EP0633950A1 - Procede de phosphatation exempte de nickel. - Google Patents

Procede de phosphatation exempte de nickel.

Info

Publication number
EP0633950A1
EP0633950A1 EP92924684A EP92924684A EP0633950A1 EP 0633950 A1 EP0633950 A1 EP 0633950A1 EP 92924684 A EP92924684 A EP 92924684A EP 92924684 A EP92924684 A EP 92924684A EP 0633950 A1 EP0633950 A1 EP 0633950A1
Authority
EP
European Patent Office
Prior art keywords
ions
phosphating solution
phosphating
phosphate
hydroxylamine
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.)
Granted
Application number
EP92924684A
Other languages
German (de)
English (en)
Other versions
EP0633950B1 (fr
Inventor
Wolf-Achim Roland
Karl-Heinz Gottwald
Matthias Hamacher
Jan-Willem Brouwer
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
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0633950A1 publication Critical patent/EP0633950A1/fr
Application granted granted Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/186—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
    • 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
    • C23C22/78—Pretreatment of the material to be coated
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12583—Component contains compound of adjacent metal

Definitions

  • the invention relates to a process for producing copper-containing, nickel-free phosphate layers on metal surfaces, and to the use of the process 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 painting depends on a variety 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 crystal water 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 polymeric titanium phosphates present in the activating agents form active centers on the metal surface from which crystal growth proceeds. The result is, on the one hand, smaller and mechanically more stable crystals, and on the other hand the pore area is reduced, making it more difficult to attack corrosive media if the coating is damaged.
  • Barium phosphate coatings do not contain zinc, but have a number of positive properties, such as, in particular, high thermal stability. However, the achievable layer weights are not sufficient to achieve a high level of corrosion protection in combination with a cataphoretic dip coating.
  • the barium phosphate coatings thus occupy an intermediate position between the "thin” iron phosphate coatings (0.3-0.5 g / n.2) and the “thicker" zinc phosphate coatings (2.0-3.5 g / m 2).
  • Aluminum ions reduce the phosphate layer weights even more, so that even at a concentration of 5 ppm Al3 + ions in the phosphating bath, so-called "passivation phenomena" occur, ie disturbances in the formation of zinc phosphate coatings.
  • 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 Zn2 +), high concentrations of accelerators such as sodium nitrite or meta-nitrobenzenesulfonate / Na- Salts do not have to be used additionally in order to produce a mass per unit area in the range from 1.5 to 2.0 g / u.2.
  • control parameters which are usually also used to reduce the layer weight, such as very low zinc concentrations (0.6 g / 1 Zn2 +), high concentrations of accelerators such as sodium nitrite or meta-nitrobenzenesulfonate / Na- Salts do not have to be used additionally in order to produce a mass per unit area in the range from 1.5 to 2.0 g / u.2.
  • EP-A-0 186 823 discloses strongly acidic phosphating solutions with a pH of 1.8-2.5 which contain 7.5-75 g / 1 zinc ions, Contain 0.1 - 10 g / 1 hydroxylamine and optionally up to 20 g / 1 manganese ions and 5 - 75 g / 1 nitrate ions.
  • the solutions tolerate an iron content of up to 25 g / 1.
  • EP-A-0315059 discloses a method for zinc phosphating iron-containing surfaces.
  • the desired morphology of the zinc phosphate crystals is set by the use of hydroxylammonium salts, hydroxyla incomplexes and / or hydroxylamine.
  • all of the examples contain nickel as another layer-forming cation.
  • the toxicological disadvantages of nickel are known.
  • the object was therefore to provide a process for producing 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.
  • the above-mentioned object is achieved with the aid of a specially selected phosphating solution which, as an active ingredient for modifying the crystal morphology ("accelerator"), contains hydroxylamine salts, hydroxylamine complexes and / or hydroxylamine in an amount of 500 to 5000 ppm hydroxylamine, based on the phosphating solution.
  • a specially selected phosphating solution which, as an active ingredient for modifying the crystal morphology
  • the present invention thus relates in a first embodiment to a process for producing copper-containing nickel-free phosphate layers with a copper content in the range from 0.1 to 5% by weight and an edge length of Phosphate crystals in the range from 0.5 to 10 ⁇ m on metal surfaces, selected from steel, galvanized steel, alloy-galvanized steel, aluminum and their alloys, by treating them in the spraying, dipping or spraying / dipping process with a phosphating solution containing the following components: zinc ions 0.2 to 2 g / 1
  • Phosphate ions 5 to 30 g / 1 (calculated as P2O5) as well as hydroxylamine salts, hydroxylamine complexes and / or hydroxylamine in an amount of 500 to 5000 ppm hydroxylamine based on the phosphating solution.
  • the zinc phosphate layers produced in this way are made up of small (0.5 to 10 ⁇ m), compact, densely grown crystals.
  • the phosphating solution contains 5 to 20 ppm of copper ions when the metal surface is brought into contact with the phosphating solution by means of immersion processes.
  • the phosphating solutions contain 1 to 10 ppm copper ions in order to incorporate correspondingly high copper contents in the conversion coating.
  • a particularly preferred embodiment of the present invention is that the phosphating solution contains 0.1 to 5 g / 1, in particular 0.5 to 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 alkaline earth metal cations of up to 2.5 g / l, in particular magnesium and / or calcium ions.
  • the method according to the invention can be applied in particular to steel, steel galvanized on one or two sides, steel galvanized on one or two sides, alloy, aluminum and its alloys.
  • steel in the sense of the present invention includes, in addition to low-alloy steels, also soft, unalloyed steels and higher as well as high-strength steels.
  • the essential content of the invention is that the aqueous, acid phosphating solutions are free of nickel. However, this means that under technical conditions a small amount of nickel ions can be contained in the phosphating baths. However, in accordance with the prior art DE-A-40 13 483, this amount should be less than 0.0002 to 0.01 g / 1, in particular less than 0.0001 g / 1.
  • iron in the form of iron (II) ions dissolves.
  • iron (II) is converted into iron (III) and can thus be precipitated as iron phosphate sludge. Accordingly, it is typical in the sense of the present invention that the phosphating solution contains up to 50 ppm - briefly in the production process but also up to 500 ppm - iron (II) ions.
  • a number of 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 phosphate solution contains oxidizing agents selected from peroxide compounds, chlorates, permanganates and organic nitro compounds.
  • the oxidizing agents of the phosphating solutions are preferably selected from peroxide compounds, in particular hydrogen peroxide, perborate, percarbonate and Perphosphate, and organic nitro compounds, especially nitrobenzenesulfonate.
  • peroxide compounds in particular hydrogen peroxide, perborate, percarbonate and Perphosphate
  • organic nitro compounds especially nitrobenzenesulfonate.
  • peroxide compound calculated as hydrogen peroxide: 0.005 to 0.1 g / 1
  • nitrobenzenesulfonate 0.005 to 1 g / 1.
  • a preferred embodiment of the present invention consists in using phosphating solutions which are essentially free of nitrite ions.
  • An important advantage of this process variant is that no toxic decomposition products of nitrites, for example nitrous gases which are hazardous to health, can arise.
  • modifying compounds from the group of surfactants hydroxycarboxylic acids, tartrate, citrate, hydrofluoric acid, alkali metal fluoride, boron trifluoride, silicon fluoride is known in principle from the prior art. While the addition of surfactants (for example 0.05 to 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 from 0.03 to 0.3 g / 1 contribute to a significant reduction in the phosphate layer weight.
  • Fluoride ions promote the phosphating of metals which are more difficult to attack, thereby shortening the phosphating time and, in addition, increasing the area coverage of the phosphate layer.
  • about 0.1 to 1 g / 1 of the fluorides are used.
  • the controlled addition of fluorides also enables the formation of 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 surfaces, which is why these complex fluorides can be used, for example, in amounts of 0.4 to 3 g / l.
  • Phosphating processes are usually used at temperatures of the bath between 40 and 60 ° C. These temperature ranges are used both in spraying and in spray-immersion and immersion applications.
  • 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 per se in the prior art prior to phosphating.
  • the phosphating baths for carrying out the process according to the invention are generally prepared in the customary manner which is known per se to the person skilled in the art.
  • the following compounds are suitable as starting products for the preparation of the phosphating bath: Zinc: in the form of zinc oxide, zinc carbonate or optionally zinc nitrate; Copper: in the form of acetate, sulfate or, where appropriate, nitrate; Manganese: in the form of carbonate, magnesium and calcium: in the form of carbonates; Phosphate: preferably in the form of phosphoric acid.
  • the fluoride ions which may be used in the bath are preferably used in the form of alkali metal or ammonium fluoride, in particular sodium fluoride, or in the form of the complex compounds mentioned above.
  • the compounds mentioned above are dissolved in water in the concentration ranges essential for the invention; then, as has also been said above, the pH of the phosphating solutions is adjusted to the desired value.
  • hydroxylamine can originate from any source. Accordingly, any compound which provides hydroxylamine or a derivative thereof, for example a hydroxylamine salt or a hydroxylamine complex, which is often in hydrate form, can be used according to the invention. Examples which can be used include hydroxylamine phosphate, optionally hydroxylamine nitrate, hydroxylamine sulfate (also called hydroxylammonium sulfate [(NH20H) -H2S04]) or a mixture thereof. Hydroxylamine sulfate and hydroxylamine phosphate are particularly preferred as the source of hydroxylamine.
  • Comparative example 1 Starting from an aqueous solution of a bath composition in step 4 of the above-mentioned process with the following ion concentrations Zn 1.0 g / 1, Mn 1.4 g / 1, P03-16.9 g / 1, N0 3 "2.0 g / 1, SiF 6 2- 1.0 g / 1, F "0.2 g / 1,
  • Accelerator (hydroxyl monium sulfate) 1.8 g / 1, total acid 21.8 points, free acid 0.9 points were at a temperature in the range of 52 to 54 ° C in the course of 3 min surfaces made of sheet steel (Sidca) (Example la ) and electrolytically galvanized thin sheet (ZE) (Example 1b) phosphated, the corrosion protection data shown in Table 1 being found.
  • test panels were phosphated at a temperature of 53 ° C in the course of 1 min from electrolytically galvanized sheet.
  • the test panels were then provided with a test coat of KTL and white topcoat and subjected to the alternating climate test according to VDA 621-415. The results after a test period of 5 cycles are also shown in Table 2.
  • Test methods were phosphated at a temperature of 53 ° C in the course of 1 min from electrolytically galvanized sheet. The test panels were then provided with a test coat of KTL and white topcoat and subjected to the alternating climate test according to VDA 621-415. The results after a test period of 5 cycles are also shown in Table 2. Test methods
  • 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 test)).
  • the testing of the corrosion protection of motor vehicle paints by outdoor exposure serves to determine the corrosion protection effect of motor vehicle paints under the influence of natural weathering in the overall construction, as in the example without light protection and additional stress by spraying with salt solution.
  • Test coats consisting of an automobile-typical structure made of KTL, filler, top coat white, each according to Ford specification, are provided with a straight scratch track parallel to the long side, which is controlled through to the metal surface.
  • the test coats 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 paint surface.
  • the average total width is used for evaluation the rust zone in mm. For this purpose, 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-rusting resulting from a paint injury, as well as the edge and edge rusting in the case of special corrosion test sheets or components with known weak points in the paint and the surface rust.
  • test panels were provided with a straight scratch mark parallel to the long side, extending through to the metal surface.
  • 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, if necessary blown dry with compressed air 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 easily recognizable as a trace of bubbles or rust on the surface of the paint.
  • an inclined knife blade e.g. B. with an eraser, the rusted paint film is carefully removed to the still adherent 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.

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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)
  • Catalysts (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
EP92924684A 1992-03-31 1992-12-07 Procede de phosphatation exempte de nickel Expired - Lifetime EP0633950B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4210513A DE4210513A1 (de) 1992-03-31 1992-03-31 Nickel-freie Phosphatierverfahren
DE4210513 1992-03-31
PCT/EP1992/002827 WO1993020259A1 (fr) 1992-03-31 1992-12-07 Procede de phosphatation exempte de nickel

Publications (2)

Publication Number Publication Date
EP0633950A1 true EP0633950A1 (fr) 1995-01-18
EP0633950B1 EP0633950B1 (fr) 1996-05-15

Family

ID=6455509

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92924684A Expired - Lifetime EP0633950B1 (fr) 1992-03-31 1992-12-07 Procede de phosphatation exempte de nickel

Country Status (8)

Country Link
US (1) US6197126B1 (fr)
EP (1) EP0633950B1 (fr)
JP (1) JPH07505445A (fr)
AT (1) ATE138112T1 (fr)
CA (1) CA2133455A1 (fr)
DE (2) DE4210513A1 (fr)
ES (1) ES2086782T3 (fr)
WO (1) WO1993020259A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0675972A4 (fr) * 1992-12-22 1995-11-02
US6497771B1 (en) 1998-02-27 2002-12-24 Metallgesellschaft Aktiengesellschaft Aqueous solution and method for phosphatizing metallic surfaces

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IT1274594B (it) * 1994-08-05 1997-07-18 Itb Srl Soluzione fosfatica acquosa acida e processo di fosfatazione di superfici metalliche che la utilizza
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
DE19500927A1 (de) * 1995-01-16 1996-07-18 Henkel Kgaa Lithiumhaltige Zinkphosphatierlösung
DE19540085A1 (de) * 1995-10-27 1997-04-30 Henkel Kgaa Nitratarme, manganfreie Zinkphosphatierung
DE19606017A1 (de) * 1996-02-19 1997-08-21 Henkel Kgaa Zinkphosphatierung mit geringen Gehalten an Kupfer und Mangan
DE19700326A1 (de) * 1997-01-08 1998-07-09 Henkel Kgaa Stabilisatoren für Hydroxylamin in Kupfer-haltigen Phosphatierlösungen
DE19716075A1 (de) * 1997-04-17 1998-10-22 Henkel Kgaa Mit Hydroxylamin und Chlorat beschleunigtes Phosphatierverfahren
WO1999007916A1 (fr) 1997-08-06 1999-02-18 Henkel Kommanditgesellschaft Auf Aktien Procede de phosphatation accelere par n-oxydes
US6720032B1 (en) 1997-09-10 2004-04-13 Henkel Kommanditgesellschaft Auf Aktien Pretreatment before painting of composite metal structures containing aluminum portions
JPH11264076A (ja) * 1998-01-14 1999-09-28 Nippon Paint Co Ltd 低鉛ｅｄ用の下地化成処理方法
US6723178B1 (en) 1999-08-16 2004-04-20 Henkel Corporation Process for forming a phosphate conversion coating on metal
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DE10110833B4 (de) * 2001-03-06 2005-03-24 Chemetall Gmbh Verfahren zum Aufbringen eines Phosphatüberzuges und Verwendung der derart phosphatierten Metallteile
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EP1453989A4 (fr) * 2001-12-13 2005-03-23 Henkel Kgaa Utilisation d'hydroxylamines substituees pour les procedes de phosphatation de metal
WO2006108108A2 (fr) * 2005-04-06 2006-10-12 Rem Technologies, Inc. Superfinition de carbures de densite elevee
DE102010001686A1 (de) 2010-02-09 2011-08-11 Henkel AG & Co. KGaA, 40589 Zusammensetzung für die alkalische Passivierung von Zinkoberflächen
CN101935831B (zh) * 2010-08-16 2011-09-14 景阳富 一种磷化液及其配制方法
PL2503025T3 (pl) * 2011-03-22 2013-12-31 Henkel Ag & Co Kgaa Chroniąca przed korozją, wielostopniowa obróbka metalowych elementów konstrukcyjnych o powierzchniach cynkowych
JP5840454B2 (ja) * 2011-10-27 2016-01-06 上村工業株式会社 還元型無電解銀めっき液及び還元型無電解銀めっき方法

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Also Published As

Publication number Publication date
DE4210513A1 (de) 1993-10-07
JPH07505445A (ja) 1995-06-15
ATE138112T1 (de) 1996-06-15
DE59206327D1 (de) 1996-06-20
ES2086782T3 (es) 1996-07-01
EP0633950B1 (fr) 1996-05-15
WO1993020259A1 (fr) 1993-10-14
US6197126B1 (en) 2001-03-06
CA2133455A1 (fr) 1993-10-14

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