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WO1997030189A1 - Procede de phosphatisation au zinc a l'aide de faibles teneurs en nickel et/ou en cobalt - Google Patents

Procede de phosphatisation au zinc a l'aide de faibles teneurs en nickel et/ou en cobalt Download PDF

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Publication number
WO1997030189A1
WO1997030189A1 PCT/EP1997/000602 EP9700602W WO9730189A1 WO 1997030189 A1 WO1997030189 A1 WO 1997030189A1 EP 9700602 W EP9700602 W EP 9700602W WO 9730189 A1 WO9730189 A1 WO 9730189A1
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WO
WIPO (PCT)
Prior art keywords
ions
phosphating
phosphating solution
zinc
free
Prior art date
Application number
PCT/EP1997/000602
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German (de)
English (en)
Inventor
Jürgen Geke
Karl-Heinz Gottwald
Bernd Mayer
Peter Kuhm
Karl-Dieter Brands
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Brands, Thomas
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
Application filed by Henkel Kommanditgesellschaft Auf Aktien, Brands, Thomas filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to PL97328085A priority Critical patent/PL328085A1/xx
Priority to BR9707433A priority patent/BR9707433A/pt
Priority to SK1124-98A priority patent/SK112498A3/sk
Priority to EP97905009A priority patent/EP0882144A1/fr
Priority to JP9528964A priority patent/JP2000504781A/ja
Priority to AU18722/97A priority patent/AU705531B2/en
Publication of WO1997030189A1 publication Critical patent/WO1997030189A1/fr

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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
    • C23C22/05—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
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel 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
    • 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
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations

Definitions

  • the invention relates to processes for phosphating metal surfaces with aqueous, acid phosphating solutions which contain zinc and phosphau ions and a maximum of 100 ppm nickel and / or cobalt ions.
  • the invention further relates to the use of such processes as pretreatment of the metal surfaces for subsequent painting. in particular an electro-dip coating or a powder coating.
  • the method can be used for the treatment of surfaces made of steel, galvanized or alloy-galvanized steel. Aluminum, aluminized or alloy-alumimized steel
  • the phosphating of metals pursues the goal of producing firmly adhered metal phosphate layers on the metal surface which already improve the corrosion resistance and, in conjunction with lacquers or other organic coatings, to a substantial increase in lacquer adhesion and resistance to infiltration in the event of corrosion Contributing to on-demand stresses
  • Such phosphate processes have long been known for the pretreatment before painting, in particular electrocoating.
  • Low-zinc phosphating processes are particularly suitable. in which the phosphating solutions have comparatively low zinc ion contents of, for example, 0.5 to 2 g / 1.
  • An essential parameter in these low-zinc zinc phosphating baths is the weight ratio of phosphating ions to zinc ions, which is usually in the range of large 8 and values up to can assume to 30.
  • a phosphating solution is known from DE-A-20 49 350 which contains 3 to 20 g / 1 phosphate ions as essential components. 0.5 to 3 g / 1 zinc ions, 0.003 to 0.7 g / 1 cobalt ions or 0.003 to 0.04 g / 1 copper ions or preferably 0.05 to 3 g / 1 nickel ions, 1 to 8 g / 1 magnesium ions. Contains 0.01 to 0.25 g / 1 nitrite ions and 0.1 to 3 g / 1 fluorine ions and / or 2 to 30 g / 1 chlorine ions. This process therefore describes zinc-magnesium phosphating. wherein the phosphating solution additionally contains one of the ions cobalt, copper or preferably nickel. Such zinc-magnesium phosphating was not able to establish itself in technology.
  • EP-B-18 841 describes a chlorate-nitrite-accelerated zinc phosphating solution. contains, inter alia, 0.4 to 1 g / 1 zinc ions, 5 to 40 g / 1 phosphate ions and optionally at least 0.2 g / 1 preferably 0.2 to 2 g / 1 one or more ions selected from nickel, cobalt , Calcium and manganese. Accordingly, the optional nickel or cobalt content is at least 0.2 g / 1. In the exemplary embodiments, nickel contents of 0.53 and 1.33 g / 1 are given.
  • EP-A-141 341 describes phosphating solutions. which in addition to 10 to 50 g / 1 zinc contain nickel or cobalt in amounts of 0.1 to 5 g / 1.
  • EP-A-287 133 describes a zinc phosphating solution. which can optionally contain cobalt in amounts of up to 0.3 g / l. The solution contains 5 to 30 g / 1 nitrate as an essential component.
  • the invention has for its object to provide a low-heavy phosphating process that achieves the performance of the trication phosphating process on the different materials used in automotive engineering.
  • This object is achieved by a method for phosphating metal surfaces made of steel, galvanized or galvanized alloy steel and / or aluminum, in which the metal surfaces are in contact with a zinc-containing phosphating solution by spraying or dipping for a time between 3 seconds and 8 minutes brings, characterized in that the phosphating solution
  • the zinc concentration is preferably in the range between about 0.3 and about 2 g / 1 and in particular between about 0.8 and about 1.6 g / 1.
  • Such zinc contents can occur in a working phosphating bath if additional zinc gets into the phosphating bath during the phosphating of galvanized surfaces due to the pickling removal.
  • Nickel and / or cobalt ions in the stated concentration range of about 1 to about 100 mg / 1 in combination with the lowest possible nitrate content of not more than about 0.5 g / 1 improve corrosion protection and paint adhesion compared to phosphating baths that do not contain nickel or cobalt or which have a nitrate content of more than 0.5 g / 1.
  • Nickel contents in the range from approximately 1 to approximately 50 mg / l and / or cobalt contents in the range from approximately 5 to approximately 100 mg / l are preferred. This achieves a favorable compromise between the performance of the phosphating baths on the one hand and the requirements for the wastewater treatment of the rinsing water on the other hand.
  • lithium ions in the quantity range from about 0.2 to about 1.5 g / l improve the corrosion protection which can be achieved with zinc phosphating baths.
  • Lithium contents in the quantity range from 0.2 to approximately 1.5 g / l and in particular from approximately 0.4 to approximately 1 g / l also have a favorable effect on the corrosion protection achieved even in the low-heavy-metal phosphating process according to the invention.
  • the phosphating solutions can further contain about 0.001 to about 0.03 g / 1 copper ions. In particular in conjunction with hydroxylamine as an accelerator, such copper contents lead to a further improvement in corrosion protection.
  • the process according to the invention is to be used as a spraying process, copper contents in the range from approximately 0.001 to approximately 0.01 g / l are particularly favorable. When used as an immersion process, copper contents in the range from 0.005 to 0.02 g / l are preferred.
  • a further improvement in the corrosion protection effect can be achieved if the phosphating solution additionally contains manganese ions together with or instead of lithium and / or copper ions.
  • the manganese is preferably in oxidation state 2.
  • Manganese contents in the range from about 0.003 to about 0.1 g ; l represents a favorable compromise between the performance of the phosphating bath and the requirements for wastewater treatment and are therefore preferred.
  • phosphating solutions are used in a preferred embodiment of the invention. which contain zinc ions, cobalt ions and copper ions in the abovementioned quantitative ranges and which are free of manganese ions.
  • phosphating baths are used, the zinc ions. Contain cobalt ions and manganese ions in the abovementioned quantitative ranges and which are free of nickel and copper ions.
  • phosphating solutions, the zinc ions are used. Cobalt ions and lithium ions and optionally contain manganese ions.
  • phosphating solutions are used which contain zinc ions, nickel ions and lithium ions in the above-mentioned quantitative ranges and optionally manganese ions.
  • the phosphating baths generally contain sodium, potassium and / or ammonium ions for adjusting the free acid.
  • free acid is familiar to the person skilled in the art of phosphating. The method of determination of free acid and total acid chosen in this document is given in the example section. Free acid and total acid make you important control parameters for phosphating baths, since they have a great influence on the layer weight. Values of the free acid between 0 and 1.5 points in the case of partial phosphating, in the case of band phosphating up to 2.5 points and the total acid between about 15 and about 30 points are within the technically customary range and are suitable within the scope of this invention.
  • phosphating baths which are said to be suitable for different substrates, it has become customary to add free and / or complex-bound fluoride in amounts of up to 2.5 g / 1 total fluoride, of which up to 1 g / 1 free fluoride.
  • the presence of such amounts of fluoride is also advantageous for the phosphating baths according to the invention.
  • the aluminum content of the bath should not exceed 3 mg / l.
  • higher Al contents are tolerated as a result of the complex formation, provided the concentration of the non-complexed AI does not exceed 3 mg / 1.
  • the use of fluoride-containing baths is therefore advantageous if the surfaces to be phosphated consist at least partially of aluminum or contain aluminum. In these cases it is favorable not to use any complex-bound fluoride, but only free fluoride, preferably in concentrations in the range from 0.5 to 1.0 g / l.
  • the phosphating baths For the phosphating of zinc surfaces, it would not be absolutely necessary that the phosphating baths contain so-called accelerators. For the phosphating of steel surfaces, however, it is necessary that the phosphating solution contain one or more accelerators.
  • accelerators are known in the prior art as components of zinc phosphating baths. These are understood to mean substances which chemically bind the hydrogen generated by the acid pickling on the metal surface by reducing them themselves. Oxidizing accelerators also have the effect of oxidizing released iron (II) ions to the trivalent stage by the pickling attack on steel surfaces, so that they can precipitate out as iron (III) phosphate.
  • the phosphating baths according to the invention can contain one or more of the following components as accelerators:
  • the phosphating solution When phosphating galvanized steel, it is necessary that the phosphating solution contain as little nitrate as possible. Nitrate concentrations of 0.5 g / 1 should not be exceeded, since at higher nitrate concentrations there is a risk of so-called "speck formation". This means white, crater-like defects in the phosphate layer. In addition, the paint adhesion on galvanized surfaces is impaired.
  • nitrite as an accelerator leads to technically satisfactory results, especially on steel surfaces. For reasons of occupational safety (risk of developing nitrous gases), however, it is recommended not to use nitrite as an accelerator. For phosphating galvanized surfaces, this is also advisable for technical reasons, since nitrite can form from nitrite. which, as explained above, can lead to the problem of speck formation and to reduced paint adhesion on zinc.
  • Hydrogen peroxide is preferred for reasons of environmental friendliness, and hydroxylamine is particularly preferred as an accelerator for technical reasons because of the simplified formulation options for replenishing solutions. However, it is not advisable to use these two accelerators together, since hydroxylamine is decomposed by hydrogen peroxide. If hydrogen peroxide is used in free or bound form as an accelerator. concentrations of 0.005 to 0.02 g / l of hydrogen peroxide are particularly preferred. The hydrogen peroxide can be added to the phosphating solution as such. However, it is also possible to use hydrogen peroxide in bound form as compounds which give hydrogen peroxide in the phosphate bath by hydrolysis reactions.
  • persalts such as perborates, percarbonates, peroxosulfates or peroxodisulfates.
  • Ionic peroxides such as, for example, alkali metal peroxides, are suitable as further sources of hydrogen peroxide.
  • a preferred embodiment of the invention is that a combination of chloratio ⁇ en and hydrogen peroxide is used in the phosphating in the immersion process.
  • the concentration of chlorate can be, for example, in the range from 2 to 4 g / l, the concentration of hydrogen peroxide in the range from 10 to 50 ppm.
  • the use of reducing sugar as an accelerator is known from US Pat. No. 5,378,292.
  • sugars can be used in amounts between about 0.01 and about 10 g / 1, preferably in amounts between about 0.5 and about 2.5 g / 1.
  • sugars are galactose. Mannose and especially glucose (dextrose).
  • hydroxylamine as an accelerator.
  • Flydroxyiamine can be used as a free base, as a hydroxylamine complex, as an oxime, which is a condensation product of hydroxylamine with a ketone, or in the form of hydroxylammonium salts.
  • free hydroxylamine is added to the phosphating bath or a phosphating bath concentrate, it will largely exist as a hydroxylammonium cation due to the acidic nature of these solutions.
  • the sulfates and the phosphates are particularly suitable. In the case of the phosphates, the acid salts are preferred because of their better solubility.
  • Hydroxylamine or its compounds are added to the phosphating bath in amounts such that the calculated concentration of the free hydroxylamine is between 0.1 and 10 g / 1, preferably between 0.3 and 5 g / 1. It is preferred that the phosphating baths contain hydroxylamine as the only accelerator, at most together with a maximum of 0.5 g / 1 nitrate. Therefore be used in a preferred Ausj * of embodiment phosphoric phatierbäder that none of the other known accelerators, such as nitrite. Contain oxo anions of halogens, peroxides or nitrobenzenesulfonate. As a positive side effect, hydroxylamine concentrations above about 1.5 g / l reduce the risk of rust formation in insufficiently flooded areas of the components to be phosphated.
  • the hydroxylamine accelerator can be slowly inactivated even if no metal parts to be phosphated are introduced into the phosphating bath. It has surprisingly been found that the inactivation of the hydroxylamine can be significantly slowed down if one or more aliphatic hydroxy- or aminocarboxylic acids with 2 to 6 carbon atoms in a total amount of 0.01 to 1.5 g are added to the phosphating bath / 1 adds.
  • the carboxylic acids are preferably selected from glycine. Lactic acid, gluconic acid. Tartronic acid, malic acid. Tartaric acid and citric acid. citric acid, lactic acid and glycine are particularly preferred.
  • iron (II) ions When the phosphating process is used on steel surfaces, iron dissolves in the form of iron (II) ions. If the phosphating baths according to the invention do not contain any substances which have an oxidizing effect on iron (II), the divalent iron only changes to the trivalent state as a result of air oxidation, so that it can precipitate out as iron (HI) phosphate. This is the case, for example, when using hydroxylamine. As a result, iron (II) contents can be built up in the phosphating baths which are significantly higher than the contents which contain baths containing oxidizing agents. In this sense, iron (II) concentrations of up to 50 ppm are normal, although values of up to 500 ppm can also appear briefly in the production process.
  • the phosphate baths may further contain the hardness-forming cations Mg (II) and Ca (II) in a total concentration of up to 7 mmol / 1.
  • Mg (II) or Ca (II) can also be added to the phosphating bath in amounts of up to 2.5 g / l.
  • the weight ratio of phosphate ions to zinc ions in the phosphating baths can vary within a wide range, provided it is in the range between 3.7 and 30. A weight ratio between 10 and 20 is particularly preferred.
  • the total phosphorus content of the phosphating bath is considered to be PO43 in the form of phosphate ions. viewed here. Accordingly, the known fact that the pH values of the phosphating baths, which are usually in the range from about 3 to about 3.6, only a very small part of the phosphate is actually in the form of the triple negatively charged anions.
  • Phosphating baths are usually sold in the form of aqueous concentrates which are adjusted to the application concentrations on site by adding water. For reasons of stability, these concentrates can contain an excess of free phosphoric acid, so that when diluted to a bath concentration, the value of the free acid is initially too high or the pH is too low. By adding alkalis such as sodium hydroxide, sodium carbonate or ammonia, the value of the free acid is reduced to the desired range.
  • the free acid content during use of the phosphating baths can increase over time due to the consumption of the layer-forming cations and, if appropriate, through decomposition reactions of the accelerator. In these cases it is necessary to readjust the value of the free acid to the desired range from time to time by adding alkalis. This means that the levels of alkali metal or ammonium ions in the phosphating baths can fluctuate within wide limits and tend to increase over the course of the service life of the phosphating baths due to the bluntness of the free acid.
  • the weight ratio of alkali metal and / or ammonium ions to zinc ions can therefore be very low in freshly prepared phosphating baths, for example ⁇ 0.5 and in extreme cases even 0, while it usually increases over time as a result of bath maintenance measures, so that this Ratio> 1 and can assume values up to 10 and larger.
  • Low-zinc phosphating baths generally require additions of alkali metal or ammonium ions in order to obtain the desired PO43 weight ratio.
  • Zn> 8 to be able to set the free acid to the setpoint range.
  • Analogous considerations can also be made about the quantitative ratios of alkali metal and / or ammonium ions to other bath components, for example to phosphations.
  • lithium-containing phosphating baths the use of sodium compounds to adjust the free acid is preferably avoided since excess sodium concentrations suppress the favorable effect of lithium on the corrosion protection.
  • basic lithium compounds are preferably used to adjust the free acid.
  • potassium compounds are also suitable.
  • the metal ions are preferably used in the form of those compounds which do not introduce any foreign ions into the phosphating solution. It is therefore best to use the metals in the form of their oxides or their carbonates. Lithium can also be used as sulfate, copper preferably as Acetate can be used. Phosphating solutions of this type fulfill the ecological objective of the process particularly well, which, apart from zinc ions, contain no more than a total of 0.5 g / l of further divalent cations.
  • Phosphating baths according to the invention are suitable for phosphating surfaces made of steel, galvanized or alloy-galvanized steel, aluminum, aluminized or alloy-aluminized steel.
  • aluminum includes the technically customary aluminum alloys such as AlMgO, 5Sil, 4. The materials mentioned can also be present side by side, as is becoming increasingly common in automobile construction.
  • Parts of the body can also consist of material that has already been pretreated, such as is produced using the Bonazink ⁇ process.
  • the base material is first chromated or phosphated and then coated with an organic resin.
  • the phosphating process according to the invention then leads to phosphating on damaged areas of this pretreatment layer or on untreated rear sides.
  • the process is suitable for use in immersion, spray or spray / immersion processes. It can be used in particular in automobile construction, where treatment times between 1 and 8 minutes, in particular 2 to 5 minutes, are common. However, use in strip phosphating in the steel mill, with treatment times between 3 and 12 seconds, is also possible. When used in tape phosphating processes, it is advisable to set the bath concentrations in the upper half of the ranges preferred according to the invention. For example, the zinc content can range from 1.5 to 2.5 g / l and the free acid content can range from 1.5 to 2.5 points.
  • a particularly suitable substrate for strip phosphating is galvanized steel, in particular electrolytically galvanized steel.
  • the suitable bath temperatures are between 30 and 70 ° C., irrespective of the field of application, the temperature range between 45 and 60 ° C. being preferred.
  • the phosphating process according to the invention is intended in particular for the treatment of the metal surfaces mentioned before painting, for example before cathodic electrical painting, as is customary in automobile construction. It is also suitable as a pretreatment before powder coating, such as that used for household appliances becomes.
  • the phosphating process is to be seen as a sub-step of the technically usual pretreatment chain. In this chain, the steps of cleaning / degreasing are usually the phosphating. Intermediate rinsing and activation upstream, the activation usually being carried out with titanium phosphate-containing activating agents.
  • the phosphating according to the invention can, with or without intermediate rinsing, optionally be followed by a passivating aftertreatment.
  • Treatment baths containing chromic acid are widely used for such a passivating aftertreatment. For reasons of work and environmental protection and for disposal reasons, however, there is a tendency to replace these chromium-containing passivation baths with chromium-free treatment baths. Purely inorganic bath solutions, in particular based on zirconium compounds, or also organic reactive bath solutions, for example based on poly (vinylphenols), are known for this.
  • An intermediate rinse with deionized water is usually carried out between this post-passivation and the subsequent coating.
  • the phosphating processes and comparative processes according to the invention were checked on ST 1405 steel sheets and on electrolytically galvanized steel sheets, as are used in automobile construction.
  • the free acid score was 1.0-1.1, the total acid 23-25.
  • the free acid score is understood to mean the consumption in ml of 0.1 normal sodium hydroxide solution in order to titrate 10 ml of bath solution up to a pH of 3.6. Similarly, the total acid score indicates consumption in ml up to a pH of 8.2.
  • the phosphated test sheets were coated with a cathodic dip coating from BASF (FT 85-7042).
  • the corrosion protection effect for electrolytically galvanized steel was tested in an alternating climate test according to VDA 621-415 over 5 rounds.
  • VDA 621-415 the paint infiltration at the scratch (half scratch width) is shown in Table 1.
  • Table 1 also contains the results of a stone chip test according to the VW standard as "K values" (the smaller K, the better the paint adhesion).

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  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Treatment Of Metals (AREA)

Abstract

Procédé de phosphatisation de surfaces métalliques en acier et/ou en aluminium galvanisé ou revêtu d'alliage et galvanisé, selon lequel les surfaces métalliques sont mises en contact, par pulvérisation ou immersion, pendant une durée comprise entre 3 secondes et 8 minutes, avec une solution de phosphatation contenant du zinc, caractérisé en ce que la solution de phosphatation renferme 0,2 à 3 g/l d'ions zinc, 3 à 50 g/l d'ions phosphate, 1 à 100 mg/l d'ions nickel et/ou d'ions cobalt, un ou plusieurs accélérateurs et une teneur inférieure à 0,5 g/l d'ions nitrate. Comme composants pouvant être éventuellement ajoutés, on mentionne le lithium, le cuivre et/ou le manganèse.
PCT/EP1997/000602 1996-02-19 1997-02-10 Procede de phosphatisation au zinc a l'aide de faibles teneurs en nickel et/ou en cobalt WO1997030189A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
PL97328085A PL328085A1 (en) 1996-02-19 1997-02-10 Zinc phosphatising process involving low ni and possibly co content
BR9707433A BR9707433A (pt) 1996-02-19 1997-02-10 Fosfatização com zinco utilizando baixas concentrações de níquel e/ou cobalto
SK1124-98A SK112498A3 (en) 1996-02-19 1997-02-10 Zinc-phosphatizing method using low nickel and/or cobalt concentrations
EP97905009A EP0882144A1 (fr) 1996-02-19 1997-02-10 Procede de phosphatisation au zinc a l'aide de faibles teneurs en nickel et/ou en cobalt
JP9528964A JP2000504781A (ja) 1996-02-19 1997-02-10 低濃度のニッケル及び／又はコバルトを用いるリン酸亜鉛処理方法
AU18722/97A AU705531B2 (en) 1996-02-19 1997-02-10 Zinc-phosphatizing using low concentrations of nickel and/or cobalt

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19606018.4 1996-02-19
DE19606018A DE19606018A1 (de) 1996-02-19 1996-02-19 Zinkphosphatierung mit geringen Gehalten an Nickel- und/oder Cobalt

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
WO1998013534A3 (fr) * 1996-09-26 1998-08-27 Henkel Kgaa Procede pour la phosphatation d'un feuillard d'acier
AU700492B2 (en) * 1994-12-09 1999-01-07 Chemetall Gmbh Method of applying phosphate coatings to metal surfaces
CN103966588A (zh) * 2014-05-15 2014-08-06 清华大学 带热轧皮钢筋预钝化液、使用法及预钝化带热轧皮钢筋
WO2020156913A1 (fr) * 2019-01-29 2020-08-06 Chemetall Gmbh Composition alternative et procédé alternatif pour la phosphatation efficace de surfaces métalliques
RU2805161C2 (ru) * 2019-01-29 2023-10-11 Хеметалл Гмбх Альтернативная композиция и альтернативный способ эффективного фосфатирования металлических поверхностей

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DE19905479A1 (de) * 1999-02-10 2000-08-17 Metallgesellschaft Ag Verfahren zur Phospatisierung von Zink- oder Aluminiumoberflächen
DE19921135A1 (de) * 1999-05-07 2000-11-09 Henkel Kgaa Verfahren zur nickelarmen Zinkphoshatierung mit anschließender Wasserbehandlung
DE102006052919A1 (de) * 2006-11-08 2008-05-15 Henkel Kgaa Zr-/Ti-haltige Phosphatierlösung zur Passivierung von Metallverbundoberflächen
US9574093B2 (en) 2007-09-28 2017-02-21 Ppg Industries Ohio, Inc. Methods for coating a metal substrate and related coated metal substrates

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GB526815A (en) * 1939-03-14 1940-09-26 Samuel Thomas Roberts Improvements relating to the rustproofing of ferrous surfaces prior to painting or enamelling
US3090709A (en) * 1953-08-10 1963-05-21 Lubrizol Corp Phosphate coating of metals
FR2203893A1 (en) * 1972-10-20 1974-05-17 Fosfa Col Sas Di A Dal Pane Et Ambient temp. phosphating - using accelerator contg. bath to produce coating espec. amenable to accepting electrophoretic paint coatings
FR2231775A1 (en) * 1973-05-29 1974-12-27 Parker Ste Continentale Phosphate-coating solns. - free from formation of water-soluble salts during neutralization
FR2401234A1 (fr) * 1977-08-25 1979-03-23 Parker Ste Continentale Procede de phosphatation au zinc avec addition de fer
FR2401236A1 (fr) * 1977-08-25 1979-03-23 Parker Ste Continentale Procede de phosphatation au zinc avec preneutralisation
DE2931693A1 (de) * 1979-05-29 1980-12-11 In Accomandita Semplice Fosfa Loesung zur phosphatisierung metallischer flaechen
EP0036689A1 (fr) * 1980-03-21 1981-09-30 Metallgesellschaft Ag Procédé pour l'application de revêtements phosphatés
EP0149720A2 (fr) * 1984-01-07 1985-07-31 Gerhard Collardin GmbH Procédé de post passivation de surfaces métalliques phosphatées, utilisant des solutions contenant des cations de titane et/ou manganèse et/ou cobalt et/ou nickel et/ou cuivre
US4717431A (en) * 1987-02-25 1988-01-05 Amchem Products, Inc. Nickel-free metal phosphating composition and method for use
EP0258922A1 (fr) * 1986-09-05 1988-03-09 Metallgesellschaft Ag Procédé pour produire des revêtements de phosphate et leur utilisation
EP0304108A1 (fr) * 1987-08-19 1989-02-22 Metallgesellschaft Ag Procédé de phosphatation de métaux
EP0361375A1 (fr) * 1988-09-27 1990-04-04 Nihon Parkerizing Co., Ltd. Procédé de production de revêtements
EP0398202A1 (fr) * 1989-05-19 1990-11-22 Henkel Corporation Composition et procédé de phosphatation du zinc
EP0564286A2 (fr) * 1992-04-03 1993-10-06 Nippon Paint Co., Ltd. Procédé de zinc-phosphatation d'une surface métallique
DE4330104A1 (de) * 1993-09-06 1995-03-09 Henkel Kgaa Nickel- und Kupfer-freies Phosphatierverfahren
WO1995027809A1 (fr) * 1994-04-12 1995-10-19 Henkel Corporation Procede de pretraitement de substrats metalliques avant application de peinture
DE19500927A1 (de) * 1995-01-16 1996-07-18 Henkel Kgaa Lithiumhaltige Zinkphosphatierlösung

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB526815A (en) * 1939-03-14 1940-09-26 Samuel Thomas Roberts Improvements relating to the rustproofing of ferrous surfaces prior to painting or enamelling
US3090709A (en) * 1953-08-10 1963-05-21 Lubrizol Corp Phosphate coating of metals
FR2203893A1 (en) * 1972-10-20 1974-05-17 Fosfa Col Sas Di A Dal Pane Et Ambient temp. phosphating - using accelerator contg. bath to produce coating espec. amenable to accepting electrophoretic paint coatings
FR2231775A1 (en) * 1973-05-29 1974-12-27 Parker Ste Continentale Phosphate-coating solns. - free from formation of water-soluble salts during neutralization
FR2401234A1 (fr) * 1977-08-25 1979-03-23 Parker Ste Continentale Procede de phosphatation au zinc avec addition de fer
FR2401236A1 (fr) * 1977-08-25 1979-03-23 Parker Ste Continentale Procede de phosphatation au zinc avec preneutralisation
DE2931693A1 (de) * 1979-05-29 1980-12-11 In Accomandita Semplice Fosfa Loesung zur phosphatisierung metallischer flaechen
EP0036689A1 (fr) * 1980-03-21 1981-09-30 Metallgesellschaft Ag Procédé pour l'application de revêtements phosphatés
EP0149720A2 (fr) * 1984-01-07 1985-07-31 Gerhard Collardin GmbH Procédé de post passivation de surfaces métalliques phosphatées, utilisant des solutions contenant des cations de titane et/ou manganèse et/ou cobalt et/ou nickel et/ou cuivre
EP0258922A1 (fr) * 1986-09-05 1988-03-09 Metallgesellschaft Ag Procédé pour produire des revêtements de phosphate et leur utilisation
US4717431A (en) * 1987-02-25 1988-01-05 Amchem Products, Inc. Nickel-free metal phosphating composition and method for use
EP0304108A1 (fr) * 1987-08-19 1989-02-22 Metallgesellschaft Ag Procédé de phosphatation de métaux
EP0361375A1 (fr) * 1988-09-27 1990-04-04 Nihon Parkerizing Co., Ltd. Procédé de production de revêtements
EP0398202A1 (fr) * 1989-05-19 1990-11-22 Henkel Corporation Composition et procédé de phosphatation du zinc
EP0564286A2 (fr) * 1992-04-03 1993-10-06 Nippon Paint Co., Ltd. Procédé de zinc-phosphatation d'une surface métallique
DE4330104A1 (de) * 1993-09-06 1995-03-09 Henkel Kgaa Nickel- und Kupfer-freies Phosphatierverfahren
WO1995027809A1 (fr) * 1994-04-12 1995-10-19 Henkel Corporation Procede de pretraitement de substrats metalliques avant application de peinture
DE19500927A1 (de) * 1995-01-16 1996-07-18 Henkel Kgaa Lithiumhaltige Zinkphosphatierlösung

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU700492B2 (en) * 1994-12-09 1999-01-07 Chemetall Gmbh Method of applying phosphate coatings to metal surfaces
WO1998013534A3 (fr) * 1996-09-26 1998-08-27 Henkel Kgaa Procede pour la phosphatation d'un feuillard d'acier
CN103966588A (zh) * 2014-05-15 2014-08-06 清华大学 带热轧皮钢筋预钝化液、使用法及预钝化带热轧皮钢筋
WO2020156913A1 (fr) * 2019-01-29 2020-08-06 Chemetall Gmbh Composition alternative et procédé alternatif pour la phosphatation efficace de surfaces métalliques
CN113366147A (zh) * 2019-01-29 2021-09-07 凯密特尔有限责任公司 用于有效磷化金属表面的替换组合物和替换方法
RU2805161C2 (ru) * 2019-01-29 2023-10-11 Хеметалл Гмбх Альтернативная композиция и альтернативный способ эффективного фосфатирования металлических поверхностей
US12203173B2 (en) 2019-01-29 2025-01-21 Chemetall Gmbh Alternative composition and alternative method for effectively phosphating metal surfaces

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HUP9901000A2 (hu) 1999-07-28
CA2247144A1 (fr) 1997-08-21
AR005909A1 (es) 1999-07-21
ID15965A (id) 1997-08-21
JP2000504781A (ja) 2000-04-18
AU1872297A (en) 1997-09-02
BR9707433A (pt) 1999-07-20
SK112498A3 (en) 1999-01-11
DE19606018A1 (de) 1997-08-21
PL328085A1 (en) 1999-01-04
EP0882144A1 (fr) 1998-12-09
CZ262398A3 (cs) 1999-01-13
KR19990087077A (ko) 1999-12-15
CN1211288A (zh) 1999-03-17
ZA971374B (en) 1997-08-19
TR199801607T2 (xx) 1998-11-23
AU705531B2 (en) 1999-05-27

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