EP0459541B1 - Procédé de phosphatation de surfaces métalliques - Google Patents

Procédé de phosphatation de surfaces métalliques Download PDF

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Publication number
EP0459541B1
EP0459541B1 EP91200532A EP91200532A EP0459541B1 EP 0459541 B1 EP0459541 B1 EP 0459541B1 EP 91200532 A EP91200532 A EP 91200532A EP 91200532 A EP91200532 A EP 91200532A EP 0459541 B1 EP0459541 B1 EP 0459541B1
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EP
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Prior art keywords
metal surfaces
phosphating
brought
contact
contain
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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
EP91200532A
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German (de)
English (en)
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EP0459541A1 (fr
Inventor
Horst Dr. Gehmecker
Werner Dr. Rausch
Peter Dr. Schubach
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Chemetall GmbH
Original Assignee
Metallgesellschaft AG
Continentale Parker SA
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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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/186—Orthophosphates containing manganese cations containing also copper 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
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/188—Orthophosphates containing manganese cations containing also magnesium cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • 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
    • C23C22/368—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 magnesium cations

Definitions

  • the invention relates to a method for phosphating metal surfaces with aqueous, acid phosphating solutions containing zinc, manganese, Cu and phosphate ions and oxidizing agents, and its use as a pretreatment of the metal surfaces for subsequent electrocoating and for the phosphating of steel, galvanized steel , galvanized steel, aluminum and its alloys.
  • phosphating of metals pursues the goal of producing firmly adherent metal phosphate layers on the metal surface, which in themselves improve the corrosion resistance and, in conjunction with paints and other organic coatings, contribute to a significant increase in the adhesion and resistance to infiltration when exposed to corrosion.
  • phosphate layers serve as insulation against the passage of electrical currents and, in conjunction with lubricants, to facilitate sliding processes.
  • the low-zinc phosphating processes are particularly suitable, in which the phosphating solutions contain comparatively low levels of zinc ions of e.g. B. 0.5 to 1.5 g / l. Under these conditions, phosphate layers with a high content of phosphophyllite (Zn2Fe (PO4) 2.4H2O) are produced on steel, which is much more corrosion-resistant than the hopite (Zn3 (PO4) 2.4H2O) deposited from zinc-rich phosphating solutions.
  • Zn2Fe (PO4) 2.4H2O phosphophyllite
  • By using nickel and / or manganese ions in the low zinc phosphating solutions further increase the protection quality in connection with paints.
  • Low zinc process with the addition of e.g. B.
  • the high content of nickel ions in the phosphating solutions of the trication processes and of Ni and Ni compounds in the phosphate layers formed has disadvantages insofar as nickel and nickel compounds can be classified as harmful from the point of view of workplace hygiene and environmental protection.
  • the object of the invention is to provide a process for the phosphating of metals, in particular steel, galvanized steel, alloy-galvanized steel and aluminum and its alloys, which leads to phosphate layers, the quality of which roughly corresponds to the layers of the trication processes based on Zn-Mn Ni corresponds without having the disadvantage of the presence of Ni and Ni compounds.
  • the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the metal surfaces are brought into contact with phosphating solutions which contain a maximum of 0.01 g / l of nickel and 0.3 to 1.7 g / l Zn 0.2 to 4.0 g / l Mn 0.001 to 0.030 g / l Cu 5 to 30 g / l phosphate (calculated as P2O5) contain and in which the concentration of Fe (II) is kept below 0.1 g / l and the pH is adjusted to 3.0 to 3.8 by means of oxygen and / or other oxidizing agents having the same effect.
  • phosphating solutions which contain a maximum of 0.01 g / l of nickel and 0.3 to 1.7 g / l Zn 0.2 to 4.0 g / l Mn 0.001 to 0.030 g / l Cu 5 to 30 g / l phosphate (calculated as P2O5)
  • the method according to the invention is applied in particular to steel, galvanized steel, alloy-galvanized steel, aluminum and its alloys.
  • steel includes soft unalloyed steels, high and high-strength steels (e.g. microalloyed, dual-phase and phosphorus alloyed) and low-alloyed steels.
  • the galvanizing layers can e.g. B. generated by electrolysis, hot dipping or vapor deposition.
  • Typical zinc qualities include pure zinc, as well as e.g. B. Alloys with Fe, Ni, Co, Al, Cr.
  • Aluminum and aluminum alloys are understood to mean the casting and kneading materials used in the metal industry, which can contain, for example, Mg, Mn, Cu, Si, Zn, Fe, Cr, Ni, Ti as alloying elements.
  • the basic requirement of the process according to the invention is that the aqueous acidic phosphating solutions are essentially free of nickel. This means that under technical conditions the Ni concentration in the phosphating baths is less than 0.0002 to 0.01 g / l. However, it is preferably below 0.0001 g / l.
  • the essential content of the invention is also the presence of the three metal cations Zn, Mn and Cu in the amounts indicated.
  • Zn concentrations below 0.3 g / l lead to a significant deterioration in the layer formation, particularly when treating steel.
  • the phosphophyllite content in phosphate layers on steel drops sharply, at the same time the quality of the phosphate layers in connection with painting is reduced.
  • Below 0.2 g / l Mn the addition of this cation brings no visible advantages, above a concentration of 4 g / l there are no further improvements in quality observe.
  • the Cu concentration is between 0.001 and 0.030 g / l. Below this range, the favorable effect on layer formation and layer quality is lost, while above 0.030 g / l Cu an annoying Cu cementation becomes increasingly noticeable.
  • Fe dissolves in the form of Fe (II) ions.
  • the phosphating bath must now contain so much oxygen and / or other oxidizing agents that the stationary Fe (II) ion concentration does not exceed a value of 0.1 g / l, i.e. H. that all other Fe is converted into Fe (III) and precipitated as iron phosphate sludge.
  • the pH value of the phosphating solution must be set between 3.0 and 3.8.
  • the higher (lower) pH values apply to lower (higher) bath temperatures and to lower (higher) bath concentrations.
  • additional cations e.g. B. alkali (Na, K, NH4 and others), and / or alkaline earth metal ions (Mg, Ca) or other anions (NO3, Cl, SiF6, SO4, BF4 and others) also used.
  • the quality of the phosphate layers produced with the aid of the method according to the invention can be improved if up to 3 g / l Mg and / or up to 3 g / l Ca are added to the phosphating solution.
  • the preferred concentration range for these cations is 0.4 to 1.3 g / l each.
  • the cations can e.g. B. as phosphate or as a salt with the above mentioned anions are introduced into the phosphating solution.
  • the oxides, hydroxides and carbonates are also suitable as a source of Mg and Ca.
  • the Zn concentration is preferably 0.3 to 1 g / l, while for the spraying / dipping and immersion method the Zn content in the bath is preferably 0.9 to 1.7 g / l is set.
  • the preferred Mn concentration is - regardless of the type of application - between 0.4 and 1.3 g / l.
  • the metal surfaces are brought into contact with a phosphating solution which contains 0.003 and 0.020 g / l Cu. Furthermore, particularly favorable phosphating results are achieved if the weight ratio between Cu and phosphate, calculated as P2O5, is 1: (170 to 30,000) in the phosphating bath and Cu and P2O5 are supplemented in a weight ratio of 1: (5 to 2000).
  • the preferred oxidizing agents include nitrite, chlorate, bromate, peroxy compounds (H2O2, perborate, percarbonate, perphosphate, etc.) and organic nitro compounds, eg. B. nitrobenzenesulfonates. These oxidizing agents can be used alone or in combination - if appropriate also with weaker oxidizing agents such as nitrate. Suitable combinations are e.g. B.
  • oxidizing agents mentioned not only serve to oxidize Fe-II ions, but also accelerate them Phosphate layer formation. Examples of typical concentration ranges of the oxidizing agents mentioned in the phosphating bath are given below.
  • Nitrite 0.04 to 0.5 g / l; Chlorate: 0.5 to 5 g / l; Bromate: 0.3 to 4 g / l; Peroxy compound, calculated as H2O2: 0.005 to 0.1 g / l; Nitrobenzenesulfonate: 0.05 to 1 g / l.
  • a further preferred embodiment of the invention consists in bringing the metal surfaces into contact with phosphating solutions which additionally contain compounds having a modifying action from the group of surfactants, hydroxycarboxylic acid, tartrate, citrate, single fluoride, boron fluoride, silicon fluoride.
  • surfactant e.g. 0.05 to 0.5 g / l
  • Hydroxycarboxylic acids e.g. B. tartaric acid, citric acid or its salts lead in the concentration range of z. B. 0.03 to 0.3 g / l to a significant reduction in the weight of the phosphate layer.
  • Single fluoride favors the phosphating of metals that are more difficult to attack and leads to a reduction in the minimum phosphating time and an increase in the area coverage of the phosphate layer.
  • z. B. F contents of 0.1 to 1 g / l.
  • the controlled addition of single fluoride also enables the formation of crystalline phosphate layers on aluminum and its alloys.
  • BF4 and SiF6 also increase the aggressiveness of the phosphating baths, which is particularly evident when treating hot-dip galvanized surfaces. These additives are used, for example, in amounts of 0.4 to 3 g / l.
  • the phosphating process according to the invention is suitable for use in spraying, spraying / dipping and dipping.
  • the bath temperatures are usually between 40 and 60 ° C.
  • the surfaces are usually cleaned, rinsed and often treated with activating agents based on titanium phosphate before they are brought into contact with the phosphating solution.
  • the phosphate layers produced with the phosphating process according to the invention are finely crystalline and uniformly opaque.
  • the weight per unit area is usually between 1.5 and 4.5 g / m2 for the treatment of steel, galvanized steel and alloy-galvanized steel and between 0.5 and 2.5 g / m2 for the treatment of aluminum and its alloys.
  • the phosphating solution e.g. B. by incorporation into the phosphate layer, by sludge formation, by mechanical bath losses over the treated metal surface and the sludge discharge, by redox reactions and also by decomposition. For this reason, the phosphating solution must be monitored analytically and supplemented with the missing components.
  • the phosphate layers can be used with advantage for corrosion protection, for facilitating non-cutting cold forming and for electrical insulation. However, they are preferably used to prepare metal surfaces for painting, in particular electrocoating, with particularly good results in connection with cathodic electrocoating be achieved. Before painting, it is recommended that the phosphate layers with passivating detergents such. B. based on Cr (VI), Cr (VI) -Cr (III), Cr (III), Cr (III) fluorozirconate, Al (III), Al (III) fluorozirconate. This further increases paint adhesion and infiltration resistance.
  • Sheets made of steel, galvanized steel and aluminum were degreased with an alkaline cleaner, rinsed with water and, if necessary after phosphating with a solution containing titanium phosphate, phosphated with the phosphating solutions 1 to 12 at 50 ° C. In all cases, uniformly covering phosphate layers were produced, which in connection with cathodic electrocoat + automotive paint build-up provided good paint adhesion and good resistance to corrosion penetration.

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  • 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)

Claims (12)

  1. Procédé de phosphatation de surfaces métalliques par des solutions aqueuses acides de phosphatation qui contiennent des ions zinc, manganèse, Cu et phosphate ainsi que des agents d'oxydation, caractérisé en ce qu'il consiste à mettre les surfaces métalliques en contact avec des solutions de phosphatation qui renferment au maximum 0,01 g/l de nickel ainsi que
       de 0,3 à 1,7 g/l de Zn
       de 0,2 à 4,0 g/l de Mn
       de 0,001 à 0,030 g/l de Cu
       de 5 à 30 g/l de phosphate (exprimé en P₂O₅)
       et dans lesquelles on maintient par de l'oxygène et/ou par d'autres agents d'oxydation équivalents, la concentration de Fe(II) inférieure à 0,1 g/l et on règle le pH entre 3,0 et 3,8.
  2. Procédé suivant la revendication 1, caractérisé en ce qu'il consiste à mettre des surfaces métalliques en contact avec des solutions de phosphatation qui renferment en plus du Mg et/ou du Ca en des quantités allant jusqu'à 3,0 g/l pour chacun d'entre eux.
  3. Procédé suivant la revendication 2, caractérisé en ce qu'il consiste à mettre des surfaces métalliques en contact avec des solutions de phosphatation qui renferment en plus du Mg et/ou du Ca en des quantités de 0,4 à 1,3 g/l.
  4. Procédé suivant la revendication 1, 2 ou 3, caractérisé en ce qu'il consiste quand on utilise un procédé de pulvérisation, à mettre les surfaces métalliques en contact avec des solutions de phosphatation qui renferment de 0,3 à 1,0 g/l de Zn.
  5. Procédé suivant la revendication 1, 2 ou 3, caractérisé en ce qu'il consiste quand on utilise un procédé de pulvérisation/immersion et un procédé d'immersion à mettre des surfaces métalliques en contact avec des solutions de phosphatation qui renferment de 0,9 à 1,7 g/l de Zn.
  6. Procédé suivant l'une ou plusieurs des revendications 1 à 5, caractérisé en ce qu'il consiste à mettre des surfaces métalliques en contact avec des solutions de phosphatation qui renferment du Mn en des quantités de 0,4 à 1,3 g/l.
  7. Procédé suivant l'une ou plusieurs des revendications 1 à 6, caractérisé en ce qu'il consiste à mettre les surfaces métalliques en contact avec des solutions de phosphatation qui renferment de 0,003 à 0,020 g/l de Cu.
  8. Procédé suivant l'une ou plusieurs des revendications 1 à 7, caractérisé en ce qu'il consiste à mettre les surfaces métalliques en contact avec des solutions de phosphatation dans lesquelles le rapport pondéral de Cu à P₂O₅ est réglé à 1:(170 à 30000) et Cu et P₂O₅ sont complétés en un rapport pondéral de 1:(5 à 2000).
  9. Procédé suivant l'une ou plusieurs des revendications 1 à 8, caractérisé en ce qu'il consiste à mettre des surfaces métalliques en contact avec des solutions de phosphatation qui renferment comme agent d'oxydation un nitrite, un chlorate, un bromate, un composé peroxydé, des composés nitro organiques.
  10. Procédé suivant l'une ou plusieurs des revendications 1 à 9, caractérisé en ce qu'il consiste à mettre les surfaces métalliques en contact avec des solutions de phosphatation qui renferment en plus des composés modifiant choisis parmi les agents tensioactifs, les acides hyrdroxycarboxyliques un tartrate, un citrate, un monofluorure, un borofluorure, un silicofluorure.
  11. Utilisation du procédé suivant l'une ou plusieurs des revendications 1 à 10 comme pré-traitement de surfaces métalliques pour un trempage électrophorètique ultérieur.
  12. Utilisation du procédé suivant l'une ou plusieurs des revendications 1 à 10 pour la phosphatation de l'acier, de l'acier zingué, de l'acier allié à du zinc, de l'aluminium et de ses alliages.
EP91200532A 1990-04-27 1991-03-12 Procédé de phosphatation de surfaces métalliques Expired - Lifetime EP0459541B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4013483A DE4013483A1 (de) 1990-04-27 1990-04-27 Verfahren zur phosphatierung von metalloberflaechen
DE4013483 1990-04-27

Publications (2)

Publication Number Publication Date
EP0459541A1 EP0459541A1 (fr) 1991-12-04
EP0459541B1 true EP0459541B1 (fr) 1995-11-22

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ID=6405232

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EP91200532A Expired - Lifetime EP0459541B1 (fr) 1990-04-27 1991-03-12 Procédé de phosphatation de surfaces métalliques

Country Status (11)

Country Link
EP (1) EP0459541B1 (fr)
JP (1) JP3063920B2 (fr)
BR (1) BR9101660A (fr)
CA (1) CA2039901C (fr)
CZ (1) CZ281471B6 (fr)
DE (2) DE4013483A1 (fr)
ES (1) ES2081420T3 (fr)
MX (1) MX172859B (fr)
PL (1) PL166676B1 (fr)
RU (1) RU2051988C1 (fr)
ZA (1) ZA913133B (fr)

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DE4210513A1 (de) 1992-03-31 1993-10-07 Henkel Kgaa Nickel-freie Phosphatierverfahren
JPH05287549A (ja) * 1992-04-03 1993-11-02 Nippon Paint Co Ltd カチオン型電着塗装のための金属表面のリン酸亜鉛処理方法
DE4214992A1 (de) * 1992-05-06 1993-11-11 Henkel Kgaa Kupfer enthaltendes, nickelfreies Phosphatierverfahren
DE4232292A1 (de) * 1992-09-28 1994-03-31 Henkel Kgaa Verfahren zum Phosphatieren von verzinkten Stahloberflächen
DE4243214A1 (de) * 1992-12-19 1994-06-23 Metallgesellschaft Ag Verfahren zur Erzeugung von Phosphatüberzügen
JPH08504890A (ja) * 1992-12-22 1996-05-28 ヘンケル コーポレーション 実質的にニッケルを含まないリン酸塩化被膜を形成するための組成物および方法
ES2111949T3 (es) * 1993-09-06 1998-03-16 Henkel Kgaa Procedimiento de fosfato exento de niquel.
FR2724395B1 (fr) * 1994-09-12 1996-11-22 Gec Alsthom Transport Sa Tole magnetique isolee et procede d'isolement de cette tole
DE4440300A1 (de) * 1994-11-11 1996-05-15 Metallgesellschaft Ag Verfahren zum Aufbringen von Phosphatüberzügen
NO312911B1 (no) * 1994-12-22 2002-07-15 Budenheim Rud A Oetker Chemie Antikorrosjonspigment og anvendelse av dette
DE19500927A1 (de) * 1995-01-16 1996-07-18 Henkel Kgaa Lithiumhaltige Zinkphosphatierlösung
DE19511573A1 (de) * 1995-03-29 1996-10-02 Henkel Kgaa Verfahren zur Phosphatierung mit metallhaltiger Nachspülung
DE19606017A1 (de) * 1996-02-19 1997-08-21 Henkel Kgaa Zinkphosphatierung mit geringen Gehalten an Kupfer und Mangan
DE19634732A1 (de) * 1996-08-28 1998-03-05 Henkel Kgaa Rutheniumhaltige Zinkphosphatierung
EP1005578B1 (fr) 1997-08-06 2002-10-09 Henkel Kommanditgesellschaft auf Aktien Procede de phosphatation accelere par n-oxydes
US6720032B1 (en) 1997-09-10 2004-04-13 Henkel Kommanditgesellschaft Auf Aktien Pretreatment before painting of composite metal structures containing aluminum portions
DE19740953A1 (de) * 1997-09-17 1999-03-18 Henkel Kgaa Verfahren zur Phosphatierung von Stahlband
JPH11264076A (ja) * 1998-01-14 1999-09-28 Nippon Paint Co Ltd 低鉛ｅｄ用の下地化成処理方法
DE19808755A1 (de) 1998-03-02 1999-09-09 Henkel Kgaa Schichtgewichtsteuerung bei Bandphosphatierung
DE10006338C2 (de) * 2000-02-12 2003-12-04 Chemetall Gmbh Verfahren zur Beschichtung von Metalloberflächen, wässeriges Konzentrat hierzu und Verwendung der beschichteten Metallteile
DE10110834B4 (de) * 2001-03-06 2005-03-10 Chemetall Gmbh Verfahren zur Beschichtung von metallischen Oberflächen und Verwendung der derart beschichteten Substrate
JP2002266080A (ja) * 2001-03-07 2002-09-18 Nippon Paint Co Ltd リン酸塩化成処理液、化成処理方法および化成処理鋼板
DE102005047424A1 (de) * 2005-09-30 2007-04-05 Henkel Kgaa Phosphatierlösung mit Wasserstoffperoxid und chelatbildenden Carbonsäuren
PL2336391T3 (pl) * 2008-10-08 2016-09-30 Materiał metalowy o doskonalej odporności na korozję
RU2572688C1 (ru) * 2014-09-10 2016-01-20 Закрытое акционерное общество "ФК" Раствор для фосфатирования металлической поверхности

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CZ281471B6 (cs) 1996-10-16
EP0459541A1 (fr) 1991-12-04
CA2039901C (fr) 2000-11-14
ZA913133B (en) 1992-12-30
PL290031A1 (en) 1992-02-24
ES2081420T3 (es) 1996-03-16
CZ118091A3 (en) 1994-04-13
JP3063920B2 (ja) 2000-07-12
JPH04228579A (ja) 1992-08-18
MX172859B (es) 1994-01-17
CA2039901A1 (fr) 1991-10-28
PL166676B1 (pl) 1995-06-30
RU2051988C1 (ru) 1996-01-10
DE4013483A1 (de) 1991-10-31
DE59106926D1 (de) 1996-01-04
BR9101660A (pt) 1991-11-26

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