EP1208246A1 - Procede de phosphatation au zinc faisant intervenir des epoxydes - Google Patents

Procede de phosphatation au zinc faisant intervenir des epoxydes

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Publication number
EP1208246A1
EP1208246A1 EP00956460A EP00956460A EP1208246A1 EP 1208246 A1 EP1208246 A1 EP 1208246A1 EP 00956460 A EP00956460 A EP 00956460A EP 00956460 A EP00956460 A EP 00956460A EP 1208246 A1 EP1208246 A1 EP 1208246A1
Authority
EP
European Patent Office
Prior art keywords
phosphating
ions
solution
zinc
suspension
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00956460A
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German (de)
English (en)
Inventor
Bernd Mayer
Bernd Schenzle
Wolfgang Krey
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1208246A1 publication Critical patent/EP1208246A1/fr
Withdrawn legal-status Critical Current

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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
    • C23C22/12—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
    • C23C22/18—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 phosphate ions.
  • the metal surfaces are brought into contact with organic polyepoxides (epoxy resins) which are present in the aqueous application medium in an amount of up to 5 g / 1 as a solution or suspension.
  • organic polyepoxides epoxy resins
  • Such methods serve in particular as pretreatment of the metal surfaces for subsequent painting, in particular electro-dip painting or powder painting.
  • the method is applicable for the treatment of surfaces made of steel, galvanized or alloy-galvanized steel, aluminum, aluminum-magnesium alloys, aluminized or alloy-aluminized steel.
  • the phosphating of metals pursues the goal of producing firmly adherent metal phosphate layers that already improve the corrosion resistance and in conjunction with paints or other organic coatings contribute to a significant increase in paint adhesion and resistance to infiltration when exposed to corrosion.
  • Such phosphating processes have long been known.
  • the low-zinc phosphating processes in which the phosphating solutions contain comparatively low zinc ion contents of e.g. Have 0.5 to 2 g / 1.
  • An important parameter in these low-zinc phosphating baths is the weight ratio of phosphate ions to zinc ions, which is usually in the range greater than 8 and can assume values up to 30.
  • EP-B-18 841 describes a chlorate-nitrite-accelerated zinc phosphating solution containing, inter alia, 0.4 to 1 g / l zinc ions, 5 to 40 g / l phosphate ions and optionally at least 0.2 g / l, preferably 0, 2 to 2 g / l of one or more ions selected from nickel, cobalt, calcium and manganese. Accordingly, the optional manganese, nickel or cobalt content is at least 0.2 g / l.
  • EP-A-459 541 describes phosphating solutions which are essentially free of nickel and which, in addition to zinc and phosphate, contain 0.2 to 4 g / l of manganese and 1 to 30 mg / l of copper.
  • DE-A-42 10 513 discloses nickel-free phosphating solutions which, in addition to zinc and phosphate, contain 0.5 to 25 mg / l of copper ions and hydroxylamine as an accelerator. These phosphating solutions optionally contain an additional 0.15 to 5 g / l manganese.
  • German patent application DE-A-196 06 017 describes a heavy metal-reduced phosphating solution which contains 0.2 to 3 g / l zinc ions, 1 to 150 mg / l manganese ions and 1 to 30 mg / l copper ions.
  • this phosphating solution can contain up to 50 mg / l nickel ions and up to 100 mg / l cobalt ions contain.
  • Another optional ingredient is lithium ions in amounts between 0.2 and 1.5 g / l.
  • German patent application DE-A-195 38 778 describes the control of the layer weight of phosphate layers by using hydroxylamine as an accelerator.
  • the use of hydroxylamine and / or its compounds to influence the shape of the phosphate crystals is known from a number of published publications.
  • EP-A-315 059 specifies the particular effect of the use of hydroxylamine in phosphating baths in the fact that the phosphate crystals are still formed in steel in a desired columnar or knot-like form when the zinc concentration in the phosphating bath corresponds to that for low-zinc Procedure exceeds the usual range. This makes it possible to operate the phosphating baths with zinc concentrations up to 2 g / l and with weight ratios of phosphate to zinc down to 3.7. No further statements are made about advantageous cation combinations of these phosphating baths, but nickel is used in all patent examples.
  • the required hydroxylamine concentration is given as 0.5 to 50 g / l, preferably 1 to 10 g / l.
  • a rinse solution for phosphated metal surfaces which contains a reaction product of an epoxy functional material with at least 2 epoxy groups and alkanolamines and a material selected from group IV-B metal ions.
  • Diethanolamine is preferably used for crosslinking the epoxides Care must be taken because of its tendency to form nitrosamines.
  • WO 97/45568 discloses a method for phosphating metal surfaces made of steel, galvanized or alloy galvanized steel and / or aluminum, in which the metal surfaces are brought into contact with a zinc-containing phosphating solution by spraying or dipping for a time between 3 seconds and 8 minutes , characterized in that the phosphating solution
  • the object of the present invention is to provide a phosphating process which manages with comparatively low nickel and / or cobalt contents of at most 200 mg / l and preferably without any addition of these metal ions. Nevertheless, paint adhesion and corrosion protection values are to be achieved, as they are required for the automotive industry and as they are currently achieved with standard trication-phosphating processes.
  • This object is achieved by a method for phosphating metal surfaces made of steel, galvanized or galvanized steel, aluminum and / or aluminum alloys, in which the metal surfaces are sprayed or dipped for a time between 3 seconds and 8 minutes with a zinc-containing phosphating solution in contact which contains 0.2 to 3 g / l zinc ions and 3 to 50 g / l phosphate ions, the weight ratio of phosphate ions to zinc ions being at least 3.7, and optionally one or more accelerators, wherein the metal surfaces during or subsequent to which the phosphating in contact with an aqueous solution or suspension of an organic polymer, characterized in that the organic polymer is a polyepoxide selected from glycidyl ether based on aliphatic polyols or based on bisphenol A or bisphenol F, which in a Amount of 0.1 to 5 g / l in the aqueous solution g or suspension is present.
  • the polyepoxides i.e
  • Phosphating solution are available. It is then used during the phosphating with the
  • the metal surfaces are first brought into contact with the phosphating solution and then with the aqueous solution or suspension of the organic polymer, that is to say the polyepoxides.
  • the solution or suspension of the polyepoxides is used as a passivating rinse solution. It then serves to close pores in the phosphate layer and thereby improve the corrosion protection. Due to the low concentration of the polyepoxides in the aqueous solution or suspension of at most 5 g / l, the organic film which is deposited is considerably thinner than a conventional coating and contains no more than 1 g of carbon per m 2 . This post-passivation is therefore not to be confused with a classic paint job, which preferably follows in the form of a cathodic electro-dip paint job - the next step after the passivating post-rinse.
  • the aqueous solution or suspension of the organic polymer additionally contains 10 to 1000, preferably 50 to 500 mg / l of complex fluorides contains titanium and / or zircon.
  • this passivating rinsing can be carried out with an aqueous solution or suspension of the organic polymer which - regardless of a possible content of complex fluorides of titanium and / or zirconium - contains 5 to 100 mg / l copper ions.
  • the pH of the aqueous solution or suspension of the organic polymers is preferably set to a value in the range from 3.8 to 5.5.
  • the passivating rinse solution can be done with the phosphated metal surface by immersing the metal parts in the rinse solution or by spraying the rinse solution are brought into contact.
  • the treatment time is preferably in the range of 0.5 to 3 minutes.
  • Rinse solution is preferably adjusted to a range between 15 and 45 ° C.
  • the zinc concentration is preferably in the range between about 0.3 and about 2 g / l and in particular between about 0.8 and about 1.6 g / l.
  • Such zinc contents can occur in a working phosphating bath if, during the phosphating of galvanized surfaces, additional zinc gets into the phosphating bath as a result of the pickling removal.
  • nickel and / or cobalt ions in the concentration range of about 1 to about 200 mg / l each, preferably in conjunction with the lowest possible nitrate content of not more than about 0.5 g / l, corrosion protection and paint adhesion to phosphating baths that do not contain nickel or Contain cobalt.
  • low levels of nickel or cobalt may be sufficient, for example levels between about 1 and about 50 mg / l for each of these cations.
  • the phosphating baths can also have low nickel contents in these cases, for example in the order of up to 10 mg / l. Such nickel contents can build up by being extracted from nickel-containing substrate material or from nickel-containing system parts.
  • the phosphating solution additionally contains about 0.001 to 3 g / l manganese ions.
  • the manganese content can be in the range from about 0.001 to about 0.2 g / l. Otherwise, manganese contents of about 0.5 to about 1.5 g / l are common.
  • the phosphating solution according to the invention can additionally contain about 1 to about 30 mg / l copper ions. This can be particularly advantageous if no nickel or cobalt ions are added. Depending on the substrate material, sufficient corrosion protection and sufficient paint adhesion can be achieved even without the addition of copper ions.
  • a special embodiment of the method according to the invention is that the phosphating solution does not contain any deliberately added nickel, cobalt and copper ions. This means that one can do without deliberately adding these three metal ions to the phosphating solution. However, as mentioned above, it cannot be excluded that small amounts of these ions, in particular nickel ions, get into the phosphating solution via the container material or via the substrate.
  • the phosphating solution can additionally each contain about 0.05 to about 3 g / l of magnesium, calcium, barium and / or iron (II) ions.
  • the iron content is preferably limited to contents below 0.5 g / l.
  • the phosphating baths generally contain sodium, potassium and / or ammonium ions to adjust the free acid.
  • free acid is familiar to the person skilled in the phosphating field. The method of determining free acid and total acid chosen in this document is given in the example section. Free acid and total acid represent an important control parameter for phosphating baths because they have a great influence on the layer weight.
  • 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 pickling 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 contains as little nitrate as possible. Nitrate concentrations of 0.5 g / l should not be exceeded, since there is a possibility of so-called "speck formation" at higher nitrate concentrations. 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 advisable to avoid nitrite as an accelerator. For the phosphating of galvanized surfaces, this is also advisable for technical reasons, since nitrite can form nitrate, 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 redosing solutions. However, using these two accelerators together is not advisable 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 hydrogen peroxide are particularly preferred. The hydrogen peroxide can be added as such to the phosphating solution. However, it is also possible to use hydrogen peroxide in bound form as compounds which are reacted in the phosphating bath by hydrolysis reactions Deliver hydrogen peroxide.
  • persalts such as perborates, percarbonates, peroxosulfates or peroxodisulfates.
  • Ionic peroxides such as, for example, alkali metal peroxides can be considered as further sources of hydrogen peroxide.
  • a preferred embodiment of the invention is that a combination of chlorate ions 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.
  • reducing sugars as accelerators is known from US-A-5 378 292. In the context of the present invention, they can be used in amounts between about 0.01 and about 10 g / l, preferably in amounts between about 0.5 and about 2.5 g / l.
  • sugars are galactose, mannose and especially glucose (dextrose).
  • hydroxylamine 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. If 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.
  • hydroxylammonium salt the sulfates and the phosphates are particularly suitable. In the case of the phosphates, the acid salts are preferred due to the 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 / l, preferably between 0.3 and 5 g / l. It is preferred that the phosphating baths contain hydroxylamine as the only accelerator, at most together with a maximum of 0.5 g / l nitrate. Accordingly, in a preferred embodiment, phosphating baths are used which do not have any of the other known accelerators such as, for example, nitrite, oxo anions of halogens, peroxides or Contain nitrobenzenesulfonate. As a positive side effect, hydroxylamine concentrations above approximately 1.5 g / l reduce the risk of rust formation in insufficiently flooded areas of the components to be phosphated.
  • 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 (III) phosphate. This is the case, for example, when using hydroxylamine. Therefore, iron (II) contents can build up in the phosphating baths, which are significantly higher than the contents containing 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 occur briefly in the production process.
  • 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.
  • Phosphating bath viewed as present in the form of phosphate ions PO ⁇ " .
  • the organic polyepoxides to be used according to the invention preferably have molecular weights (which can be determined, for example, by
  • the phosphating baths or the aqueous solutions or suspensions used for the passivating rinsing preferably contain the organic polyepoxides in a concentration between about 0.5 and about 1.5 g / l. At lower concentrations, the desired positive effect on paint adhesion and corrosion protection occurs less and less. Higher concentrations no longer significantly increase the effect and are therefore becoming increasingly uneconomical.
  • Polyepoxides to be used preferably have an epoxy equivalent weight between about 150 and about 1,500.
  • the polyepoxides can be introduced in various forms into the phosphating solution or into the aqueous solutions or suspensions used for the passivating rinsing.
  • it can be water-emulsifiable liquid resins that can be reactively diluted.
  • aqueous solid resin dispersions which can also be reactively diluted. Combinations of these two types of use are also possible.
  • the following compounds may be present as reactive diluents: alkyl monoglycidyl ether with a C chain between 4 and 18, preferably between 8 and 14 C atoms, Kresy Ig lycidyl ether, neopentyl glycol diglycidyl ether or other commercially available compounds.
  • Phosphating processes according to the invention are suitable for phosphating surfaces made of steel, galvanized or alloy-galvanized steel, aluminum, aluminized or alloy-aluminized steel and aluminum-magnesium alloys.
  • aluminum includes the technically customary aluminum alloys such as AIMgO, 5Si1, 4. The materials mentioned can - as is becoming increasingly common in automotive engineering - also coexist.
  • Parts of the body can also consist of pre-treated material, such as after arises.
  • the base material is first chromated or phosphated and then coated with an organic resin.
  • 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, it can also be used for strip phosphating in the steel mill, with treatment times between 3 and 12 seconds. 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.
  • 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., regardless 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 treating the metal surfaces mentioned before painting, for example before cathodic electrocoating, as is customary in automobile construction. It is also suitable as a pre-treatment before a powder coating, such as that used for household appliances.
  • 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, rinsing and activating are usually preceded by the phosphating, the activation usually taking place with activating agents containing titanium phosphate.
  • post-passivation can take place on the phosphating.
  • substrate material and corrosion protection requirements can also be dispensed with.
  • post-passivation a rinse with water, in particular with deionized water, is preferably used.
  • Different post-passivation solutions can be used for the post-passivation.
  • chromium (VI) -containing solutions can be used, but one is aimed at
  • Polyvinylphenol compounds are used. Furthermore, a
  • Rinse solution based on complex fluorides of titanium or zircon can be used. Furthermore, the rinsing can be carried out with an aqueous solution
  • This copper-containing post-passivation solution can additionally contain complex fluorides of titanium or zircon.
  • the phosphating processes and comparative processes according to the invention were checked on steel sheets ST 1405, as are used in automobile construction.
  • the following process, common in body production, was carried out as an immersion process:
  • the nitrate-free phosphating baths contained sodium ions to adjust the free acid if necessary.
  • the free acid score was 0.9-1.1, the total acid 20-22.
  • the free acid score is understood to mean the consumption in ml of 0.1 normal sodium hydroxide solution, to 10 ml bath solution up to a pH of 3.6 to titrate. Similarly, the total acid score indicates consumption in ml up to a pH of 8.2.
  • the phosphated test panels were coated with a cathodic dip coating from BASF (FT 85-7042).
  • the corrosion protection effect was tested in an alternating climate test according to VDA 621-415 over 10 laps.
  • sample sheets were phosphated as described above.
  • a passivating aftertreatment was additionally carried out between substeps 6 and 7 by immersing the phosphated and rinsed sheets in an aqueous solution at room temperature for 1 minute, which had a pH in the range from 4.1 to 4.2 and 50 ppm contained copper ions.
  • the polymer addition to the phosphating bath and the corrosion protection results are shown in Table 2.
  • Table 2 Phosphating baths and phosphating results
  • phosphating was carried out in a spraying process.
  • the substeps 1, 2 and 3 were carried out as described above.
  • the phosphating was carried out by spraying for two minutes with a phosphating solution at 50 ° C., which contained 1.2 g / l zinc, 0.9 g / l manganese, 14.0 g / l phosphate and 2.5 g / l hydroxylammonium sulfate.
  • the following sub-steps 5 to 7 and the painting were carried out as above. Polymer addition to the phosphating bath and corrosion protection results are given in Table 3.

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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)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention concerne un procédé de phosphatation au zinc de surfaces métalliques en acier, acier zingué ou acier revêtu d'un alliage, aluminium et/ou en alliage d'aluminium. Selon ce procédé, on met les surfaces métalliques en contact avec une solution de phosphatation renfermant du zinc, par pulvérisation ou immersion pendant une période comprise entre 3 secondes et 8 minutes, ladite solution renfermant 0,2 à 3 g/l d'ions zinc et 3 à 50 g/l d'ions phosphate, le rapport en poids entre les ions phosphate et les ions zinc s'élevant au moins à 3,7. Eventuellement, cette solution renferme en outre un ou plusieurs accélérateurs. Selon l'invention, on met les surfaces métalliques, pendant ou après la phosphatation, en contact avec une solution ou une suspension aqueuse d'un polymère organique. L'invention est caractérisée en ce que le polymère organique est un polyépoxyde sélectionné parmi les éthers de glycidyle à base de polyols aliphatiques ou à base de bisphénol A ou bisphénol F, ledit polymère organique étant présent dans des proportions comprises entre 0,1 et 5 g/l dans la solution ou la suspension aqueuse.
EP00956460A 1999-08-27 2000-08-18 Procede de phosphatation au zinc faisant intervenir des epoxydes Withdrawn EP1208246A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE1999140619 DE19940619A1 (de) 1999-08-27 1999-08-27 Zinkphosphatierung mit Epoxiden
DE19940619 1999-08-27
PCT/EP2000/008069 WO2001016397A1 (fr) 1999-08-27 2000-08-18 Procede de phosphatation au zinc faisant intervenir des epoxydes

Publications (1)

Publication Number Publication Date
EP1208246A1 true EP1208246A1 (fr) 2002-05-29

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EP (1) EP1208246A1 (fr)
JP (1) JP2003515668A (fr)
AR (1) AR025396A1 (fr)
AU (1) AU6839400A (fr)
DE (1) DE19940619A1 (fr)
WO (1) WO2001016397A1 (fr)

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DE10110833B4 (de) * 2001-03-06 2005-03-24 Chemetall Gmbh Verfahren zum Aufbringen eines Phosphatüberzuges und Verwendung der derart phosphatierten Metallteile
JP3992561B2 (ja) * 2002-04-16 2007-10-17 新日本製鐵株式会社 耐食性、耐アルカリ性に優れたクロメートフリー処理金属板

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US5591275A (en) * 1993-01-13 1997-01-07 Henkel Corporation Composition and process for surface treating metal prior to cold working
JP3239312B2 (ja) * 1994-03-31 2001-12-17 川崎製鉄株式会社 耐食性に優れた電気絶縁被膜を有する電磁鋼板
US5693371A (en) * 1996-10-16 1997-12-02 Betzdearborn Inc. Method for forming chromium-free conversion coating

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WO2001016397A1 (fr) 2001-03-08
AU6839400A (en) 2001-03-26
DE19940619A1 (de) 2001-03-01
AR025396A1 (es) 2002-11-27
JP2003515668A (ja) 2003-05-07

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