EP2507408B1 - Procédé de prétraitement à étapes multiples pour des composants métalliques présentant des surfaces en zinc et en fer - Google Patents

Procédé de prétraitement à étapes multiples pour des composants métalliques présentant des surfaces en zinc et en fer Download PDF

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EP2507408B1
EP2507408B1 EP10776723.8A EP10776723A EP2507408B1 EP 2507408 B1 EP2507408 B1 EP 2507408B1 EP 10776723 A EP10776723 A EP 10776723A EP 2507408 B1 EP2507408 B1 EP 2507408B1
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ions
ppm
aqueous
metal
acidic
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EP2507408A1 (fr
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Jan-Willem Brouwer
Frank-Oliver Pilarek
Jens KRÖMER
William E. Fristad
Helene Maechel
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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
    • C23C22/78—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
    • C23C22/05—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

Definitions

  • the present invention relates to a multi-stage process using an acidic, aqueous, chromium-free composition (A) for the corrosion-protective treatment of steel and / or galvanized steel surfaces, comprising metal ions (M) selected from ions of at least one of the elements nickel, cobalt, molybdenum , Iron or tin. Furthermore, the invention relates to metallic surfaces of iron comprising a passive layer system comprising at least 30 mg / m 2 nickel and at least 10 mg / m 2 zirconium, titanium and / or hafnium and sulfur, wherein nickel is at least 30 at .-% in metallic form present, obtainable in a method according to the invention.
  • Anticorrosion agents which are an acidic aqueous solution of fluoro-complexes, have long been known and substitute for the passivating pretreatment the chromating processes long used in the prior art. Recently, such anticorrosive agents, which merely cause a thin conversion layer on the treated metal surfaces, are also being discussed as substitutes for phosphating processes and used particularly in the automotive supply industry to reduce the multistage phosphating process involving high throughputs to lower conversion processes and lower process outlay to substitute. As a rule, such solutions of fluoro-complexes contain further anti-corrosive agents that further improve the anti-corrosion effect and paint adhesion.
  • WO 07/065645 aqueous compositions containing fluorocomplexes of, inter alia, titanium and / or zirconium, wherein additionally a further component is selected, 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, the donor atoms or derivatives of such carboxylic acids, silica particles having a mean particle size below 1 micron.
  • WO 2009045845 is an electroless metallizing pre-treatment before a zirconium-based conversion treatment of metal surfaces, in particular of steel and galvanized steel known.
  • a pretreatment with an acidic aqueous composition containing water-soluble salts of electropositive metals selected from nickel, copper, silver and / or gold is carried out before the conversion treatment.
  • Such a composition for metallization may additionally contain defoamers and wetting agents.
  • the aqueous composition may contain electropositive metal cations of the elements copper, silver, tin and / or bismuth.
  • Electrolytic film formation compositions disclosed are ionogenic compounds which improve film formation, including inorganic and organic sulfur compounds. According to the teaching of US 5032236 For example, such an electrolytic layer formation can be followed by a chromating followed by the deposition of an immersion paint to build up a corrosion-protecting layer system on steel surfaces, wherein coated steel surfaces according to this process sequence offer good protection against corrosion with good paint adhesion values.
  • alkaline aqueous composition containing metal cations selected from ions of the elements cobalt, nickel, iron and / or tin in an amount of 0.01-1 g / l, a complexing agent selected from pyrophosphate and / or nitrilotriacetic acid to prevent the Precipitation of sparingly soluble heavy metal salts and optionally a reducing agent, preferably sulfite.
  • metal cations selected from ions of the elements cobalt, nickel, iron and / or tin in an amount of 0.01-1 g / l
  • a complexing agent selected from pyrophosphate and / or nitrilotriacetic acid to prevent the Precipitation of sparingly soluble heavy metal salts and optionally a reducing agent, preferably sulfite.
  • Such alkaline compositions are suitable according to the teaching of US 4278477 for electroless coating of zinc surfaces, wherein such a coated zinc surface after chromating and application of
  • the object of the present invention is therefore to establish a method for corrosion-protective pretreatment, which is suitable for the subsequent application of organic coating systems, does not comprise electrolytic process steps and in which the deposition of small amounts of active components is sufficient for effective corrosion protection, without causing Depositing significant amounts of these active components by precipitation reactions due to the process in the treatment and have to be worked up if necessary.
  • a method according to the invention it should be possible, as it were, to provide different metal surfaces of a component, which are surfaces of steel, galvanized steel and aluminum, with an anticorrosive coating at least equivalent to a trication zinc phosphating.
  • the composition (A) is chromium-free, if less than 10 ppm, preferably less than 1 ppm of chromium, in particular no chromium (VI) at all.
  • a deposition of the metal ions (M) (active component) on the metal surfaces is brought about.
  • the layer formation takes place at least partially in the form of metallic phases of the elements nickel, cobalt, molybdenum, iron or tin.
  • the layer-forming deposition of the metal ions (M) in the presence of the reducing water-soluble compound containing sulfur in an oxidation state less than +6 is inhibited in the presence of zinc ions.
  • the composition (A) according to the invention therefore contains less than 10 g / l.
  • the composition (A) may additionally contain chelating organic compounds which have at least two functional groups with oxygen and / or nitrogen atoms selected from carboxyl, hydroxyl, amine, phosphoric acid or phosphonic acid groups. Particular preference is given to chelating organic compounds which contain phosphoric acid, phosphonic acid and / or hydroxyl groups, for example 1-hydroxyethane- (1,1-diphosphonic acid). It has been found that such chelating agents in the composition (A) according to the invention mainly complex zinc ions and therefore weaken the inhibition of the deposition of the metal ions (M) on the metal surfaces.
  • the chelating organic compounds are preferably contained in such an amount that the molar excess of zinc ions relative to the chelating organic Compounds not greater than 2 g / l, preferably not greater than 1 g / l, more preferably not greater than 0.5 g / l of zinc ions.
  • compositions (A) are preferred whose content of zinc ions is not greater than 2 g / l, preferably not greater than 1 g / l, more preferably not greater than 0.5 g / l of zinc ions.
  • compositions (A) according to the invention are preferred in which the proportion of dissolved phosphate is not more than 500 ppm, particularly preferably not more than 200 ppm, particularly preferably not more than 50 ppm, calculated as PO 4 .
  • compositions (A) according to the invention can inhibit the deposition of the metal ions (M) on the steel surfaces.
  • such compositions (A) do not result in precipitation of zirconium, titanium and / or hafnium so that the use of these compounds provides no advantage and is uneconomical.
  • the at least one water-soluble compound containing sulfur in an oxidation state of less than +6 is selected from inorganic oxo acids of sulfur such as sulphurous acid, thiosulphuric acid, dithionic acid, polythionic acid, sulphurous acid, dibasic acid and / or dithionic acid and salts thereof, most preferably sulphurous acid.
  • the oxidation state is defined in the context of the present invention in accordance with IUPAC Rule 5.5.2.1 ("Nomenclature of Inorganic Chemistry - Recommendations 1990", Blackwell: Oxford, 1990) and denotes the hypothetical charge that would be assigned to an element in a molecule if this element were to be assigned all electrons shared with other elements of the molecule for which the element has a higher electronegativity than that of the element with which it shares the electrons.
  • the preferred concentration of water-soluble compounds containing sulfur in an oxidation state less than +6 is at least 1 mM, preferably at least 5 mM, but not more than 100 mM, preferably not more than 50 mM. Below 1 mM, a layer-forming deposition of the metal ions (M) in typical treatment times of a few minutes is not given or does not take place. Above 100 mM, on the one hand, no further acceleration of the layer formation on contacting a cleaned steel surface with such a composition (A) is found, and on the other hand, higher amounts of sulfur-containing compounds are rejected for economic and occupational hygiene reasons.
  • reducing agents based on water-soluble compounds containing phosphorus and / or nitrogen in an oxidation state of less than +5 are surprisingly unsuitable for the deposition of the metal ions (M), in particular for the deposition of nickel and / or cobalt ions that these reducing agents in the composition (A) for economic reasons, preferably not or only in very small amounts below 50 ppm are included.
  • compositions (A) are preferably at least 0.2 g / l, but not more than 5 g / l, preferably not more than 2 g / l of metal ions (M) selected from ions of at least one of the elements nickel, cobalt , Molybdenum, iron or tin. If this value is undershot, the activity of the metal ions (M) in the composition (A) is usually too low for adequate deposition. Above 5 g / l there is no additional benefit, whereas the increased precipitation of insoluble salts of the metal ions (M) increases, so that such high concentrations of metal ions (M) in treatment baths according to step ii) of the process according to the invention are uneconomical and also require increased processing costs.
  • M metal ions
  • Metal surfaces of steel and / or galvanized steel, which are brought into contact with an aqueous composition (A) containing nickel and / or cobalt ions, particularly preferably nickel ions, independently of the sequence of process steps ii) and iii) are provided within a short treatment time with a thin layer containing the elements nickel and / or Kolbalt, which gives an excellent paint adhesion to subsequently applied organic paint systems and thereby meets the highest standards of corrosion protection.
  • Preferred water-soluble compounds which release metal ions (M) are all water-soluble salts which do not contain chloride ions. Particular preference is given to sulfates, nitrates and acetates.
  • a preferred composition (A) according to the invention has a molar ratio of metal ions (M) selected from ions of at least one of nickel, cobalt, molybdenum, iron or tin to water-soluble compounds containing sulfur of not greater than 1: 1, preferably not greater than 2: 3 but not less than 1: 5. Above this preferred molar ratio of 1: 1, the formation of the thin layer containing the elements of the metal ions (M) is slower, so that in particular for the application of the composition (A) in process step ii) of a strip coating process according to the invention such compositions (A) preferred are those in which relative to the total amount of metal ions (M) a sufficient amount of water-soluble compounds containing sulfur is present.
  • M metal ions
  • a molar ratio of metal ions (M) to water-soluble compounds containing sulfur below 1: 5 may be detrimental to the stability of compositions (A) of the invention because the reducing sulfur compounds can then cause precipitation of the containing metals in colloidal form.
  • compositions (A) according to the invention it may be advantageous to add electropositive metal cations in order to accelerate the layer formation.
  • a preferred embodiment of the invention therefore additionally contains copper ions and / or silver ions, preferably copper ions, in an amount of at least 1 ppm, but not more than 100 ppm. Above 100 ppm, the deposition of the electropositive metal in elemental form on the steel and / or galvanized steel surfaces dominate so far that the layer formation based on the metal ions (M) is pushed back so far that the paint adhesion applied subsequently in the process according to the invention organic paints is significantly deteriorated or inhomogeneous layer coatings are produced after step ii) of the method according to the invention, which offer a poorer corrosion protection.
  • Preferred water-soluble compounds that release copper ions are all water-soluble copper salts that do not contain chloride ions, as well as all water-soluble silver salts. Particular preference is given to sulfates, nitrates and acetates.
  • the addition of water-soluble compounds which are a source of fluoride ions to a composition (A) according to the invention may be preferred, wherein the concentration of total fluoride in the composition (A) is preferably at least 50 ppm but not more than 2000 ppm.
  • the addition of fluoride is particularly advantageous when, in a process according to the invention, step ii), with or without a rinsing step between them, immediately follows the purification step i) and in particular when hot-dip galvanized steel surfaces are treated. In such a case, the pickling rate increases on the metal surfaces and a faster deposition kinetics of the thin coating consisting of elements of the metal ions (M) and a more homogeneous coating of the metal surface is the immediate consequence.
  • Preferred water-soluble compounds which serve as a source of fluoride ions are hydrogen fluoride, alkali fluorides, ammonium fluoride and / or ammonium bifluoride.
  • a cleaning and degreasing of the metal surface is necessary for a homogeneous formation of the passivating coating according to process steps ii) and iii).
  • those purification steps i) are preferred according to the invention, which are carried out by means of an aqueous cleaning solution, wherein the cleaning a Beizabtrag of at least 0.4 g / m 2 , but not more than 0.8 g / m 2 of zinc based on a surface of Electrolytic galvanized steel causes.
  • a Beizabtrag of at least 0.4 g / m 2 , but not more than 0.8 g / m 2 of zinc based on a surface of Electrolytic galvanized steel causes.
  • cleaners which have a corresponding pickling rate for a given cleaning time. It has surprisingly been found that such a preferred purification leads to better results in terms of corrosion protection and paint adhesion of the steel and / or galvanized steel surfaces treated according to the invention.
  • the acidic aqueous compositions (B) used in step iii) of the process according to the invention are chromium-free, ie they contain less than 10 ppm, preferably less than 1 ppm of chromium, in particular no chromium (VI). Furthermore, the acidic compositions (B) in the process according to the invention preferably contain a total of 20 to 1000 ppm of water-soluble compounds of the elements zirconium, titanium and / or hafnium based on the elements zirconium, titanium and / or hafnium.
  • metal surface may be the result so that only small amounts of hydroxides and / or oxides of these elements deposited and the passivating effect is too low.
  • a further improvement in the corrosion properties of the metal surfaces treated according to the invention can not be determined.
  • Preferred water-soluble compounds of the elements zirconium, titanium and / or hafnium are compounds which dissociate in aqueous solution into anions of fluorocomplexes of the elements zirconium, titanium and / or hafnium.
  • 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.
  • fluorine-free compounds of the elements zirconium, titanium and / or hafnium can be used according to the invention as water-soluble compounds, for example (NH 4 ) 2 Zr (OH) 2 (CO 3 ) 2 or TiO (SO 4 ).
  • a composition (B) in step iii) of the process according to the invention may contain 1 to 100 ppm of copper ions and optionally up to 200 ppm of free fluoride.
  • the addition of copper ions accelerates the conversion of the purified or treated in step ii) metal surfaces and also increases the passivating effect.
  • Preferred water-soluble compounds that release copper ions are all water-soluble copper salts that do not contain chloride ions. Particular preference is given to sulfates, nitrates and acetates.
  • fluoride ions in the preferred range based on free fluoride which in turn can be determined by means of an ion-sensitive measuring electrode, facilitates the homogeneous conversion of the purified or in step ii) treated metal surfaces.
  • Preferred water-soluble compounds which serve as a source of fluoride ions are hydrogen fluoride, alkali fluorides, ammonium fluoride and / or ammonium bifluoride.
  • the concrete conditions for bringing the metal surfaces into contact with the aqueous treatment stages ii) and iii) are preferably to be selected such that in step ii) a layer coverage of at least 30 mg / 2 , more preferably at least 50 mg / m2 of one or more of the metal ions (M) on the surfaces of zinc, while the temperature and duration of treatment in step iii) are to be adjusted such that a coating of at least 10 mg / m 2 zirconium and / or titanium, more preferably at least 25 mg / m 2 zirconium and / or titanium on the surfaces of zinc results.
  • the corrosion protection properties of the pretreatment are usually insufficient.
  • the individual steps i-iii) of the process according to the invention can be carried out with or without an intermediate rinsing step. However, it is preferred that after the purification step i) at least one additional rinsing step with city water or deionized water ( ⁇ ⁇ 1 ⁇ Scm -1 ) takes place.
  • the electroless treatment according to method step ii) takes place directly, i. with or without intermediate rinsing step, after the purification step i).
  • the layer formation is first carried out on the basis of the elements of the metal ions (M), followed by a conversion of the metal surface treated in this way with the aid of the zirconium- and / or titanium-containing composition (B).
  • the method according to the invention is suitable for metallic components which have iron, steel and / or galvanized steel surfaces and the corresponding pre-phosphated surfaces. Irrespective of the sequence of steps ii) and iii), adequate layer formation on the basis of the elements of the metal ions (M) always takes place on these surfaces, which in turn is a prerequisite for the outstanding properties with regard to corrosion and paint adhesion. Likewise, surfaces of aluminum are passivated in step iii) in the process according to the invention, so that the process is particularly suitable for the corrosion-protective pretreatment of multi-metal construction surfaces, for example.
  • aqueous compositions in steps i-iii) can be brought into contact with the metal surfaces in both immersion and spraying processes.
  • the method can also be used in the pretreatment of metal strip and there, for example, by means of the roller application method known to those skilled in the art.
  • the process of the invention is usually followed by the application of a coating system, so that after passing through the process steps i-iii) with or without intermediate rinsing and / or drying step preferably followed by dip coating or powder coating, more preferably a dip coating, in particular a cathodic dip coating.
  • the present invention further comprises a metal surface of iron and / or steel with passive layer system comprising at least 30 mg / m 2 nickel and at least 10 mg / m 2 zirconium, titanium and / or hafnium, preferably at least 10 mg / m 2 zirconium, and sulfur wherein nickel is at least 30 at.% in metallic form, obtainable in a preferred process according to the invention, in which process step i) with or without intermediate rinsing step immediately follows the electroless treatment according to step ii) (A) in process step ii) at least 100 ppm, but not more than 5 g / l of nickel ions and at least 1 mM sulfurous acid and / or salt thereof and the iron and / or steel surface at a treatment temperature in the range of 20 to 50 ° C is brought into contact with such a composition (A) for at least one minute.
  • passive layer system comprising at least 30 mg / m 2 nickel and at least 10 mg / m 2 zirconium, titanium
  • the present invention comprises a metal surface of zinc and / or galvanized steel with a passive layer system comprising at least 30 mg / m 2 nickel and at least 10 mg / m 2 zirconium, titanium and / or hafnium, preferably at least 10 mg / m 2 zirconium, and Containing at least 30 at.% Of nickel in metallic form, obtainable in a process according to the invention, in which process step ii), with or without intermediate rinsing step, directly follows process step iii) and in which the composition (A) according to the invention in process step ii) at least 100 ppm, but not more than 5 g / l of nickel ions and at least 1 mM sulfurous acid and / or salt thereof and the zinc and / or galvanized steel surface at a treatment temperature in the range of 20 to 50 ° C is contacted with such a composition (A) for at least one minute.
  • a passive layer system comprising at least 30 mg / m 2 nickel and
  • the invention also relates to the use of the metallic components treated according to the invention or of the metal strip treated according to the invention in the manufacture of automobile bodies.
  • the metal sheets treated according to the invention and the comparative sheets were dried after the last rinsing step with compressed air and electrocoated with the following cathodic dip coating: Aqua® 3000 (Dupont, KTL layer thickness: 20 ⁇ m non-destructively determined with commercially available coating thickness gauge) and then the paint baked at 175 ° C for 25 min in the oven.
  • the nickel layer coating was determined by means of X-ray fluorescence analysis after the individual step iii)
  • the nickel layer coating was determined by means of X-ray fluorescence analysis after the individual step iii)
  • XPS X-ray photoelectron spectroscopy

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Claims (12)

  1. Procédé de prétraitement anticorrosion à étapes multiples de composants métalliques, qui présentent des surfaces en acier et/ou en acier galvanisé, comprenant les étapes de procédé i-iii), qui contiennent chacune la mise en contact du composant métallique avec une solution de traitement aqueuse, les étapes de traitement i-iii) successives, chacune avec ou sans étape de rinçage intercalée, étant caractérisées de la manière suivante :
    i) nettoyage et dégraissage de la surface métallique ;
    ii) traitement sans courant parasite par mise en contact de la surface métallique avec une composition aqueuse acide exempte de chrome (A), contenant
    a) au moins 100 ppm d'ions métalliques choisis parmi les ions d'au moins un des éléments nickel, cobalt, molybdène, fer ou étain,
    b) au moins un composé hydrosoluble contenant du soufre à un degré d'oxydation inférieur à +6 choisi dans les oxyacides anorganiques du soufre et de ses sels,
    c) moins de 10 g/l d'ions zinc,
    d) au total moins de 1 g/l de phosphates dissous exprimés en PO4 ;
    iii) traitement de passivation par mise en contact de la surface métallique avec une composition aqueuse acide (B) contenant au moins un composé hydrosoluble des éléments Zr, Ti et/ou Hf dans une concentration d'au moins 5 ppm rapporté aux éléments Zt et/ou Ti,
    les compositions aqueuses acides (A) et (B) contenant chacune moins de 10 ppm de chrome.
  2. Procédé selon la revendication 1, caractérisé en ce que le nettoyage et le dégraissage de la surface métallique sont réalisés au cours de l'étape de procédé i) au moyen d'une solution de nettoyage aqueuse, un enlèvement par décapage d'au moins 0,4 g/m2 de zinc rapporté à une surface d'acier galvanisé de manière électrolytique devant être réalisé au cours de l'étape de procédé i).
  3. Procédé selon l'une des revendications précédentes ou les deux revendications précédentes, caractérisé en ce que la composition aqueuse acide exempte de chrome (A) pour le traitement sans courant parasite des composants métalliques comportant de l'acier et de l'acier galvanisé, le composant métallique étant constitué au moins à 10 % de surfaces en acier galvanisé, présentant un pH dans la plage de 4,0 à 6,8, de préférence dans la plage de 5,0 à 6,8, de manière particulièrement préférée dans la plage de 6,0 à 6,8.
  4. Procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que dans la composition aqueuse acide exempte de chrome (A), au moins 0,2 g/l, mais pas plus de 5 g/l, de préférence pas plus de 2 g/l d'ions métalliques choisis parmi les ions d'au moins un des éléments nickel, cobalt, molybdène, fer ou zinc, sont contenus.
  5. Procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que dans la composition aqueuse acide exempte de chrome (A), le rapport molaire des ions métalliques (M) choisis parmi les ions d'au moins un des éléments nickel, cobalt, molybdène, fer ou étain sur les composés hydrosolubles contenant du soufre n'est pas supérieur à 1:1, de préférence non supérieur à 2:3, mais non inférieur à 1:5.
  6. Procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que les oxyacides anorganiques du soufre dans la composition aqueuse acide exempte de chrome (A) sont choisis parmi l'acide sulfureux.
  7. Procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que dans la composition aqueuse acide exempte de chrome (A), des ions cuivre et/ou des ions argent, de préférence des ions cuivre, sont contenus en plus à raison d'au moins 1 ppm, mais non supérieure à 100 ppm.
  8. Procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que dans la composition aqueuse acide exempte de chrome (A), des composés hydrosolubles sont contenus en plus, qui représentent une source d'ions fluorure, la concentration en fluorure total dans la composition (A) étant de préférence d'au moins 50 ppm, mais non supérieure à 2000 ppm.
  9. Procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que dans la composition aqueuse acide exempte de chrome (A), des composés organiques chélateurs contenant au moins deux groupes fonctionnels comprenant des atomes d'oxygène et/ou d'azote choisis parmi les groupe carboxyle, hydroxyle, amine, acide phosphorique ou phosphonique sont contenus en plus.
  10. Procédé selon la revendication 9, caractérisé en ce que les composés organiques chélateurs dans la composition aqueuse acide exempte de chrome (A) sont contenus dans une quantité telle que l'excédent molaire d'ions zinc rapporté aux composés organiques chélateurs n'est pas supérieur à 2 g/l, de préférence non supérieur à 1 g/l, de manière particulièrement préférée non supérieur à 0,5 g/l d'ions zinc.
  11. Procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que la composition aqueuse acide (B) contient au total 20 à 1000 ppm de composés hydrosolubles des éléments zircon et/ou titane rapporté aux éléments zircon et/ou titane et éventuellement 1 à 100 ppm d'ions cuivre (II) ainsi qu'éventuellement jusqu'à 200 ppm de fluorure libre.
  12. Surface métallique en fer comprenant un système de couche passive, qui contient au moins 30 mg/m2 de Ni et au moins 10 mg/m2 de zircon, de titane et/ou de hafnium ainsi que de soufre, le nickel étant présent au moins à raison de 30 % atomiques sous forme métallique, pouvant être obtenue dans un procédé selon l'une ou plusieurs des revendications précédentes, la surface en fer nettoyée étant amenée en contact au cours de l'étape de procédé ii) avec une composition (A) contenant au moins 100 ppm, mais pas plus de 5 g/l d'ions nickel ainsi qu'au moins 1 mM d'acide sulfureux et/ou son sel à une température de traitement dans la plage de 20 à 50°C et pendant une durée de traitement d'au moins une minute.
EP10776723.8A 2009-12-04 2010-11-15 Procédé de prétraitement à étapes multiples pour des composants métalliques présentant des surfaces en zinc et en fer Active EP2507408B1 (fr)

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DE102009047522A DE102009047522A1 (de) 2009-12-04 2009-12-04 Mehrstufiges Vorbehandlungsverfahren für metallische Bauteile mit Zink- und Eisenoberflächen
PCT/EP2010/067448 WO2011067094A1 (fr) 2009-12-04 2010-11-15 Procédé de prétraitement à étapes multiples pour des composants métalliques présentant des surfaces en zinc et en fer

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DE (1) DE102009047522A1 (fr)
ES (1) ES2642079T3 (fr)
HU (1) HUE035823T2 (fr)
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EP3504356A1 (fr) 2016-08-24 2019-07-03 PPG Industries Ohio, Inc. Composition alcaline destiné au traitement de substrats métalliques
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WO2021116320A1 (fr) * 2019-12-11 2021-06-17 Salzgitter Flachstahl Gmbh Tôle métallique comportant un revêtement promoteur d'adhérence en tant que produit semi-fini pour la fabrication de composants composites métal-thermoplastique, et procédé de production d'une tôle métallique de ce type
EP3872231A1 (fr) * 2020-02-28 2021-09-01 voestalpine Stahl GmbH Procédé de conditionnement de la surface d'un bande métallique revêtu d'une couche de protection contre la corrosion en alliage de zinc

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DE102009047522A1 (de) 2011-06-09
JP2013513022A (ja) 2013-04-18
EP2507408A1 (fr) 2012-10-10
JP5837885B2 (ja) 2015-12-24
BR112012013126A2 (pt) 2017-03-21
ES2642079T3 (es) 2017-11-15
BR112012013126B1 (pt) 2019-08-27
PL2507408T3 (pl) 2017-12-29
HUE035823T2 (hu) 2018-08-28
CN102639750A (zh) 2012-08-15
US8715403B2 (en) 2014-05-06
US20120325110A1 (en) 2012-12-27
WO2011067094A1 (fr) 2011-06-09
CN102639750B (zh) 2015-03-11

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