel surface, preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0737672B2 (en) * | 1990-06-15 | 1995-04-26 | ヤマキ工業株式会社 | Rust weatherproof steel plate |
| EP1793016A1 (en) * | 2005-12-01 | 2007-06-06 | Elpochem AG | Polishing and deburring composition for workpieces of carbon steel and method of chemical polishing and deburring |
| EP1903081B1 (en) * | 2006-09-19 | 2015-01-28 | Poligrat Gmbh | Stabiliser for acid, metallic polishing baths |
| EP2145980A1 (en) * | 2008-07-07 | 2010-01-20 | Poligrat Gmbh | Coloured stainless steel surface and method for colouring stainless steel |
| DE102009038795A1 (en) * | 2009-08-25 | 2011-05-05 | Poligrat Gmbh | Pickling process for stainless steel |
| CN102925884B (en) * | 2012-11-29 | 2015-02-11 | 北京科技大学 | Hydrojet pretreatment method for accelerating stabilization of rust layer on surface of weathering resistant steel |
-
2013
- 2013-06-14 DE DE102013010080.1A patent/DE102013010080A1/en not_active Withdrawn
-
2014
- 2014-06-13 WO PCT/EP2014/062416 patent/WO2014198917A1/en active Application Filing
- 2014-06-13 US US14/896,931 patent/US20160177454A1/en not_active Abandoned
- 2014-06-13 EP EP14731592.3A patent/EP3008226B1/en not_active Not-in-force
Also Published As
| Publication number | Publication date |
|---|---|
| WO2014198917A1 (en) | 2014-12-18 |
| DE102013010080A1 (en) | 2014-12-18 |
| EP3008226A1 (en) | 2016-04-20 |
| US20160177454A1 (en) | 2016-06-23 |
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