WO2011067094A1 - Mehrstufiges vorbehandlungsverfahren für metallische bauteile mit zink- und eisenoberflächen - Google Patents
Mehrstufiges vorbehandlungsverfahren für metallische bauteile mit zink- und eisenoberflächen Download PDFInfo
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- WO2011067094A1 WO2011067094A1 PCT/EP2010/067448 EP2010067448W WO2011067094A1 WO 2011067094 A1 WO2011067094 A1 WO 2011067094A1 EP 2010067448 W EP2010067448 W EP 2010067448W WO 2011067094 A1 WO2011067094 A1 WO 2011067094A1
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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
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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
Definitions
- the present invention relates to an acidic, aqueous, chromium-free composition (A) for the anticorrosive 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, and a multi-stage process using the composition (A) for the anticorrosive pretreatment of metallic components having surfaces of steel and / or galvanized steel.
- metal ions selected from ions of at least one of the elements nickel, cobalt, molybdenum, iron or tin
- the invention relates to metallic surfaces of zinc or iron, which have a passive layer system containing 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, obtainable in a method according to the invention.
- Corrosion inhibitors which are an acidic aqueous solution of fluoro complexes, have long been known and substitute those long used in the art
- WO 07/065645 describes aqueous compositions containing fluorocomplexes of, inter alia, titanium and / or zirconium, wherein in addition a further component is present, 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 with at least two groups containing donor atoms, or derivatives of such carboxylic acids, silica particles having a mean particle size below 1 ⁇ .
- Pretreatment 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.
- sparingly soluble copper salts it is proposed to use complexing agents in WO 2009045845 in order to increase the concentration of copper ions in the metallizing composition. It turns out that in the WO
- Chromium (VI) -free electrolyte containing at least 50 g / l of zinc ions and at least 50-300 g / l of metal cations selected from cations of the elements iron, cobalt and / or nickel.
- the aqueous composition may contain electropositive metal cations of the elements copper, silver, tin and / or bismuth.
- Further constituents of the electrolytic layer formation compositions disclosed in US Pat. No. 5,032,236 are ionogenic compounds which improve the formation of layers, including inorganic and organic sulfur compounds. According to the teaching of US Pat. No.
- 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 for preventing 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 for preventing the precipitation of sparingly soluble heavy metal salts
- a reducing agent preferably sulfite.
- Zinc surfaces wherein such a coated zinc surface after chromating and application of a paint system high corrosion resistance at good paint adhesion values having. Due to the low ionic concentrations and the presence of the complexing agent, a high bath stability is ensured. However, that allows in the
- Corrosion protection and paint adhesion properties of a trication zinc phosphating is at least equivalent and can be operated in a resource-saving manner.
- the object of the present invention is therefore to provide a method for
- Pretreatment of metallic components having surfaces of steel and / or galvanized steel comprising the method steps i-iii), each of which involve contacting the metallic component with an aqueous treatment solution, wherein the respective method steps i-iii) follows are characterized:
- An acidic aqueous, chromium-free composition (A) according to the invention which, when brought into contact with steel and / or galvanized steel, in a process according to the invention effective corrosion protection already effected by deposition of small amounts of active components contains
- metallic components comprising steel and galvanized steel are treated with a composition (A) according to the invention, the surface of the metallic component consisting of at least 10% galvanized steel surfaces, the pH is preferably in the range from 4.0 to 7.0, more preferably in a range of 5.0 to 7.0, especially in the range of 6.0 to 6.8.
- the composition (A) is chromium-free, if less than 10 ppm,
- chromium preferably less than 1 ppm of chromium, in particular no chromium (VI) are contained.
- Composition (A) causes deposition of the metal ions (M) (active component) on the metal surfaces.
- 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. Particularly preferred are chelating organic compounds containing 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.
- the amount of phosphate ions is limited in the compositions (A) according to the invention, since higher proportions can cause the formation of a thin phosphate passivation, which is disadvantageous for the deposition of the metal ions (M) on the metal surfaces. This is surprising as the passivating treatment of the metal surface with a
- compositions based on zirconium, titanium and / or hafnium analogously to the treatment step iii) according to the invention, is not detrimental to the layer-forming deposition of the metal ions (M). Therefore, such compositions (A) according to the invention are preferred in which the proportion of dissolved phosphate is not more than 500 ppm, more preferably not more than
- 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 preferably selected from inorganic compounds, more preferably from oxo acids of sulfur such as sulphurous acid, thiosulphuric acid, dithionic acid, polythionic acid, sulphurous acid, dibasic acid and / or dithionic acid and their salts, especially preferably from sulphurous acid.
- the water-soluble compound containing sulfur may also be selected from salts of the organic acids thiocyanic acid and / or thiourea, with the aforementioned water-soluble inorganic compounds containing sulfur being preferred over organic acids and salts.
- the oxidation state in the context of the present invention, is defined according to IUPL Rule I-5.5.2.1 ("Nomenclature of Inorganic Chemistry - Recommendations 1990", Blackwell: Oxford, 1990) and designates the hypothetical charge assigned to an element in a molecule would be if this element were to be assigned all the 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 is one
- Layer-forming deposition of metal ions (M) in typical treatment times of a few minutes is not given or does not occur. 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 ions (M) which are deposited on the metal surfaces in process step ii) from the acidic aqueous composition (A) in a preferred embodiment, in particular nickel and / or cobalt, more preferably nickel.
- 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.
- A aqueous composition 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
- a coating process is preferably those compositions (A) in which a sufficient amount of water-soluble compounds containing sulfur relative to the total amount of metal ions (M) is present.
- 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.
- electropositive metal cations for compositions (A) according to the invention, it may be advantageous to add electropositive metal cations in order to accelerate the layer formation.
- 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.
- M metal ions
- Preferred water-soluble compounds that release copper ions are all
- water-soluble copper salts containing no chloride ions and all water-soluble silver salts Particular preference is given to sulfates, nitrates and acetates.
- 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 on the metal surfaces and faster deposition kinetics of the thin increases
- Coating consisting of elements of metal ions (M) and a more homogeneous
- Preferred water-soluble compounds which serve as a source of fluoride ions are hydrogen fluoride, alkali fluorides, ammonium fluoride and / or
- 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.
- 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.
- compositions (B) are preferably free of chromium, i. 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.
- compositions (B) in the process according to the invention which contain, as water-soluble compounds of the elements zirconium, titanium and / or hafnium, only water-soluble compounds of the elements zirconium and / or titanium, more preferably water-soluble compounds of the element zirconium.
- 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 as water-soluble
- 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.
- copper ions accelerates the conversion of the purified or treated in step ii) metal surfaces and also increases the passivating effect. Especially in the event that first the passivating treatment of steel and / or galvanized
- 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.
- Preferred water-soluble compounds which serve as a source of fluoride ions are hydrogen fluoride, alkali fluorides, ammonium fluoride and / or ammonium bifluoride.
- the treatment temperature and the duration of the respective treatment are different in the individual steps i-iii) of the process according to the invention and strongly dependent on the bath system and the type of application, but can be varied over a wide range, without sacrificing corrosion properties.
- the treatment in steps i-iii) should be carried out as follows:
- 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 ⁇ 8 ⁇ " ) takes place. Surprisingly, exceptionally good results with regard to corrosion protection properties and paint adhesion can be achieved independently of the sequence of steps ii) and iii) in the process according to the invention. In a preferred embodiment, however, the electroless treatment according to method step ii) takes place directly, ie with or without an intermediate rinsing step, after the purification step i). For these preferred
- a first step the layer formation based on the elements of the metal ions (M) is carried out and then a conversion of the metal surface treated in this way is carried out 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), sufficient 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 respect 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 a dip coating or a
- Powder coating particularly preferably a dip coating, in particular a cathodic dip coating follows.
- 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 one
- step i) in which step i) with or without intermediate rinsing step directly followed by the electroless treatment according to step ii), the composition (A) in process step ii) at least 100 ppm, but not more than 5 g / l 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.
- 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 Contains sulfur, wherein nickel is at least 30 at .-% in metallic form, obtainable in a process according to the invention, in which the process step ii) with or without intermediate rinsing step immediately following the process step iii) and in which the inventive
- Composition (A) in process step ii) comprises at least 100 ppm, but not more than 5 g / l of nickel ions and at least 1 mM sulphurous 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 brought into contact with such a composition (A) for at least one minute.
- the invention additionally 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
- the preferred composition (A) according to the invention has a pH of 3.7 and following
- composition (Examples B1 and B2):
- a cleaning and degreasing with a cleaning solution as in Example B2 causes a pickling of 0.5 g / m 2 on electrolytically galvanized substrates, while a
- the metal sheets treated according to the invention and the comparative sheets were dried with compressed air after the last rinsing step and electrocoated with the following cathodic dip coating: Aqua® 3000 (Dupont Co., KTL layer thickness: 20 ⁇ m, determined nondestructively using a commercially available layer thickness gauge)
- Cleaning solution a further significantly improved performance of the present invention treated and coated with the dip coating zinc surfaces (B2 vs. B1) causes in the stone impact test.
- Such an improvement on zinc surfaces by the cleaning effect of the cleaner occurs only in the process according to the invention and is omitted both in the exclusive zirconium-based conversion treatment (V4 vs. V3) and the exclusive trication zinc phosphating (V2 vs. V1).
- Table 1
- 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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Abstract
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Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10776723.8A EP2507408B1 (de) | 2009-12-04 | 2010-11-15 | Mehrstufiges vorbehandlungsverfahren für metallische bauteile mit zink- und eisenoberflächen |
ES10776723.8T ES2642079T3 (es) | 2009-12-04 | 2010-11-15 | Procedimiento de pretratamiento de múltiples etapas para piezas de construcción metálicas con superficies de cinc y hierro |
MX2012006324A MX2012006324A (es) | 2009-12-04 | 2010-11-15 | Metodo de pre-tratamiento de multiples etapas para componentes de metal que tienen superficies de zinc y hierro. |
JP2012541391A JP5837885B2 (ja) | 2009-12-04 | 2010-11-15 | 金属部材の耐腐食前処理のための多段階法 |
PL10776723T PL2507408T3 (pl) | 2009-12-04 | 2010-11-15 | Wieloetapowy sposób obróbki wstępnej dla metalicznych elementów konstrukcyjnych o powierzchniach z cynku i żelaza |
CN201080054392.XA CN102639750B (zh) | 2009-12-04 | 2010-11-15 | 具有锌和铁表面的金属组件的多步骤预处理方法 |
BR112012013126A BR112012013126B1 (pt) | 2009-12-04 | 2010-11-15 | processo de pré-tratamento de multiestágios para componentes metálicos com superfícies de aço e/ou aço zincado, e superfície metálica de ferro com sistema de camada passiva |
US13/484,848 US8715403B2 (en) | 2009-12-04 | 2012-05-31 | Multi-stage pre-treatment method for metal components having zinc and iron surfaces |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102009047522A DE102009047522A1 (de) | 2009-12-04 | 2009-12-04 | Mehrstufiges Vorbehandlungsverfahren für metallische Bauteile mit Zink- und Eisenoberflächen |
DE102009047522.2 | 2009-12-04 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US13/484,848 Continuation US8715403B2 (en) | 2009-12-04 | 2012-05-31 | Multi-stage pre-treatment method for metal components having zinc and iron surfaces |
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WO2011067094A1 true WO2011067094A1 (de) | 2011-06-09 |
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PCT/EP2010/067448 WO2011067094A1 (de) | 2009-12-04 | 2010-11-15 | Mehrstufiges vorbehandlungsverfahren für metallische bauteile mit zink- und eisenoberflächen |
Country Status (10)
Country | Link |
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US (1) | US8715403B2 (de) |
EP (1) | EP2507408B1 (de) |
JP (1) | JP5837885B2 (de) |
CN (1) | CN102639750B (de) |
BR (1) | BR112012013126B1 (de) |
DE (1) | DE102009047522A1 (de) |
ES (1) | ES2642079T3 (de) |
HU (1) | HUE035823T2 (de) |
PL (1) | PL2507408T3 (de) |
WO (1) | WO2011067094A1 (de) |
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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 |
US10400337B2 (en) | 2012-08-29 | 2019-09-03 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates |
CN115279945A (zh) * | 2020-02-28 | 2022-11-01 | 奥钢联钢铁有限责任公司 | 对钢带进行电解镀锌形成条件锌层的方法 |
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DE102010001686A1 (de) * | 2010-02-09 | 2011-08-11 | Henkel AG & Co. KGaA, 40589 | Zusammensetzung für die alkalische Passivierung von Zinkoberflächen |
EP2503025B1 (de) | 2011-03-22 | 2013-07-03 | Henkel AG & Co. KGaA | Mehrstufige korrosionsschützende Behandlung metallischer Bauteile, die zumindest teilweise Oberflächen von Zink oder Zinklegierungen aufweisen |
FR3002545B1 (fr) * | 2013-02-22 | 2016-01-08 | Alchimer | Procede de formation d'un siliciure metallique a l'aide d'une solution contenant des ions or et des ions fluor |
JP5952485B2 (ja) * | 2013-02-28 | 2016-07-13 | 日鉄住金鋼板株式会社 | アルミニウム含有亜鉛系めっき鋼板及びその製造方法 |
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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 |
US10400337B2 (en) | 2012-08-29 | 2019-09-03 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing lithium, 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 |
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Also Published As
Publication number | Publication date |
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US8715403B2 (en) | 2014-05-06 |
EP2507408A1 (de) | 2012-10-10 |
BR112012013126A2 (pt) | 2017-03-21 |
EP2507408B1 (de) | 2017-07-19 |
PL2507408T3 (pl) | 2017-12-29 |
ES2642079T3 (es) | 2017-11-15 |
US20120325110A1 (en) | 2012-12-27 |
JP5837885B2 (ja) | 2015-12-24 |
HUE035823T2 (hu) | 2018-08-28 |
CN102639750A (zh) | 2012-08-15 |
CN102639750B (zh) | 2015-03-11 |
BR112012013126B1 (pt) | 2019-08-27 |
JP2013513022A (ja) | 2013-04-18 |
DE102009047522A1 (de) | 2011-06-09 |
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