WO1993022474A1 - Procede de phosphatation sans nickel avec du cuivre - Google Patents

Procede de phosphatation sans nickel avec du cuivre Download PDF

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Publication number
WO1993022474A1
WO1993022474A1 PCT/EP1993/001015 EP9301015W WO9322474A1 WO 1993022474 A1 WO1993022474 A1 WO 1993022474A1 EP 9301015 W EP9301015 W EP 9301015W WO 9322474 A1 WO9322474 A1 WO 9322474A1
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WO
WIPO (PCT)
Prior art keywords
copper
ions
phosphating
phosphating solution
metal surface
Prior art date
Application number
PCT/EP1993/001015
Other languages
German (de)
English (en)
Inventor
Wolf-Achim Roland
Karl-Heinz Gottwald
Matthias Hamacher
Jan-Willem Brouwer
Frank-Oliver Pilarek
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
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Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1993022474A1 publication Critical patent/WO1993022474A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—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
    • 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
    • C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite 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
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/186—Orthophosphates containing manganese cations containing also copper 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
    • C23C22/22—Orthophosphates containing alkaline earth metal cations

Definitions

  • the invention relates to a method for producing copper-containing nickel-free phosphate layers on metal surfaces and to the use of the method as pretreatment of the metal surfaces before painting, in particular cataphoretic dip painting (KTL).
  • KTL cataphoretic dip painting
  • the quality of phosphate coatings before cataphoretic dip coating depends on a large number of parameters. These include physical quantities such as the shape and size of the crystals, their mechanical stability and in particular the free metal surface after phosphating, the so-called pore surface. Of particular interest in the chemical parameters are the alkali stability during the cataphoretic coating, the binding strength of the water of crystallization of the zinc phosphate crystals when the lacquers are stoved, and the rehydration capacity.
  • the layer weight can be controlled, in particular reduced, by using activating agents prior to phosphating.
  • the oligomeric / polymeric titanium phosphates present in the activating agents form active centers on the metal surface, from which the crystal growth proceeds. As a result, smaller and mechanically more stable crystals are obtained on the one hand, and on the other hand the pore area is reduced, making it more difficult to attack corrosive media if the coating is damaged.
  • the layer weight reduction by magnesium ions is so strong that other control parameters, which are usually also used to reduce the layer weight, such as very low zinc concentrations (0.6 g / 1 Zn 2+ ), high concentrations of accelerators such as sodium nitrite or meta-nitrobenzenesulfonate / Na salts cannot be used additionally in order not to press the area-related mass below 1.5-2.0 g / m 2 .
  • DE 40 13 483 AI discloses a method for phosphating metal surfaces, in which one works with phosphating solutions which are generally are free of nickel. Zinc, manganese and low copper contents are mentioned as essential bath components. In addition, the concentration of Fe (II) is kept below a maximum value by means of oxygen and / or other oxidizing agents having the same effect.
  • the method serves in particular for the phosphating of steel, galvanized steel, alloy-galvanized steel, aluminum and their alloys for the pretreatment for a subsequent painting, in particular an electrocoating. Additions of small amounts of copper ions to phosphating baths have been known for 40 years.
  • the object was therefore to provide a process for the production of copper-containing nickel-free phosphate layers which, in the absence of nickel on metal surfaces such as cold-rolled steel, electrolytically galvanized steel and aluminum, ensures very good paint adhesion and excellent corrosion protection, and in particular the formation avoided by specks on galvanized steel.
  • the above-mentioned object is achieved with the aid of a specially selected phosphating solution, with which it is possible to produce copper-containing phosphate layers with a defined copper content while avoiding speck formation.
  • the present invention thus relates to a process for the production of copper-containing nickel-free phosphate layers with a copper content in the range of 0.5-5% by weight on metal surfaces containing a phosphate solution
  • Phosphate 5.0 - 30 g / 1 (calculated as P2 ⁇ 5) r nitrate 0.1 to 15 g / 1, the product of the proportions of Cu ions (in mg / 1) and nitrate ions (mg / 1) contained in the phosphating solution ) is less than 50,000 when using immersion processes and less than 15,000 when using spraying processes.
  • the zinc phosphate ten are made up of small (0.5 - 10 ⁇ ), compact, densely grown crystals.
  • II copper
  • the phosphating solution contains 5-20 pp of copper (II) ions when the metal surface is brought into contact with the phosphating solution by means of immersion processes.
  • the phosphating solutions contain 1-10 ppm of copper (II) ions in order to incorporate corresponding copper contents in the conversion coating without producing the disruptive specks on electrolytically galvanized steel surfaces.
  • the method according to the invention can be used in particular on steel, galvanized steel, alloy galvanized steel, aluminum and the like 1
  • Alloys are applied.
  • steel in the sense of the present invention encompasses not only low-alloy steels but also soft, unalloyed steels and higher as well as high-strength steels.
  • this amount should be less than 0.0002-0.01 g / 1, in particular less than 0.0001 g / 1.
  • iron dissolves in the form of iron (II) ions.
  • iron (II) is converted into iron (III) and can thus be precipitated as iron phosphate sludge.
  • oxidizing agents are known in the prior art for limiting the iron (II) ion concentration.
  • the contact of the phosphating solution with oxygen for example atmospheric oxygen and / or the addition of suitable oxidizing agents serves to limit the iron (II) ion concentration.
  • the oxidizing agents of the phosphating solutions are selected from nitrite, chlorate, hydroxylain and its salts, bromate, permanganate, peroxide compounds (in particular hydrogen peroxide, perborate, percarbonate, perphosphate) and organic nitro compounds, in particular nitrobenzenesulfonate.
  • the amounts of oxidizing agents to be used are known from the prior art.
  • oxidizing agents known as “accelerators” also have the task of "depolarizing" the metal surface when the acid is attacked, ie To prevent the formation of elemental hydrogen by reducing the accelerators instead of the hydrogen ions.
  • the phosphating solution contains 0.1-5 g / 1, in particular 0.5-1.5 g / 1, of manganese (II) ions.
  • the quality of the copper-containing nickel-free phosphate layers produced with the aid of the method according to the invention is not impaired if the phosphating solution contains up to 2.5 g / l, alkaline earth metal cations, in particular magnesium and / or calcium ions, for example from the process water.
  • modifying compounds from the group of surfactants hydroxycarboxylic acids, tartrate, citrate, hydrofluoric acid, alkali metal fluorides, boron tetrafluorides, silicon fluorides is known in principle from the prior art. While the addition of surfactants (for example 0.05-0.5 g / l) leads to an improvement in the phosphating of lightly greased metal surfaces, it is known that hydroxycarboxylic acids, in particular tartaric acid, citric acid and their salts, in a concentration range of 0.03-0.3 g / 1 contribute to a significant reduction in the weight of the phosphate layer.
  • Fluoride ions promote phosphating metals which are more difficult to attack and thereby leads to a reduction in the phosphating time and, in addition, to an increase in the surface coverage of the phosphate layer.
  • about 0.1-1 g / 1 of the fluorides mentioned are used.
  • the controlled addition of the fluorides also makes it possible to form crystalline phosphate layers on aluminum and its alloys. Salts of boron tetrafluoride and silicon hexafluoride increase the aggressiveness of the phosphating baths, which is particularly noticeable in the treatment of hot-dip galvanized or aluminum surfaces, which is why these complex fluorides can be used, for example, in amounts of 0.4-3 g / l.
  • Phosphating processes are usually used at bath temperatures between 40 and 60 ° C. These temperature ranges are used in spraying as well as in spray-immersion and immersion applications.
  • the treatment of the surfaces is chosen to be as short as possible for economic reasons; for example, exposure times of 1 to 5 minutes are sufficient to produce a uniformly covering phosphate layer.
  • the method can also be used in fast-running conveyor systems. In such systems, however, downtimes occur relatively frequently, so that it happens that the metal surfaces remain in contact with the phosphating solution for a much longer time. With galvanized substrates, this can lead to the harmful speck formation mentioned above.
  • the metal surfaces to be phosphated are cleaned, rinsed and, if necessary, treated with activating agents, in particular based on titanium phosphates, according to methods known in the art prior to phosphating.
  • the corrosion protection effect of the phosphating according to the invention was determined in accordance with the standards of the German Association of the Automotive Industry (VDA 621-414 (outdoor weathering) and VDA 621-415 (alternating climate)).
  • the testing of the corrosion protection of motor vehicle paints by exposure to the weather serves to determine the corrosion protection effect of motor vehicle paints under the influence of natural weathering with additional stress by spraying with salt solution.
  • Test coats consisting of an automobile-typical structure made of KTL, filler, top coat white, each with Ford specification, are provided with a straight scratch mark, parallel to the long side, which is controlled through to the metal surface.
  • the trial dashes are stored on suitable racks. They are sprayed liberally once a week with a dilute sodium chloride solution.
  • the test time in the present case was 6 months.
  • the sample coats are rinsed with clear, flowing water, blown dry with compressed air if necessary and examined for visible changes.
  • the under rusting visible from both sides of the scoring is determined.
  • the width of the metal surface damaged by rust next to the scratch is generally easy to see on the surface of the paint.
  • the average total width of the rust zone is measured in mm.
  • the width is measured at several places and the arithmetic mean is formed.
  • the test of the corrosion protection of motor vehicle paints in the case of cyclically changing loads serves to assess the corrosion protection of motor vehicle paints using a time-consuming laboratory method, which causes corrosion processes and corrosion patterns which are well comparable with those occurring during driving operation.
  • the short test simulates in particular the under rust caused by a paint injury, as well as the edge and edge rust in the case of special corrosion test sheets or components with known weak points in the paint and the surface rust.
  • sample plates were provided with a straight scratch track running parallel to the long side down to the metal background.
  • test panels were set up in the tester at an angle of 60 ° to 75 ° to the horizontal.
  • a test cycle takes 7 days and consists of
  • the test time is 10 cycles corresponding to 70 days.
  • sample plates are rinsed with clear, flowing water, blown dry with compressed air if necessary, and examined for visible changes. The under rusting visible from both sides of the scoring is determined.
  • the width of the rust surface damaged by rust along with the scratch is easily recognizable as a trace of bubbles or rust on the lacquer surface.
  • an obliquely held knife blade e.g. B. with an eraser, carefully remove the undersized paint film to the still firmly adhering zone.
  • the average overall width of the rust area in mm is also measured here.
  • the width is measured at several places and the arithmetic mean is formed.
  • Example 1 (process according to the invention) a) steel 0.4 0.6 0.4 0.6 0.6 0.5 1-2 1 1 b) ZE 0 0 0 0.9 0.8 1.0 1 1 1
  • Table 3 shows a comparison test without nitrate with a treatment time of 4 min.
  • electrolytically galvanized steel sheets were treated with the following phosphating bath concentrations for 2 min at 50 - 55 ° C:

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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)

Abstract

Un procédé permet de produire des couches de phosphate sans nickel ayant une teneur définie en cuivre dans les couches de phosphate insoluble. Lors du réglage d'un rapport approprié entre le cuivre et le nitrate dans le bain de phosphatation, on n'observe aucune formation de piqûres sur la surface du métal, notamment sur de l'acier galvanisé par électrolyse.
PCT/EP1993/001015 1992-05-06 1993-04-27 Procede de phosphatation sans nickel avec du cuivre WO1993022474A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4214992.4 1992-05-06
DE19924214992 DE4214992A1 (de) 1992-05-06 1992-05-06 Kupfer enthaltendes, nickelfreies Phosphatierverfahren

Publications (1)

Publication Number Publication Date
WO1993022474A1 true WO1993022474A1 (fr) 1993-11-11

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DE (1) DE4214992A1 (fr)
WO (1) WO1993022474A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0675972A1 (fr) * 1992-12-22 1995-10-11 Henkel Corporation Composition et procede de revetement de conversion de phosphate pratiquement sans nickel
EP0695817A1 (fr) * 1994-08-05 1996-02-07 Itb S.R.L. Solution aqueuse acide de phosphation et procédé de phosphatation de surfaces métalliques
US5597465A (en) * 1994-08-05 1997-01-28 Novamax Itb S.R.L. Acid aqueous phosphatic solution and process using same for phosphating metal surfaces
WO1997016581A2 (fr) * 1995-10-27 1997-05-09 Henkel Kommanditgesellschaft Auf Aktien Phosphatation au zinc, a l'aide d'une solution sans manganese et a faible teneur en nitrate
WO1997030190A1 (fr) * 1996-02-19 1997-08-21 Henkel Kommanditgesellschaft Auf Aktien Phosphatation du zinc avec faible quantite de cuivre et de manganese
WO2002070782A2 (fr) * 2001-03-06 2002-09-12 Chemetall Gmbh Procede de revetement de surfaces metalliques et utilisation des substrats ainsi revetus

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR880958A (fr) * 1939-12-20 1943-04-12 Metallgesellschaft Ag Procédé pour produire des enduits phosphatiques sur le fer et l'acier
DE881138C (de) * 1943-05-30 1953-06-29 Metallgesellschaft Ag Phosphatierungsverfahren
US2813812A (en) * 1952-06-24 1957-11-19 Parker Rust Proof Co Method for coating iron or zinc with phosphate composition and aqueous solution therefor
US3467589A (en) * 1966-10-19 1969-09-16 Hooker Chemical Corp Method of forming a copper containing protective coating prior to electrodeposition of paint
DE2049350A1 (de) * 1969-10-08 1971-04-15 Lubrizol Corp Phosphatierungslosungen und ihre Verwendung zum Korrosionsschutz von Eisen metall und Zinkoberflachen
FR2203893A1 (en) * 1972-10-20 1974-05-17 Fosfa Col Sas Di A Dal Pane Et Ambient temp. phosphating - using accelerator contg. bath to produce coating espec. amenable to accepting electrophoretic paint coatings
EP0459541A1 (fr) * 1990-04-27 1991-12-04 METALLGESELLSCHAFT Aktiengesellschaft Procédé de phosphatation de surfaces métalliques

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR880958A (fr) * 1939-12-20 1943-04-12 Metallgesellschaft Ag Procédé pour produire des enduits phosphatiques sur le fer et l'acier
DE881138C (de) * 1943-05-30 1953-06-29 Metallgesellschaft Ag Phosphatierungsverfahren
US2813812A (en) * 1952-06-24 1957-11-19 Parker Rust Proof Co Method for coating iron or zinc with phosphate composition and aqueous solution therefor
US3467589A (en) * 1966-10-19 1969-09-16 Hooker Chemical Corp Method of forming a copper containing protective coating prior to electrodeposition of paint
DE2049350A1 (de) * 1969-10-08 1971-04-15 Lubrizol Corp Phosphatierungslosungen und ihre Verwendung zum Korrosionsschutz von Eisen metall und Zinkoberflachen
FR2203893A1 (en) * 1972-10-20 1974-05-17 Fosfa Col Sas Di A Dal Pane Et Ambient temp. phosphating - using accelerator contg. bath to produce coating espec. amenable to accepting electrophoretic paint coatings
EP0459541A1 (fr) * 1990-04-27 1991-12-04 METALLGESELLSCHAFT Aktiengesellschaft Procédé de phosphatation de surfaces métalliques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 80, no. 1, 14. Januar 1974, Columbus, Ohio, US; abstract no. 6279w, IMAO H. 'Pretreating metal before electrocoating' Seite 195 ; *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0675972A1 (fr) * 1992-12-22 1995-10-11 Henkel Corporation Composition et procede de revetement de conversion de phosphate pratiquement sans nickel
EP0675972A4 (fr) * 1992-12-22 1995-11-02
EP0695817A1 (fr) * 1994-08-05 1996-02-07 Itb S.R.L. Solution aqueuse acide de phosphation et procédé de phosphatation de surfaces métalliques
US5597465A (en) * 1994-08-05 1997-01-28 Novamax Itb S.R.L. Acid aqueous phosphatic solution and process using same for phosphating metal surfaces
WO1997016581A2 (fr) * 1995-10-27 1997-05-09 Henkel Kommanditgesellschaft Auf Aktien Phosphatation au zinc, a l'aide d'une solution sans manganese et a faible teneur en nitrate
WO1997016581A3 (fr) * 1995-10-27 1997-06-19 Henkel Kgaa Phosphatation au zinc, a l'aide d'une solution sans manganese et a faible teneur en nitrate
WO1997030190A1 (fr) * 1996-02-19 1997-08-21 Henkel Kommanditgesellschaft Auf Aktien Phosphatation du zinc avec faible quantite de cuivre et de manganese
WO2002070782A2 (fr) * 2001-03-06 2002-09-12 Chemetall Gmbh Procede de revetement de surfaces metalliques et utilisation des substrats ainsi revetus
WO2002070782A3 (fr) * 2001-03-06 2003-12-11 Chemetall Gmbh Procede de revetement de surfaces metalliques et utilisation des substrats ainsi revetus

Also Published As

Publication number Publication date
DE4214992A1 (de) 1993-11-11

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