EP0882144A1 - Zinkphosphatierung mit geringen gehalten an nickel und/oder cobalt - Google Patents

Zinkphosphatierung mit geringen gehalten an nickel und/oder cobalt

Info

Publication number
EP0882144A1
EP0882144A1 EP97905009A EP97905009A EP0882144A1 EP 0882144 A1 EP0882144 A1 EP 0882144A1 EP 97905009 A EP97905009 A EP 97905009A EP 97905009 A EP97905009 A EP 97905009A EP 0882144 A1 EP0882144 A1 EP 0882144A1
Authority
EP
European Patent Office
Prior art keywords
ions
phosphating
phosphating solution
zinc
free
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Withdrawn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
EP97905009A
Other languages
German (de)
English (en)
French (fr)
Inventor
Karl-Dieter Brands
Jürgen Geke
Karl-Heinz Gottwald
Bernd Mayer
Peter Kuhm
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 EP0882144A1 publication Critical patent/EP0882144A1/de
Withdrawn legal-status Critical Current

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
    • C23C22/18—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
  • 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 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 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.
  • 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.
  • 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 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).

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)
EP97905009A 1996-02-19 1997-02-10 Zinkphosphatierung mit geringen gehalten an nickel und/oder cobalt Withdrawn EP0882144A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19606018 1996-02-19
DE19606018A DE19606018A1 (de) 1996-02-19 1996-02-19 Zinkphosphatierung mit geringen Gehalten an Nickel- und/oder Cobalt
PCT/EP1997/000602 WO1997030189A1 (de) 1996-02-19 1997-02-10 Zinkphosphatierung mit geringen gehalten an nickel und/oder cobalt

Publications (1)

Publication Number Publication Date
EP0882144A1 true EP0882144A1 (de) 1998-12-09

Family

ID=7785749

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97905009A Withdrawn EP0882144A1 (de) 1996-02-19 1997-02-10 Zinkphosphatierung mit geringen gehalten an nickel und/oder cobalt

Country Status (17)

Country Link
EP (1) EP0882144A1 (cs)
JP (1) JP2000504781A (cs)
KR (1) KR19990087077A (cs)
CN (1) CN1211288A (cs)
AR (1) AR005909A1 (cs)
AU (1) AU705531B2 (cs)
BR (1) BR9707433A (cs)
CA (1) CA2247144A1 (cs)
CZ (1) CZ262398A3 (cs)
DE (1) DE19606018A1 (cs)
HU (1) HUP9901000A2 (cs)
ID (1) ID15965A (cs)
PL (1) PL328085A1 (cs)
SK (1) SK112498A3 (cs)
TR (1) TR199801607T2 (cs)
WO (1) WO1997030189A1 (cs)
ZA (1) ZA971374B (cs)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4443882A1 (de) * 1994-12-09 1996-06-13 Metallgesellschaft Ag Verfahren zum Aufbringen von Phosphatüberzügen auf Metalloberflächen
DE19639596A1 (de) * 1996-09-26 1998-04-02 Henkel Kgaa Verfahren zur Phosphatierung von Stahlband
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
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
MX2021009075A (es) * 2019-01-29 2021-09-10 Chemetall Gmbh Composicion alternativa y metodo alternativo para fosfatar eficazmente superficies metalicas.

Family Cites Families (18)

* 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
IT975560B (it) * 1972-10-20 1974-08-10 Sec Accomandita Semplice Fosfa Procedimento di fosfatazione di su perfici metalliche destinate a ver niciatura particolarmente per elet troforesi e soluzione relativa a tale procedimento
DE2327304C3 (de) * 1973-05-29 1982-01-21 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zum Aufbringen von Phosphatüberzügen auf Metalle
DE2738281A1 (de) * 1977-08-25 1979-03-01 Metallgesellschaft Ag Verfahren zur phosphatierung von metallen
DE2738283A1 (de) * 1977-08-25 1979-03-01 Metallgesellschaft Ag Verfahren zur phosphatierung von metallen
IT1120362B (it) * 1979-05-29 1986-03-19 Fosfa Col S A S Di A Dal Pane Soluzione per la fosfatazione a freddo di superfici metalliche
GB2072225B (en) * 1980-03-21 1983-11-02 Pyrene Chemical Services Ltd Process and composition for coating metal surfaces
DE3400339A1 (de) * 1984-01-07 1985-08-29 Gerhard Collardin GmbH, 5000 Köln Verfahren zur nachpassivierung von phosphatierten metalloberflaechen unter verwendung von nickel- und/oder kupfer-kationen enthaltenden loesungen
DE3630246A1 (de) * 1986-09-05 1988-03-10 Metallgesellschaft Ag Verfahren zur erzeugung von phosphatueberzuegen sowie dessen anwendung
US4717431A (en) * 1987-02-25 1988-01-05 Amchem Products, Inc. Nickel-free metal phosphating composition and method for use
DE3871031D1 (de) * 1987-08-19 1992-06-17 Metallgesellschaft Ag Verfahren zur phosphatierung von metallen.
JPH0730455B2 (ja) * 1988-09-27 1995-04-05 日本パーカライジング株式会社 リン酸塩化成処理液
ZA903498B (en) * 1989-05-19 1992-01-29 Henkel Corp Composition and process for zinc phosphating
US5328526A (en) * 1992-04-03 1994-07-12 Nippon Paint Co., Ltd. Method for zinc-phosphating metal surface
DE4330104A1 (de) * 1993-09-06 1995-03-09 Henkel Kgaa Nickel- und Kupfer-freies Phosphatierverfahren
JPH07278891A (ja) * 1994-04-12 1995-10-24 Nippon Parkerizing Co Ltd 金属材料の塗装前処理方法
DE19500927A1 (de) * 1995-01-16 1996-07-18 Henkel Kgaa Lithiumhaltige Zinkphosphatierlösung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9730189A1 *

Also Published As

Publication number Publication date
CN1211288A (zh) 1999-03-17
CZ262398A3 (cs) 1999-01-13
WO1997030189A1 (de) 1997-08-21
BR9707433A (pt) 1999-07-20
AU705531B2 (en) 1999-05-27
PL328085A1 (en) 1999-01-04
JP2000504781A (ja) 2000-04-18
AU1872297A (en) 1997-09-02
HUP9901000A2 (hu) 1999-07-28
KR19990087077A (ko) 1999-12-15
TR199801607T2 (xx) 1998-11-23
CA2247144A1 (en) 1997-08-21
ZA971374B (en) 1997-08-19
SK112498A3 (en) 1999-01-11
ID15965A (id) 1997-08-21
AR005909A1 (es) 1999-07-21
DE19606018A1 (de) 1997-08-21

Similar Documents

Publication Publication Date Title
WO2009115504A1 (de) Optimierte passivierung auf ti-/zr-basis für metalloberflächen
EP0717787B1 (de) Nickelfreies phosphatierverfahren
WO1997045568A1 (de) Zinkphosphatierung mit integrierter nachpassivierung
EP1114202A1 (de) Verfahren zur phosphatierung, nachspülung und kathodischer elektrotauchlackierung
WO1996030559A1 (de) Verfahren zur phosphatierung mit metallhaltiger nachspülung
EP1929070A1 (de) Phosphatierlösung mit wasserstoffperoxid und chelatbildenden carbonsäuren
EP0922123B1 (de) Wässrige lösung und verfahren zur phosphatierung metallischer oberflächen
EP0931179B1 (de) Verfahren zur phosphatierung von stahlband
EP0889977B1 (de) Zinkphosphatierung mit geringen gehalten an kupfer und mangan
EP1208247A1 (de) Verfahren zur korrosionsschützenden behandlung oder nachbehandlung von metalloberflächen
DE19705701A1 (de) Verfahren zur Niedrig-Nickel-Phosphatierung mit metallhaltiger Nachspülung
EP0882144A1 (de) Zinkphosphatierung mit geringen gehalten an nickel und/oder cobalt
WO2001038605A2 (de) Verfahren zur phosphatierung mit metallhaltiger nachspülung
DE4330104A1 (de) Nickel- und Kupfer-freies Phosphatierverfahren
WO1997014821A1 (de) Schichtgewichtssteuerung bei hydroxylamin-beschleunigten phosphatiersystemen
DE4341041A1 (de) Nickelfreies Phosphatierverfahren mit m-Nitrobenzolsulfonat
WO2001040546A1 (de) Verfahren zur phosphatierung, nachspülung und kathodischer elektrotauchlackierung
WO1997016581A2 (de) Nitratarme, manganfreie zinkphosphatierung
DE19500927A1 (de) Lithiumhaltige Zinkphosphatierlösung
EP1208246A1 (de) Zinkphosphatierung mit epoxiden
WO1998009000A1 (de) Rutheniumhaltige zinkphosphatierung
DE19500562A1 (de) Silberhaltige Zinkphosphatierlösung
DE19716075A1 (de) Mit Hydroxylamin und Chlorat beschleunigtes Phosphatierverfahren

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19980808

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE DE ES FR GB IT NL PT SE

17Q First examination report despatched

Effective date: 19990916

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20000127