EP3093370B1 - Prétraitement des surfaces en zinc avant une zinc - phosphatation - Google Patents

Prétraitement des surfaces en zinc avant une zinc - phosphatation Download PDF

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EP3093370B1
EP3093370B1 EP16175371.0A EP16175371A EP3093370B1 EP 3093370 B1 EP3093370 B1 EP 3093370B1 EP 16175371 A EP16175371 A EP 16175371A EP 3093370 B1 EP3093370 B1 EP 3093370B1
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Prior art keywords
water
acid
component
zinc
soluble
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EP16175371.0A
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German (de)
English (en)
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EP3093370A1 (fr
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Andreas Arnold
Michael Wolpers
Marcel Roth
Uta Sundermeier
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL16175371T priority patent/PL3093370T3/pl
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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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/02—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • 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
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • 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
    • C23C22/60—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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
    • 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

Definitions

  • the present invention relates to a wet-chemical pretreatment of zinc surfaces prior to the application of a corrosion-protective coating.
  • the wet-chemical pretreatment causes the deposition of a thin inorganic coating consisting essentially of oxidic and / or metallic iron.
  • a layer of iron applied according to the invention - referred to below as icing - necessitates an improvement in the achievable corrosion protection of zinc phosphating on zinc surfaces, in which the presence of the heavy metals Ni and / or Cu is largely dispensed with.
  • the icing causes both a reduction in the contact corrosion of assembled metallic components which have zinc and iron surfaces and a reduction of the corrosive paint infiltration at cutting edges of galvanized steel strip with lacquer layer structure.
  • car bodies consist of a large number of sheet-metal parts which are joined together by spot welding.
  • the metallic zinc coatings applied to the steel strip either electrolytically or by hot dip impart a cathodic protective effect which effectively prevents active dissolution of the nobler core material by mechanically induced damage to the zinc coating.
  • the galvanic coupling between the core material and the metallic coating causes a local dissolution of the coating material, which in turn may result in corrosive infiltration of the organic barrier layers at these locations.
  • the phenomenon of Lackenthaftung or "blistering" is therefore observed especially at the cut edges of the sheets.
  • the local activation of such a "defect" cut edge, damage in the metallic coating, spot welding point
  • the corrosive paint release resulting from these "defects” is all the more pronounced the greater the electrical potential difference between the metals in direct contact.
  • the prior art describes various pretreatments that address the problem of edge protection.
  • An essential strategy is to improve the paint adhesion of the organic barrier layer on the surface-treated steel strip.
  • the German Offenlegungsschrift teaches DE 197 33 972 A1 a process for the alkaline passivating pretreatment of galvanized and alloy-galvanized steel surfaces in strip lines.
  • the surface-treated steel strip is brought into contact with an alkaline treatment agent containing magnesium ions, iron (III) ions and a complexing agent.
  • the zinc surface is passivated thereby forming the corrosion protection layer.
  • Such a passivated surface offers according to the teaching of DE19733972 already a paint adhesion, which is comparable to nickel and cobalt-containing processes.
  • this pretreatment can be followed by further treatment steps such as chromium-free post-passivation to improve the corrosion protection before the paint system is applied.
  • the alkaline passivation serves primarily to improve the corrosion protection of chromium-free conversion coatings.
  • the aim is to achieve an alkaline cleaning step that leads to alkaline passivation and subsequent acidic passivation to provide a coating base which is comparable to zinc phosphating and protects against corrosion.
  • the pursued DE 10 2007 021 364 A1 the goal by means of electroless metal cations without electroless deposition to realize a thin metallic coating layer on galvanized steel surfaces, which together with a subsequent passivation to significantly reduce corrosion at cut edges and bimetallic contacts of cut and assembled surface-coated strip steel should make.
  • the icing and tinning of galvanized and alloy-galvanized steel strip is proposed to improve the edge protection.
  • the icing preferably acidic compositions containing iron ions, a complexing agent with oxygen and / or nitrogen ligands and phosphinic acid are used as the reducing agent.
  • the FR 2 352 070 A1 discloses a method and an alkaline aqueous composition for pretreating zinc or zinc alloy surfaces, wherein first the surface is cleaned or degreased with an alkaline cleaner, then contacted with an aqueous alkaline solution, and then an acidic aqueous phosphating solution is subjected.
  • the alkaline aqueous pretreatment solution contains at least one or more ions of a metal selected from iron, nickel, cobalt, titanium, antimony, chromium or manganese, an organic chelating agent and other auxiliaries.
  • the US 3 444 007 A discloses a method and an alkaline aqueous composition for pretreating zinc or zinc alloys, wherein the surface is contacted with an aqueous alkaline solution and then subjected to a chromic acid solution.
  • the alkaline aqueous solution contains iron ions and cobalt ions and an organic chelating agent.
  • the object of the present invention is to further develop the icing of metallic components having zinc surfaces such that, in conjunction with subsequent wet-chemical conversion coatings, improved corrosion protection and paint adhesion on the zinc surfaces results, in particular the edge protection at cut edges of galvanized steel surfaces is to be improved ,
  • Water solubility in the context of the present invention means that the solubility of the compound at a temperature of 25 ° C. and a pressure of 1 bar in deionized water with a conductivity of less than 11 ⁇ Scm -1 is greater than 1 g / l.
  • oxidation level is meant, according to the invention, the hypothetical charge of an atom resulting from the number of electrons of the atom compared to its atomic number that the corresponding atom hypothesizes when electrons are attributed to the electronegativity of the elements forming the molecule or salt where the higher electronegativity element combines all of the electrons it shares with the lower electronegativity elements, while electrons shared by equal elements are each given half to one and half to the other atom.
  • surfaces of galvanized steel and alloy-galvanized steel are considered as zinc surfaces in addition to surfaces of metallic zinc if the zinc coating is at least 5 g / m 2 based on the element zinc and the proportion of zinc in the zinc layer on the steel is at least 40 at% ,
  • Suitable sources of iron ions dissolved in water are all compounds which release iron ions in water.
  • one or more water-soluble salts of di- or trivalent iron in an alkaline composition may serve as a source of iron ions dissolved in water, with the use of water-soluble salts of divalent iron ions being preferred, such as ferrous nitrate or iron (II) sulfate.
  • Particularly suitable water-soluble compounds are the corresponding salts of the ⁇ -hydroxycarboxylic acids having not more than 8 carbon atoms, which in turn are preferably selected from salts of polyhydroxymonocarboxylic acid, polyhydroxydicarboxylic acid each having at least 4 carbon atoms, tartronic acid, glycolic acid, lactic acid and / or ⁇ -hydroxybutyric acid.
  • alkaline compositions for a sufficiently rapid kinetics of icing from aqueous solution, preference is given to those alkaline compositions in which at least 0.1 g / l, preferably at least 1 g / l, particularly preferably at least 2 g / l, of iron ions dissolved in the aqueous phase are included.
  • additional amounts of dissolved iron ions initially cause a further increase in the deposition kinetics, so that, depending on the duration of the application process-related application, a different minimum amount of iron ions in the alkaline composition is opportune.
  • the composition preferably contains at least 3 g / l of iron ions.
  • the upper limit for the amount of iron ions is determined primarily by the stability of the composition and is preferably 50 g / l for an alkaline composition.
  • the amounts with respect to the iron ions in an alkaline composition of course relate to the amount of iron ions available for the icing and thus to the amount of iron ions dissolved in the aqueous phase, for example in hydrated and / or complexed form. Iron ions in non-icing form, eg bound in undissolved iron salts, do not contribute to the proportion of iron ions in the alkaline composition.
  • the molar ratio of iron ions to water-soluble organic carboxylic acids according to component b) and their water-soluble salts in the alkaline composition is not greater than 2: 1. Above this molar ratio, the accelerating effect of the organic carboxylic acids according to component decreases b) already noticeable on icing. Therefore, particularly preferred are alkaline compositions in which the aforementioned molar ratio is not greater than 1: 1. Conversely, a reduction of the aforementioned molar ratio below 1:12 with a constant amount of iron ions, ie a further increase in the proportion of component b), causes no appreciable additional acceleration in the icing of zinc surfaces. Therefore, those alkaline compositions are preferred in which the molar ratio of iron ions to water-soluble organic carboxylic acids according to component b) and their water-soluble salts is at least 1: 12, preferably at least 1: 8.
  • organic carboxylic acids and / or their salts according to component b) are particularly suitable in alkaline compositions, uniform and adequate coating levels of iron on zinc surfaces in to produce a typical for the wet chemical pretreatment time interval.
  • an alkaline composition contains as component b) lysine, serine, threonine, alanine, glycine, aspartic acid, glutamic acid, glutamine and / or their water-soluble salts, particularly preferably lysine, glycine, glutamic acid, glutamine and / or their water-soluble salts, especially preferred is glycine and / or its water-soluble salts.
  • an alkaline composition for the pretreatment of metallic surfaces which have zinc surfaces for which the proportion of glycine and / or its water-soluble salts of water-soluble organic carboxylic acids according to component b) and / or their water-soluble salts is at least 50% by weight. , particularly preferably at least 80 wt .-%, particularly preferably at least 90 wt .-% is.
  • the oxo acids of phosphorus or nitrogen according to component c) of the alkaline composition have reducing properties and thus cause a rapid and homogeneous freezing of the contacted with the alkaline composition zinc surfaces.
  • such alkaline compositions are used for the icing, which contain at least one oxo acid of phosphorus with at least one phosphorus atom in a middle oxidation state and their water-soluble salts as component c).
  • the molar ratio of iron ions to oxo acids of phosphorus or nitrogen according to component c) and their water-soluble salts for economic reasons in the alkaline composition is at least 1:10, preferably at least 1: 6 on these compounds according to component c) be sufficiently large for a sufficient icing of the zinc surfaces.
  • the aforementioned molar ratio in an alkaline composition is not greater than 3: 1, more preferably not greater than 2: 1. It is further preferred if the proportion of oxo acids of phosphorus in an alkaline composition based on the total amount of Components c) at least 50 mol .-%, particularly preferably at least 80 mol .-% is.
  • the compounds according to component c) of an alkaline composition are preferably selected from hyposalphurous acid, hypo nitric acid, nitrous acid, hypophosphoric acid, hypodiphosphonic acid, diphosphoric (III, V) acid, phosphonic acid, diphosphonic acid and phosphinic acid and their water-soluble salts, phosphinic acid and their water-soluble salts are particularly preferred.
  • the alkaline composition therefore preferably additionally contains chelating complexing agents with oxygen and / or nitrogen ligands which are not water-soluble carboxylic acids according to component b) of the alkaline compositions for stabilization.
  • chelating complexing agents with oxygen and / or nitrogen ligands which are not water-soluble carboxylic acids according to component b) of the alkaline compositions for stabilization.
  • alkaline compositions which contain as additional component d) one or more such complexing agents which are selected from water-soluble ⁇ -hydroxycarboxylic acids which have at least one hydroxyl and one carboxyl group and no water-soluble organic carboxylic acids according to component b ), as well as from their water-soluble salts.
  • the water-soluble ⁇ -hydroxycarboxylic acids according to component d) preferably have not more than 8 carbon atoms and are in particular selected from polyhydroxymonocarboxylic acids and / or polyhydroxydicarboxylic acids each having at least 4 carbon atoms, tartronic acid, glycolic acid, lactic acid and / or ⁇ -hydroxybutyric acid and from their water-soluble salts, most preferably selected from lactic acid and / or 2,3,4,5,6-pentahydroxyhexanoic acid and from their water-soluble salts.
  • a particularly effective formulation of the alkaline composition with the above-mentioned complexing agents according to component d) has a molar ratio of iron ions to water-soluble ⁇ -hydroxycarboxylic acids and their water-soluble salts of at least 1: 4, preferably of at least 1: 3, but not greater than 2: 1, preferably not greater than 1: 1.
  • reducing accelerators may be used which are those skilled in the art from the prior art in the phosphating are known. These include hydrazine, hydroxylamine, nitroguanidine, N-methylmorpholine N-oxide, glucoheptonate, ascorbic acid and reducing sugars.
  • the pH of the alkaline composition is preferably not greater than 11.0, more preferably preferably not greater than 10.5, more preferably not greater than 10.0.
  • the alkaline compositions may also contain surface-active compounds, preferably nonionic surfactants, to effect additional cleaning and activation of the metal surfaces so that homogeneous icing on the zinc surfaces is additionally promoted.
  • the nonionic surfactants are preferably selected from one or more ethoxylated and / or propoxylated C 10 -C 18 fatty alcohols having a total of at least two but not more than 12 alkoxy groups, particularly preferably ethoxy and / or propoxy groups, some with an alkyl radical, more preferably with one Methyl, ethyl, propyl, butyl radical may be end-group-capped.
  • the proportion of nonionic surfactants in an alkaline composition for sufficient cleaning and activation of the metal surfaces is preferably at least 0.01 g / l, more preferably at least 0.1 g / l, and for economic reasons preferably not more than 10 g / l nonionic surfactants are included.
  • alkaline compositions do not contain zinc ions in an amount for which the ratio of the total molar fraction of zinc ions and iron ions to the total molar fraction of water-soluble organic carboxylic acids according to component b) and water-soluble organic ⁇ -hydroxycarboxylic acids according to component d) and their respective water-soluble salts greater than 1: 1, more preferably greater than 2: 3.
  • the present invention is further characterized in that no further heavy metals have to be added to an alkaline composition in order to provide improved corrosion protection on the zinc surfaces as part of the icing in conjunction with a subsequent wet chemical conversion treatment.
  • An alkaline composition therefore preferably contains in total less than 50 ppm of metal ions of the elements Ni, Co, Mo, Cr, Ce, V and / or Mn, particularly preferably less than 10 ppm, particularly preferably less than 1 ppm of these elements.
  • the alkaline composition preferably contains less than 1 g / l of water-soluble or water-dispersible organic polymers, since a Carryover of polymeric components from the pretreatment for icing in the subsequent baths for wet-chemical conversion treatment can adversely affect the formation of the conversion layer.
  • water-soluble or water-dispersible polymers are understood as meaning organic compounds which remain in the retentate in an ultrafiltration with a nominal cutoff limit (NMWC) of 10,000 ⁇ .
  • step ii) first of all, a coating layer consisting essentially of oxidic and / or metallic iron is produced on the zinc surfaces ("icing").
  • the metallic component which may be, for example, surfaces of iron, steel and / or aluminum, such an inorganic layer is not detectable.
  • the specific deposition of the passive layer on the zinc surfaces leads in the process according to the invention, in which the icing a passivating wet chemical conversion treatment, surprisingly to a significant improvement in paint adhesion properties of these surfaces and effectively prevents the corrosion of cut edges of galvanized steel and the contact corrosion of the zinc surfaces connected ferrous metals.
  • a passivating wet-chemical conversion treatment is a standard procedure in the steel and automotive industry for pre-treatment before an organic topcoat composition.
  • the metallic component has galvanized steel surfaces.
  • the method in the treatment of galvanized steel strip as it provides excellent edge corrosion protection, and of components consisting of mixed composite and / or assembled metallic components made of galvanized steel, iron and / or steel and possibly aluminum, as it the contact corrosion is greatly reduced.
  • the alkaline cleaning step i) in the process according to the invention is optional and necessary when the surfaces of zinc have impurities in the form of salts and fats, for example drawing fats and corrosion protection oils.
  • step ii) of the process according to the invention takes place in step ii) of the process according to the invention, wherein the manner of bringing into contact with the alkaline composition is not restricted in terms of process technology to a particular method.
  • the zinc surfaces are contacted with the alkaline composition for icing by dipping or spraying.
  • the metallic component is for at least 3 seconds, but not more than 4 minutes at a temperature of at least 30 ° C, more preferably at least 40 ° C, but not more than 70 ° C, more preferably not more than 60 ° C with an alkaline composition brought into contact.
  • the alkaline compositions cause, as already described, an icing of the zinc surfaces.
  • the formation of icing is self-limiting, ie with increasing icing of the zinc surfaces, the deposition rate of iron decreases.
  • the preferred treatment or contact times should be selected in the method according to the invention so that the layer of iron is at least 20 mg / m 2 based on the element iron.
  • the coating of iron on the zinc surfaces can be determined after dissolution of the coating by means of a spectroscopic method which is described in the examples of the present invention.
  • step ii) of the process according to the invention is preferably carried out without external current, i. without applying an external voltage source to the metallic component.
  • step iii) of the process according to the invention step ii) with or without intervening rinsing step as a passivating wet chemical conversion treatment, a zinc phosphating, wherein in the zinc phosphating on the presence of heavy metals Ni and / or Cu due to the previous icing of Zinc surfaces of the metallic component in step ii) can be largely dispensed with.
  • the icing of the zinc surfaces thus provides for subsequent zinc phosphating the unexpected advantage that results for such phosphated zinc surfaces corrosion protection and paint adhesion, which is comparable to the Zinkphosphatleiter of iron or steel surfaces.
  • the pretreated metallic components which have surfaces of zinc directly resulting from a method according to the invention, are then preferably provided with an organic covering layer, with or without an intermediate rinsing and / or drying step.
  • the first cover layer in the pretreatment of already cut, formed and assembled components is usually an electrodeposition paint, more preferably a cathodic dip.
  • organic primer coatings are preferably applied as the first organic cover layer in the anticorrosive or decorative coating of galvanized steel strip following the inventive method.
  • metallic components having surfaces of zinc find use in body construction in automotive manufacturing, shipbuilding, construction and for the production of white goods.
  • compositions (C1-C4) thin coatings of oxidic and / or metallic iron are obtained on the zinc surfaces ("icing"), however, forming particularly homogeneous coatings especially of compositions (C1; C5) containing glycine.
  • the concentration of the active components in an alkaline composition has an immediate effect on the deposition rate, so that dilute compositions must be brought into contact with the galvanized steel surface for longer to obtain a homogeneously coated zinc surface (see C1 compared to C5).
  • Table 2 shows the corrosive infiltration of an immersion paint on electrolytically galvanized steel after the respective process chain for corrosion-protective pretreatment in
  • Nickel-free phosphating 0.13% by weight zinc 0.09% by weight manganese 0.12% by weight nitrate 1.63% by weight phosphate 0.25% by weight Hydroxylamine 0.02% by weight Ammonium 0.10% by weight H 2 SiF 6 Remaining deionized water ( ⁇ ⁇ 1pScm -1 )
  • Free fluoride 40 mg / L Free acid: 1.3 points (pH 3.6) Total acidity: 26 points (pH 8.5) Treatment time at 50 ° C: 180 seconds E3.
  • Nickel-containing phosphating (trication-phosphating): 0.13% by weight zinc 0.09% by weight manganese 0.10% by weight nickel 0.32% by weight nitrate 1.63% by weight phosphate 0.25% by weight Hydroxylamine 0.02% by weight Ammonium 0.10% by weight H 2 SiF 6 Remaining deionized water ( ⁇ ⁇ 1 ⁇ Scm -1 ) Free fluoride: 40 mg / L Free acid: 1.3 points (pH 3.6) Total acid: 26.5 points (pH 8.5) Treatment time at 50 ° C: 180 seconds F. Coating structure: EV2007 (PPG): layer thickness 17-19 ⁇ m
  • the coating weight of zinc phosphate results from the multiplication of the area-related amount of phosphorus with the factor 6.23. 3 quantitative determination of the amount of iron (III) ions by means of a UV photometer (WTW, PhotoFlex®) in 300 ⁇ l sample volume of a 5% strength by weight nitric acid solution, which is used immediately after process step "C" using a measuring cell ring ( Helmut-Fischer) was pipetted onto a defined area of the 1.33 cm 2 galvanized sheet and, after 30 seconds of action at a temperature of 25 ° C., picked up by the same pipette and placed in the UV measuring cuvette in which 5 ml of a 1 , 0% sodium thiocyanate solution were presented, to determine the absorption at a wavelength of 517 nm and temperature of 25 ° C was transferred.
  • WTW UV photometer
  • the calibration was carried out in a two-point method by determining the absorption values of identical volumes (300 ⁇ l) of two standard solutions of ferric nitrate in 5% strength by weight nitric acid, which was used to determine the absorption values at 25 ° C. in the measuring cuvette containing 5 ml of a 1.0% sodium thiocyanate solution.

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  • Engineering & Computer Science (AREA)
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Claims (12)

  1. Procédé de prétraitement de surfaces d'acier galvanisé, caractérisé en ce que les surfaces galvanisées
    ii) sont mises en contact avec une composition alcaline ayant un pH d'au moins 8,5 contenant
    a) au moins 0,01 g/l d'ions fer,
    b) au moins un acide organique hydrosoluble présentant au moins un groupe amino en position α, β ou γ du groupe acide, ainsi que ses sels hydrosolubles,
    c) au moins un oxyacide du phosphore ou de l'azote ainsi que ses sels hydrosolubles, où au moins un atome de phosphore ou d'azote est dans un niveau d'oxydation intermédiaire, et
    iii) sont ensuite mises en contact avec une composition acide aqueuse pour conversion passivante par voie humide, présentant un pH entre 2,5 et 3,6 et
    a) 0,2 à 3,0 g/l d'ions zinc (II),
    b) 5,0 à 30 g/l d'ions phosphate, calculés comme P2O5, et
    c) respectivement moins de 0,1 g/l de composés ioniques des métaux nickel et cobalt, rapportés respectivement à l'élément métallique.
  2. Procédé selon la revendication 1, caractérisé en ce qu'est contenu dans la composition alcaline à l'étape ii) au moins 1 g/l, de préférence au moins 2 g/l, mais en tout pas plus de 10g/l d'ions fer.
  3. Procédé selon une ou deux des revendications précédentes, caractérisé en ce que, dans la composition alcaline à l'étape ii), le rapport molaire des ions fer aux acides carboxyliques organiques hydrosolubles selon les composants b) et leurs sels hydrosolubles est au moins 1 : 12, de préférence au moins 1 : 8, mais pas plus que 2 : 1, de préférence pas plus que 1 : 1.
  4. Procédé selon au moins une des revendications précédentes, caractérisé en ce que, dans la composition alcaline à l'étape ii), les acides carboxyliques organiques hydrosolubles selon les composants b) sont choisis parmi des acides α-aminés présentant de préférence, outre des groupes amino et carboxyles, exclusivement des groupes hydroxyles, et sont particulièrement préférentiellement choisis parmi la lysine, la sérine, la thréonine, l'alanine, la glycine, l'acide asparagique et/ou l'acide glutamique.
  5. Procédé selon au moins une des revendications précédentes, caractérisé en ce que, dans la composition alcaline à l'étape ii), le rapport molaire des ions fer aux oxyacides du phosphore ou de l'azote selon les composants c) et leurs sels hydrosolubles est au moins 1 : 10, de préférence au moins 1 : 6, mais pas plus que 3 : 1, de préférence pas plus de 2 : 1.
  6. Procédé selon au moins une des revendications précédentes, caractérisé en ce que, dans la composition alcaline à l'étape ii), les oxyacides du phosphore ou de l'azote selon les composants c) sont choisis parmi l'acide hyponitreux, l'acide nitreux, l'acide nitrique, l'acide hypophosphorique, l'acide hypodiphosphonique, l'acide (III,V) diphosphorique, l'acide phosphonique, l'acide diphosphonique et/ou l'acide hypophosphoreux, ainsi que leurs sels hydrosolubles.
  7. Procédé selon au moins une des revendications précédentes, caractérisé en ce que, sont contenus en plus dans la composition alcaline à l'étape ii), comme composants d), au moins un acide α-hydroxycarboxylique hydrosoluble présentant au moins un groupe hydroxyle et un groupe carboxyle et aucun acide carboxylique organique hydrosoluble selon les composants b), ainsi que leurs sels hydrosolubles.
  8. Procédé selon la revendication 7, caractérisé en ce que, dans la composition alcaline à l'étape ii), le rapport molaire des ions fer aux acides α-hydroxycarboxyliques hydrosolubles selon les composants d) et leurs sels hydrosolubles est au moins 1 : 4, de préférence au moins 1 : 3, mais pas plus que 2 : 1, de préférence pas plus que 1 : 1.
  9. Procédé selon une ou deux des revendications précédentes 7 et 8, caractérisé en ce que, dans la composition alcaline à l'étape ii), les acides α-hydroxycarboxyliques hydrosolubles selon les composants d) ne présentent pas plus de 8 atomes de carbone et sont choisis de préférence parmi des polyacides hydroxymonocarboniques et/ou des polyacides hydroxydicarboniques avec respectivement au moins 4 atomes de carbone, l'acide tartronique, l'acide glycolique, l'acide lactique et/ou l'acide α-hydroxybutyrique.
  10. Procédé selon au moins une des revendications précédentes, caractérisé en ce que, dans la composition alcaline à l'étape ii), le pH n'est pas supérieur à 11,0, de préférence pas supérieur à 10,5, particulièrement préférentiellement pas supérieur à 10,0.
  11. Procédé selon au moins une des revendications précédentes, caractérisé en ce que, dans la composition alcaline à l'étape ii), les ions zinc ne sont pas contenus à une hauteur telle que le rapport des proportions molaires en ions zinc et fer à la proportion molaire en acides carboxyliques organiques hydrosolubles selon les composants b) et en acides α-hydroxycarboxyliques organiques hydrosolubles selon les composants d) et leurs sels hydrosolubles respectifs est supérieur à 1 : 1, de préférence supérieur à 2 : 3.
  12. Procédé selon au moins une des revendications précédentes, caractérisé en ce que l'étape ii) se fait sans courant externe.
EP16175371.0A 2012-02-24 2013-02-22 Prétraitement des surfaces en zinc avant une zinc - phosphatation Active EP3093370B1 (fr)

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EP16175371.0A EP3093370B1 (fr) 2012-02-24 2013-02-22 Prétraitement des surfaces en zinc avant une zinc - phosphatation
PL16175371T PL3093370T3 (pl) 2012-02-24 2013-02-22 Obróbka wstępna powierzchni cynkowych przed fosforanowaniem cynkowym

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EP12156863.8A EP2631333A1 (fr) 2012-02-24 2012-02-24 Prétraitement de surfaces en zinc avant une passivation
EP16175371.0A EP3093370B1 (fr) 2012-02-24 2013-02-22 Prétraitement des surfaces en zinc avant une zinc - phosphatation
EP13705479.7A EP2817434B1 (fr) 2012-02-24 2013-02-22 Prétraitement de surfaces en zinc avant une passivation

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WO2016120671A1 (fr) * 2015-01-30 2016-08-04 Arcelormittal Procédé de préparation d'une tôle revêtue comprenant l'application d'une solution aqueuse comprenant un aminoacide et utilisation associée pour améliorer les propriétés tribologiques
WO2016120670A1 (fr) * 2015-01-30 2016-08-04 Arcelormittal Procédé de préparation d'une tôle revêtue comprenant l'application d'une solution aqueuse comprenant un aminoacide et utilisation associée pour améliorer la compatibilité avec un adhésif
WO2016120669A1 (fr) 2015-01-30 2016-08-04 Arcelormittal Procédé de préparation d'une tôle revêtue comprenant l'application d'une solution aqueuse comprenant un aminoacide et utilisation associée pour améliorer la résistance à la corrosion
US10882771B2 (en) * 2015-02-06 2021-01-05 Baker Hughes, A Ge Company, Llc Use of phosphino polymer and polyhydroxypolycarboxylic acid as corrosion inhibitor
WO2017109541A1 (fr) 2015-12-21 2017-06-29 Arcelormittal Procédé de production d'une tôle d'acier revêtue de haute résistance présentant une ductilité et une aptitude au formage améliorées, et tôle d'acier revêtue ainsi obtenue
US10683576B2 (en) * 2017-03-27 2020-06-16 Baker Hughes, A Ge Company, Llc Corrosion inhibitors for passivation of galvanized coatings and carbon steel
US10655217B2 (en) * 2018-05-01 2020-05-19 Spts Technologies Limited Method of forming a passivation layer on a substrate
EP3569734A1 (fr) 2018-05-18 2019-11-20 Henkel AG & Co. KGaA Composition de passivation à base de chrome trivalent
FI3663435T3 (fi) 2018-12-05 2024-05-24 Henkel Ag & Co Kgaa Fosfori- ja fosfonihappojen seoksiin perustuva passivointikoostumus
WO2021139955A1 (fr) 2020-01-06 2021-07-15 Henkel Ag & Co. Kgaa Composition de passivation appropriée pour des surfaces internes de réservoirs d'acier revêtus de zinc stockant des hydrocarbures
WO2022148536A1 (fr) 2021-01-06 2022-07-14 Henkel Ag & Co. Kgaa Passivation améliorée à base de cr(iii) pour un acier revêtu de zinc-aluminium
GB2603194A (en) 2021-02-01 2022-08-03 Henkel Ag & Co Kgaa Improved cr(iii) based dry-in-place coating composition for zinc coated steel
CN113913827B (zh) * 2021-09-09 2023-05-16 东风汽车集团股份有限公司 一种调质态镀锌碳素钢金相腐蚀剂及其应用
EP4174211A1 (fr) * 2021-11-02 2023-05-03 Henkel AG & Co. KGaA Traitement en plusieurs étages permettant d'activer le phosphatation au zinc des composants métalliques pourvus de surfaces en zinc

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JP6526968B2 (ja) 2019-06-12
US10227686B2 (en) 2019-03-12
EP3093370A1 (fr) 2016-11-16
AU2013224115B2 (en) 2017-02-02
AU2013224115A1 (en) 2014-09-11
WO2013124400A1 (fr) 2013-08-29
CN104185693A (zh) 2014-12-03
HUE038740T2 (hu) 2018-11-28
EP2817434B1 (fr) 2017-02-01
CA2864467C (fr) 2020-05-05
EP2631333A1 (fr) 2013-08-28
KR20140129238A (ko) 2014-11-06
HUE033958T2 (en) 2018-01-29
CN104185693B (zh) 2016-06-29
US20140360630A1 (en) 2014-12-11
CA2864467A1 (fr) 2013-08-29
PL2817434T3 (pl) 2017-07-31
PL3093370T3 (pl) 2018-07-31
ES2624195T3 (es) 2017-07-13
KR102095832B1 (ko) 2020-04-01
JP2015510550A (ja) 2015-04-09
EP2817434A1 (fr) 2014-12-31
ES2658337T3 (es) 2018-03-09

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