EP2907894B2 - 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
EP2907894B2
EP2907894B2 EP14155058.2A EP14155058A EP2907894B2 EP 2907894 B2 EP2907894 B2 EP 2907894B2 EP 14155058 A EP14155058 A EP 14155058A EP 2907894 B2 EP2907894 B2 EP 2907894B2
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European Patent Office
Prior art keywords
passivation
composition
acidic
alkaline
silane
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EP14155058.2A
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German (de)
English (en)
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EP2907894A1 (fr
EP2907894B1 (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/EP2907894B2/fr
Priority to ES14155058T priority patent/ES2732264T5/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
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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
    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
    • C23C22/73—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
    • 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

  • Chromium(VI) compounds can often no longer be used, and elements such as cobalt and nickel are also often no longer desirable.
  • a chromium(VI)-free and cobalt-free passivation composition is used in the US$4,578,122
  • Nitrate ions and chromium(III) compounds are used in an aqueous acidic solution, with additional activating metal ions, e.g., iron, aluminum, lanthanum, or cerium ions, being added.
  • additional activating metal ions e.g., iron, aluminum, lanthanum, or cerium ions.
  • the ratio of nitrate ions to chromium(III) ions and activating metal ions 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 is not yet optimized with regard to corrosion protection.
  • the WO 95/24517 A1 relates to a coated metal sheet pretreated with an insoluble composite layer containing a siloxane.
  • the composite layer is obtained by rinsing the metal sheet with a basic solution containing at least 0.005 mol/L of a dissolved silicate or a dissolved aluminate, at least 0.1 vol.% of an organofunctional silane, and at least 0.02 vol.% of a crosslinking agent having 2 or 3 trialkoxysilyl groups.
  • the US 2006/0054248 A1 relates to a method for coloring and protecting metal parts from corrosion by applying a solution containing a trivalent chromium compound and at least one other metal salt selected from the group of iron salts, nickel salts, and cobalt salts, which, together with the chromium compound, are capable of coloring the surface of the metal part, and a phosphate, to a surface of the metal part to obtain a colored surface.
  • a top coat is then applied to the colored surface to achieve high corrosion resistance.
  • the cover layer can, for example, be based on an organosilane silicate coating.
  • solutions for treating metal surfaces further 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) and F), a soluble silicate compound compatible with the treatment solution or A), B), C) and D) and G), a mixture of 1-hydroxyethylidene-1,1-diphosphonic acid and citric acid or mixtures of A), B), C) and D) with two or more compounds selected from E), F) and G).
  • the solution can further optionally contain halides or a wetting agent.
  • the US 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 silicon dioxide and/or a colloidal silicate.
  • the agent is preferably used for the direct coating of metallic substrates without prior chromating.
  • 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 passivation solution consists of 20 to 200 g/l of chromium(III) compounds, e.g.
  • chromium chloride or chromium nitrate 20 to 600 g/l of soluble nitrate selected from sodium, potassium or ammonium nitrate, 5 to 100 g/l of fluoride selected from sodium, potassium or ammonium chloride, 5 to 20 g/l of 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 consists of 1 to 200 g/l of a tin(II) or tin(IV) salt and 10 to 700 g/l of a phosphonic acid or its derivatives.
  • the task is therefore to provide a process for the passivation of metallic substrates that produces good corrosion protection and avoids unnecessary risks to health and the environment.
  • the present invention therefore relates to a method for producing a metallic substrate provided with a chromium(VI)-free and cobalt-free passivation by applying (a) a first acidic passivation, wherein to produce the first acidic passivation an aqueous acidic composition is applied to the substrate which comprises a chromium(III) compound selected from the group consisting of 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, wherein the composition comprises the chromium(III) compound in amounts of at least 0.05 g/L, based on the aqueous acidic composition, and a phosphonic acid in amounts of 0.5 to 3 wt.%,
  • the method according to the invention provides for the production of a metallic substrate provided with a chromium(VI)-free and cobalt-free passivation by applying a first acidic and a second alkaline passivation.
  • An aqueous alkaline composition used to produce the second alkaline passivation contains silane-modified silicates. The combination of the two passivations, acidic and alkaline, provides good corrosion protection.
  • the first acidic and second alkaline passivation are applied as aqueous compositions.
  • the term "passivation” refers to both the aqueous composition for passivating the substrate or for applying the aqueous compositions, as well as 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, i.e., the passivation. The coating(s) provide improved protection against corrosion.
  • the first, acidic passivation is chromium(VI)-free and cobalt-free.
  • it is also nickel-free.
  • the substrate or workpiece coated with a first acidic passivation is coated with a second passivation, wherein the second passivation is an alkaline passivation.
  • Corrosion protection is significantly increased by this second alkaline passivation.
  • Workpieces in which the acidic passivation does not contain vanadium or tungsten become significantly more resistant to corrosion by a second alkaline passivation applied to the first acidic passivation.
  • corrosion protection is particularly improved when the first acidic passivation is produced 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 to coat the first acidic passivation.
  • a silicate compound is applied to the first acidic passivation.
  • Typical silicate compounds are water glasses, but aqueous polysilicates or colloidal silicates are also well suited for the second, alkaline passivation. It is preferred that the second alkaline passivation comprises sodium, potassium, lithium, and/or ammonium silicate.
  • a second alkaline passivation comprising a mixture of silicate compounds can also be applied to the workpiece. Both colloidal silicates and dissolved silicates can be used.
  • silane-modified or siloxane-modified silicates in which silanes or siloxanes are bonded to the silicates, preferably polysilicates, have also proven to be well suited for the implementation of the invention. Most silicates form alkaline Solutions or suspensions. However, if necessary, alkalinity can be increased by adding alkalis, such as caustic soda.
  • lithium polysilicate in the aqueous composition for passivating metallic substrates has proven particularly advantageous for producing the second alkaline passivation.
  • Applying an aqueous composition of lithium polysilicate or mixing lithium polysilicate with other water glasses (sodium and/or potassium silicate) or colloidal silica sols to the first acidic passivation results in significantly improved corrosion protection.
  • the use of lithium polysilicate to produce the second alkaline passivation prevents the formation of gray haze on the surface of the metallic substrate passivated according to the invention, which is common for passivations made from aqueous compositions containing 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 enhance corrosion protection.
  • a vinyl and/or aminosilane is used to produce the second alkaline passivation; however, epoxysilanes and the siloxanes of the silanes mentioned above and below are also suitable.
  • alkylalkoxysilanes here: mono-, di-, or trialkylalkoxysilanes, are suitable, individually or in combination with silicates, for building up a corrosion-protective coating on the metallic workpiece already treated with an acidic aqueous composition.
  • silane compounds can be used in mixtures with one another.
  • Particularly suitable silane compounds are methacryloxymethyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane.
  • Silane or siloxane can be used in amounts ranging from 1% to 99% by weight, based on the total amount of the aqueous composition of the second alkaline passivation.
  • aqueous compositions containing only small amounts of silane e.g., up to 20% by weight, demonstrate significantly improved corrosion protection.
  • an aqueous alkaline composition is used to produce the second alkaline passivation, which composition 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, hereinafter: silane-modified silicates, or compounds of a silicate and a siloxane component, hereinafter: siloxane-modified silicates.
  • silanes or siloxanes are typically bound to the silicate(s) as covalent side chains, for example by hydrolysis.
  • silane-modified or siloxane-modified silicates form excellent corrosion protection on a first acidic passivation, far exceeding the effect of a simple acidic or alkaline passivation.
  • the silane-modified or siloxane-modified silicates can be detected on the metallic substrate by means of NMR spectroscopy. In particular, silicon-carbon bonds (SiC bonds) can be detected.
  • the second alkaline passivation forms an excellent basis for further coatings, e.g., color-imparting coatings or coatings containing lubricants or other additives that further improve the usability of the coated surface.
  • silane-modified silicates are mentioned or described in connection with this invention, the use of siloxane-modified silicates is always also meant and encompassed.
  • the second alkaline passivation can be produced from partially or—preferably—fully hydrolyzed silicate and silane or siloxane compounds.
  • the joint hydrolysis of silicates and silanes or siloxanes in aqueous solution results in the formation of the silane-modified or siloxane-modified silicates.
  • the factory-based hydrolysis can remove released alcohols, so that users can be provided with aqueous alkaline compositions that are low in volatile organic compounds (low VOC) or that are free of volatile organic compounds (VOC-free).
  • Typical aqueous alkaline compositions according to the invention for passivating metallic substrates contain a maximum of 1% by weight of alcohol, preferably a maximum of 0.3% by weight of alcohol.
  • additives to the aqueous composition for the second alkaline passivation.
  • These additives are usually added to the liquid composition from which the second alkaline passivation is produced. They exert their effect either during application, as in the case of defoamers or stabilizers, or after application and, if necessary, drying of the second alkaline passivation, as in the case of lubricants or dyes.
  • an aqueous, acidic cobalt- and chromium(VI)-free composition which comprises a chromium(III) compound, an inorganic acid and optionally a fluorine source, and which is characterized in that the aqueous composition comprises a compound of the metals vanadium or tungsten, wherein this metal compound can be used individually or in a mixture with other vanadium or tungsten compounds.
  • Molybdenum, vanadium, and tungsten compounds in combination with the aforementioned, known components of the first acid passivation, already provide excellent corrosion protection.
  • the composition according to the invention exhibits a significantly reduced risk of health and environmental damage both during handling of the aqueous composition, e.g., during coating, and as a fully applied passivation, and can therefore be used with high operational reliability.
  • Molybdenum, vanadium, and tungsten compounds are incorporated into the first acid passivation and provide improved corrosion protection.
  • the aqueous acidic and alkaline compositions used according to the invention for passivating metallic substrates are generally suitable for all metallic surfaces or substrates, but are particularly suitable for workpieces with a surface made of steel, iron, aluminum, or zinc, and in particular for workpieces whose surface is provided with an alloy of one or both of the metals aluminum and zinc with other metals.
  • Typical examples are a zinc-aluminum alloy, an aluminum or zinc alloy with other metals such as iron or magnesium, e.g., with a zinc-iron alloy, all of which can be provided with a corrosion protection coating.
  • the layer thickness of the applied coating of metal or alloy is between 5 ⁇ m and 100 ⁇ m.
  • the metallic alloy applied to a substrate appears as a discrete layer.
  • a typical application is coil coating, i.e., the passivation of strip steel.
  • 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 following compounds are used in the aqueous acidic composition: potassium orthovanadate, potassium metavanadate, sodium orthovanadate, sodium metavanadate, sodium tungstate, sodium paratungstate, and vanadium pentoxide, as well as sodium molybdate and potassium molybdate.
  • compounds of the metals molybdenum, vanadium, and/or tungsten are used, which dissociate in the aqueous acidic composition for passivation, thereby releasing molybdate, vanadate, and/or tungstate anions. Molybdate, vanadate, and tungstate anions are incorporated into the passivation layer and, even during the acidic passivation alone, ensure the development of very good corrosion protection.
  • 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, ethylenediaminetetramethylenephosphonic acid or diethylenetriaminepentamethylenephosphonic acid or mixtures thereof.
  • phosphonic acid salts can also prove advantageous in connection with the invention.
  • phosphonates are particularly suitable, used individually or as a mixture: tetrasodium (1-hydroxyethane-1,1-diyl)bisphosphonate, trisodium (1-hydroxyethane-1,1-diyl)bisphosphonate, pentasodium ethylenediaminetetramethylenephosphonate or heptosodium diethylenetriaminepentamethylenephosphonate.
  • These salts dissociate in the aqueous, acidic passivation composition, making the phosphonates available as complexing agents.
  • Phosphonic acids can also be advantageously used in combination with vanadium and tungsten compounds in acidic aqueous compositions. The use of phosphonic acid as a complexing agent has proven effective in this case.
  • the acidic aqueous compositions for passivating metallic substrates contain one or more elements or compounds from the group comprising molybdenum, manganese, cerium, and lanthanum.
  • the aqueous, acidic passivation composition comprises a chromium(III) compound or a mixture of chromium(III) compounds selected from the group consisting of 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 proven that an aqueous, acidic passivation composition has good corrosion protection 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 up to a maximum of saturation.
  • nitrate compound or a mixture of nitrate compounds to the acidic aqueous passivation composition.
  • nitrogen-containing acids such as nitric acid
  • salts of these acids are also preferably used.
  • Typical salts that are particularly suitable for use in the passivation composition are salts of alkali metals, ammonium salts, or salts of the metal ions contained in the passivation composition, e.g., chromium(III) nitrate.
  • the nitrogen and chromium(III) compounds described above are present in the aqueous, acidic passivation composition essentially in dissociated form.
  • the proportion of nitrate compounds is preferably 5% to 20% by weight, based on the total composition used for passivation.
  • an aqueous, acidic cobalt- and chromium(VI)-free composition for passivating metallic substrates which composition comprises a chromium(III) compound, an acid, metal ions, nitrate ions, and optionally a fluorine source, as well as a phosphonic acid, and which is characterized in that nitrate ions are used to the sum of chromium and metal ions in a ratio of maximum 3:1, preferably maximum 1:3.
  • the reduced use of nitrate proves to be advantageous when using this aqueous acidic composition for passivation because fewer nitrous gases are released.
  • the acidic aqueous composition for passivation be adjusted to a pH value of ⁇ 4, preferably ⁇ 3.
  • an acid or a mixture of acids is added.
  • organic and/or inorganic Acids typically one or more of the acids from 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 organic acids alone do not always ensure the desired pH is achieved, but their addition proves useful because the organic acids also act as complexing agents in the acidic aqueous composition.
  • the aqueous, acidic composition preferably contains a fluorine source.
  • a fluorine source is preferably a compound or a mixture of compounds selected from the group comprising hydrofluoric acid, hexafluorotitanic acid, hexafluorozirconic acid, sodium fluoride (NaF), potassium fluoride (KF), ammonium fluoride (NH4F), sodium bifluoride (NaHF2), potassium bifluoride (KHF2), and ammonium bifluoride (NH4HF2).
  • the fluorine compounds used as fluorine sources are used in an amount of 0.1% 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 essentially composed of substances that are largely harmless to health and have little or no environmental impact. It is free of cobalt, nickel, and chromium(VI) compounds. It is also preferably free of peroxide compounds and can be produced without the use of carboxylic acids. Furthermore, in preferred embodiments, the use of nitrate compounds is minimized, thus significantly reducing the emission of nitrous gases.
  • the application of the aqueous acidic passivation composition takes place at room temperature, at maximum temperatures up to 80 °C.
  • the metallic substrate is immersed in a bath of the aqueous acidic and then the aqueous alkaline passivation composition, but the passivation compositions can also be applied by other common and
  • the passivating compositions can be applied to the metallic substrate using known application methods (spraying, dipping, dip-spin coating, doctor blade coating, rolling).
  • the aqueous passivating compositions are usually applied for a treatment time of between 1 second and 180 seconds, preferably approximately 30 seconds to 120 seconds.
  • the application of the passivating composition can be followed by drying, which can be carried out at temperatures between room temperature and approximately 250°C. Drying is aimed solely at removing excess liquid; complete reaction, e.g., hydrolysis or condensation of the components that form the passivating coating on the metallic substrate, is not necessary.
  • the metallic substrate can be cleaned, especially degreased, before applying the passivation composition.
  • Aqueous solutions for cleaning and degreasing are known in the art.
  • the first acidic passivation layer 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 layer is applied in 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 required to carry out the process according to the invention are preferably supplied as a concentrate that is diluted with water for use in a concentrate:water ratio of 1:5 to 1:20, frequently 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 followed by an alkaline passivation to the metallic substrate. Accordingly, an analysis of the finished coated substrate shows that, starting from the substrate, a first passivation layer is detected, which contains chromium and nitrogen and possibly fluorine, vanadium and/or tungsten, or alternatively other metallic or rare earth elements.
  • this first passivation layer usually does not contain silicon or the elements sodium, potassium, or lithium.
  • a second passivation layer is applied onto 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 generally does not contain chromium, fluorine, tungsten, vanadium, or other metallic or rare earth elements.
  • Non-metallic elements such as carbon, phosphorus, or nitrogen may be detected in both passivation layers.
  • aqueous acidic or alkaline composition for passivation is prepared by mixing or dissolving the individual components.
  • the water is introduced into the liquid composition for passivation, for example, through the aqueous chromium(III) salt solution, in this case a sulfate or nitrate. Smaller amounts are added at the end.
  • aqueous chromium(III) salt solution in this case a sulfate or nitrate. Smaller amounts are added at the end.
  • the aqueous alkaline composition is typically produced by adjusting the solids content or proportion of aqueous silicates by adding appropriate amounts of water and, where appropriate, by mixing in silanes. If silicates and fully or partially hydrolyzed silanes or siloxanes are used, the hydrolysis is carried out in the factory so that the ready-to-use products have a lower alcohol content than the non-hydrolyzed products or release less alcohol during processing.
  • a passivation layer is created on the metallic substrate.
  • the application is carried out by a roller arrangement through which the steel sheet passes. Rinsing is then carried out to remove excess acidic composition. Subsequent drying is carried out in a drying oven at 150 °C, which the steel sheet provided with the initial passivation passes through. within a maximum of 10 minutes.
  • the second alkaline coating is created in the same way.
  • Tables 1 and 2 predominantly show compositions of an aqueous acidic composition for a first acid passivation containing vanadium and tungsten compounds.
  • Chromium(III) sulfate and chromium(III) nitrate are, individually or together, the main components of the passivation composition, as in Experiment 11. When used as a 20% solution, the proportion of the chromium(III) compound in the passivation composition is between 64.0% and 77.2% by weight.
  • a nitrate compound can also be added in the form of chromium(III) nitrate
  • a nitrate salt in this case sodium nitrate, is preferably added, as shown in Tables 1 and 2.
  • the proportion of the nitrate compound is preferably between 13% and 16% by weight, but can also be between 5% and 10% by weight.
  • a fluorine salt is preferably used as an optional fluorine source.
  • the examples shown in Tables 1 and 2 are sodium hydrogen difluoride; however, other fluorine compounds listed above are also suitable.
  • composition according to the invention in Tables 1 and 2 show that organic acids can be used individually or in combination. These acids act as complexing agents but also support a low pH. However, the addition of an inorganic acid, preferably nitric acid, is essential for adjusting the pH.
  • Table 1 Compositions for acid passivation (chromium(III) sulfate) Experiment No.: 1 2 3 4 5 no 1 no 1 no 1 no 1 required 2 Chromium(III) compound Chromium(III) sulfate (solution, 20%) 77.2% 72.7% 72.2% 64.0% 70.0% Nitrate compound Sodium nitrate 9.7% 15.8% 15.8% 13.5% 13.5% Fluorine compound Sodium hydrogen difluoride 3.5% 2.8% 2.8% 2.8% 1.2% Organic acid citric acid 2.5% 2.5% 2.5% Oxalic acid 2.5% 2.5% Inorganic acid Nitric acid HNO 3 3.1% 2.2% 2.2% 2.2% 2.2% Vanadium or tungsten compound Sodium vanadate 1.5% 1.5% Potassium vanadate Vanadyl sulfate 15.0% Sodium tungstate Sodium olybdate 0.5%.
  • nitric acid is only preferred because it is considered an additional source of nitrate ions.
  • the pH value preferably below 4
  • Vanadates and tungstates are added in amounts between 0.1% and 5% by weight, preferably in amounts between 0.5% and 3% by weight.
  • Tables 1 and 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 have proven beneficial. They act as complexing agents. The addition of individual phosphonic acids is already effective. However, the addition of mixtures of different phosphonic acids also 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 expressly noted here again that the use of elements or compounds containing vanadium, tungsten, molybdenum, manganese, cerium, or lanthanum, as well as phosphonic acid, individually or in any combination, ensures good corrosion protection properties even with an initial acid passivation.
  • the first, acidic passivation is applied to steel sheets with a zinc-iron alloy surface, which may have been pretreated in a known manner, in particular, for example, cleaned or degreased.
  • a second alkaline passivation is applied to the dried first acidic passivation, which was applied from an aqueous acidic composition to the steel sheet with an iron-zinc alloy surface.
  • the aqueous alkaline compositions explained in more detail below are applied to the first acidic passivation according to embodiments 1 and 2 to produce a second alkaline passivation.
  • the aqueous coating composition is alkaline, although a pH value > 9, preferably between pH 10 and pH 12, can also be achieved through the use of alkalis.
  • an alkaline pH is usually already established through the use of silicates, e.g. alkali silicates.
  • Polysilicates are used to carry out embodiments 3 and 4.
  • the solids content (solids based on the total amount of the aqueous solution) is 20% for the preferably used lithium polysilicates, 40% for sodium and potassium silicate solutions (water glasses), and 20% for colloidal silicates, although colloidal silicates with a solids content of up to 30% are also 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 100% solids form.
  • Table 3 Second alkaline passivation (aqueous composition polysilicate and silane) Silane component Experiment No. Lithium polysilicate Experiment No. Soda water glass Experiment No.
  • Table 3 shows compositions for a second alkaline passivation, each of which, with the exception of two reference tests with lithium polysilicate (test no. 1) and methyltrimethoxysilane (test no. 9), consists of a silane-modified silicate.
  • the numerical values indicate the amount of silane used in weight percent based on the total composition of silane and silicate. It is supplemented with silicate to 100 weight percent.
  • an aqueous alkaline composition for producing a second alkaline passivation from vinyltrimethoxysilane and lithium polysilicate (test no. 7) consists of 5.9 weight percent silane and 94.1 weight percent lithium polysilicate (solids content 20%).
  • the aqueous alkaline composition therefore contains an amino-functional, silane-modified lithium polysilicate.
  • An alternative second alkaline passivation is prepared from an aqueous alkaline composition comprising vinyltrimethoxysilane and sodium silicate (Test No. 20).
  • This aqueous alkaline composition consists of 70.2% by weight silane and 29.8% by weight silicate (solids content 40%).
  • the aqueous alkaline composition contains a vinyl-functional, silane-modified silicate.
  • Colloidal silicate, sodium silicate (sodium polysilicate), and lithium polysilicate are used, with the latter being preferred.
  • a fully hydrolyzed product is used, allowing for a 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 immersed in the aqueous composition or coating liquid of a silane-modified silicate and then dried using the same conditions as described for the production of the first acid passivation.
  • alkaline, aqueous compositions containing a silicate modified with various silanes are also well-suited as a second alkaline passivation.
  • Table 4 shows such compositions, in which up to eight different silanes are used, each to modify a silicate.
  • the experiments in Tables 3 and 4 show that the proportions of silane and silicate for the silane-modified silicate can be varied within a wide range.
  • the silicate content can vary between 1% and 99% by weight; preferably, it is between 20% 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 specified here. Preferably, up to 20% by weight of silane is used.
  • lithium polysilicate and silane are used in a ratio of approximately 1:1.
  • the first passivation very thin layers of up to 300 nm are applied, usually up to 150 nm, preferably up to 100 nm. Despite the thin layer thickness, the first passivation according to the invention provides 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.
  • the aqueous composition for the second alkaline passivation was prepared by joint hydrolysis of the silanes or siloxanes and the silicates, here polysilicates, and subsequent removal of the released alcohols by vacuum distillation.
  • compositions described in Tables 1-4 for the first, acidic passivation (Tables 1, 2) and the second, alkaline passivation (Tables 3, 4) were applied sequentially to steel sheets as explained above in connection with the application of the first, acidic passivation.
  • Row 1 of Table 5 shows the corrosion protection results for steel sheets tested with the first acid passivation but without the second alkaline passivation.
  • Column 1 of Table 5 shows steel sheets tested without the first acid passivation but with the second alkaline passivation.
  • the test results in column 1 and row 1 show the test results for a steel sheet without passivation.
  • compositions of the first acid passivation of experiments 1, 5 and 7 were carried out without vanadium or tungsten compounds.
  • compositions for the second alkaline passivation containing a silane-modified lithium polysilicate predominantly provide excellent corrosion protection when applied over an acidic passivation (tests 1-13 of the second passivation).
  • Acidic and alkaline passivations according to the invention provide particularly good results when the acidic passivation contains vanadium, tungsten, or their compounds.
  • the aqueous alkaline compositions consisting of a silicate modified with multiple silanes also predominantly provide excellent corrosion protection on the substrate of an acidic passivation.
  • Steel sheets with no or only acid or alkaline passivation and a surface coated with a zinc-iron alloy coated, and the steel sheets having a zinc-iron alloy surface provided according to the invention with a first acid passivation and a second alkaline passivation were also tested for their corrosion resistance in the neutral salt spray test as explained above.
  • a steel sheet with a zinc-iron alloy surface, but without any coating, shows a corrosion resistance of less than 24 hours (test column 1, line 1: --).
  • Zinc-iron alloy-coated steel sheets that had at least received acid passivation (tests in line 1) or that had only received alkaline passivation (tests in column 1) show low to average corrosion resistance in the salt spray test.
  • Steel sheets with a zinc-iron alloy surface to which both a first acid passivation and a second, alkaline passivation comprising silane-modified silicates have been applied generally show at least good, but often excellent, corrosion protection.
  • alkaline passivations with lithium polysilicate predominantly provide excellent corrosion protection, especially when lithium polysilicate is modified with one or more silanes or siloxanes.
  • colloidal silicates or silica sols also provide good corrosion protection, especially when the colloidal silicates are modified in combination with silanes or siloxanes (tests lines 28-39; 41, 44). The same applies to silicates modified in a mixture with several silanes or siloxanes simultaneously. In these cases, excellent results are predominantly achieved in the salt spray test.
  • these passivations which offer good to excellent corrosion protection, do not contain cobalt or chromium(VI) compounds. It is also worth noting that these acidic and alkaline passivations can be applied and dried essentially VOC-free, not least because fully hydrolyzed silane-modified silicates, especially polysilicates, are preferred.
  • the effect of the second alkaline passivation does not depend on the composition of the first acidic passivation. Rather, it is shown that the combination of an acidic and an alkaline passivation can achieve good to very good corrosion protection even if, for example, the acidic passivation contains few or no vanadium or tungsten compounds or phosphonic acid.

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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 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-triméthoxy-silane, 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 EP2907894B2 (fr)

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EP14155058.2A EP2907894B2 (fr) 2014-02-13 2014-02-13 Procédé de fabrication d'un substrat avec passivation exempte de chrome VI et de cobalt
ES14155058T ES2732264T5 (en) 2014-02-13 2014-02-13 Method for production of a substrate with a chromium vi free and cobalt-free passivation
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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EP2907894A1 (fr) 2015-08-19
RU2015104265A (ru) 2016-08-27
KR20150095583A (ko) 2015-08-21
BR102015002873A2 (pt) 2016-06-21
ES2732264T5 (en) 2025-06-26
CN104846361B (zh) 2019-07-19
MX369943B (es) 2019-11-27
US20150225856A1 (en) 2015-08-13
BR102015002873B1 (pt) 2022-01-25
US10011907B2 (en) 2018-07-03
ES2732264T3 (es) 2019-11-21
RU2652324C2 (ru) 2018-04-25
EP2907894B1 (fr) 2019-04-10
MX2015001916A (es) 2015-09-21
CN104846361A (zh) 2015-08-19

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