EP2255026B1 - Passivation optimisée à base de ti-zr de surfaces métalliques - Google Patents

Passivation optimisée à base de ti-zr de surfaces métalliques Download PDF

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Publication number
EP2255026B1
EP2255026B1 EP09721282.3A EP09721282A EP2255026B1 EP 2255026 B1 EP2255026 B1 EP 2255026B1 EP 09721282 A EP09721282 A EP 09721282A EP 2255026 B1 EP2255026 B1 EP 2255026B1
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agent
water
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English (en)
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EP2255026A1 (fr
Inventor
Jan-Willem Brouwer
Jens KRÖMER
Sophie Cornen
Michael Frank
Nicole Heischkamp
Franz-Adolf Czika
Nicole TEUBERT
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/20—Pretreatment

Definitions

  • the present invention relates to a chromium-free aqueous agent based on water-soluble compounds of titanium and / or zirconium and a process for the corrosion-protective conversion treatment of metallic surfaces.
  • the chromium-free aqueous agent is suitable for treating various metallic materials joined together in composite structures, including steel or galvanized or alloy-galvanized steel, and any combination of these materials.
  • surfaces of aluminum and its alloys can be treated with the agent according to the invention to protect against corrosion.
  • the corrosion protection treatment is intended above all as a pretreatment for a subsequent dip coating.
  • the invention further comprises a metallic substrate, which has been treated according to a predetermined sequence of processes with the chromium-free agent according to the invention, and its use, in particular in the automotive production of bodies.
  • Anticorrosion agents which are an acidic aqueous solution of fluoro complexes, have long been known. They are increasingly used as a replacement for chromating, which are increasingly less used because of the toxicological properties of chromium compounds. As a rule, such solutions of fluoro-complexes contain further anti-corrosive agents that further improve the anti-corrosion effect and paint adhesion.
  • a treating solution which is an aqueous solution of ammonium hexafluorozirconate, sodium nitrate, cobalt nitrate and sodium m-nitrobenzenesulfonate and a pH of 5.2.
  • the solution can be used to treat zinc, steel or aluminum surfaces.
  • EP-A-1 571 237 describes a treatment solution and treatment method for iron, zinc, aluminum and magnesium containing surfaces. This solution has a pH in the range of 2 to 6 and contains 5 to 5000 ppm of zirconium and / or titanium and 0.1 to 100 ppm of free fluoride.
  • the solution may contain further components selected from chlorate, bromate, nitrite, nitrate, permanganate, vanadate, hydrogen peroxide, tungstate, molybdate or in each case the associated acids.
  • Organic polymers may also be present.
  • the WO 93/05198 describes a "dry-in-place" process in which chromium-free compositions containing as one component fluorocomplexes of titanium, zirconium, hafnium, silicon and boron and as a second component cations of elements selected from cobalt, magnesium, titanium, zinc, nickel, tin , Zirconium, iron, aluminum and copper, both components must be in a certain minimum ratio to one another, in particular be applied to galvanized steel surfaces.
  • the advantageous effect of compositions containing compounds of cobalt or magnesium as the second component is documented.
  • WO 07/065645 From the WO 07/065645 are also aqueous compositions that contain fluorocomplexes of, inter alia, titanium and / or zirconium, wherein in addition a further component is included, which is selected from: nitrate ions, copper ions, silver ions, vanadium or vanadate ions , Bismuth ions, magnesium ions, zinc ions, manganese ions, cobalt ions, nickel ions, tin ions, buffer systems for the pH range from 2.5 to 5.5, aromatic carboxylic acids having at least two groups containing donor atoms, or derivatives of such carboxylic acids, silica particles having a mean particle size below 1 micron.
  • a further component which is selected from: nitrate ions, copper ions, silver ions, vanadium or vanadate ions , Bismuth ions, magnesium ions, zinc ions, manganese ions, cobalt ions, nickel ions, tin ions,
  • WO 07/065645 further teaches that for the suppression of excess free fluoride aluminum ions as "Fluoride scavengers" can be added, but without specifying what characterizes an excess of free fluoride and under what conditions aluminum ions can be used as a "fluoride scavenger".
  • the EP 1405933 discloses a composition for the treatment of surfaces of iron and / or zinc containing at least one metal from the group Ti, Zr, Hf and Si and a fluorine ion source, wherein as a condition of the concentration ratios of these two components is provided that the amount of free Fluoride ions does not exceed 500 ppm.
  • fluoride scavenger compounds containing the elements silver, aluminum, copper, iron, manganese, magnesium, nickel, cobalt and zinc are named.
  • the object of the present invention is now to provide an aqueous chromium-free, titanium and / or zirconium-based agent for the conversion treatment of metallic surfaces which, for high fluoride contents of the composition, further optimally passivates the treated metal surface so that the directly treated metallic component on the one hand, a sufficient temporary protection against corrosion is imparted and on the other hand, in cooperation with an organic primer coating or an organic dip paint the high demands on a permanent corrosion protection are met, with an extremely good paint adhesion is guaranteed.
  • High fluoride contents according to the task are then present in the aqueous medium, if the total number of fluorine atoms is greater than the number of maximum complexable by the elements of titanium and / or zirconium fluorine atoms, ie if the molar ratio of the total Fluorine atoms to the total number of titanium and / or zirconium atoms exceeds 6.
  • compositions according to the invention which have this concrete molar ratio D: B of z - 6 4 ⁇ z do not fall below, produce a sufficiently passivating conversion of the metal surfaces, especially when used in the dipping process.
  • the minimum concentration according to the invention of the elements titanium and / or zirconium of the components (A) represents a threshold value with regard to the conversion layer formation and must therefore be present in the aqueous medium. If the concentration is below this value, there is no homogeneous conversion of the metallic surface to form a mixed oxydic-hydroxidic zirconium-containing passive layer and the layer supports based on the elements titanium and / or zirconium are significantly below 20 mg / m 2 . In such a case, the deposition of copper dominates, while the passivating surface layer formation almost completely disappears.
  • concentrations of the elements titanium and / or zirconium according to the components (A) of more than 2.0 ⁇ 10 -2 mol / l in the aqueous medium are not economical and, in addition, do not give any additional advantages in the treatment of metallic components of corrosion protection. Rather, such high concentrations complicate the processability and increase the operating costs of the conversion baths due to inevitably incurred additional regeneration and reprocessing measures.
  • aqueous chromium-free compositions whose component (A) consists exclusively of water-soluble compounds of zirconium.
  • the quotient D: B of at least z - 6 4 ⁇ z can therefore also be regarded as a guideline for a composition according to the invention which, regardless of the special procedure when contacting the composition causes a sufficient passivating conversion of the metal surface, wherein for such a sufficient conversion additionally the condition must be satisfied that the quotient D: B does not fall below a value of less than 20 mg on the layer after contact of the agent with an iron surface, preferably with an unalloyed steel surface, for a treatment time of 90 s and a treatment temperature of 30 ° C. m 2 is obtained based on the elements of component (A) selected from titanium and / or zirconium.
  • aqueous agents are advantageous for conversion layer formation in which the molar ratio D: B of the total number of metal atoms of component (D) to the total number of fluorine atoms of component (B) is not less than z - 6 3 ⁇ z . preferably not less than z - 6 2 ⁇ z is.
  • the advantageous effect consists in the displacement of the composition of the conversion layer after treatment of a metallic surface with the agent according to the invention in favor of higher layer supports with respect to the elements titanium and / or zirconium, in particular relative to the layer of copper, so that increased corrosion protection and improved adhesion properties applied to subsequently organic topcoats are the result.
  • the chromium-free and titanium and / or zirconium-based agent is preferably used according to the invention when the molar ratio D: B does not exceed values for which, after contacting the agent with an iron surface, preferably with a carbon steel surface at a treatment time of 90 s and a treatment temperature of 30 ° C on this a layer of less than 20 mg / m 2 based on the elements the component (A) selected from titanium and / or zirconium results. It could be shown in this context that closed homogeneous conversion layers are formed only at layer supports of the elements titanium and / or zirconium of about 20 mg / m 2 .
  • such passive layers preferably have a layer support based on the elements titanium and / or zirconium of component (A) of at least 20 mg / m 2 , more preferably of at least 40 mg / m 2 , wherein at the same time based on the layer support preferably does not exceed 100 mg / m 2 , more preferably 80 mg / m 2 , but preferably at least 10 mg / m 2 of copper deposited according to component (C).
  • those agents according to the invention are preferred for which the molar ratio A: C of the total number of atoms of the elements titanium and / or zirconium of component (A) to the total number of copper atoms of component (C) is not less than 1: 3, preferably not less than 2: 3. If the ratio A: C falls short of the preferred range in the composition according to the invention, although sufficient inorganic conversion of the metallic surface can take place, the layer deposits with respect to copper are generally above 100 mg / m 2 . In the extreme case, ie, significantly below the preferred ratio, the titanium and / or zirconium-based conversion is largely suppressed and wipeable coatings of amorphous metallic copper are the result.
  • those agents according to the invention are preferred in which the ratio A: C of the total number of atoms of the elements titanium and / or zirconium the component (A) to the total number of copper atoms of component (C) does not exceed values for which, after contacting the agent with an iron surface, preferably with a carbon steel surface at a treatment time of 90 s and a treatment temperature of 30 ° C on this one layer of less than 20 mg / m 2 based on the elements of component (A) selected from titanium and / or zirconium or more than 100 mg / m 2 based on the element copper of component (C) results ,
  • Water-soluble compounds according to the invention corresponding to components (A) - (D) are characterized by being themselves in chemical equilibrium in aqueous solution with ionic species containing the respective named elements or with ionic species of the named elements themselves.
  • the resulting in the aqueous solution chemical equilibrium between ionic species and undissociated water-soluble compound according to the components (A) - (D) must be qualitatively detectable by conventional methods, i. the ionic species must be present in the aqueous phase as such at least in an analytically determinable amount.
  • water-dispersible compounds of the invention corresponding to component (D) are characterized solely by their ionogenic structure and contain at least one of the respective named elements according to component (D) as an ionic constituent in an inorganic matrix.
  • the proportion of the ionic species in the aqueous phase is predetermined by the solubility product of the water-dispersible compound.
  • Preferred water-soluble compounds of component (A) are compounds which dissociate in aqueous solution into anions of fluorocomplexes of the elements titanium and / or zirconium. Such preferred compounds are, for example, H 2 ZrF 6 , K 2 ZrF 6 , Na 2 ZrF 6 and (NH 4 ) 2 ZrF 6 and the analogous titanium compounds. Such fluorine-containing compounds according to component (A) are simultaneously inventive water-soluble compounds according to component (B) and vice versa. Also fluorine-free compounds of the elements titanium and / or zirconium can be used according to the invention as water-soluble compounds according to component (A), for example (NH 4 ) 2 Zr (OH) 2 (CO 3 ) 2 or TiO (SO 4 ).
  • Preferred water-soluble compounds of component (B) which serve as a source of fluoride ions are, in addition to the fluorometallates already mentioned, hydrogen fluoride, alkali fluorides, ammonium fluoride and / or ammonium bifluoride.
  • Preferred water-soluble compounds of component (C) which release copper ions are all water-soluble copper salts containing no chloride ions. Particularly preferred are copper sulfate, copper nitrate and copper acetate.
  • component (D) these include all water-soluble salts of the aforementioned metals according to component (D), which contain neither fluoride nor chloride ions.
  • typical compounds according to component (D) may be mentioned at this point: calcium citrate, aluminum nitrate, iron (III) nitrate, iron (II) sulfate.
  • Preferred water-dispersible compounds of component (D) are compounds based on silicates containing aluminum, more preferably compounds of aluminum silicates with a ratio of aluminum to silicon atoms of at least 1: 3.
  • aluminum silicates are the Molar formula (Na, K) x (Ca, Mg) 1-x Al 2-x Si 2 + x O 8 (where 0 ⁇ x ⁇ 1) is preferred, wherein the compound is preferably a zeolite with respect to their crystal morphology.
  • chromium-free compositions according to the invention in which the total content of fluorine atoms corresponding to component (B) is limited to 3 g / l, preferably to 2 g / l and more preferably to 1 g / l.
  • Higher levels of fluorine are uneconomical because of the then significant levels of compounds according to component (D) and increase the operating costs of the conversion baths due to the inevitable additional regeneration and reprocessing measures.
  • the present invention is further characterized in that the chromium-free agent is not an additional polymeric agent for effective passivating treatment Must contain connections.
  • organic polymers such as derivatives of polyacrylates, polyvinyl alcohols, polyvinylphenols, polyvinylpyrrolidones or block copolymers consisting of structural units of the aforementioned polymers may be useful for the stability of compositions of the invention containing water-dispersible compounds according to component (D). It is therefore preferred that the total content of organic polymers in the composition according to the invention is less than 50 ppm, preferably less than 10 ppm and more preferably less than 1 ppm. In a specific embodiment, the agent according to the invention contains no organic polymer.
  • a proportion of phosphate anions in the composition according to the invention generally results in the treatment of metallic surfaces to phosphate-containing conversion layers containing a high proportion of bonded metal cations of the respective pickled substrate, especially zinc and iron cations.
  • passive layers also have anti-corrosive properties, but are significantly different from titanium and / or zirconium-based conversion layers based on phosphate-free agents of the invention.
  • the agent according to the invention therefore contains less than 5 ppm and particularly preferably no oxo anions of phosphorus.
  • the pH of the agent according to the invention is preferably not less than 2.5, more preferably not less than 3.5, but wherein a pH of preferably 5, more preferably 4.5 is not exceeded.
  • the pH is adjusted to the said acidic range by using, as component (A) or component (B), the fluoro-complexes of the elements titanium and / or zirconium at least partially in the form of an acid.
  • it can also be adjusted by another acid, for example nitric acid and sulfuric acid.
  • the pH may be adjusted accordingly by the addition of alkali metal hydroxides or carbonates, ammonia or organic amines.
  • a buffer system which has at least one protolysis equilibrium with a pK value in the range from 2.5 to 5 is additionally contained for adjusting the total acid content.
  • a buffer system for said pH range an acetic acid / acetate buffer is particularly suitable.
  • Another suitable buffer system based on potassium hydrogen phthalate.
  • An increase in the total acid content by the addition of a buffer system increases the stability of the agent according to the invention and facilitates the pH fixation of the agent.
  • the adjustment of the agent according to the invention to a defined pH value is necessary when using it, for example as a dip bath in a continuous process for the corrosion-protective treatment of metallic components for a constant quality of the conversion layer.
  • Such a buffer capacity of the agent according to the invention is also present when the total acid content based on the total fluorine content is preferably not less than 5 points, more preferably not less than 6 points, but preferably not more than 10 points per 100 ppm fluorine.
  • the aqueous treatment solution may contain compounds which are used as so-called “accelerators” in the layer-forming phosphating. These accelerators have the property of trapping hydrogen atoms which form during the pickling attack of the acid on the metal surface. This reaction, also referred to as "depolarization", facilitates the attack of the acidic treatment solution on the metal surface and thereby accelerates the formation of the corrosion protection layer.
  • a non-exhaustive list of preferred accelerators in the respective preferred concentration ranges is given below: 0.05 to 2 g / l m-nitrobenzenesulfonate ions, 0.1 to 10 g / l Hydroxylamine in free or bound form, 0.05 to 2 g / l m-nitrobenzoate ions, 0.05 to 2 g / l pN itrophenol, 1 to 70 mg / l Hydrogen peroxide in free or bound form, 0.05 to 10 g / l organic N-oxides 0.1 to 3 g / l nitroguanidine 1 to 500 mg / l Nitrite ions 1 to 1000 mg / l Nitrate ions 0.5 to 5 g / l Chlorate ions.
  • the agent of the present invention can be prepared on-site by dissolving said components (A) - (D) in water and adjusting the pH.
  • this procedure is unusual in practice.
  • aqueous concentrates are usually provided, from which the ready-to-use chromium-free agent is prepared on site by dilution with water and, if necessary, adjusting the pH.
  • an aqueous concentrate which when diluted with water includes an acidic, chromium-free, by a factor of about 10 to about 100, more preferably a factor in the range of about 20 to about 50 and, if necessary, after adjusting the pH.
  • aqueous solution according to the above description of the invention also forms the subject of the present invention.
  • the present invention relates to a process for the anticorrosive conversion treatment of metallic surfaces, wherein the cleaned metallic surface is brought into contact with the aqueous chromium-free agent according to the invention.
  • the temperature of the composition according to the invention is preferably in the range of 15 to 60 ° C, in particular in the range of 25 to 50 ° C.
  • the time required for treatment is a time interval which is matched to the convection in the bath system and typical for the composition of the metallic component to be treated.
  • the contact time with the chromium-free agent is preferably at least 30 seconds, more preferably at least 1 minute, but should preferably be 10 minutes , more preferably 5 minutes. After this contact is preferably rinsed with water, especially with demineralized water.
  • the metal surfaces to be treated are previously freed of oil and grease residues in a cleaning step. At the same time a reproducible metal surface is produced, which ensures a consistent layer quality after the conversion treatment with the agent according to the invention. This is preferably an alkaline cleaning with commercially available products known to the person skilled in the art.
  • the metallic surfaces which can be pretreated with the agent according to the invention to protect against corrosion also include aluminum and zinc as well as the respective alloys having an aluminum or zinc alloy content of at least 50 at.%.
  • the metallic surface treated in the method according to the invention is preferably a "bare" metal surface.
  • bare metal surfaces are meant metal surfaces that do not yet carry a corrosion-protective coating.
  • the method according to the invention is the first or only treatment step which produces a corrosion protection layer, which in turn can serve as the basis for a subsequent coating. It is therefore not a post-treatment of a previously generated corrosion protection layer such as a phosphate layer.
  • no measures are required and should preferably even be avoided by which the metal surface is dried after contact with the chromium-free agent and before coating with a dip paint, for example a cathodic electrodeposition paint.
  • a dip paint for example a cathodic electrodeposition paint.
  • unintentional drying may occur during system downtime when the treated metal surface, such as an automobile body or part thereof, is in the air between the bath containing the agent of the invention and the dip bath.
  • this unintentional drying is harmless.
  • immersion paint refers to those aqueous dispersions of organic polymers which are applied to the metal surface in the immersion process both without external current, ie self-deposited, and those in which coating with the paint from the aqueous phase takes place by applying an external voltage source.
  • the present invention comprises a metallic substrate which has been treated with the agent according to the invention in accordance with the method described above, the surface of the metallic substrate having a titanium and / or zirconium deposit of preferably not less than 20 mg / m 2 and preferably not more than 150 mg / m 2 .
  • the layer based on copper pad does not exceed 100 mg / m 2, preferably 80 mg / m 2, but a minimum of 10 mg / m 2 of copper deposited.
  • conversion-treated metallic materials, components and composite structures are used in the manufacture of semi-finished products, in automotive production in body construction, in shipbuilding, in construction and in the field of architecture as well as for the production of white goods and electronic housings.
  • aqueous chromium-free composition according to the invention and the corresponding process sequence for the conversion treatment of metallic surfaces were tested on cold rolled steel test sheets (CRS ST1405, Sidca or MBS 25, Chemetall).
  • the sheets were first cleaned alkaline at 60 ° C for 5 min and degreased.
  • surfactant mixtures of commercial products of the applicant were used: a mixture containing 3% Ridoline ® 1574A and 0.3% Ridosol ® 1270. This was followed by a rinsing with hot water followed by a further rinse with deionized water ( ⁇ ⁇ 1 ⁇ Scm -1) before the cold-rolled steel sheets were treated with a chromium-free agent at 30 ° C for 90 seconds.
  • the freshly treated steel sheets were subjected to a "hot water test".
  • the homogeneity of the conversion coating is checked and evaluated after treatment with the agent according to the invention.
  • the freshly treated steel sheets were first blown dry, then immediately dipped at 20 ° C for 30 sec in process water and then dried in air.
  • service water is the water which has a predetermined range of values for specific characteristics selected from the conductivity, the pH, the chloride and nitrate ion content and the copper content.
  • domestic hot water for use in the "domestic water test" according to the invention must comply with the requirements of EU Directive 98/83 / EC, whereby in particular the chemical parameters for the process water listed in the following table are binding for the performance of the "domestic water test". are.
  • parameter Key figures conductivity 500-900 ⁇ Scm -1 at 20 ° C PH value 6.5-7.5 chloride ⁇ 250 ppm nitrate ⁇ 50 ppm copper ⁇ 0.1 ppm Remaining heavy metals ⁇ 500 ppb
  • Red rust refers to the red-appearing corrosion products of iron, typically iron oxide.
  • the formation of red rust occurs almost instantaneously on exposure of iron in a humid atmosphere.
  • a thin process water film on a surface of iron is sufficient to initiate the formation of red rust.
  • the formation of red rust comes to a standstill in a dry atmosphere, so that a good assessment of the homogeneity of a corrosion-protective conversion layer formation on iron surfaces via the induced formation of red rust is possible. If the steel surface treated with the chromium-free agent yields a homogeneous, closed conversion layer, the formation of red rust is minimal or invisible to the human eye. Conversely, in the "process water test" macroscopic defects are formed Insufficient layer formation or clearly visible on too thin passive layers Red rust.
  • Table 1 shows chromium-free zirconium-based anticorrosive pretreatment agents for metal surfaces applied to cold-rolled steel according to the method described above.
  • the synergistic effect which is that the conversion layer formation is accelerated, is independent of the total amount of zirconium (B2) at a constant molar ratio of zirconium to copper fraction (A: C). At least with regard to the formation of red rust after the "hot water test", higher proportions of copper deposited in the conversion layer behave indifferent, as can be seen from the comparison of the inventive examples B1 and B2.
  • Another aspect of the present invention consists in the total fluoride content relative to the proportion of "fluoride scavenger” (component D), which according to the invention must not fall below a certain value.
  • component D the proportion of "fluoride scavenger”
  • the examples VB2 and B1 is clear in comparison that the doubled fluoride content (component B) (to a complete inhibition of the conversion layer formation while maintaining the same amount of iron ions (VB2) layer pad Zr: ⁇ 1.5 mg / m 2 ) leads and only metallic copper deposits on the steel surface (coating layer Cu: 67 mg / m 2 ).
  • the molar ratio D: B according to the invention of the "fluoride scavenger" iron to the total fluorine content of 1: 7.6 is significantly below the actual ratio 1:22.
  • chromium-free compositions according to the invention containing exclusively aluminum as the "fluoride scavenger" (component D)
  • component D the relative content of aluminum based on the fluorine content determines the quality of the conversion layer formation.
  • Table 2 lists this chromium-free agent with increasing zirconium content (component A) and at the same time decreasing proportion of copper ions (component C), the example according to the invention has a molar ratio D: B of aluminum to fluorine of 1: 4.

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Claims (14)

  1. Agent aqueux exempt de chrome pour le traitement par conversion anticorrosion de surfaces métalliques contenant
    (A) un ou plusieurs composés solubles dans l'eau contenant au moins un atome choisi parmi les éléments titane et/ou du zirconium, la concentration totale de ces éléments de dépassant 2,5•104 mol/l, mais n'étant non supérieure à 2,0•102 mol/l.
    (B) un ou plusieurs composés solubles dans l'eau servant de source d'ions fluorure contenant au moins un atome de fluor,
    l'agent contenant lesdits éléments des composants respectifs (A) et (B) dans un rapport molaire A:B de 1 :z, z étant un nombre réel supérieur à 6,
    caractérisé en ce que l'agent contient en plus
    (C) un ou plusieurs composés solubles dans l'eau qui libèrent des ions de cuivre, contenant au moins un atome de cuivre, et
    (D) un ou plusieurs composés solubles dans l'eau et/ou dispersibles dans l'eau qui libèrent des ions métalliques, mais pas de source d'ions fluorure, contenant au moins un atome de métal choisi dans le groupe constitué par le calcium, l'aluminium et/ou le fer,
    le rapport molaire D:B du nombre total d'atomes métalliques du composant (D) sur le nombre total d'atomes de fluor du composant (B) n'étant pas inférieur à z - 6 4 ⁢ z ,
    Figure imgb0019
    le composant (D) se composant d'au moins un composé soluble dans l'eau et/ou dispersible dans l'eau qui contient un atome d'aluminium, et le rapport molaire du nombre total d'ions aluminium du composant (D) sur le nombre total d'atomes de fluor du composant (B) n'étant pas supérieur à z - 6 z .
    Figure imgb0020
  2. Agent selon la revendication I, caractérisé en ce que le rapport molaire D:B du nombre total d'atomes métalliques du composant (D) sur le nombre total d'atomes de fluor du composant (B) est inférieur à une valeur pour laquelle, après mise en contact de l'agent avec une surface en fer pendant une durée de traitement de 90 s et à une température de traitement de 30°C, il résulte sur ladite surface une couche de moins de 20 mg/m2 par rapport aux éléments du composant (A) choisis parmi le titane et/ou le zirconium.
  3. Agent selon l'une des revendications précédentes ou les deux, caractérisé en ce que le rapport molaire D:B du nombre total d'atomes métalliques du composant (D) sur le nombre total d'atomes de fluor du composant (B) n'est pas inférieur à z - 6 3 ⁢ z ,
    Figure imgb0021
     de préférence pas inférieur à z - 6 2 ⁢ z .
    Figure imgb0022
  4. Agent selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que le rapport molaire A:C du nombre total d'atomes des éléments titane et/ou zirconium du composant (A) sur le nombre total d'atomes de cuivre du composant (C) n'est pas inférieur à 1:3, de préférence pas inférieur à 2:3.
  5. Agent selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que les rapports D:B et A:C ne dépassent pas chacun une valeur pour laquelle, après mise en contact de l'agent avec une surface en fer, de préférence avec une surface en acier non allié, pendant une durée de traitement de 90 s et à une température de traitement de 30°C, il résulte sur ladite surface une couche de moins de 20 mg/m2 par rapport aux éléments du composant (A) choisis parmi le titane et/ou le zirconium.
  6. Agent selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que le composant (D) se compose d'au moins un composé dispersible dans l'eau à base de silicates contenant de l'aluminium, de préférence du silicate d'aluminium avec un rapport aluminium sur atomes de silicium d'au moins 1:3.
  7. Agent selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que la teneur totale en atomes de fluor correspondant au composant (B) ne dépasse pas 3 g/l, de préférence 2 g/l, de manière particulièrement préférée 1 g/l.
  8. Agent selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que la teneur totale en oxoanions de phosphore est inférieur à 1 ppm.
  9. Agent selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que le pH de l'agent n'est pas inférieur à 2,5, de préférence pas inférieur à 3,5, mais ne dépasse pas une valeur de 5, de préférence de 4,5.
  10. Agent selon la revendication 8, caractérisé en ce que, pour régler l'acidité totale, en outre, l'agent contient en plus un système tampon qui présente au moins un équilibre protolytique ayant une valeur de pK dans la gamme allant de 2,0 à 5,0.
  11. Procédé de traitement par conversion anticorrosion de surfaces métalliques qui sont choisies parmi les surfaces en fer, en acier, en fer et acier galvanisés et galvanisés par alliage, en aluminium et/ou en zinc ainsi que les alliages respectifs avec une proportion d'aluminium et/ou de zinc dans l'alliage d'au moins 50% en nombre de atomes, caractérisé en ce que la surface métallique est mise en contact avec l'agent aqueux exempt de chrome selon l'une ou plusieurs des revendications précédentes.
  12. Procédé selon la revendication 11, caractérisé en ce qu'après la mise en contact de l'agent avec la surface métallique et avant un revêtement ultérieur avec une peinture à immersion, la surface métallique n'est pas séchée.
  13. Substrat métallique qui a été traité selon l'une des revendications 11 et 12 ou les deux et comportant sur sa surface une couche à base de titane et/ou de zirconium d'au moins 20 mg/m2 mais de pas plus de 150 mg/m2.
  14. Utilisation d'un substrat métallique selon la revendication 13 pour la production de d'équipements électroménagers, de boîtiers électroniques, de produits semi-finis, de carrosseries dans le secteur de la construction automobile, ainsi que dans ceux du bâtiment et de l'architecture.
EP09721282.3A 2008-03-17 2009-03-17 Passivation optimisée à base de ti-zr de surfaces métalliques Revoked EP2255026B1 (fr)

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PL09721282T PL2255026T3 (pl) 2008-03-17 2009-03-17 Zoptymalizowane pasywowanie na bazie-Ti/Zr dla powierzchni metalowych

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DE102008014465A DE102008014465B4 (de) 2008-03-17 2008-03-17 Mittel zur optimierten Passivierung auf Ti-/Zr-Basis für Metalloberflächen und Verfahren zur Konversionsbehandlung
PCT/EP2009/053109 WO2009115504A1 (fr) 2008-03-17 2009-03-17 Passivation optimisée à base de ti-zr de surfaces métalliques

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US10125424B2 (en) 2012-08-29 2018-11-13 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
US10920324B2 (en) 2012-08-29 2021-02-16 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
US11998946B2 (en) 2018-06-14 2024-06-04 Voestalpine Stahl Gmbh Method for producing lacquer-coated electrical strips, and lacquer-coated electrical strip

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AU2009226945A1 (en) 2009-09-24
HUE027024T2 (en) 2016-08-29
DE102008014465B4 (de) 2010-05-12
WO2009115504A1 (fr) 2009-09-24
DE102008014465A1 (de) 2009-09-24
EP2255026A1 (fr) 2010-12-01
KR101596293B1 (ko) 2016-02-22
US20110041957A1 (en) 2011-02-24
JP2011514448A (ja) 2011-05-06
CN102066612B (zh) 2013-11-13
AU2009226945B2 (en) 2013-09-12
JP5854834B2 (ja) 2016-02-09
KR20110004384A (ko) 2011-01-13
ES2544430T3 (es) 2015-08-31
CN102066612A (zh) 2011-05-18
PL2255026T3 (pl) 2015-10-30

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