EP2907894B1 - Procédé de fabrication d'un substrat avec passivation exempte de chrome VI et de cobalt - Google Patents

Procédé de fabrication d'un substrat avec passivation exempte de chrome VI et de cobalt Download PDF

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Publication number
EP2907894B1
EP2907894B1 EP14155058.2A EP14155058A EP2907894B1 EP 2907894 B1 EP2907894 B1 EP 2907894B1 EP 14155058 A EP14155058 A EP 14155058A EP 2907894 B1 EP2907894 B1 EP 2907894B1
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EP
European Patent Office
Prior art keywords
passivation
composition
acidic
alkaline
silane
Prior art date
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EP14155058.2A
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German (de)
English (en)
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EP2907894A1 (fr
Inventor
Verena Grossmann
Ingo KLÜPPEL
Christopher Köster
Gerhard Reusmann
Marcel Roth
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Ewald Doerken AG
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Ewald Doerken AG
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Application filed by Ewald Doerken AG filed Critical Ewald Doerken AG
Priority to EP14155058.2A priority Critical patent/EP2907894B1/fr
Priority to ES14155058T priority patent/ES2732264T3/es
Priority to RU2015104265A priority patent/RU2652324C2/ru
Priority to BR102015002873-3A priority patent/BR102015002873B1/pt
Priority to KR1020150020590A priority patent/KR101897771B1/ko
Priority to MX2015001916A priority patent/MX369943B/es
Priority to US14/621,434 priority patent/US10011907B2/en
Priority to CN201510079622.2A priority patent/CN104846361B/zh
Publication of EP2907894A1 publication Critical patent/EP2907894A1/fr
Publication of EP2907894B1 publication Critical patent/EP2907894B1/fr
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—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 characterised by the process
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/42—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also phosphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/46—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing oxalates
    • 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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • 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
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/06—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly alkaline liquids
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

Definitions

  • the invention relates to a method for producing a substrate provided with a chromium (VI) -free and cobalt-free passivation.
  • chromium (VI) compounds are often no longer used and also elements such as cobalt and nickel are often no longer desirable.
  • a chromium (VI) -free and cobalt-free passivation composition is used in the US 4,578,122 disclosed.
  • activating metal ions eg. As iron, aluminum, lanthanum or cerium ions are added.
  • the ratio of nitrate ions on the one hand to chromium (III) ions and activating metal ions on the other hand should not be less than 4: 1.
  • the DE-OS 3 213 384 discloses a first acidic and a second alkaline passivation that is chromium (VI) free and cobalt free. However, this two-stage passivation has not yet been optimized with regard to corrosion protection.
  • the WO 95/24517 A1 relates to a coated metal sheet which has been pretreated with an insoluble composite layer containing a siloxane.
  • the composite layer is obtained by rinsing the metal sheet with a basic solution which is at least 0.005 at least 0.1% by volume of an organofunctional silane and at least 0.02% by volume of a crosslinking agent having 2 or 3 trialkoxysilyl groups.
  • the US 2006/0054248 A1 relates to a method of dyeing and anticorrosion of metal parts by applying a solution comprising a trivalent chromium compound and at least one other metal salt selected from the group of iron salts, nickel salts and cobalt salts capable of coloring the surface of the metal part together with the chromium compound , and a phosphate and having a pH in the range of 0.5 to 5, on a surface of the metal part to obtain a colored surface. Subsequently, a top coat is applied to the colored surface to achieve high corrosion resistance.
  • the cover layer may be formed, for example, on the basis of an organosilane-silicate coating.
  • the concerns GB 0297024 A a method of treating metal surfaces, in particular zinc surfaces and zinc alloy surfaces, by treatment with an aqueous acidic solution containing effective amounts of A) hydrogen ions to achieve a pH of from about 1.5 to about 2.2, B) an oxidizing agent , C) at least one element selected from iron, cobalt, nickel, molybdenum, manganese, aluminum, lanthanum, lanthanide mixture or cerium ions or mixtures thereof, or instead of C) iron and cobalt ions ,
  • Other solutions for the treatment of the metal surfaces also contain D) chromium ions, which are essentially in the oxidation state +3, and iron ions in combination with another metal selected from C) or cerium ions, or A), B), C) and D.
  • the solution may also optionally contain halides or a wetting agent.
  • the US Pat. No. 6,478,886 B1 relates to an agent for sealing metallic substrates, in particular zinc or zinc alloy substrates, which consists of an aqueous dispersion of A) at least one silane derivative and B) at least one colloidal silica and / or a colloidal silicate.
  • the agent is preferably used for direct coating of metallic substrates without previous chromating.
  • the EP 0 337 411 B1 discloses a process for preparing an acidic chromium (III) -containing and fluoride-containing passivation bath for zinc, zinc alloy and cadmium surfaces.
  • the DE 10 2009 042 861 A1 relates to a composition for passivating zinc and its alloys consisting of a passivation solution and an activating solution, wherein the passivating solution comprises from 20 to 200 g / l of chromium (III) compounds, e.g.
  • chromium chloride or chromium nitrate 20 to 600 g / l soluble nitrate selected from sodium, potassium or ammonium nitrate, 5 to 100 g / l fluoride selected from sodium, potassium or ammonium chloride, 5 to 20 g / l organic acids selected from oxalic acid, malonic acid, tartaric acid, formic acid, acetic acid and citric acid, hydrochloric or nitric acid, and wherein the activating solution of 1 to 200 g / l of a stannous or tin (IV) salt and 10 bis 700 g / l of a phosphonic acid or its derivatives.
  • the method according to the invention provides that a first acidic and a second alkaline passivation are applied, wherein an aqueous alkaline composition used for producing the second alkaline passivation contains silane-modified silicates ,
  • an aqueous alkaline composition used for producing the second alkaline passivation contains silane-modified silicates .
  • the first acid and the second alkaline passivation are applied as aqueous compositions.
  • passivation is used in the context of this invention both for the aqueous composition for passivating the substrate and for applying the aqueous compositions as well as for the coating applied to the surface of the metallic workpiece. Treating the surface of the metallic substrate with the acidic and alkaline aqueous compositions results in the deposition of chemical components contained therein which form a coating on the surface of the substrate, ie, the passivation. The or the coatings provide improved protection against corrosion.
  • the first, acidic passivation is according to the invention chromium (VI) -free and cobalt-free.
  • chromium (VI) -free and cobalt-free Preferably, it is also nickel-free
  • the substrate or workpiece coated with a first acidic passivation is coated according to the invention with a second passivation, wherein the second passivation is an alkaline passivation.
  • the corrosion protection is significantly increased by this second alkaline passivation.
  • Workpieces in which the acidic passivation contains no vanadium or tungsten are significantly more resistant to corrosion by a second, alkaline passivation applied to the first, acidic passivation. Specifically, however, corrosion protection is improved when the first acidic passivation is made using an aqueous acidic composition containing vanadium and / or tungsten or their compounds.
  • An essential feature of the invention is the application of a silicate-containing aqueous composition as a second, alkaline passivation for coating the first acidic passivation.
  • a silicate compound is applied to the first acidic passivation.
  • Typical silicate compounds are water glasses, but also aqueous polysilicates or colloidal silicates are well suited for the second, alkaline passivation.
  • the second alkaline passivation comprises sodium, potassium, lithium and / or ammonium silicate.
  • a second alkaline passivation may also be applied to the workpiece, which comprises a mixture of silicate compounds. Both colloidal silicates and dissolved silicates can be used.
  • silane-modified or siloxane-modified silicates in which silanes or siloxanes are attached to the silicates, preferably polysilicates, have also proven to be suitable for the implementation of the invention. Most silicates form alkaline solutions or suspensions in the presence of water. If necessary, however, by addition of alkalis, z. As sodium hydroxide, the alkalinity can be increased.
  • lithium polysilicate in the aqueous composition for passivating has proven particularly advantageous for producing the second alkaline passivation proved metallic substrates.
  • the application of an aqueous composition of lithium polysilicate or the mixture of lithium polysilicate with other water glasses (sodium and / or potassium silicate) or colloidal silica sols on the first acidic passivation provides an extremely improved corrosion protection.
  • the use of lithium polysilicate for the production of the second alkaline passivation achieves the avoidance of the formation of gray films on the surface of the metallic substrate passivated according to the invention, which is customary for passivations of aqueous compositions with sodium or potassium water glasses.
  • the aqueous alkaline composition used for the second alkaline passivation comprises a silane or siloxane.
  • the addition of the silane or siloxane serves to further increase the corrosion protection.
  • a vinyl and / or aminosilane is used to prepare the second alkaline passivation; but are also suitable Expoxysilane and the siloxanes of the above and below mentioned silanes.
  • alkylalkoxysilanes here: mono-, di- or trialkylalkoxysilanes, are suitable individually or in combination in combination with silicates to build up a corrosion-protective coating on the metallic workpiece already treated with an acidic aqueous composition.
  • silane compounds can be used together in a mixture.
  • Particularly suitable silane compounds are methacryloxymethyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane, N - (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane.
  • Silane or siloxane can be used in an amount of 1% by weight to 99% by weight based on the total amount of the second alkaline passivation aqueous composition.
  • an aqueous alkaline composition is used for producing the second alkaline passivation, which comprises both silicates and silanes and / or Siloxanes or mixtures of silicates and silanes or siloxanes or compounds of a silicate and a silane component in the following: silane-modified silicates, or compounds of a silicate and a siloxane, hereinafter siloxane-modified silicates.
  • the silanes or siloxanes are typically z. B. bound by hydrolysis as covalent side chains of the silicates or.
  • silane-modified or siloxane-modified silicates form excellent corrosion protection on a first acidic passivation, which far exceeds the effect of simple acidic or alkaline passivation.
  • the silane-modified or siloxane-modified silicates are detectable by NMR spectroscopy on the metallic substrate. In particular, silicon-carbon bonds (SiC bonds) can be detected.
  • the second alkaline passivation forms an excellent basis for further coatings, eg. As coloring coatings or coatings containing lubricants or other additives that further improve the use of the coated surface. If silane-modified silicates are mentioned or described in connection with this invention, the use of siloxane-modified silicates is always meant and included as well.
  • the second alkaline passivation can according to a further preferred embodiment of the invention from partially or preferably completely hydrolyzed silicate and silane or. Siloxane compounds be prepared.
  • the common hydrolysis of silicates and silanes or siloxanes in aqueous solution on the one hand, the formation of silane-modified or siloxane-modified silicates.
  • alcohols released by the factory hydrolysis can be removed, so that users can be supplied with aqueous alkaline compositions which are low in volatile organic compounds (low in VOC) or free from volatile organic compounds (VOC-free).
  • the liberated by the hydrolysis alcohols for example, by ultramembrane filtration or reverse osmosis, but also by distillation, for. B. vacuum distillation can be removed.
  • Typical inventive aqueous alkaline compositions for passivating metallic substrates contain at most 1% by weight of alcohol, preferably at most 0.3% by weight of alcohol.
  • the aqueous composition for the second alkaline passivation add additives.
  • the additives are usually already added to the liquid composition from which the second alkaline passivation is prepared. They either exert their effect, for example with defoamers or stabilizers, during application or, for example, with lubricants or dyes, after the application and, if appropriate, drying of the second alkaline passivation.
  • an aqueous, acidic cobalt and chromium (VI) -free composition comprising a chromium (III) compound, an inorganic acid and optionally a fluorine source and characterized in that the aqueous composition comprises a compound of the metals vanadium or tungsten, which metal compound may be used individually or in admixture with other vanadium or tungsten compounds.
  • the aqueous acidic and alkaline compositions used according to the invention for passivating metallic substrates in general are suitable for all metallic surfaces or substrates, but particularly well for workpieces having a surface made of steel, iron, aluminum or zinc, but especially for workpieces whose surface has a surface Alloy of one or both of the metals aluminum and zinc is provided with other metals.
  • a suitable zinc-aluminum alloy, an aluminum or a zinc alloy with other metals such.
  • iron or magnesium for. B. with a zinc-iron alloy, all with a Corrosion protection coating can be provided.
  • the layer thickness of the applied coating of metal or alloy is between 5 .mu.m and 100 .mu.m.
  • the metallic alloy deposited on a substrate shows up as a discrete layer.
  • a typical application is coil coating, ie the passivation of steel strip.
  • metal-oxygen compounds of the metals molybdenum, vanadium and / or tungsten are used in the aqueous acidic composition for passivation.
  • One or more of the compounds listed below are preferably used in the aqueous acidic composition: potassium orthovanadate, potassium metavanadate, sodium orthovanadate, sodium metavanadate, sodium tungstate, sodium paratungstate and vanadium pentoxide and sodium molybdate and potassium molybdate.
  • compounds of the metals molybdenum, vanadium and / or tungsten which dissociate in the aqueous acidic composition for passivation and thereby release molybdate, vanadate and / or tungstate anions.
  • Molybdate, vanadate and tungstate anions are incorporated into the passivation layer and cause the construction of a very good corrosion protection already in the acidic passivation alone.
  • the acidic aqueous composition contains a phosphonic acid or a mixture of phosphonic acids.
  • organic phosphonic acids for example (1-hydroxyethane-1,1-diyl) -bisphosphonic acid, 2-phosphonobutanol-1,2,4-tricarboxylic acid, aminotrimethylenephosphonic acid, ethylenediamine tetramethylenephosphonic acid or diethylenetriaminepentamethylenephosphonic acid or mixtures thereof.
  • salts of phosphonic acid may prove advantageous in connection with the invention.
  • phosphonates listed below, each used individually or in admixture: tetrasodium (1-hydroxyethane-1, 1-diyl) bisphosphonate, trisodium (1-hydroxyethane-1,1-diyl) bisphosphonate, pentasodium ethylenediamine tetramethylenephosphonate or heptasodium diethylenetriamine.
  • These salts dissociate in the aqueous, acidic passivating composition, so that the phosphonates are available as complexing agents.
  • Phosphonic acids and their derivatives can also be advantageously used in conjunction with vanadium and tungsten compounds in acidic aqueous compositions. Here is the use of phosphonic acid as a complexing agent proven.
  • the acidic aqueous compositions for passivating metallic substrates comprise one or more elements or compounds of the group comprising molybdenum, manganese, cerium and lanthanum.
  • the aqueous, acidic passivating composition comprises a chromium (III) compound or a mixture of chromium (III) compounds selected from the group chromium (III) sulfate, chromium (III) Hydroxide, chromium (III) dihydrogen phosphate, chromium (III) chloride, chromium (III) nitrate, sodium chromium (III) sulfate, potassium chromium (III) sulfate and chromium (III) salts of organic acids , It has been found that an aqueous, acidic passivating composition has good anti-corrosive properties even without the use of a chromium (VI) compound.
  • the chromium (III) compound is used in an amount of at least 0.05 g / l to a maximum of saturation.
  • nitrate compound or a mixture of nitrate compounds.
  • nitrogen-containing acids such as nitric acid and salts of these acids are preferably used.
  • Typical salts particularly suitable for use in the passivation composition are salts of the alkali metals, ammonium salts or salts of the metal ions contained in the passivating composition, e.g. B. chromium (III) nitrate.
  • the nitrogen and chromium (III) compounds described above are present in the aqueous, acidic passivating composition in substantially dissociated form.
  • the proportion of nitrate compounds is preferably 5% by weight to 20% by weight based on the total composition used for the passivation.
  • an aqueous, acidic cobalt and chromium (VI) -free A composition for the passivation of metallic substrates, which has a chromium (III) compound, an acid, metal ions, nitrate ions and optionally a fluorine source and a phosphonic acid and / or derivatives thereof and which is characterized in that nitrate ions to the sum of chromium and Metal ions are used in a ratio of not more than 3: 1, preferably of not more than 1: 3.
  • the reduced nitrate usage proves advantageous in the use of this aqueous acidic passivating composition because fewer nitrous gases are released.
  • the acidic aqueous composition for passivation to a pH ⁇ 4, preferably a pH ⁇ 3 is set.
  • an acid or a mixture of acids is added.
  • organic and / or inorganic acids typically one or more of the group consisting of phosphoric acid, hydrochloric acid, nitric acid and / or sulfuric acid as inorganic acids and formic acid, succinic acid, acetic acid, oxalic acid, peracetic acid Salicylic acid and citric acid as organic acids.
  • the aqueous, acidic composition preferably comprises a fluorine source.
  • a fluorine source is preferably a compound or mixture of compounds selected from the group comprising hydrofluoric acid, hexafluorotitanic acid, hexafluorozirconic acid, sodium fluoride (NaF), potassium fluoride (KF), ammonium fluoride (NH 4 F), sodium bifluoride (NaHF 2 ), potassium bifluoride (KHF 2 ) and ammonium bifluoride (NH 4 HF 2 ).
  • the fluorine compounds used as the fluorine source are used in an amount of 0.1% by weight to 5% by weight based on the aqueous composition.
  • the fluorine compounds are preferably used as technically pure, soluble powders.
  • the preferred aqueous, acidic composition for passivating metallic substrates is composed essentially of substances that are largely harmless to health and that do not pollute the environment or are only slightly polluting. It is free of cobalt, nickel and chromium (VI) compounds. It is also preferably free of peroxide compounds and can be prepared without the use of carboxylic acids. In addition, in preferred embodiments, the use of nitrate compounds is minimized so that the emission of nitrous gases is greatly reduced.
  • the application of the aqueous acidic composition for passivation takes place at room temperature, at a maximum at temperatures up to 80 ° C.
  • the metallic substrate is in most cases immersed in a bath of the aqueous acid and then the aqueous alkaline composition for passivation, but the passivating compositions may also be prepared by other conventional and known application methods (spraying, dipping, dip-spinning, knife coating, rolling). be applied to the metallic substrate.
  • the application of the aqueous compositions for passivation is usually carried out with a treatment time which is between 1 second and 180 seconds, preferably about 30 seconds to 120 seconds.
  • the application of the composition for passivation may be followed by drying, which may be carried out at temperatures between room temperature and about 250 ° C. Drying is only aimed at removing excess liquid; a reaction, z.
  • Example, a hydrolysis or condensation of the components which form the passivating coating on the metallic substrate is not required.
  • the metallic substrate may be cleaned, in particular degreased, prior to application of the composition for passivation.
  • Aqueous solutions for cleaning and degreasing are known from the prior art.
  • the first acidic passivation is applied in a layer thickness of 10 nm to 1 ⁇ m, preferably in a layer thickness of 20 nm to 500 nm.
  • the second alkaline passivation is applied to a layer thickness of 10 nm to 1 ⁇ m, preferably in a layer thickness of 10 nm to 500 nm.
  • aqueous acidic and alkaline compositions needed to carry out the process of the invention are preferably supplied as a concentrate which is diluted with water for use in a ratio of concentrate: water of from 1: 5 to 1:20, often 1:10.
  • the respective aqueous acidic or alkaline compositions are each offered as one-component products.
  • the excellent corrosion protection is achieved by first applying an acidic passivation and then an alkaline passivation to the metallic substrate. Accordingly, an analysis of the finished coated substrate shows that, starting from the substrate, first a first passivation layer is detected which comprises chromium and nitrogen and optionally fluorine, vanadium and / or tungsten, alternatively also other metallic or rare earth elements.
  • this first passivation layer usually contains no silicon and none of the elements sodium, potassium or lithium.
  • a second passivation layer is applied to this first passivation layer. The second passivation layer is therefore not applied directly to the metallic substrate.
  • silicon as well as sodium, potassium and / or lithium can be detected in the second passivation layer.
  • this second passivation layer typically does not include chromium, fluorine, tungsten, vanadium, or other metallic or rare earth elements.
  • Non-metallic elements such. As carbon, phosphorus or nitrogen may optionally be detected in both passivation layers.
  • aqueous acid or alkaline passivation composition is prepared by mixing or dissolving the individual constituents.
  • the water is in the acidic aqueous composition mainly z. B. by the aqueous chromium (III) salt solution, here a sulfate or a nitrate, introduced into the liquid composition for passivation. Smaller quantities are finally added.
  • aqueous chromium (III) salt solution here a sulfate or a nitrate.
  • the preparation of the aqueous alkaline composition is typically carried out by adjusting the solids content or proportion of aqueous silicates by adding appropriate amounts of water and, if provided, by mixing in silanes. If silicates and completely or partially hydrolyzed optionally silanes or siloxanes are used, the hydrolysis is carried out at the factory, so that the ready-to-use products have a reduced alcohol content compared to the unhydrolyzed products or release less alcohol during processing.
  • a passivation layer is generated.
  • the application is effected by a roller arrangement which is passed by the steel sheet. It is then rinsed to remove excess acidic composition.
  • the subsequent drying is carried out here by a drying oven at 150 ° C, which passes through the provided with the first passivation steel sheet within a maximum of 10 minutes. In the same way, the second alkaline coating is produced.
  • Tables 1 and 2 show predominantly compositions of an aqueous acidic composition for a first acidic passivation containing vanadium and tungsten compounds.
  • Chromium (III) sulfate and chromium (III) nitrate are, individually or, as in Experiment 11, together also the main constituent of the composition for passivation. When used as a 20% solution, the proportion of the chromium (III) compound in the passivating composition is between 64.0% by weight and 77.2% by weight.
  • a nitrate compound may also be added in the form of chromium (III) nitrate, it is preferred to add, as shown in Tables 1, 2, a nitrate salt, here sodium nitrate.
  • the proportion of the nitrate compound is preferably between 13% by weight and 16% by weight, but may also be between 5% by weight and 10% by weight.
  • a fluorine salt is preferably used as an optional fluorine source.
  • the statements in Table 1 and 2 are sodium hydrogen difluoride; however, other fluorine compounds named above are also suitable.
  • compositions according to the invention in Tables 1, 2 show that organic acids can be used individually or in combination. These acids act as complexing agents, but also support a low pH. Essential for the adjustment of the pH, however, is above all the addition of an inorganic acid, preferably nitric acid.
  • nitric acid is preferred only because it is considered to be an additional source of nitrate ions.
  • the pH of preferably below 4 is also good with e.g. Sulfuric acid, hydrochloric acid or phosphoric acid, as well as mixtures of inorganic and / or organic acids can be used, see Experiments 11, 12 in Table 2. Small amounts of up to 5% by weight of inorganic acid are usually sufficient to a pH Value ⁇ 4.
  • vanadates and tungstates are carried out in amounts between 0.1% by weight and 5% by weight, preferably in amounts of from 0.5% by weight to 3% by weight.
  • Tables 1, 2 show that even small amounts of vanadates or tungstates or mixtures of vanadates and tungstates significantly increase the corrosion protection effect of a passivation composition.
  • phosphonic acids proves to be advantageous. They act as complexing agents. The addition of individual phosphonic acids is already effective. But also the addition of mixtures of different phosphonic acids shows good results. Phosphonic acids are added in amounts of 0.01% to 5% by weight, preferably in amounts of 0.5% to 3% by weight. It is again expressly noted here that the use of elements or compounds, the vanadium, tungsten, molybdenum, manganese, cerium or lanthanum and phosphonic acid and derivatives thereof, each individually or in any compound good corrosion protection properties guaranteed even at a first acidic passivation.
  • the first acidic passivation is applied to steel sheets having a zinc-iron alloy surface which may be pretreated in a known manner, in particular e.g. cleaned or degreased.
  • first acidic passivation which consists of an aqueous acidic composition was applied to the steel sheet with iron-zinc alloy surface
  • a second alkaline passivation is applied according to the invention.
  • the aqueous acidic compositions for producing a second alkaline passivation which are explained in more detail below, are applied to the first acidic passivation according to embodiments 1 and 2.
  • the aqueous coating composition is alkaline, although a pH of> 9, preferably between pH 10 and pH 12, although by the use of alkalis can be achieved.
  • an alkaline pH is usually already established by using silicates, for example alkali metal silicates.
  • silicates for example alkali metal silicates.
  • polysilicates are used.
  • the solids content (solids based on the total amount of the aqueous solution) is 20% for the preferred lithium polysilicates, 40% for sodium and potassium silicate solutions (water glasses) and 20% for colloidal silicates, with colloidal silicates having a solids content of up to 30%. available and suitable.
  • the molecular weight of the lithium polysilicate is between 200 and 300 g / mol and is thus lower than the molecular weight of the water glasses used. Silane is used in each case with 100% solids. Second alkaline passivation (aqueous composition polysilicate and silane) Silane component Experiment No. lithium polysilicate Experiment No. Natronwasserglas Experiment No.
  • Table 3 shows compositions for a second alkaline passivation, each consisting of a silane-modified silicate, except two reference experiments with lithium polysilicate (Experiment No. 1) and methyltrimethoxysilane (Experiment No. 9).
  • the numerical values give in each case the amount of silane used in% by weight based on the Total composition of the silane and silicate on. It is supplemented with silicate to 100% by weight.
  • an aqueous alkaline composition for producing a second alkaline passivation from vinyltrimethoxysilane and lithium polysilicate (Experiment No. 7) is composed of 5.9% by weight of silane and 94.1% by weight of lithium polysilicate (solids content 20%).
  • the aqueous alkaline composition has an amino-functional, silane-modified lithium polysilicate.
  • An alternative second alkaline passivation is prepared from an aqueous alkaline composition comprising vinyltrimethoxysilane and soda water glass (Run No. 20); this aqueous alkaline composition is composed of 70.2% by weight of silane and 29.8% by weight of silicate (solids content 40%).
  • the aqueous alkaline composition has a vinyl-functional, silane-modified silicate. Used are colloidal silicate, sodium silicate (sodium polysilicate) and lithium polysilicate, the latter being preferred. A fully hydrolyzed product is used so as to allow substantially VOC-free application of the second alkaline passivation.
  • the steel sheet treated with the first acidic passivation according to Embodiments 1 and 2 is dipped in the aqueous composition or coating liquid of a silane-modified silicate and then dried, using the same conditions as described for producing the first acidic passivation.
  • alkaline aqueous compositions which have a silicate modified with various silanes.
  • Table 4 shows those compositions in which up to eight different silanes are used, each for the modification of a silicate.
  • the experiments in Tables 3, 4 show that for the silane-modified silicate, the proportions of silane and silicate can be varied within a wide range.
  • the silicate content can vary between 1% and 99% by weight; it is preferably between 20% by weight and 90% by weight.
  • the silane can be used in the same amounts as the silicate; both are used in complementary proportions, so that they add up to 100% by weight in the formulations given here. Preferably up to 20% by weight of silane are used.
  • lithium polysilicate and silane are used in a ratio of about 1: 1.
  • the first, acidic passivation very thin layers of up to 300 nm are applied, usually up to 150 nm, preferably up to 100 nm. Despite the low layer thickness, the first passivation according to the invention produces good corrosion protection.
  • the second alkaline passivation is applied in a layer thickness of up to 1 ⁇ m, advantageously from 10 nm to 500 nm. The thickness of the second layer is preferably 300 nm here.
  • the aqueous composition for the second alkaline passivation was prepared by co-hydrolysis of the silanes or siloxanes and the silicates, here polysilicates, and then removing the liberated alcohols by means of vacuum distillation.
  • Line 1 of Table 5 shows in each case the corrosion protection results for steel sheets which were tested with first acidic passivation but without second alkaline passivation.
  • Column 1 of Table 5 shows steel sheets tested without first acid passivation but with second alkaline passivation.
  • the test result in column 1 and line 1 shows the test results for a sheet steel without passivation.
  • compositions of the first, acidic passivation of Experiments 1, 5 and 7 were carried out without vanadium or tungsten compounds.
  • second alkaline passivation compositions containing a silane-modified lithium polysilicate are predominantly effective in providing excellent corrosion protection when applied to an acidic passivation (Run 1-13 second passivation).
  • acidic and alkaline passivations according to the invention if the acidic passivation contains vanadium, tungsten or compounds thereof. But even the aqueous alkaline compositions of a silicate modified with several silanes cause predominantly excellent corrosion protection on the surface of an acidic passivation.
  • Alkaline passivation using colloidal silicate or waterglass in combination with silane, ie silane-modified, and applied to an acidic passivation leads to good and sometimes excellent results in the neutral salt spray test.
  • the steel sheets which are not or only provided with an acidic or an alkaline passivation, with a surface coated with a zinc-iron alloy and which also contain a zinc-iron alloy according to the invention with a first acidic passivation and a second alkaline passivation. Alloy surface steel sheets were tested for corrosion resistance in the neutral salt spray test as discussed above. A steel sheet having a zinc-iron alloy surface, however, without any coating shows a corrosion resistance of less than 24 hours (experiment column 1, line 1: -). Zinc-iron alloy-coated steel sheets which had at least obtained an acidic passivation (line 1 tests) or which alone had undergone alkaline passivation (column 1 tests) have low to average corrosion resistance in the salt spray test.
  • Steel sheets with a zinc-iron alloy surface to which both a first acidic passivation and a second, alkaline passivation comprising silane-modified silicates has been applied, generally show at least good, but often outstanding corrosion protection.
  • alkaline passivations with lithium polysilicate predominantly provide excellent corrosion protection, particularly when lithium polysilicate is modified with one or more silanes or siloxanes.
  • colloidal silicates or silica sols also lead to good corrosion protection resistance, especially when the colloidal silicates are modified in conjunction with silanes or siloxanes (experiments lines 28-39, 41, 44). The same applies to silicates which are simultaneously modified in a mixture with several silanes or siloxanes. Here, predominantly excellent results are achieved in the salt spray test.
  • these passivation the good to excellent corrosion protection offer, without cobalt and without chromium (VI) compounds.
  • these acidic and alkaline passivations can be applied substantially VOC-free and dried, not least because preference is given to using completely hydrolyzed silane-modified silicates, in particular polysilicates.

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Claims (18)

  1. Procédé de fabrication d'un substrat métallique pourvu d'une passivation sans chrome-VI et sans cobalt, par application
    (a) d'une première passivation acide, une composition acide aqueuse étant appliquée sur le substrat pour la fabrication de la première passivation acide, composition qui présente un composé du chrome(III) qui est choisi dans le groupe sulfate de chrome(III), hydroxyde de chrome(III), dihydrogénophosphate de chrome(III), chlorure de chrome(III), nitrate de chrome(III), sulfate de sodium et de chrome(III), sulfate de potassium et de chrome(III) et sels de chrome(III) d'acides organiques, la composition présentant le composé de chrome(III) en des quantités d'au moins 0,05 g/l rapporté à la composition acide aqueuse, et un acide phosphonique et/ou ses dérivés en des quantités de 0,5 à 3 % en poids, rapporté à la composition acide aqueuse, et
    (b) d'une seconde passivation alcaline sur le substrat métallique, une composition alcaline aqueuse qui présente des silicates modifiés par un silane et/ou modifiés par un siloxane étant utilisée pour la fabrication de la seconde passivation alcaline.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on applique sur le substrat, avec la seconde passivation alcaline, une composition alcaline aqueuse qui présente un silicate modifié par un silane et/ou modifié par un siloxane, selon une proportion comprise entre 1 % en poids et 99 % en poids de silane.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'on applique sur le substrat métallique, pour la fabrication de la seconde passivation alcaline, une composition alcaline aqueuse qui présente un ou plusieurs silicates du groupe comprenant les sols de silice colloïdaux, le silicate de sodium, de potassium, de lithium et d'ammonium, tous les silicates, même présents sous forme de polysilicates.
  4. Procédé selon la revendication 3, caractérisé en ce qu'on applique pour la fabrication de la seconde passivation alcaline une composition alcaline aqueuse qui présente du polysilicate de lithium ou un mélange de polysilicate de lithium et de sols de silice colloïdaux, du silicate de sodium, de potassium et/ou d'ammonium.
  5. Procédé selon au moins l'une des revendications 1 à 4, caractérisé en ce que la composition alcaline aqueuse appliquée pour la fabrication de la seconde passivation alcaline présente un silane à fonctionnalité vinyle, amino ou époxy et/ou un siloxane ou un mélange de ces silanes ou siloxanes.
  6. Procédé selon la revendication 5, caractérisé en ce que la solution aqueuse appliquée pour la fabrication de la seconde passivation alcaline présente un ou plusieurs silanes du groupe qui comprend le méthacryloxyméthyltriéthoxysilane, le méthacryloxyméthyltriéthoxysilane, le 3-aminopropylméthyldiéthoxysilane, le 3-aminopropyltriéthoxysilane, le N-(2-aminoéthyl)-3-aminopropylméthyldiméthoxysilane, le 3-glycidyloxypropyl-triméthoxysilane, le vinyltriméthoxysilane, le vinyltriéthoxysilane, le méthyltriméthoxysilane, ainsi que le 3-mercaptopropyltriméthoxy-silane, ainsi que les siloxanes.
  7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que la composition alcaline aqueuse utilisée pour la fabrication de la seconde passivation alcaline présente des silicates, des silanes, des siloxanes, des silicates modifiés par un silane et/ou modifiés par un siloxane, qui sont utilisés sous forme partiellement ou complètement hydrolysée.
  8. Procédé selon au moins l'une des revendications précédentes 1 à 7, caractérisé en ce qu'on revêt un substrat qui présente une surface métallique du groupe qui comprend une surface de zinc, d'aluminium, d'un alliage zinc-aluminium, d'un alliage zinc-fer ou d'un alliage de zinc ou d'aluminium avec un ou plusieurs autres métaux.
  9. Procédé selon au moins l'une des revendications précédentes 1 à 9, caractérisé en ce que la seconde passivation alcaline présente une épaisseur de couche de 10 nm à 1 µm, de préférence de 20 nm à 500 nm.
  10. Procédé selon au moins l'une des revendications 1 à 10, caractérisé en ce qu'on applique une première passivation acide, qui éventuellement est ensuite séchée, et qu'on applique sur la première passivation séchée une seconde passivation alcaline.
  11. Procédé selon au moins l'une des revendications 1 à 10, caractérisé en ce qu'on applique sur le substrat, pour la fabrication de la première passivation acide, une composition acide aqueuse qui présente un composé nitrate.
  12. Procédé selon au moins l'une des revendications 1 à 11, caractérisé en ce qu'on applique sur le substrat pour la fabrication de la première passivation acide une composition acide aqueuse qui présente une source de fluor, en choisissant pour la source de fluor un composé du groupe qui comprend l'acide fluorhydrique, l'acide hexafluorotitanique, l'acide hexafluorozirconique, le fluorure de sodium, le fluorure de potassium, le fluorure d'ammonium, le bifluorure de sodium, le bifluorure de potassium et le bifluorure d'ammonium.
  13. Procédé selon au moins l'une des revendications 1 à 12, caractérisé en ce qu'on applique sur le substrat pour la fabrication de la première passivation acide une composition acide aqueuse qui présente un ou plusieurs composés des métaux molybdène, vanadium ou tungstène.
  14. Procédé selon au moins l'une des revendications 1 à 13, caractérisé en ce qu'on applique sur le substrat pour la fabrication de la première passivation acide une composition acide aqueuse qui présente un ou plusieurs des composés du groupe qui comprend le molybdate de potassium, le molybdate de sodium, l'orthovanadate de potassium, le méthavanadate de potassium, l'orthovanadate de sodium, le méthavanadate de sodium, le tungstate de sodium, le paratungstate de sodium et le pentoxyde de vanadium.
  15. Procédé selon l'une des revendications 1 à 14, caractérisé en ce qu'on applique sur le substrat pour la fabrication de la première passivation acide une composition acide, par utilisation d'un ou plusieurs acides du groupe qui comprend l'acide (1-hydroxéthane-1,1-diyl)biphosphonique, l'acide 2-phosphonobutane-1,2,4-tricarboxylique, l'acide aminotriméthylènephosphonique, l'acide éthylènediaminetétraméthylènephosphonique ou l'acide diéthylènetriaminepentaméthylènephosphonique.
  16. Procédé selon l'une des revendications 1 à 14, caractérisé en ce qu'on applique sur le substrat pour la fabrication de la première passivation acide une composition acide aqueuse qui présente des phosphonates seuls ou en mélange, du groupe qui comprend le (1-hydroxyéthane-1,1-diyl)biphosphonate tétrasodique, le (1-hydroxyéthane-1,1-diyl)biphosphonate trisodique, l'éthylènediaminetétraméthylènephosphonate pentasodique ou le diéthylènetriaminepentaméthylènephosphonate heptasodique.
  17. Procédé selon au moins l'une des revendications 1 à 16, caractérisé en ce qu'on applique sur le substrat pour la fabrication de la première passivation acide une composition acide aqueuse qui présente un ou plusieurs des éléments, ou de leurs composés, du groupe qui comprend le molybdène, le manganèse, le cérium, le lanthane.
  18. Procédé selon au moins l'une des revendications précédentes 1 à 17, caractérisé en ce que la première passivation acide présente une épaisseur de couche de 10 nm à 1 µm, de préférence allant jusqu'à 500 nm.
EP14155058.2A 2014-02-13 2014-02-13 Procédé de fabrication d'un substrat avec passivation exempte de chrome VI et de cobalt Active EP2907894B1 (fr)

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EP14155058.2A EP2907894B1 (fr) 2014-02-13 2014-02-13 Procédé de fabrication d'un substrat avec passivation exempte de chrome VI et de cobalt
ES14155058T ES2732264T3 (es) 2014-02-13 2014-02-13 Procedimiento para la preparación de un sustrato provisto de una pasivación libre de cobalto y libre de cromo-VI
RU2015104265A RU2652324C2 (ru) 2014-02-13 2015-02-09 Способ обработки подложки, обеспечивающий пассивацию без участия хрома vi и кобальта
BR102015002873-3A BR102015002873B1 (pt) 2014-02-13 2015-02-10 Processo para a fabricação de um substrato provido com uma apassivação livre de cobalto e livre de cromo vi
KR1020150020590A KR101897771B1 (ko) 2014-02-13 2015-02-11 무-크롬 및 무-코발트 패시베이션이 제공된 기판의 제조방법
MX2015001916A MX369943B (es) 2014-02-13 2015-02-12 Metodo para la fabricacion de un sustrato proporcionado con un pasivado sin cromo vi y sin cobalto.
US14/621,434 US10011907B2 (en) 2014-02-13 2015-02-13 Method for the manufacture of a substrate provided with a chromium VI-free and cobalt-free passivation
CN201510079622.2A CN104846361B (zh) 2014-02-13 2015-02-13 用于制造设置有不含铬vi且不含钴的钝化物的基底的方法

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BR102015002873A2 (pt) 2016-06-21
US20150225856A1 (en) 2015-08-13
KR101897771B1 (ko) 2018-10-04
US10011907B2 (en) 2018-07-03
KR20150095583A (ko) 2015-08-21
RU2015104265A (ru) 2016-08-27
ES2732264T3 (es) 2019-11-21
MX369943B (es) 2019-11-27
MX2015001916A (es) 2015-09-21
CN104846361A (zh) 2015-08-19
EP2907894A1 (fr) 2015-08-19
RU2652324C2 (ru) 2018-04-25
CN104846361B (zh) 2019-07-19

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