+

WO1997016581A2 - Phosphatation au zinc, a l'aide d'une solution sans manganese et a faible teneur en nitrate - Google Patents

Phosphatation au zinc, a l'aide d'une solution sans manganese et a faible teneur en nitrate Download PDF

Info

Publication number
WO1997016581A2
WO1997016581A2 PCT/EP1996/004541 EP9604541W WO9716581A2 WO 1997016581 A2 WO1997016581 A2 WO 1997016581A2 EP 9604541 W EP9604541 W EP 9604541W WO 9716581 A2 WO9716581 A2 WO 9716581A2
Authority
WO
WIPO (PCT)
Prior art keywords
ions
phosphating
zinc
free
phosphating solution
Prior art date
Application number
PCT/EP1996/004541
Other languages
German (de)
English (en)
Other versions
WO1997016581A3 (fr
Inventor
Jan-Willem Brouwer
Jürgen Geke
Karl-Heinz Gottwald
Peter Kuhm
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to AU72960/96A priority Critical patent/AU7296096A/en
Publication of WO1997016581A2 publication Critical patent/WO1997016581A2/fr
Publication of WO1997016581A3 publication Critical patent/WO1997016581A3/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—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
    • C23C22/14—Orthophosphates containing zinc cations containing also chlorate anions
    • 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
    • C23C22/362—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 zinc cations

Definitions

  • the invention relates to a process for phosphating metal surfaces with aqueous, acidic phosphating solutions which contain zinc and phosphate ions and accelerators in free or bound form, and to their use as pretreatment of the metal surfaces for subsequent painting, in particular electrocoating.
  • the method can be used for the treatment of surfaces made of steel, galvanized or alloy-galvanized steel, aluminum, aluminized or alloy-aluminized steel.
  • the phosphating of metals pursues the goal of producing firmly adhered metal phosphate layers on the metal surface, which in themselves improve corrosion resistance and, in conjunction with lacquers and other organic coatings, to a substantial increase in adhesion and resistance to migration under corrosion contribute.
  • Such phosphating processes have long been known in the prior art.
  • the low-zinc phosphating processes in which the phosphating solutions are comparatively low in zinc ion contents of z. B. 0.5 to Have 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> 12 and can take values up to 30.
  • phosphate layers with significantly improved corrosion protection and paint adhesion properties can be formed.
  • z. B. 0.5 to 1.5 g / 1 manganese ions and z. B. 0.3 to 2.0 g / 1 of nickel ions as a so-called trication process for preparing metal surfaces for painting, for example for the cathodic electrocoating of car bodies, widely used.
  • DE-A-39 20 296 describes a phosphating process which dispenses with nickel and uses magnesium ions in addition to zinc and manganese ions.
  • the phosphating baths described here contain, in addition to 0.2 to 10 g / 1 nitrate ions, further oxidizing agents which act as accelerators, selected from nitrite, chlorate or an organic oxidizing agent. Concerns about the accelerators nitrite and nitrate are being raised due to the possible formation of nitrous gases.
  • the phosphating process disclosed in WO 86/04931 works without nitrates.
  • the accelerator system is based on a combination of bromate and m-nitrobenzenesulfonate. Only zinc is given as the essential polyvalent cation, and nickel, manganese or cobalt is given as further optional cations.
  • the phosphating solutions preferably contain at least 2 of these optional metals.
  • DE-A-40 13 483 discloses phosphating processes with which good corrosion protection properties can be achieved as with the trication processes. These processes do without nickel and instead use copper in low concentrations, 0.001 to 0.03 g / 1.
  • Oxygen and / or other oxidizing agents having the same effect are used to oxidize the divalent iron formed in the pickling reaction of steel surfaces to the trivalent stage.
  • Nitrite, chlorate, bromate, peroxy compounds and organic nitro compounds, such as nitrobenzenesulfonate, are specified as such.
  • the German patent application DE 42 10513 modifies this process by adding hydroxylamine, its salts or complexes in an amount of 0.5 to 5 g / 1 hydroxylamine as a modifying agent for the morphology of the phosphate crystals formed.
  • EP-A-315059 specifies as a special effect of the use of hydroxylamine in phosphating baths the fact that on steel the phosphate crystals are still formed in a desired columnar or knot-like form when the zinc concentration in the phosphating bath is the same for low-zinc Ver ⁇ driving exceeds the usual range. This makes it possible to operate the phosphating baths with zinc concentrations of up to 2 g / 1 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.
  • Nitrates and nitric acid are also used in the patent examples, even if the description of the presence of nitrate in large amounts is not advised in the description.
  • the required hydroxylamine concentration is given as 0.5 to 50 g / 1, preferably 1 to 10 g / 1.
  • the incorporation of nickel and manganese in the phosphate layers compensated for disadvantages with regard to paint adhesion and corrosion protection, which resulted from the fact that only hopeit crystals, but no phosphophyllite crystals, were formed on galvanized substrates.
  • This object is achieved by a method for phosphating steel, galvanized or alloy-galvanized steel and / or aluminum or its alloys by treatment with a zinc phosphating solution in the immersion, spray or spray immersion process, characterized in that the zinc phosphating solution paints a maximum Has nitrate ion content of 0.5 g / 1 and is free of manganese, nickel and cobalt ions and that they
  • the phosphating baths are free from manganese, nickel and cobalt ions means that these ions are not deliberately added to the phosphating baths.
  • phosphating metal surfaces which contain these metals as alloy components, it cannot be ruled out that small amounts of the corresponding cations may get into the phosphating baths as a result of the pickling attack. This can be the case in particular when steel coated with a zinc-nickel alloy is phosphated. In practice, however, the expectation is placed on the phosphating baths that they contain less than 0.05 g / 1 of the cations mentioned.
  • phosphating baths In addition to zinc ions, phosphating baths generally contain sodium, potassium and / or ammonium ions to adjust the free acid.
  • the term free acid is familiar to those skilled in the phosphating field. The method of determining free acid and total acid selected in this document is given in the example section.
  • the process according to the invention is preferably characterized in that the phosphating solution additionally contains one or more of the following cations:
  • the weight ratio of phosphate ions to zinc ions in the phosphate baths can vary within wide limits, provided it is in the range between 3.7 and 30. A weight ratio between 10 and 20 is particularly preferred.
  • the skilled worker is familiar with the free acid and total acid contents as further parameters for controlling phosphating baths. The method of determining these parameters used in this document is given in the example section. Values of the free acid between about 0.3 and about 1.5 points and the total acid between about 15 and about 35 points are in the technically customary range and are suitable for the purposes of this invention.
  • nitrate content of the phosphating bath When phosphating surfaces containing zinc, it has proven to be advantageous to limit the nitrate content of the phosphating bath to a maximum of 0.5 g / l. This suppresses the problem of so-called speck formation and improves corrosion protection. Phosphating baths containing less than 0.05 g / l and in particular no nitrate are particularly preferred.
  • 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 800 mg / l 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.
  • the concentration of the non-complexed AI does not exceed 3 mg / l.
  • Suitable accelerators are the substances listed above and known in the prior art. On the one hand, these accelerate the layer formation, since they have a “depolarizing” effect by oxidizing the elemental hydrogen which forms on the metal surface during the pickling attack to water. However, certain accelerators such as hydroxylamine can also influence the shape of the phosphate crystals that are formed. Oxidizing accelerators also lead to the fact that iron (II) ions formed on steel surfaces during the pickling reaction are oxidized to the trivalent stage, so that they precipitate out as iron (III) phosphate.
  • nitrite could also be used within the scope of the invention. However, this is less preferred since the present invention is intended to provide a phosphating process which has particularly few toxicological and disposal problems. From the point of view of occupational safety, however, nitrite is to be assessed as particularly critical, since nitrous gases which are harmful to health can be generated when it is used. Furthermore, when nitrite is used, nitrate could be formed by its oxidation, so that the low nitrate contents according to the invention would be exceeded.
  • the accelerators listed above can be used individually, but in chemical compatibility they can also be used in combination.
  • 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 hydrogen peroxide can 7/16581 PO7EP96 / 04541
  • 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 / 1, preferably in amounts between about 0.5 and about 1.5 g / 1. Examples of such sugars are galactose, mannose and in particular glucose (dextrose).
  • Hydroxylamine can be used as a free base, as a hydroxylamine complex or in the form of hydroxylammonium salts. If free hydroxylamine is added to the phosphating bath or a phosphating bath concentrate, it will largely be present 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 sole accelerator, at most together with a maximum of 0.5 g / l of nitrate. Accordingly, in a preferred Embodiment phosphating baths are used which do not contain any of the other known accelerators such as nitrite, oxo anions of halogens, peroxides or nitrobenzenesulfonate.
  • the accelerator hydroxylamine 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 hydroxycarboxylic acids having 3 to 6 carbon atoms in a total amount of 0.5 to 1.5 g / l are added to the phosphating bath .
  • the hydroxycarboxylic acids are preferably selected from lactic acid, gluconic acid, tartronic acid, malic acid, tartaric acid and citric acid, citric acid being particularly preferred.
  • the zinc content of the phosphating bath will be set according to EP-A-315059 to values between 0.45 and 1.1 g / 1.
  • the current zinc content of the working bath is above a value of 1.1 g / l.
  • Zinc levels up to 2 g / l are harmless in the context of the present invention.
  • zinc contents of up to 2 g / l can also reduce the risk of rust formation during phosphating.
  • the form in which the cations are introduced into the phosphating baths is in principle irrelevant. It is particularly useful to use oxides and / or carbonates as the cation source.
  • iron (II) ions When the phosphating process is used on steel surfaces, iron dissolves in the form of iron (II) ions. Since the phosphating baths according to the invention preferably do not contain any substances contain that have an oxidizing effect on iron (II), the divalent iron only changes into the trivalent state as a result of air oxidation, so that it can precipitate out as iron (III) phosphate. Therefore, iron (II) contents can be built up in the phosphate baths according to the invention which are clearly above 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 occur briefly in the production process.
  • the phosphating baths can further contain the hardness-forming cations Mg (II) and Ca (II) in a total concentration of up to 7 mmol / l.
  • Mg (II) or Ca (II) can also be added to the phosphate bath in amounts of up to 2.5 g / l.
  • a phosphate solution is used which is the only one containing cations with an actual or potential oxidation state of> 1 zinc and copper ions.
  • Zinc and copper ions will generally be present in oxidation level 2 in the phosphate solution.
  • accelerators with a principally reducing action such as, for example, hydroxylamine, can at least partially reduce the copper ions to the monovalent stage.
  • this preferred phosphating solution can also contain sodium, potassium and / or ammonium ions, which, as usual, can be used in the form of their basic compounds to adjust the free acidity of the phosphating solution.
  • the phosphating solution contains 3 to 20 mg / l copper ions when used in the dipping process and 1 to 10 mg / l copper ions when used in the spraying process.
  • the temperature of the phosphating solution is preferably in the range between about 40 and about 60 ° C. It has emerged as a positive side effect of the phosphating process according to the invention that hydroxylamine concentrations above approximately 1.5 g / l significantly reduce the risk of rust formation at insufficiently flooded areas of the components to be phosphated.
  • the method according to the invention is suitable for phosphating surfaces made of steel, galvanized or alloy-galvanized steel, aluminum, aluminized or alloy-aluminized steel.
  • the materials mentioned can also be present side by side, as is becoming increasingly common in automobile construction.
  • Parts of the bodywork can also consist of material that has already been pretreated, such as is produced using the Bonazink R 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 method can be used in particular in automotive engineering, where treatment times between 1 and 8 minutes are common. It is intended in particular for the treatment of the metal surfaces mentioned before painting, in particular before cathodic electrocoating, as is customary in automobile construction.
  • 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 being carried out using activating agents containing titanium phosphate.
  • the phosphating according to the invention can be followed, if appropriate after an intermediate rinse, by a passivating aftertreatment. For such a passivating aftertreatment, treatment baths containing chromic acid are widespread.
  • the phosphating processes according to the invention and comparative processes were checked on electrolytically galvanized steel sheets, as are used in automobile construction.
  • the following process step, customary in body production, was carried out as an immersion process:
  • 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 8.5.
  • the mass per unit area was determined by dissolving in 5% chromic acid solution in accordance with DIN 50942.
  • the phosphated test sheets 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 rounds.
  • Table 1 also contains the results of a stone chip test according to the VW standard as "K values”.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Coating With Molten Metal (AREA)

Abstract

Procédé de phosphatation d'acier, d'acier zingué ou d'acier zingué allié et/ou d'aluminium ou de ses alliages, par traitement par une solution de phosphatation au zinc, par immersion, projection ou projection-immersion, caractérisé en ce que la solution de phosphatation au zinc présente une teneur maximale en ions nitrate de 0,5 g/l et est exempte d'ions manganèse, nickel et cobalt, et en ce qu'elle renferme 0,3 à 2 g/l d'ions zinc, 5 à 40 g/l d'ions phosphate, ainsi qu'un ou plusieurs accélérateurs.
PCT/EP1996/004541 1995-10-27 1996-10-18 Phosphatation au zinc, a l'aide d'une solution sans manganese et a faible teneur en nitrate WO1997016581A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU72960/96A AU7296096A (en) 1995-10-27 1996-10-18 Low-nitrate, manganese-free zinc phosphatization

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1995140085 DE19540085A1 (de) 1995-10-27 1995-10-27 Nitratarme, manganfreie Zinkphosphatierung
DE19540085.2 1995-10-27

Publications (2)

Publication Number Publication Date
WO1997016581A2 true WO1997016581A2 (fr) 1997-05-09
WO1997016581A3 WO1997016581A3 (fr) 1997-06-19

Family

ID=7775975

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/004541 WO1997016581A2 (fr) 1995-10-27 1996-10-18 Phosphatation au zinc, a l'aide d'une solution sans manganese et a faible teneur en nitrate

Country Status (3)

Country Link
AU (1) AU7296096A (fr)
DE (1) DE19540085A1 (fr)
WO (1) WO1997016581A2 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10204649A (ja) * 1997-01-24 1998-08-04 Nippon Parkerizing Co Ltd 金属表面のりん酸塩処理水溶液及び処理方法
US6179934B1 (en) 1997-01-24 2001-01-30 Henkel Corporation Aqueous phosphating composition and process for metal surfaces
DE10006338C2 (de) * 2000-02-12 2003-12-04 Chemetall Gmbh Verfahren zur Beschichtung von Metalloberflächen, wässeriges Konzentrat hierzu und Verwendung der beschichteten Metallteile
DE102008017523A1 (de) 2008-03-20 2009-09-24 Henkel Ag & Co. Kgaa Optimierte Elektrotauchlackierung von zusammengefügten und teilweise vorphosphatierten Bauteilen
CN107937892A (zh) * 2017-12-26 2018-04-20 廊坊京磁精密材料有限公司 高效环保钕铁硼磁体的磷化防锈方法

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU30515A1 (fr) *
DE860307C (de) * 1942-10-17 1952-12-18 Parker Rust Proof Company Verfahren zur Vorbereitung von Eisenblechen zur Anfertigung von Behaeltern
CH391420A (de) * 1959-09-23 1965-04-30 Metallgesellschaft Ag Verfahren zur Aufbringung von Phosphatüberzügen mit chlorathaltigen Phosphatierungslösungen
FR1312108A (fr) * 1961-11-29 1962-12-14 Parker Ste Continentale Procédé de régénération de solutions de phosphate de zinc chloratées et bromatées pour la phosphatation du fer et de l'acier
GB1272772A (en) * 1968-08-16 1972-05-03 Ici Ltd Phosphating solutions
JPS52119435A (en) * 1976-04-01 1977-10-06 Nippon Packaging Kk Phosphating process
JPS5811514B2 (ja) * 1979-05-02 1983-03-03 日本ペイント株式会社 金属表面の保護方法
ES8606528A1 (es) * 1985-02-22 1986-04-01 Henkel Iberica Procedimiento para el fosfatado de superficies metalicas, especialmente ferreas
DE3630246A1 (de) * 1986-09-05 1988-03-10 Metallgesellschaft Ag Verfahren zur erzeugung von phosphatueberzuegen sowie dessen anwendung
US4865653A (en) * 1987-10-30 1989-09-12 Henkel Corporation Zinc phosphate coating process
DE4210513A1 (de) * 1992-03-31 1993-10-07 Henkel Kgaa Nickel-freie Phosphatierverfahren
DE4214992A1 (de) * 1992-05-06 1993-11-11 Henkel Kgaa Kupfer enthaltendes, nickelfreies Phosphatierverfahren
DE69326021T2 (de) * 1992-12-22 1999-12-23 Henkel Corp., Plymouth Meeting Im wesentlichen nickelfreier phosphatkonversionsüberzug-zusammensetzung und verfahren
DE19500562A1 (de) * 1995-01-11 1996-07-18 Henkel Kgaa Silberhaltige Zinkphosphatierlösung
DE19500927A1 (de) * 1995-01-16 1996-07-18 Henkel Kgaa Lithiumhaltige Zinkphosphatierlösung
BR9607700A (pt) * 1995-03-07 1998-07-07 Henkel Corp Composição líquido aquosa e processo para formar um revestimento de conversão de fosfato em uma superfície de metal

Also Published As

Publication number Publication date
DE19540085A1 (de) 1997-04-30
WO1997016581A3 (fr) 1997-06-19
AU7296096A (en) 1997-05-22

Similar Documents

Publication Publication Date Title
EP0717787B1 (fr) Procede de phosphatage sans nickel
WO1996030559A1 (fr) PROCEDE DE PHOSPHATATION COMPORTANT UNE ETAPE DE RINçAGE FINAL A BASE DE METAL
EP1114202A1 (fr) Procede pour la phosphatation, le rin age ulterieur et le trempage electrophoretique cathodique
EP0931179B1 (fr) Procede pour la phosphatation d'un feuillard d'acier
DE19933189A1 (de) Verfahren zur korrosionsschützenden Behandlung oder Nachbehandlung von Metalloberflächen
DE19705701A1 (de) Verfahren zur Niedrig-Nickel-Phosphatierung mit metallhaltiger Nachspülung
EP0889977B1 (fr) Phosphatation du zinc avec faible quantite de cuivre et de manganese
EP1005578B1 (fr) Procede de phosphatation accelere par n-oxydes
DE19606018A1 (de) Zinkphosphatierung mit geringen Gehalten an Nickel- und/oder Cobalt
DE4330104A1 (de) Nickel- und Kupfer-freies Phosphatierverfahren
WO1997016581A2 (fr) Phosphatation au zinc, a l'aide d'une solution sans manganese et a faible teneur en nitrate
DE19956383A1 (de) Verfahren zur Phospatierung mit metallhaltiger Nachspülung
WO1997014821A1 (fr) Ajustement du poids de couche dans des systemes de phosphatation acceleres a l'hydroxylamine
DE4341041A1 (de) Nickelfreies Phosphatierverfahren mit m-Nitrobenzolsulfonat
DE19958192A1 (de) Verfahren zur Phosphatierung, Nachspülung und kathodischer Elektrotauchlackierung
EP0866888B1 (fr) Procede pour la phosphatation de surfaces metalliques
DE19500927A1 (de) Lithiumhaltige Zinkphosphatierlösung
DE19733978A1 (de) Mit N-Oxiden beschleunigtes Phosphatierverfahren
WO1998009000A1 (fr) Traitement au phosphate de zinc contenant du ruthenium
EP1208246A1 (fr) Procede de phosphatation au zinc faisant intervenir des epoxydes
DE10310680A1 (de) Verfahren zur Phosphatierung mit einer Kombination von Beschleunigern
DE19716075A1 (de) Mit Hydroxylamin und Chlorat beschleunigtes Phosphatierverfahren
DE19500562A1 (de) Silberhaltige Zinkphosphatierlösung
DE19750301A1 (de) Mit N-Oxiden und Clorat beschleunigtes Phosphatierverfahren

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AU BR CA CN CZ JP KR MX PL SK TR US

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

AK Designated states

Kind code of ref document: A3

Designated state(s): AU BR CA CN CZ JP KR MX PL SK TR US

AL Designated countries for regional patents

Kind code of ref document: A3

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: JP

Ref document number: 97517024

Format of ref document f/p: F

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载