EP1005578B1 - Procede de phosphatation accelere par n-oxydes - Google Patents

Procede de phosphatation accelere par n-oxydes Download PDF

Info

Publication number
EP1005578B1
EP1005578B1 EP98943785A EP98943785A EP1005578B1 EP 1005578 B1 EP1005578 B1 EP 1005578B1 EP 98943785 A EP98943785 A EP 98943785A EP 98943785 A EP98943785 A EP 98943785A EP 1005578 B1 EP1005578 B1 EP 1005578B1
Authority
EP
European Patent Office
Prior art keywords
ions
oxide
phosphating
phosphating solution
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP98943785A
Other languages
German (de)
English (en)
Other versions
EP1005578A1 (fr
Inventor
Bernd Mayer
Peter Kuhm
Pietro Balboni
Markus Senner
Horst-Dieter Speckmann
Jürgen Geke
Jan-Willem Brouwer
Annette Willer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19733978A external-priority patent/DE19733978A1/de
Priority claimed from DE1997150301 external-priority patent/DE19750301A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1005578A1 publication Critical patent/EP1005578A1/fr
Application granted granted Critical
Publication of EP1005578B1 publication Critical patent/EP1005578B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations

Definitions

  • the invention relates to a phosphating solution, a phosphating concentrate and a method for phosphating metal surfaces with aqueous, acid phosphating solutions, the zinc and phosphate ions and contain at least one organic N-oxide, and their Application as pretreatment of the metal surfaces for a subsequent Painting, especially an electro dip painting.
  • the method can be used to treat steel surfaces, galvanized or alloy galvanized steel, aluminum, aluminized or alloy aluminum steel.
  • the phosphating of metals pursues the goal on the metal surface to produce firmly grown metal phosphate layers that are in themselves Improve corrosion resistance and in connection with paints and other organic coatings to a significant increase in Liability and resistance to infiltration Corrosion stress contribute.
  • Such phosphating processes are has long been known in the art.
  • the low-zinc phosphating processes are particularly suitable for painting, where the phosphating solutions are comparatively low levels of zinc ions of e.g. B. 0.5 to 2 g / l.
  • Weight ratio of phosphate ions to zinc ions which is usually in the Range is> 12 and can take values up to 30.
  • DE-A-40 13 483 discloses phosphating processes with which similar good corrosion protection properties as achieved with the trication process can be. These processes do without and use nickel instead copper in low concentrations, 0.001 to 0.03 g / l. to Oxidation of the formed in the pickling reaction of steel surfaces divalent iron in the trivalent stage serves oxygen and / or other oxidizing agents with the same effect. Nitrite, chlorate, Bromate, peroxy compounds and organic nitro compounds, such as Nitrobenzenesulfonate.
  • German patent application DE 42 10 513 modifies this process in that as a modifying one Agent for the morphology of the formed phosphate crystals hydroxylamine, its salts or complexes in an amount of 0.5 to 5 g / l Hydroxylamine can be added.
  • Hydroxylamine has the great procedural advantage that it generally in the phosphating bath and in phosphating concentrates not decomposed by itself. This makes phosphating bath concentrates and Supplementary solutions for phosphating baths can be produced that the required accelerator quantities included directly. An expensive one separate replenishment, such as when using Nitrite or hydrogen peroxide may be required as an accelerator thus eliminated.
  • the phosphating solution contains copper ions, for what there is currently a technical trend, hydroxylamine decomposes gradually under the catalytic influence of these ions. In this case the accelerator must separate the phosphating bath and increase it Amounts are added.
  • Accelerators which are similar to hydroxylamine in phosphating baths, have their concentrates and supplementary solutions incorporated without they decompose in a short time. They should also have this property still have when copper ions are present.
  • GB-A-510 684 describes a method for phosphating metal surfaces Iron or steel is described, whereby as an accelerator in addition to organic nitro compounds, Nitroso compounds, trichloromethyl compounds and aldehydes also organic amine oxides can be used. Hydroxylamine is used as the amine oxide called. These accelerators are used in phosphating baths based on zinc dihydrogen phosphate or used manganese dihydrogen phosphate, which also May contain copper compounds.
  • the object of the invention is to provide a phosphating process make the benefits of hydroxylamine accelerated processes, but not which has disadvantages with regard to decomposition in the presence of copper ions.
  • the phosphating process is said to be by spraying, spray-immersion or immersion be applicable.
  • the invention accordingly relates to an acidic, aqueous phosphating solution containing zinc ions, phosphate ions and an organic N-oxide as an accelerator, characterized in that the solution 0.2 to 3 g / l zinc ions 3 to 50 g / l phosphate ions, calculated as PO 4 3- Contains 0.05 to 4 g / l of an organic N-oxide which has a saturated, unsaturated or aromatic five- or six-membered ring system, the N atom of the N-oxide being part of this ring system, and the weight ratio of phosphate ions to zinc ions is between 3.7 and 30.
  • N-oxides substituted or unsubstituted pyrroles imidazoles, oxazoles, pyridines, Pyrimidines, pyrazines, oxazines or their hydrogenation products, the have saturated or partially unsaturated rings.
  • N-oxides substituted or unsubstituted pyridines and morpholines such as in particular pyridine N-oxide, 2-methylpyridine-N-oxide, 4-methylpyridine-N-oxide, morpholine-N-oxide and N-methylmorpholine-N-oxide. The latter is particularly preferred.
  • the phosphating solution can contain one or more of these N-oxides contain.
  • the total concentration of N-oxides in the phosphating solution is preferably in the range from 0.1 to 3 g / l and in particular in Range from 0.3 to 2 g / l. At lower concentrations, the accelerating effect after, higher concentrations do no harm, However, they have no technical advantage and are therefore economical disadvantageous.
  • phosphating baths In addition to zinc ions, phosphating baths generally contain sodium, potassium and / or ammonium ions to adjust the free acid.
  • free acid is familiar to the person skilled in the phosphating field. The method of determining free acid and total acid chosen in this document is given in the example section. Values of the free acid between 0 and 1.5 points and the total acid between about 15 and about 35 points are within the technically customary range and are suitable for the purposes of this invention.
  • the zinc contents are preferably in the range from 0.4 to 2 g / l and in particular from 0.5 to 1.5 g / l, as is customary for low-zinc processes are.
  • the weight ratio of phosphate ions to zinc ions in the phosphating baths can vary widely, provided it is in the range is between 3.7 and 30. A weight ratio between 10 and 20 is particularly preferred
  • Hydrogen peroxide can be added to the phosphating solution as such become. However, it can also be in bound form in the form of Compounds are used which are hydrogen peroxide in the phosphating bath form or split off. Examples of such compounds are Perborates, percarbonates, salts of peroxy acids such as, for example Peroxodisulfate or peroxides such as sodium or Potassium peroxide.
  • Chlorate ions and / or m-nitrobenzenesulfonate ions are preferably used in the form of their water-soluble salts, for example their alkali metal salts on.
  • the phosphating solutions can additionally contain nickel ions contain.
  • the lowest possible levels of nickel ions have or, if desired, can also be nickel-free.
  • the phosphating solution according to the invention contains in one preferred embodiment except zinc ions as additional cations 0.1 to 4 g / l manganese ions and 0.002 to 0.2 g / l copper ions and no more than 0.05 g / l, in particular not more than 0.001 g / l nickel ions.
  • phosphating baths according to the invention which except Zinc ions, 0.1 to 4 g / l manganese ions and additionally 0.1 to 2.5 g / l Contain nickel ions.
  • phosphating baths are irrelevant. It offers in particular to oxides and / or carbonates as a cation source use.
  • phosphating baths can be made by dissolving the individual Components in the water in the desired concentration range directly in front Location.
  • concentrates use the individual components in the desired Quantity ratio included and from those on site by diluting with Water the operational phosphating bath is produced or as Supplement solution are added to a working phosphating bath, to balance the consumption of the active components.
  • phosphating concentrates are strongly acidic for stabilization set. After dilution with water, the pH value must be checked frequently and / or the free acid blunted to the desired range become.
  • alkaline substances such as Sodium hydroxide solution or sodium carbonate or basic salts or hydroxides of Ca, Mg, Zn added.
  • the invention also relates to an aqueous concentrate which after dilution with water by a factor between 10 and 100 and if necessary, adjust the pH to a working range between 2.5 and 3.6 a phosphating solution according to one or more of the Claims 1 to 12 results.
  • the invention further comprises a method for phosphating Metal surfaces made of steel, galvanized or alloy galvanized steel and / or aluminum.
  • the materials mentioned can, as in Automobile manufacturing is becoming increasingly common, also side by side. you brings the metal surfaces by spraying or dipping or by a Combination thereof with the phosphating solution according to the invention in Contact.
  • the temperature of the phosphating solution is preferably in the Range between about 40 and about 60 ° C.
  • the phosphating process can be used to phosphate tapes Steel or galvanized steel can be used in conveyor systems.
  • the Phosphating times are in the range from about 3 to about 20 Seconds.
  • the method can be used in particular in automotive engineering are used where treatment times are between 1 and 8 minutes are common. It is especially used to treat the above Metal surfaces before painting, especially before cathodic electrocoating.
  • the phosphating process is to be seen as a sub-step of the technically usual pretreatment chain. In This chain of phosphating is usually the steps Cleaning / degreasing, intermediate rinsing and activation upstream, whereby the activation usually with titanium phosphate-containing activating agents he follows.
  • the phosphating according to the invention can, if appropriate after an intermediate rinse, follow a passivating after-treatment.
  • Chromic acid-containing ones are used for such a passivating aftertreatment Treatment baths widely used. For reasons of work and environmental protection however, and for reasons of disposal, there is a tendency these chrome-containing passivation baths through chrome-free treatment baths to replace. Purely inorganic baths are used for this, especially on the Basis of zirconium compounds, or also organic baths, for example based on poly (vinylphenols).
  • Phosphating solutions that contain neither nickel nor copper ions can a significant improvement in corrosion protection can be achieved if the baths for passivating post-treatment copper or Adds silver ions.
  • passivating Rinse solutions that contain 0.001 to 10 g / l copper ions included and, if desired, can be free from others passivating components. Between this post-passivation and the usually subsequent electrocoating is in usually performed an intermediate rinse with deionized water.
  • the mass per unit area (“layer weight”) was determined by dissolving in 5% chromic acid solution in accordance with DIN 50942. Accelerators and phosphating results
  • N-oxides were determined by high pressure liquid chromatography (HPLC). Accelerator, accelerator stability, phosphating results
  • VDA 621-415 painted metal sheets
  • Measure undermining of paint on a scratch half the scratch width
  • Degree of corrosion determined after a stone chip test according to the VW standard (Scale values from 1 to 10 after increasing corrosion).
  • Comparative example 5 differs from embodiment 15 in that that instead of N-morpholine-N-oxide as accelerator 2 g / l hydroxylammonium sulfate were used.
  • the phosphating solution for Example 18 is included in Table 4. It also contained 1750 ppm of complex-bound fluoride (H 2 SiF 6 ). In this way, the substrates CRS, EG and HDG were phosphated at temperatures of 45 ° C. and 50 ° C. in the aforementioned process. The layer weights are shown in Table 6. In all cases, optically perfect layers were obtained. Phosphating parameters and results of phosphating solution according to Example 18 Temperature (° C) Free acidity (points) Total acidity (points) substratum Layer weight (g / m 2 ) 45 0.2 19.3 CRS 2.60 EC 1.81 HDG 2.71 50 0.5 19.6 CRS 1.55 EC 1.53 HDG 2.07
  • the mass per unit area (“layer weight”) was determined by dissolving in 5% chromic acid solution in accordance with DIN 50942.
  • Variable bath parameters and layer weights Example No. Activating solution concentration (% by weight) N-methylmorpholine-N-oxide (g / l) Chlorate (g / l) Free acidity (points) Layer weight (g / m 2 ) Vergl.6 0.1 0 3 0.7 ng Beisp.19 0.1 2 3 0.7 2.8 Beisp.20 0.1 2 3 1.2 3.2 Vergl.7 0.5 0 3 0.7 ng Beisp.21 0.5 2 3 0.7 2.3 Beisp.22 0.5 2 3 1.2 2.5 Variable bath parameters and layer weights Example No.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Claims (14)

  1. Solution aqueuse acide de phosphatation, contenant des ions zinc, des ions phosphate ainsi qu'un N-oxyde organique en tant qu'accélérateur,
    caractérisée en ce que
    la solution contient
    de 0,2 à 3 g/l d'ions zinc,
    de 3 à 50 g/l d'ions phosphate, calculé en PO4 3- et
    de 0,05 à 4 g/l d'un N-oxyde organique qui comporte un système cyclique saturé, insaturé ou aromatique à cinq ou six chaínons, l'atome d'azote du N-oxyde faisant partie de ce système cyclique, et le rapport pondéral des ions phosphate aux ions zinc étant compris entre 3,7 et 30.
  2. Solution de phosphatation selon la revendication 1,
    caractérisée en ce que
    le N-oxyde organique est choisi parmi les N-oxydes de pyrroles, imidazoles, oxazoles, pyridines, pyrimidines, pyrazines, oxazines, portant ou non des substituants, ou leurs produits d'hydrogénation.
  3. Solution de phosphatation selon la revendication 1 ou 2,
    caractérisée en ce que
    le N-oxyde est choisi parmi les N-oxydes de pyridines et de morpholines substituées ou non substituées, en particulier parmi le N-oxyde de pyridine, le N-oxyde de 2-méthylpyridine, le N-oxyde de 4-méthylpyridine, le N-oxyde de morpholine et le N-oxyde de N-méthylmorpholine.
  4. Solution de phosphatation selon une ou plusieurs des revendications 1 à 3,
    caractérisée en ce qu'
    elle contient de 0,1 à 3 g/l du N-oxyde organique.
  5. Solution de phosphatation selon une ou plusieurs des revendications 1 à 4,
    caractérisée en ce qu'
    elle contient en outre de 0,3 à 4 g/l d'ions chlorate.
  6. Solution de phosphatation selon une ou plusieurs des revendications 1 à 5,
    caractérisée en ce qu'
    elle contient en outre un ou plusieurs des accélérateurs suivants :
    de 0,003 à 0,03 g/l de peroxyde d'hydrogène sous forme libre ou liée,
    de 0,2 à 1 g/l de nitroguanidine,
    de 0,15 à 0,8 g/l d'ions m-nitrobenzènesulfonate.
  7. Solution de phosphatation selon une ou plusieurs des revendications 1 à 6,
    caractérisée en ce qu'
    elle contient en outre un ou plusieurs des cations suivants :
    de 0,1 à 4 g/l de manganèse-(II),
    de 0,2 à 2,5 g/l de magnésium-(II),
    de 0,2 à 2,5 g/l de calcium-(II),
    de 0,002 à 0,2 g/l de cuivre-(II),
    de 0,1 à 2 g/l de cobalt-(II).
  8. Solution de phosphatation selon la revendication 7,
    caractérisée en ce qu'
    elle contient de 0,1 à 4 g/l d'ions manganèse et de 0,002 à 0,2 g/l d'ions cuivre et au maximum 0,05 g/l d'ions nickel.
  9. Solution de phosphatation selon la revendication 7,
    caractérisée en ce qu'
    elle contient de 0,1 à 4 g/l d'ions manganèse ainsi qu'en outre de 0,1 à 2,5 g/l d'ions nickel.
  10. Solution de phosphatation selon une ou plusieurs des revendications 1 à 9,
    caractérisée en ce qu'
    elle contient de 0,4 à 2 g/l d'ions zinc.
  11. Solution de phosphatation selon une ou plusieurs des revendications 1 à 10,
    caractérisée en ce qu'
    elle ne contient pas plus de 0,5 g/l d'ions nitrate.
  12. Solution de phosphatation selon une ou plusieurs des revendications 1 à 11,
    caractérisée en ce qu'
    elle contient en outre un fluorure libre et/ou sous forme de complexe, en quantités allant jusqu'à 2,5 g/l de fluorure total, dont 750 mg/l de fluorure libre, dans chaque cas calculé en tant que F-.
  13. Concentré aqueux qui donne, après dilution avec de l'eau par un facteur compris entre 10 et 100 et éventuellement ajustement du pH dans une plage de travail comprise entre 2,5 et 3,6, une solution de phosphatation selon une ou plusieurs des revendications 1 à 12.
  14. Procédé pour la phosphatation de surfaces métalliques en acier, acier zingué ou acier zingué et allié et/ou en aluminium, selon lequel on met les surfaces métalliques en contact avec une solution de phosphatation selon une ou plusieurs des revendications 1 à 12, par pistolage ou trempage ou par une association de ces techniques, pendant une durée comprise entre 3 secondes et 8 minutes.
EP98943785A 1997-08-06 1998-07-25 Procede de phosphatation accelere par n-oxydes Expired - Lifetime EP1005578B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19733978A DE19733978A1 (de) 1997-08-06 1997-08-06 Mit N-Oxiden beschleunigtes Phosphatierverfahren
DE19733978 1997-08-06
DE19750301 1997-11-13
DE1997150301 DE19750301A1 (de) 1997-11-13 1997-11-13 Mit N-Oxiden und Clorat beschleunigtes Phosphatierverfahren
PCT/EP1998/004669 WO1999007916A1 (fr) 1997-08-06 1998-07-25 Procede de phosphatation accelere par n-oxydes

Publications (2)

Publication Number Publication Date
EP1005578A1 EP1005578A1 (fr) 2000-06-07
EP1005578B1 true EP1005578B1 (fr) 2002-10-09

Family

ID=26038895

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98943785A Expired - Lifetime EP1005578B1 (fr) 1997-08-06 1998-07-25 Procede de phosphatation accelere par n-oxydes

Country Status (7)

Country Link
US (1) US6379474B1 (fr)
EP (1) EP1005578B1 (fr)
AU (1) AU9156398A (fr)
CA (1) CA2300276A1 (fr)
DE (1) DE59805918D1 (fr)
ES (1) ES2185213T3 (fr)
WO (1) WO1999007916A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008044143A1 (de) * 2008-11-27 2010-06-02 Atotech Deutschland Gmbh Konversionsschichten für zinkhaltige Oberflächen

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19933189A1 (de) * 1999-07-15 2001-01-18 Henkel Kgaa Verfahren zur korrosionsschützenden Behandlung oder Nachbehandlung von Metalloberflächen
US6391384B1 (en) * 2000-07-10 2002-05-21 Carus Corporation Method for providing a corrosion inhibiting solution
DE10155666A1 (de) * 2001-11-13 2003-05-22 Henkel Kgaa Mit Hydroxylamin und organischen Stickstoffverbindungen beschleunigtes Phosphatierverfahren
CA2467751A1 (fr) * 2001-12-13 2003-07-03 Henkel Kommanditgesellschaft Auf Aktien Utilisation d'hydroxylamines substituees pour les procedes de phosphatation de metal
AU2003250917A1 (en) 2002-07-10 2004-02-02 Chemetall Gmbh Method for coating metallic surfaces
DE10320313B4 (de) * 2003-05-06 2005-08-11 Chemetall Gmbh Verfahren zum Beschichten von metallischen Körpern mit einer Phosphatierungslösung, Phosphatierungslösung und die Verwendung des beschichteten Gegenstandes
DE10323305B4 (de) * 2003-05-23 2006-03-30 Chemetall Gmbh Verfahren zur Beschichtung von metallischen Oberflächen mit einer Wasserstoffperoxid enthaltenden Phosphatierungslösung, Phosphatierlösung und Verwendung der behandelten Gegenstände
DE102005047424A1 (de) * 2005-09-30 2007-04-05 Henkel Kgaa Phosphatierlösung mit Wasserstoffperoxid und chelatbildenden Carbonsäuren
US20080314479A1 (en) * 2007-06-07 2008-12-25 Henkel Ag & Co. Kgaa High manganese cobalt-modified zinc phosphate conversion coating

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE432557A (fr) * 1938-02-04
GB1365291A (en) * 1970-09-25 1974-08-29 Ici Ltd Inhibition of corrosion
US4596607A (en) * 1985-07-01 1986-06-24 Ford Motor Company Alkaline resistant manganese-nickel-zinc phosphate conversion coatings and method of application
US4865653A (en) 1987-10-30 1989-09-12 Henkel Corporation Zinc phosphate coating process
DE4013483A1 (de) 1990-04-27 1991-10-31 Metallgesellschaft Ag Verfahren zur phosphatierung von metalloberflaechen
US5268041A (en) 1990-04-27 1993-12-07 Metallgesellschaft Ag Process for phosphating metal surfaces
DE4210513A1 (de) 1992-03-31 1993-10-07 Henkel Kgaa Nickel-freie Phosphatierverfahren
DE4441710A1 (de) * 1994-11-23 1996-05-30 Henkel Kgaa Korrosionsschutz und Reibungsverminderung von Metalloberflächen
US5935348A (en) 1995-11-14 1999-08-10 Henkel Kommanditgesellschaft Auf Aktien Composition and process for preventing corrosion and reducing friction on metallic surfaces

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008044143A1 (de) * 2008-11-27 2010-06-02 Atotech Deutschland Gmbh Konversionsschichten für zinkhaltige Oberflächen
DE102008044143B4 (de) * 2008-11-27 2011-01-13 Atotech Deutschland Gmbh Wässrige Behandlungslösung und Verfahren zur Erzeugung von Konversionsschichten für zinkhaltige Oberflächen

Also Published As

Publication number Publication date
US6379474B1 (en) 2002-04-30
AU9156398A (en) 1999-03-01
DE59805918D1 (de) 2002-11-14
EP1005578A1 (fr) 2000-06-07
WO1999007916A1 (fr) 1999-02-18
CA2300276A1 (fr) 1999-02-18
ES2185213T3 (es) 2003-04-16

Similar Documents

Publication Publication Date Title
EP0633950B1 (fr) Procede de phosphatation exempte de nickel
EP0717787B1 (fr) Procede de phosphatage sans nickel
EP1929070A1 (fr) Solution de phosphatation contenant du peroxyde d'hydrogene et des acides carboxyliques chelateurs
EP1114202A1 (fr) Procede pour la phosphatation, le rin age ulterieur et le trempage electrophoretique cathodique
EP0155547B1 (fr) Procédé pour la phosphatation au zinc-calcium de surfaces métalliques à basse température de traitement
EP1005578B1 (fr) Procede de phosphatation accelere par n-oxydes
DE10323305A1 (de) Verfahren zur Beschichtung von metallischen Oberflächen mit einer Wasserstoffperoxid enthaltenden Phosphatierungslösung
EP0656957B1 (fr) Procede de phosphatation d'acier zingue d'un seul cote
EP0134895B1 (fr) Procédé et composés pour l'application accélérée et affinée de couches de phosphate sur des surfaces métalliques
DE19705701A1 (de) Verfahren zur Niedrig-Nickel-Phosphatierung mit metallhaltiger Nachspülung
EP1060290B1 (fr) Solution aqueuse et procede pour phosphater des surfaces metalliques
EP0931179A2 (fr) Procede pour la phosphatation d'un feuillard d'acier
EP0889977B1 (fr) Phosphatation du zinc avec faible quantite de cuivre et de manganese
DE19733978A1 (de) Mit N-Oxiden beschleunigtes Phosphatierverfahren
DE4330104A1 (de) Nickel- und Kupfer-freies Phosphatierverfahren
EP1019564A1 (fr) Procede de phosphatation d'un feuillard d'acier
DE4341041A1 (de) Nickelfreies Phosphatierverfahren mit m-Nitrobenzolsulfonat
DE19958192A1 (de) Verfahren zur Phosphatierung, Nachspülung und kathodischer Elektrotauchlackierung
WO1997014821A1 (fr) Ajustement du poids de couche dans des systemes de phosphatation acceleres a l'hydroxylamine
WO1997016581A2 (fr) Phosphatation au zinc, a l'aide d'une solution sans manganese et a faible teneur en nitrate
EP1206589B1 (fr) Catalyseur pour la phosphatation de surfaces metalliques
DE19500927A1 (de) Lithiumhaltige Zinkphosphatierlösung
DE10310680A1 (de) Verfahren zur Phosphatierung mit einer Kombination von Beschleunigern
DE19541285C2 (de) Verfahren und Mittel zur Phosphatierung von Metalloberflächen
DE19750301A1 (de) Mit N-Oxiden und Clorat beschleunigtes Phosphatierverfahren

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20000129

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE ES FR GB IT

17Q First examination report despatched

Effective date: 20000809

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE ES FR GB IT

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REF Corresponds to:

Ref document number: 59805918

Country of ref document: DE

Date of ref document: 20021114

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20030205

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2185213

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20030710

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20130724

Year of fee payment: 16

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20140725

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140725

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 19

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20170728

Year of fee payment: 20

Ref country code: FR

Payment date: 20170724

Year of fee payment: 20

Ref country code: DE

Payment date: 20170724

Year of fee payment: 20

Ref country code: ES

Payment date: 20170825

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 59805918

Country of ref document: DE

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20220126

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20180726