US20090071573A1 - Phosphating solution with hydrogen peroxide and chelating carboxylic acids - Google Patents

Phosphating solution with hydrogen peroxide and chelating carboxylic acids Download PDF

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US20090071573A1
US20090071573A1 US12/055,984 US5598408A US2009071573A1 US 20090071573 A1 US20090071573 A1 US 20090071573A1 US 5598408 A US5598408 A US 5598408A US 2009071573 A1 US2009071573 A1 US 2009071573A1
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phosphating solution
solution according
ions
phosphating
acid
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Jan-Willem Brouwer
Jerzy-Tadeusz Wawrzyniak
Jens Kroemer
Maximilian Schoenherr
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Assigned to HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN (HENKEL KGAA) reassignment HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN (HENKEL KGAA) ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WAWRZYNIAK, JERSY-TADEUSZ, SCHOENHERR, MAXIMILIAN, BROUWER, JAN-WILLEM, KROEMER, JENS
Publication of US20090071573A1 publication Critical patent/US20090071573A1/en
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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
    • C23C22/07—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
    • C23C22/07—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
    • C23C22/16—Orthophosphates containing zinc cations containing also peroxy-compounds
    • 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
    • C23C22/17—Orthophosphates containing zinc cations containing also organic acids
    • 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
    • C23C22/365—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 containing also zinc and nickel cations

Definitions

  • the invention relates to a phosphating solution and a process for the phosphating of metallic surfaces with aqueous, acidic phosphating solutions that comprise zinc ions and phosphate ions as well as accelerators in free or bonded states, as well as their application as a pre-treatment of metal surfaces for subsequent coating, in particular an electro deposition.
  • the process may be used to treat surfaces made from steel, galvanized or alloy-galvanized steel, aluminum, aluminized or alloy-aluminized steel.
  • the object of phosphating metals is to produce on the metal surface strongly adhering metal phosphate layers which in themselves improve corrosion resistance and, in conjunction with lacquers and other organic coatings, contribute towards a substantial increase in lacquer adhesion and resistance to corrosive delamination.
  • Such phosphating processes have been known for a long time.
  • Low-zinc phosphating processes in which the phosphating solutions have relatively low contents of zinc ions of 0.5 to 2 g/l, are particularly suitable for pre-treatment prior to lacquer coating.
  • phosphate layers having distinctly improved corrosion protection and lacquer adhesion properties may be formed by also using polyvalent cations other than zinc in the phosphating baths.
  • polyvalent cations other than zinc in the phosphating baths.
  • low-zinc processes with the addition of, for example, 0.5 to 1.5 g/l of manganese ions and, for example, 0.3 to 2.0 g/l of nickel ions are widely used as the so-called tri-cation process for preparing metal surfaces for lacquer coating, for example for cathodic electrocoating of automotive bodywork.
  • phosphating solutions comprise accelerators. They accelerate the layer formation, since they have a “depolarizing” effect in that they oxidize the elementary hydrogen that results from the pickling reaction to form water.
  • accelerators such as for example hydroxylamine, can also influence the form of the resulting phosphate crystals.
  • Oxidizing accelerators also have the effect of oxidizing iron (II) ions resulting from the pickling reaction on steel surfaces to the trivalent state, so that they precipitate out as iron (III) phosphate.
  • a process for zinc phosphating is known from EP 414296, in which a combination of nitrate and hydrogen peroxide is employed as the accelerator.
  • the maximum peroxide concentration should be 17 mg/l.
  • DE 4243214 describes a phosphating process based on magnesium phosphate, which should be free of those inorganic substances that cannot be precipitated with calcium hydroxide in the neutral or alkaline range.
  • H 2 O 2 in amounts of 0.02 to 0.2 g/l, can be comprised as the accelerator.
  • zinc phosphate solutions that comprise 0.005 to 0.5 g/l H 2 O 2 together with 0.01 to 10 g/l formate find use.
  • WO 97/16581 discloses a process for phosphating steel, galvanized or alloy galvanized steel and/or aluminum or its alloys by treatment with a zinc phosphating solution in dip, spray or spray-dip processes, wherein the zinc phosphating solution exhibits a maximum nitrate ion content of 0.5 g/l and is free of manganese-, nickel- and cobalt ions and that it comprises:
  • the phosphating solution when it comprises hydroxylamine as the sole accelerator, should then preferably additionally comprise one or more aliphatic hydroxycarboxylic acids containing 3 to 6 carbon atoms in a total amount of 0.5 to 1.5 g/l.
  • hydroxycarboxylic acids are preferably selected from lactic acid, glycolic acid, tartronic acid, malic acid, tartaric acid and citric acid.
  • EP 154367 describes a zinc phosphating solution that comprises nitrobenzene sulfonate as the accelerator and that can additionally comprise citrate or tartrate.
  • EP 287133 discloses a zinc phosphating solution that comprises 5 to 30 g/l nitrate as the essential accelerator. Preferably, it further comprises 0.5 to 5 g/l iron (II), thereby excluding the presence of an oxidizing accelerator like H 2 O 2 .
  • This phosphating solution can further comprise up to 3 g/l tartaric acid or citric acid.
  • a phosphating solution is known from EP 433118 which comprises nitrate ions, iron (II)- or iron (III) ions as well as at least one organic chelating agent.
  • This chelating agent can be a polyhydroxycarboxylic acid, such as for example tartaric acid or citric acid.
  • WO 94/13856 The subject matter of WO 94/13856 is zinc phosphating solutions, particularly for strip processes, which exhibit a relatively high content of free acid (for the definition: see below) of 2 to 6 points.
  • These phosphating solutions comprise water-soluble organic acids, whose dissociation constant lies between the dissociation constants of the first and second step of phosphoric acid.
  • a whole range of suitable acids are mentioned, among others citric acid.
  • the phosphating solution can comprise an oxidizing agent selected from nitrite, chlorate, bromate, hydroxylamine, organic aromatic nitro compounds as well as hydrogen peroxide or peroxy compounds.
  • the concentration of the organic acids should be in the range 0.008 to 0.15 mol/l, the concentration of hydrogen peroxide in the range 0.01 to 0.1 g/l. Neither hydrogen peroxide nor citric acid was used in the examples.
  • FIG. 1A is a scanning electron microscope photograph of a phosphate layer of Comparative Example 6 at 400 ⁇ magnification.
  • FIG. 1B is a scanning electron microscope photograph of a phosphate layer of Comparative Example 6 at 800 ⁇ magnification.
  • FIG. 1C is a scanning electron microscope photograph of a phosphate layer of Comparative Example 6 at 2000 ⁇ magnification.
  • FIG. 2A is a scanning electron microscope photograph of a phosphate layer of Example 1 at 400 ⁇ magnification.
  • FIG. 2B is a scanning electron microscope photograph of a phosphate layer of Example 1 at 800 ⁇ magnification.
  • FIG. 2C is a scanning electron microscope photograph of a phosphate layer of Example 1 at 2000 ⁇ magnification.
  • the present invention relates to an acidic, aqueous phosphating solution, comprising
  • Chelating carboxylic acids are understood to mean carboxylic acids with at least two functional groups (including the carboxyl groups) that possess atoms with at least one free electron pair. Complexes with suitable metal ions, particularly transition metal cations, can be formed through the electron pairs of these functional groups. Chelate complexes result if at least two such functional groups of the same carboxylic acid coordinate the same metal cation, such that a cyclic structure is formed that incorporates the metal cation. Preferably, these rings possess five to seven atoms, including the metal cation.
  • the aliphatic chelating carboxylic acids preferably possess at least two carboxyl groups as well as at least one hydroxyl group that is not part of a carboxyl group. They can be selected from tartronic acid, malic acid, tartaric acid and citric acid, for example.
  • carboxylic acids in the phosphating solution exist as free acids or as acid anions depends on the acid constant of the particular carboxylic acid and on the pH of the phosphating solution. Generally, a chemical equilibrium between free carboxylic acid and carboxylic acid anions will be reached.
  • concentration data are to be understood as the total concentration, i.e. as the sum of the concentrations of the free carboxylic acids and their anions.
  • Typical parameters for controlling phosphating baths known to the person skilled in the art are the free acid and total acid contents.
  • the term “free acid” is commonly used by the person skilled in the field of phosphating.
  • the free acid content is limited to a maximum value of one point. Values of free acid between about 0.3 and 1 point and of total acid between about 15 and about 35 points are suitable in the context of this invention.
  • the phosphating solution preferably comprises 20 to 25 mg/l hydrogen peroxide or an equivalent amount of a substance that splits off hydrogen peroxide as a favorable compromise between acceleration, controllability and decomposition losses.
  • An equivalent amount will be understood by those of skill in the art to mean the amount of a substance that is the source of the hydrogen peroxide that provides the desired amount of free form H 2 O 2 .
  • the phosphating solution further comprises one or more cations that are incorporated into the crystalline phosphate layer. Accordingly, it is also preferred in the context of the invention that the phosphating solution additionally comprises one or more of the following cations:
  • the phosphating solution is poor in nickel or free of nickel.
  • the positive action of the nickel ions on the paint adhesion and corrosion protection is then assumed by the ecologically less risky copper ions.
  • the phosphating solution comprises 0.1 to 4 g/l manganese (II) ions, 0.002 to 0.2 g/l copper ions and not more than 0.05 g/l nickel ions.
  • the content of zinc ions is preferably 0.4 to 2 g/l and particularly 0.5 to 1.5 g/l.
  • the weight ratio of phosphate ions to zinc ions in the phosphating baths can vary widely in so far as it is the range between 3.7 and 30. A weight ratio between 10 and 20 is particularly preferred.
  • phosphating baths which are intended to be suitable for different substrates, one may add free and/or complexed fluoride in quantities of up to 2.5 g/l total fluoride, up to 750 mg/l of which as free fluoride, each calculated as F ⁇ .
  • the presence of such quantities of fluoride is advantageous for the inventive phosphating baths.
  • the aluminum content of the bath should not exceed 3 mg/l.
  • higher Al contents may be tolerated, provided that the concentration of non-complexed Al does not exceed 3 mg/l.
  • hydrogen peroxide as such i.e. in free form or also in bound form, for example as ionic peroxide or in the form of peroxy compounds, such as for example peroxydisulfuric acid, Caro's acid or also peroxyphosphoric acid.
  • Sodium perborate also is a further carrier for hydrogen peroxide in bound form.
  • the phosphating solution could be made up at the point of use by dissolving the individual components in water to the application concentrations. However, in practice this rarely occurs. It is much more usual to provide concentrates for initial use and for the replenishment of a phosphating solution.
  • the make-up concentrate is then diluted at the point of use with water to the application concentration, wherein the content of free acid and/or the pH generally have to be adjusted to the application range. Ranges for the free acid content have already been given above.
  • the pH is then generally between 2.7 and 3.6.
  • the replenishment concentrates are used in order to keep the active substances in a phosphating solution in the prescribed range during operation.
  • a further aspect of the present invention also relates to an aqueous concentrate that after dilution with water by a factor between 10 and 100 and adjustment if needed of the free acid content to a value of maximum one point, adjustment of the pH to a working range between 2.7 and 3.6 as well as adjustment if needed of the concentration of H 2 O 2 or of a substance that splits off hydrogen peroxide to the prescribed range, results in an above described phosphating solution.
  • Phosphating bath concentrates are generally adjusted to be strongly acidic on the grounds of stability, such that the free acid content after dilution with water is initially significantly above the desired working range.
  • the value of free acid is lowered to the required range by adding an alkaline substance such as, for example caustic soda or a sodium carbonate solution.
  • H 2 O 2 or a substance that splits off H 2 O 2 as sources of H 2 O 2 , is generally required, as these accelerators are not sufficiently stable in concentrated form in the amounts required for a phosphating bath concentrate.
  • the inventive concentrate comprises the active principles of the phosphating solution except for H 2 O 2 or a substance that splits off H 2 O 2 .
  • a further aspect of the present invention relates to a process for the phosphating of metal surfaces made of steel, galvanized or alloy galvanized steel and/or of aluminum, in which the metal surfaces are brought into contact with an above described phosphating solution by spraying or dipping or by a combination thereof for a period between 3 seconds and 8 minutes.
  • the temperature of the phosphating solution is in the range of about 30 to about 70 and in particular from about 40 to about 60° C. In practice, the temperatures are especially adjusted to the range 50 to 55° C.
  • the inventive process is suitable for phosphating surfaces made of steel, galvanized or alloy-galvanized steel, aluminum, aluminized or alloy-aluminized steel.
  • bodywork parts can also consist of already pre-treated material, as is the case for example in the Granocoat® process.
  • the base material is first pre-treated and then coated with a weldable coating of an organic resin.
  • the inventive phosphating process then leads to a phosphating of damaged spots of this pre-treatment layer or of the untreated reverse sides.
  • the process can be employed particularly in the automotive construction industry, where treatment times between 1 and 8 minutes are typical. It has been conceived for the treatment of the cited metal surfaces prior to lacquering, especially before a cathodic electrodepositioning, as is typical in the automotive construction industry.
  • the phosphating process should be regarded as a partial step of the industrially conventional pre-treatment chain. In this chain, the steps cleaning/degreasing, intermediate rinsing and activation are usually upstream of the phosphating, wherein the activation usually occurs with titanium phosphate-containing activators. However, the activation can also be effected with a suspension of finely divided ( ⁇ 5 ⁇ m) particulate phosphates of divalent or trivalent metals in an alkali metal phosphate solution. This activation process is described, for example in EP 1368508.
  • the inventive phosphating can be followed, optionally after an intermediate rinse, by a post-passivation treatment.
  • Treatment baths containing chromium salts were widely used for this purpose. However, for reasons of occupational hygiene and environmental protection as well as for disposal, there is the tendency to replace these chromium-containing passivation baths with chromium-free treatment baths. For this, purely inorganic baths, in particular based on zirconium compounds, or also organic baths, for example based on polyvinylphenols, are known. Generally, an intermediate rinse with totally deionized water is carried out between this post-passivation and the typically subsequent electro deposition coating.
  • composition of the phosphating bath was as follows:
  • layer weight was determined according to DIN 50942 by dissolution in a 5% conc. chromic acid solution.
  • Comparative examples 16 and 17 demonstrate that an adequate phosphating result is obtained by the use of nitrite or hydroxylamine as the accelerator even without the addition of a chelating carboxylic acid. However, if one wants to use H 2 O 2 as the accelerator, for example from ecological grounds, then at a free acid content of maximum one point, an adequate phosphating result is obtained only with the addition of the chelating carboxylic acid. On increasing the free acid content to 1.2 points, then rust formation occurs even with a combination of citric acid/H 2 O 2 (see exp. 13 to 15).
  • FIG. 1 shows scanning electron microscope photographs of a phosphate layer of Comparative Example 6.
  • FIG. 2 shows scanning electron microscope photographs of a phosphate layer of Example 1, according to the invention.
  • FIG. 2 shows a complete phosphate layer obtained according to the invention which has significantly smaller and more compact phosphate crystals than FIG. 1 .

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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)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
US12/055,984 2005-09-30 2008-03-26 Phosphating solution with hydrogen peroxide and chelating carboxylic acids Abandoned US20090071573A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102005047424.1 2005-09-30
DE102005047424A DE102005047424A1 (de) 2005-09-30 2005-09-30 Phosphatierlösung mit Wasserstoffperoxid und chelatbildenden Carbonsäuren
PCT/EP2006/008063 WO2007039015A1 (de) 2005-09-30 2006-08-16 Phosphatierlösung mit wasserstoffperoxid und chelatbildenden carbonsäuren

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PCT/EP2006/008063 Continuation WO2007039015A1 (de) 2005-09-30 2006-08-16 Phosphatierlösung mit wasserstoffperoxid und chelatbildenden carbonsäuren

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US (1) US20090071573A1 (zh)
EP (1) EP1929070A1 (zh)
CN (1) CN101278075B (zh)
DE (1) DE102005047424A1 (zh)
RU (1) RU2428518C2 (zh)
WO (1) WO2007039015A1 (zh)
ZA (1) ZA200802778B (zh)

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US10113070B2 (en) 2015-11-04 2018-10-30 Ppg Industries Ohio, Inc. Pretreatment compositions and methods of treating a substrate
WO2022135778A1 (de) * 2020-12-22 2022-06-30 M-M-Morant-Gmbh Chrom(vi)-freies beschichtungsmittel für metalle

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RU2428518C2 (ru) 2011-09-10
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