EP0713539B1 - Phosphate treatment process for steel strip with one galvanised surface - Google Patents

Phosphate treatment process for steel strip with one galvanised surface Download PDF

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Publication number
EP0713539B1
EP0713539B1 EP94924298A EP94924298A EP0713539B1 EP 0713539 B1 EP0713539 B1 EP 0713539B1 EP 94924298 A EP94924298 A EP 94924298A EP 94924298 A EP94924298 A EP 94924298A EP 0713539 B1 EP0713539 B1 EP 0713539B1
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Prior art keywords
plated
zinc
steel strip
sheet
acid
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EP94924298A
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German (de)
French (fr)
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EP0713539A1 (en
Inventor
Klaus Bittner
Walter K.M. Jansen
Klaus-Peter Mohr
Thomas Wendel
Hardy Wietzoreck
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Chemetall GmbH
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Metallgesellschaft AG
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    • 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
    • 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
    • C23C22/07—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
    • 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
    • C23C22/40—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 molybdates, tungstates or vanadates
    • C23C22/44—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 molybdates, tungstates or vanadates containing also fluorides or complex fluorides
    • 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
    • C23C22/46—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 oxalates
    • C23C22/47—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 oxalates containing also phosphates

Definitions

  • the invention relates to a method for phosphating treatment of one-sided galvanized or galvanized steel strip or sheet with Using phosphating solutions containing zinc, nitrate and contain nitrite.
  • the phosphating of metals pursues the goal of the metal surface
  • the low-zinc phosphating processes are particularly suitable, in which the phosphating solutions contain comparatively low zinc ion contents of e.g. B. 0.5 to 1.5 g / l (DE-C-22 32 067, EP-B-39 093). Under these conditions, phosphate layers with a high content of phosphophyllite (Zn 2 Fe (PO 4 ) 2 • 4 H 2 O) are produced on steel, which is considerably more corrosion-resistant than the hopite (Zn 3 (PO 4 ) 2 • 4 H 2 O).
  • the protection quality in connection with paints can be further increased (EP-A-228 151, EP-B-414 296, EP-B-414 301, EP-A- 544 650, DE-A-39 18 136).
  • Low zinc process with the addition of z. B. 0.5 to 1.5 g / l of manganese ions and z. B. 0.3 to 2.0 g / l of nickel ions are widely used as a so-called trication process for preparing metal surfaces for painting, for example for the cathodic electrocoating of car bodies.
  • Processes have been developed specifically for the phosphating of electrolytically galvanized or hot-dip galvanized steel strip, which allow the formation of a phosphate layer within short treatment times.
  • it is known from DE-A-32 45 411 to provide, in particular, electrolytically galvanized steel strips with a phosphate layer with a layer weight of less than 2 g / m 2 , solutions being used which are about 1 to 2.5 g / l Contain zinc ions, have a free acid content of 0.8 to 3 points and a total acid / free acid acid ratio of 5 to 10.
  • the duration of treatment should not be significantly longer than 5 seconds.
  • Another method for the phosphating of electrolytically and / or hot-dip galvanized steel strip provides for phosphating solutions which contain 0.02 to 0.75 g / l of zinc, 0 , 2 to 2.0 g / l manganese, 0.1 to 2.0 g / l nickel, 10 to 20 g / l phosphate and 0.5 to 30 g / l nitrate ions.
  • the free acid content in the range from 1.6 to 3.0 points, the total acid content in the range from 12 to 40 points and the weight ratio of nickel ions to nitrate ions in the range from 1:10 to 1:60 and the weight ratio from manganese ions to nitrate ions are in the range from 1: 1 to 1:40 (DE-A-39 27 131).
  • the object of the invention is to provide a method for phosphating treatment of one-sided galvanized or galvanized steel strip or sheet To provide sludge formation to a large extent suppresses the formation of a phosphate layer the steel side prevents the emergence and quality the phosphate layer on the galvanized or alloy galvanized steel side not affected and yet simple in terms of procedure and is economical.
  • the limits of the specified ranges for Complexing agents are important in that they are too high Complexing agent concentrations Phosphate layer formation by complexing the affect layer-forming cations.
  • complexing agent is one Phosphate sludge formation in the phosphating solution and a beginning phosphate layer formation on the Unavoidable steel side.
  • nitrite concentration setting phosphating on the galvanized or alloy galvanized steel side and the complexation of the detached iron can be adversely affected. So can e.g. B. at too high a nitrite concentration starting layer formation on the steel side not be avoided.
  • Such a beginning The subsequent phosphating can form layers affect in the automotive plant, but leads in any case to undesirable sludge formation.
  • a special one a suitable countermeasure is to Nitrite concentration of the phosphating solution using nitrite-degrading substances, such as urea and / or To keep amidosulfonic acid within the stated limits. This can be done through continuous or discontinuous addition happen.
  • a special one elegant method provides for the nitrite concentration by keeping within the necessary limits that one in the phosphating solution Urea concentration of 1 to 3 g / l and / or one Amidosulfonic acid concentration from 0.5 to 2 g / l sets. This becomes a steady state created by the urea or Amidosulfonic acid content is reduced as much nitrite as created by auto-catalysis.
  • Steel strips or sheets to be used can be on the galvanized or alloy galvanized side layers made of electrolytic zinc (ZE), hot zinc (Z), or Alloys based on zinc / nickel (ZNE), zinc / iron (ZF) or zinc / aluminum (ZA or AZ). To the latter are usually also alloys e.g. B. 55 wt .-% Al and 45 wt .-% Zn counted.
  • the quality of the phosphate layer produced can be improved if according to another Embodiment of the invention the galvanized or alloy galvanized steel strip or sheet with one Phosphating solution is brought into contact with the further divalent cations, especially manganese and or nickel ions.
  • the concentrations in the Phosphating solution to 1 to 3 g / l, in particular 1.5 to 2.5 g / l manganese ions, and / or 0.1 to 2.5 g / l, in particular 0.5 to 1.5 g / l of nickel ions.
  • Phosphating solution is in the treatment of it hot-dip galvanized or hot dip galvanized steel strip or sheet indispensable to work with phosphating solutions, which contain complex and / or simple fluoride.
  • inventions are also used in the treatment of electrolytically galvanized steel strip or sheet Phosphating solutions used that complex and / or simple fluoride, preferably in Amounts from 0.1 to 3 g / l (calculated as F).
  • complex fluoride is fluoroborate, fluorosilicate. Fluorotitanate and / or fluorozirconate preferred.
  • Phosphating treatment of the strip or sheet can by conventional methods, i.e. in diving or syringes. It is particularly advantageous however, to apply the solution by spraying.
  • the phosphating solution is usually supplemented by a supplementary concentrate, with the control e.g. B. is done automatically via a conductivity measurement.
  • a suitable supplement concentrate contains e.g. B. 10 to 30 wt .-% P 2 O 5 , 3 to 20 wt .-% NO 3 and 0 to 2 wt .-% zinc.
  • the zinc content in the supplemental concentrate depends essentially on the reactivity of the zinc or alloy zinc layer on the steel strip or sheet. If this layer has a higher reactivity and thus larger amounts of zinc get into the bath due to the pickling of the phosphating solution, a supplementary solution with lower zinc concentrations within the range of 0 to 2% by weight is possible.
  • the supplemental concentrate can also be zinc-free.
  • the supplemental solution can also already contain the complexing agent for iron and, if necessary, the NO 2 -degrading substance; however, for reasons of better adjustability of the required concentrations, it will generally be preferable to supplement these two substances separately.
  • phosphate layers are produced, the layer weight of which is approximately 1 to 2 g / m 2 .
  • phosphating was carried out with a solution which had the following components: zinc 1.8 g / l P 2 O 5 14.5 g / l nickel 1.3 g / l manganese 2.0 g / l Tartaric acid 1 g / l urea 1 g / l NO 3 7 g / l NO 2 0.040 g / l.
  • the S value of the phosphating solution was 0.17% Temperature of the phosphating solution was 50 to 55 ° C set. The application was done by spraying for a period of 8 seconds.
  • the phosphating treatment was carried out over a period of 16 hours with a bath size of 25 m 3 . Then a wet sludge amount of 2 ml / 1 phosphating solution was determined. This corresponds to approx. 0.6 ml of sludge per m 2 of penetrated steel surface.
  • a perfect phosphate layer had formed on the zinc side, the layer weight of which was 1.6 g / m 2 .
  • the steel side was in perfect condition, ie showed practically no layer formation.

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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)
  • Coating With Molten Metal (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

PCT No. PCT/EP94/02510 Sec. 371 Date Jul. 8, 1996 Sec. 102(e) Date Jul. 8, 1996 PCT Filed Jul. 29, 1994 PCT Pub. No. WO95/04842 PCT Pub. Date Feb. 16, 1995The process forms a phosphate coating on a steel strip or sheet having a galvanized or alloy galvanized side and a steel side so that the phosphate coating is only present on the galvanized or alloy galvanized side. This process includes contacting the galvanized or alloy galvanized side of the steel strip or sheet with a phosphatizing solution for 4 to 20 seconds at a temperature of from 45 DEG C. to 80 DEG C. The phosphatizing solution has an S value of from 0.08 to 0.30 and contains 0.5 to 5 g/l zinc, 3 to 20 g/l P2O5, 0.020 to 0.2 g/l nitrite, 3 to 30 g/l nitrate and 0.2 to 2.5 g/l complexing agent for iron. Chelate forming substances, such as tartaric acid, citric acid, ethylenediamine-tetraacetic acid, nitrilotriacetic acid and/or oxalic acid, may be used as the complexing agent for iron. The phosphatizing solutions may also contain other bivalent cations, particularly manganese and/or nickel cations.

Description

Die Erfindung betrifft ein Verfahren zur phosphatierenden Behandlung von einseitig verzinktem oder legierungsverzinktem Stahlband oder -blech mit Hilfe von Phosphatierungslösungen, die Zink, Nitrat und Nitrit enthalten.The invention relates to a method for phosphating treatment of one-sided galvanized or galvanized steel strip or sheet with Using phosphating solutions containing zinc, nitrate and contain nitrite.

Die Phosphatierung von Metallen verfolgt das Ziel, auf der Metalloberfläche fest verwachsene Metallphosphatschichten zu erzeugen, die für sich bereits die Korrosionsbeständigkeit verbessern und in Verbindung mit Lacken und anderen organischen Beschichtungen zu einer wesentlichen Erhöhung der Haftung und der Resistenz gegen Unterwanderung bei Korrosionsbeanspruchung beitragen. Außerdem dienen Phosphatschichten als Isolierung gegen den Durchtritt elektrischer Ströme und in Verbindung mit Schmierstoffen zur Erleichterung von Gleitvorgängen.The phosphating of metals pursues the goal of the metal surface To create metal phosphate layers that stand out already improve the corrosion resistance and in Connection with paints and other organic Coatings to a significant increase in Liability and resistance to infiltration Corrosion stress contribute. Also serve Phosphate layers as insulation against the passage electrical currents and in connection with Lubricants to facilitate sliding processes.

Für die Vorbehandlung vor der Lackierung eignen sich insbesondere die Niedrigzink-Phosphatierverfahren, bei denen die Phosphatierungslösungen vergleichsweise geringe Gehalte an Zinkionen von z. B. 0,5 bis 1,5 g/l aufweisen (DE-C-22 32 067, EP-B-39 093). Unter diesen Bedingungen werden auf Stahl Phosphatschichten mit einem hohen Gehalt an Phosphophyllit (Zn2Fe(PO4)2 • 4 H2O) erzeugt, der wesentlich korrosionsbeständiger ist als der aus zinkreicheren Phosphatierungslösungen abgeschiedene Hopeit (Zn3(PO4)2 • 4 H2O). Durch Mitverwendung von Nickel- und/oder Manganionen in den Niedrigzink-Phosphatierungslösungen läßt sich die Schutzqualität in Verbindung mit Lacken weiter steigern (EP-A-228 151, EP-B-414 296, EP-B-414 301, EP-A-544 650, DE-A-39 18 136). Niedrigzink-Verfahren mit Zusatz von z. B. 0,5 bis 1,5 g/l Manganionen und z. B. 0,3 bis 2,0 g/l Nickelionen finden als sogenannte Trikation-Verfahren zur Vorbereitung von Metalloberflächen für die Lackierung, beispielsweise für die kathodische Elektrotauchlackierung von Autokarosserien, weite Anwendung.For the pretreatment before painting, the low-zinc phosphating processes are particularly suitable, in which the phosphating solutions contain comparatively low zinc ion contents of e.g. B. 0.5 to 1.5 g / l (DE-C-22 32 067, EP-B-39 093). Under these conditions, phosphate layers with a high content of phosphophyllite (Zn 2 Fe (PO 4 ) 2 • 4 H 2 O) are produced on steel, which is considerably more corrosion-resistant than the hopite (Zn 3 (PO 4 ) 2 • 4 H 2 O). By using nickel and / or manganese ions in the low zinc phosphating solutions, the protection quality in connection with paints can be further increased (EP-A-228 151, EP-B-414 296, EP-B-414 301, EP-A- 544 650, DE-A-39 18 136). Low zinc process with the addition of z. B. 0.5 to 1.5 g / l of manganese ions and z. B. 0.3 to 2.0 g / l of nickel ions are widely used as a so-called trication process for preparing metal surfaces for painting, for example for the cathodic electrocoating of car bodies.

Speziell für die Phosphatierung von elektrolytisch verzinktem oder schmelztauchverzinktem Stahlband sind Verfahren entwickelt worden, die die Ausbildung einer Phosphatschicht innerhalb kurzer Behandlungszeiten gestatten. So ist es beispielsweise aus der DE-A-32 45 411 bekannt, insbesondere elektrolytisch verzinkte Stahlbänder mit einer Phosphatschicht eines Schichtgewichtes unterhalb von 2 g/m2 zu versehen, wobei Lösungen zum Einsatz gelangen, die etwa 1 bis 2,5 g/l Zinkionen enthalten, einen Gehalt an Freier Säure von 0,8 bis 3 Punkten und ein Säureverhältnis Gesamtsäure/Freie Säure von 5 bis 10 aufweisen. Dabei soll die Behandlungsdauer nicht wesentlich über 5 Sekunden liegen. Ein anderes Verfahren zur Phosphatierung von elektrolytisch und/oder schmelztauchverzinktem Stahlband sieht vor, während einer Zeit von 2 bis 30 Sekunden im Temperaturbereich von 40 bis 70°C Phosphatierungslösungen zu applizieren, die 0,02 bis 0,75 g/l Zink-, 0,2 bis 2,0 g/l Mangan-, 0,1 bis 2,0 g/l Nickel-, 10 bis 20 g/l Phosphat- und 0,5 bis 30 g/l Nitrationen enthalten. Dabei soll der Gehalt an Freier Säure im Bereich von 1,6 bis 3,0 Punkten, der Gehalt an Gesamtsäure im Bereich von 12 bis 40 Punkten und das Gewichtsverhältnis von Nickelionen zu Nitrationen im Bereich von 1:10 bis 1:60 und das Gewichtsverhältnis von Manganionen zu Nitrationen im Bereich von 1:1 bis 1:40 liegen (DE-A-39 27 131).Processes have been developed specifically for the phosphating of electrolytically galvanized or hot-dip galvanized steel strip, which allow the formation of a phosphate layer within short treatment times. For example, it is known from DE-A-32 45 411 to provide, in particular, electrolytically galvanized steel strips with a phosphate layer with a layer weight of less than 2 g / m 2 , solutions being used which are about 1 to 2.5 g / l Contain zinc ions, have a free acid content of 0.8 to 3 points and a total acid / free acid acid ratio of 5 to 10. The duration of treatment should not be significantly longer than 5 seconds. Another method for the phosphating of electrolytically and / or hot-dip galvanized steel strip provides for phosphating solutions which contain 0.02 to 0.75 g / l of zinc, 0 , 2 to 2.0 g / l manganese, 0.1 to 2.0 g / l nickel, 10 to 20 g / l phosphate and 0.5 to 30 g / l nitrate ions. The free acid content in the range from 1.6 to 3.0 points, the total acid content in the range from 12 to 40 points and the weight ratio of nickel ions to nitrate ions in the range from 1:10 to 1:60 and the weight ratio from manganese ions to nitrate ions are in the range from 1: 1 to 1:40 (DE-A-39 27 131).

Soweit die vorgenannten, eine kurzzeitige Behandlung gestattenden Phosphatierungslösungen auf Band angewendet werden, die beidseitig verzinkt bzw. schmelztauchverzinkt sind, treten größere Komplikationen nicht auf. In jüngerer Zeit gelangen jedoch zunehmend, insbesondere in der Automobilindustrie, Stahlbänder zum Einsatz, die lediglich einseitig verzinkt sind. Bei Anwendung der vorgenannten Kurzzeitverfahren auf einseitig verzinkte Bänder tritt jedoch eine starke Bildung von Phosphatschlamm in der Phosphatierungslösung auf, die in diesem Ausmaß stört. Darüber hinaus erfolgt auf der Stahlseite eine beginnende Phosphatschichtausbildung, die insbesondere dann unerwünscht ist, wenn eine spätere Phosphatierung, z.B. der Automobilkarosserie, beabsichtigt ist.As far as the aforementioned, a short-term treatment permitting phosphating solutions on tape are used that are galvanized on both sides or are hot-dip galvanized, larger ones occur Complications not. Arrived more recently however increasingly, especially in the Automotive industry, steel strips used, the are galvanized on one side only. When using the aforementioned short-term procedures on one-sided galvanized However, bands form a strong formation of Phosphate sludge in the phosphating solution that to such an extent. In addition, the On the steel side a beginning phosphate layer formation which is particularly undesirable if a later phosphating, e.g. the automobile body, is intended.

Aufgabe der Erfindung ist es, ein Verfahren zur phosphatierenden Behandlung von einseitig verzinktem oder legierungsverzinktem Stahlband oder -blech bereitzustellen, das eine Schlammbildung weitgehend unterdrückt, die Ausbildung einer Phosphatschicht auf der Stahlseite verhindert, die Entstehung und Qualität der Phosphatschicht auf der verzinkten bzw. legierungsverzinkten Stahlseite nicht beeinträchtigt und dennoch in der Verfahrensführung einfach und wirtschaftlich ist. The object of the invention is to provide a method for phosphating treatment of one-sided galvanized or galvanized steel strip or sheet To provide sludge formation to a large extent suppresses the formation of a phosphate layer the steel side prevents the emergence and quality the phosphate layer on the galvanized or alloy galvanized steel side not affected and yet simple in terms of procedure and is economical.

Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derartig ausgestaltet wird, daß man das verzinkte oder legierungsverzinkte Stahlband oder -blech für die Dauer von 4 bis 20 sec. mit einer Lösung einer Temperatur von 45 bis 80°C in Kontakt bringt, die

  • 0,5 bis 5 g/l Zink
  • 3 bis 20 g/l P2O5
  • 0,005 bis 0,2 g/l NO2
  • 3 bis 30 g/l NO3
  • 0,2 bis 2,5 g/l Komplexbildner für Eisen
    • enthält, einen S-Wert von 0,08 bis 0,30 sowie im Falle der phosphatierenden Behandlung von schmelztauchverzinktem oder schmelztauchlegierungsverzinktem Stahlband oder -blech einen zusätzlichen Gehalt an 0,2 bis 4 g/l komplexem und/oder einfachem Fluorid (ber. als F) aufweist.The object is achieved in that the method of the type mentioned according to the invention is designed in such a way that the galvanized or alloy-galvanized steel strip or sheet for 4 to 20 seconds with a solution of a temperature of 45 to 80 ° C in Brings contact that
  • 0.5 to 5 g / l zinc
  • 3 to 20 g / l P 2 O 5
  • 0.005 to 0.2 g / l NO 2
  • 3 to 30 g / l NO 3
  • 0.2 to 2.5 g / l complexing agent for iron
    • contains, an S-value of 0.08 to 0.30 and, in the case of the phosphating treatment of hot-dip galvanized or hot-dip galvanized steel strip or sheet, an additional content of 0.2 to 4 g / l of complex and / or simple fluoride (calc. as F).

    Bei der Konzeption der vorliegenden Erfindung wurde festgestellt, daß bei der vorstehend genannten Bemessung der Konzentrationen von Komplexbildner für Eisen und Nitrit das von der nicht verzinkten bzw. legierungsverzinkten Seite des Stahlbandes oder -bleches in Lösung gehende Eisen zum weit überwiegenden Teil komplex gebunden wird. Eine Schichtbildung auf der Stahlseite ist nicht festzustellen. Die Entstehung von Phosphatschlamm in der Phosphatierungslösung wird gänzlich unterbunden oder aber auf einen Wert, der maximal 10 % der sonst zu beobachtenden Schlammmenge ausmacht, reduziert. Das erwünschte Phosphatierungsergebnis auf der verzinkten bzw. legierungsverzinkten Seite wird nicht beeinträchtigt. In designing the present invention found that at the above Dimensioning the concentrations of complexing agents for Iron and nitrite from the non-galvanized or alloy galvanized side of the steel strip or -plate iron going in solution to the far predominantly complex bound. A Layering on the steel side is not ascertain. The formation of phosphate sludge in the phosphating solution is completely prevented or to a value that is a maximum of 10% of the otherwise amount of sludge to be observed is reduced. The Desired phosphating result on the galvanized or alloy galvanized side will not impaired.

    Die Grenzen der angegebenen Bereiche für Komplexbildner sind insofern wichtig, als zu hohe Komplexbildnerkonzentrationen die Phosphatschichtausbildung durch Komplexierung der schichtbildenden Kationen beeinträchtigen. Bei zu geringer Komplexbildnerzugabe ist eine Phosphatschlammbildung in der Phosphatierungslösung und eine beginnende Phosphatschichtausbildung auf der Stahlseite nicht zu vermeiden. Bei einer höheren oder niedrigeren Einstellung der Nitritkonzentration kann die Phosphatierung auf der verzinkten bzw. legierungsverzinkten Stahlseite und die Komplexierung des abgelösten Eisens nachteilig beeinflußt werden. So kann z. B. bei einer zu hohen Nitritkonzentration eine beginnende Schichtausbildung auf der Stahlseite nicht vermieden werden. Eine derartige beginnende Schichtausbildung kann die nachfolgende Phosphatierung in der Automobilanlage beeinträchtigen, führt aber auf jeden Fall zu unerwünschter Schlammbildung.The limits of the specified ranges for Complexing agents are important in that they are too high Complexing agent concentrations Phosphate layer formation by complexing the affect layer-forming cations. In to low addition of complexing agent is one Phosphate sludge formation in the phosphating solution and a beginning phosphate layer formation on the Unavoidable steel side. At a higher or lower nitrite concentration setting phosphating on the galvanized or alloy galvanized steel side and the complexation of the detached iron can be adversely affected. So can e.g. B. at too high a nitrite concentration starting layer formation on the steel side not be avoided. Such a beginning The subsequent phosphating can form layers affect in the automotive plant, but leads in any case to undesirable sludge formation.

    Um infolge autokatalytischer Nitritbildung bei normaler Durchsatzleistung einen Anstieg der Nitritkonzentration über den oberen Grenzwert zu verhindern, wird es üblicherweise erforderlich sein, geeignete Gegenmaßnahmen zu ergreifen. Eine besonders geeignete Gegenmaßnahme besteht darin, die Nitritkonzentration der Phosphatierungslösung mittels nitritabbauender Substanzen, wie Harnstoff und/oder Amidosulfonsäure in den genannten Grenzen zu halten. Dies kann durch kontinuierliche oder diskontinuierliche Zugabe geschehen. Eine besonders elegante Methode sieht vor, die Nitritkonzentration dadurch in den erforderlichen Grenzen zu halten, daß man in der Phosphatierungslösung eine Harnstoffkonzentration von 1 bis 3 g/l und/oder eine Amidosulfonsäurekonzentration von 0,5 bis 2 g/l einstellt. Hierdurch wird ein stationärer Zustand geschaffen, indem durch den Harnstoff- bzw. Amidosulfonsäuregehalt ebensoviel Nitrit abgebaut wird wie durch Autokatalyse entsteht.To due to autocatalytic nitrite formation normal throughput an increase in Nitrite concentration above the upper limit prevent, it will usually be necessary take appropriate countermeasures. A special one a suitable countermeasure is to Nitrite concentration of the phosphating solution using nitrite-degrading substances, such as urea and / or To keep amidosulfonic acid within the stated limits. This can be done through continuous or discontinuous addition happen. A special one elegant method provides for the nitrite concentration by keeping within the necessary limits that one in the phosphating solution Urea concentration of 1 to 3 g / l and / or one Amidosulfonic acid concentration from 0.5 to 2 g / l sets. This becomes a steady state created by the urea or Amidosulfonic acid content is reduced as much nitrite as created by auto-catalysis.

    Die innerhalb des erfindungsgemäßen Verfahrens einzusetzenden Stahlbänder oder -bleche können auf der verzinkten bzw. legierungsverzinkten Seite Schichten aus Elektrolytzink (ZE), Feuerzink (Z), oder Legierungen auf Basis Zink/Nickel (ZNE), Zink/Eisen (ZF) oder Zink/Aluminium (ZA bzw. AZ) aufweisen. Zu letzteren werden üblicherweise auch Legierungen mit z. B. 55 Gew.-% Al und 45 Gew.-% Zn gezählt.The within the inventive method Steel strips or sheets to be used can be on the galvanized or alloy galvanized side layers made of electrolytic zinc (ZE), hot zinc (Z), or Alloys based on zinc / nickel (ZNE), zinc / iron (ZF) or zinc / aluminum (ZA or AZ). To the latter are usually also alloys e.g. B. 55 wt .-% Al and 45 wt .-% Zn counted.

    Eine bevorzugte Ausführungsform der Erfindung besteht darin, das verzinkte oder legierungsverzinkte Stahlband oder -blech mit einer Phosphatierungslösung in Kontakt zu bringen, die

  • 1 bis 2,5 g/l Zink
  • 10 bis 20 g/l P2O5
  • 0,020 bis 0,060 g/l NO2
  • 5 bis 15 g/l NO3
  • 0,2 bis 2,5 g/l Komplexbildner für Eisen
    • enthält und einen S-Wert von 0,12 bis 0,20 aufweist. Diese Ausführungsform der Erfindung hat den Vorzug, daß die Schlammbildung besonders gering ist und daß zudem gute Phosphatschichten auf der verzinkten bzw. legierungsverzinkten Seite entstehen.A preferred embodiment of the invention is to bring the galvanized or alloy galvanized steel strip or sheet into contact with a phosphating solution which
  • 1 to 2.5 g / l zinc
  • 10 to 20 g / l P 2 O 5
  • 0.020 to 0.060 g / l NO 2
  • 5 to 15 g / l NO 3
  • 0.2 to 2.5 g / l complexing agent for iron
    • contains and has an S value of 0.12 to 0.20. This embodiment of the invention has the advantage that the sludge formation is particularly low and that good phosphate layers are also formed on the galvanized or alloy-galvanized side.

    Besonders vorteilhafte Ergebnisse werden erzielt, wenn entsprechend einer vorteilhaften Ausgestaltung der Erfindung das verzinkte oder legierungsverzinkte Stahlband oder -blech mit einer Lösung in Berührung gebracht wird, die als Komplexbildner Chelatbildner, wie Weinsäure, Zitronensäure, Ethylendiamintetraessigsäure, Nitrilotriessigsäure und/oder Oxalsäure, enthält. Die Gehalte der Phosphatierungslösungen an den vorgenannten Komplexbildnern sollten dabei vorzugsweise

  • 0,5 bis 2,5 g/l Weinsäure
  • 0,2 bis 0,4 g/l Zitronensäure
  • 0,2 bis 2,5 g/l Nitrilotriessigsäure oder Ethylendiamintetraessigsäure (berechnet als Ethylendiamintetraessigsäure)
    • Particularly advantageous results are achieved if, according to an advantageous embodiment of the invention, the galvanized or alloy-galvanized steel strip or sheet is brought into contact with a solution which contains chelating agents, such as tartaric acid, citric acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid and / or oxalic acid, as complexing agents. The contents of the phosphating solutions in the aforementioned complexing agents should preferably be used
  • 0.5 to 2.5 g / l tartaric acid
  • 0.2 to 0.4 g / l citric acid
  • 0.2 to 2.5 g / l nitrilotriacetic acid or ethylenediaminetetraacetic acid (calculated as ethylenediaminetetraacetic acid)

    • betragen.be.

    Die Qualität der erzeugten Phosphatschicht kann verbessert werden, wenn entsprechend einer weiteren Ausführungsform der Erfindung das verzinkte oder legierungsverzinkte Stahlband oder -blech mit einer Phosphatierungslösung in Kontakt gebracht wird, die weitere zweiwertige Kationen, insbesondere Mangan- und oder Nickelionen, enthält. In diesem Fall ist es vorteilhaft, die Konzentrationen in der Phosphatierungslösung auf 1 bis 3 g/l, insbesondere 1,5 bis 2,5 g/l Manganionen, und/oder 0,1 bis 2,5 g/l, insbesondere 0,5 bis 1,5 g/l Nickelionen einzustellen.The quality of the phosphate layer produced can be improved if according to another Embodiment of the invention the galvanized or alloy galvanized steel strip or sheet with one Phosphating solution is brought into contact with the further divalent cations, especially manganese and or nickel ions. In this case it is advantageous, the concentrations in the Phosphating solution to 1 to 3 g / l, in particular 1.5 to 2.5 g / l manganese ions, and / or 0.1 to 2.5 g / l, in particular 0.5 to 1.5 g / l of nickel ions.

    Wegen der benötigten höheren Aggressivität der Phosphatierungslösung ist es bei der Behandlung von schmelztauchverzinktem oder schmelztauchlegierungsverzinktem Stahlband oder -blech unerläßlich, mit Phosphatierungslösungen zu arbeiten, die komplexes und/oder einfaches Fluorid enthalten. Because of the higher aggressiveness needed Phosphating solution is in the treatment of it hot-dip galvanized or hot dip galvanized steel strip or sheet indispensable to work with phosphating solutions, which contain complex and / or simple fluoride.

    Gemäß einer weiteren vorteilhaften Ausgestaltung der Erfindung werden jedoch auch bei der Behandlung von elektrolytisch verzinktem Stahlband oder -blech Phosphatierungslösungen zum Einsatz gebracht, die komplexes und/oder einfaches Fluorid, vorzugsweise in Mengen von 0,1 bis 3 g/l (ber. als F), enthalten. Als komplexes Fluorid ist Fluoroborat, Fluorosilikat. Fluorotitanat und/oder Fluorozirkonat bevorzugt.According to a further advantageous embodiment of the However, invention are also used in the treatment of electrolytically galvanized steel strip or sheet Phosphating solutions used that complex and / or simple fluoride, preferably in Amounts from 0.1 to 3 g / l (calculated as F). As complex fluoride is fluoroborate, fluorosilicate. Fluorotitanate and / or fluorozirconate preferred.

    Die phosphatierende Behandlung des Bandes oder Bleches kann nach herkömmlichen Verfahren, also im Tauchen oder Spritzen, erfolgen. Besonders vorteilhaft ist es jedoch, die Lösung im Spritzverfahren aufzubringen.Phosphating treatment of the strip or sheet can by conventional methods, i.e. in diving or syringes. It is particularly advantageous however, to apply the solution by spraying.

    Die Phosphatierungslösung wird üblicherweise durch ein Ergänzungskonzentrat ergänzt, wobei die Steuerung z. B. automatisch über eine Leitfähigkeitsmessung erfolgt. Ein geeignetes Ergänzungskonzentrat enthält z. B. 10 bis 30 Gew.-% P2O5, 3 bis 20 Gew.-% NO3 und 0 bis 2 Gew.-% Zink. Der Gehalt an Zink im Ergänzungskonzentrat richtet sich im wesentlichen nach der Reaktivität der auf dem Stahlband oder -blech befindlichen Zink- oder Legierungszinkschicht. Sofern diese Schicht eine höhere Reaktivität hat und dadurch größere Zinkmengen durch den Beizangriff der Phosphatierungslösung in das Bad gelangen, ist eine Ergänzungslösung mit geringeren Zinkkonzentrationen innerhalb des Bereiches von 0 bis 2 Gew.-% möglich. Im Extremfall, d. h. insbesondere bei einer phosphatierenden Behandlung unmittelbar im Anschluß an eine Verzinkung des Stahlbandes, kann das Ergänzungskonzentrat auch zinkfrei sein.The phosphating solution is usually supplemented by a supplementary concentrate, with the control e.g. B. is done automatically via a conductivity measurement. A suitable supplement concentrate contains e.g. B. 10 to 30 wt .-% P 2 O 5 , 3 to 20 wt .-% NO 3 and 0 to 2 wt .-% zinc. The zinc content in the supplemental concentrate depends essentially on the reactivity of the zinc or alloy zinc layer on the steel strip or sheet. If this layer has a higher reactivity and thus larger amounts of zinc get into the bath due to the pickling of the phosphating solution, a supplementary solution with lower zinc concentrations within the range of 0 to 2% by weight is possible. In an extreme case, ie in particular in the case of a phosphating treatment immediately after galvanizing the steel strip, the supplemental concentrate can also be zinc-free.

    In der bevorzugten Ausgestaltung des erfindungsgemäßen Verfahrens - mit einem Gehalt der Phosphatierungslösung an Nickel- und/oder Manganionen - enthält das Ergänzungskonzentrat noch 0,2 bis 2 Gew.-% Nickel und/oder 1 bis 4 Gew.-% Mangan.In the preferred embodiment of the invention Procedure - containing the Phosphating solution on nickel and / or manganese ions - the supplement concentrate still contains 0.2 to 2% by weight of nickel and / or 1 to 4% by weight of manganese.

    Prinzipiell kann die Ergänzungslösung auch bereits den Komplexbildner für Eisen und erforderlichenfalls die NO2-abbauende Substanz enthalten; aus Gründen einer besseren Einstellbarkeit der erforderlichen Konzentrationen wird es jedoch im allgemeinen vorzuziehen sein, diese beiden Substanzen separat zu ergänzen.In principle, the supplemental solution can also already contain the complexing agent for iron and, if necessary, the NO 2 -degrading substance; however, for reasons of better adjustability of the required concentrations, it will generally be preferable to supplement these two substances separately.

    Mit Hilfe des erfindungsgemäßen Verfahrens werden Phosphatschichten erzeugt, deren Schichtgewicht etwa 1 bis 2 g/m2 beträgt.With the aid of the method according to the invention, phosphate layers are produced, the layer weight of which is approximately 1 to 2 g / m 2 .

    Die Erfindung wird anhand des folgenden Beispiels beispielsweise und näher erläutert.The invention is illustrated by the following example for example and explained in more detail.

    Beispiel:Example:

    Unmittelbar im Anschluß an die elektrolytische Verzinkung von Stahlband wurde mit einer Lösung phosphatiert, die folgende Bestandteile aufwies: Zink 1,8 g/l P2O5 14,5 g/l Nickel 1,3 g/l Mangan 2,0 g/l Weinsäure 1 g/l Harnstoff 1 g/l NO3 7 g/l NO2 0,040 g/l. Immediately following the electrolytic galvanizing of steel strip, phosphating was carried out with a solution which had the following components: zinc 1.8 g / l P 2 O 5 14.5 g / l nickel 1.3 g / l manganese 2.0 g / l Tartaric acid 1 g / l urea 1 g / l NO 3 7 g / l NO 2 0.040 g / l.

    Der S-Wert der Phosphatierungslösung betrug 0,17, die Temperatur der Phosphatierungslösung war auf 50 bis 55°C eingestellt. Die Applikation erfolgte im Spritzen für die Dauer von 8 Sekunden.The S value of the phosphating solution was 0.17% Temperature of the phosphating solution was 50 to 55 ° C set. The application was done by spraying for a period of 8 seconds.

    Die Phosphatierbehandlung erfolgte über einen Zeitraum von 16 Stunden bei einer Badgröße von 25 m3. Danach wurde eine Naß-Schlamm-Menge von 2 ml/1 Phosphatierungslösung ermittelt. Dies entspricht ca. 0,6 ml Schlamm pro m2 durchgesetzter Stahloberfläche. Auf der Zinkseite hatte sich eine einwandfreie Phosphatschicht gebildet, deren Schichtgewicht 1,6 g/m2 betrug. Die Stahlseite war in einwandfreiem Zustand, d. h. zeigte praktisch keine Schichtausbildung.The phosphating treatment was carried out over a period of 16 hours with a bath size of 25 m 3 . Then a wet sludge amount of 2 ml / 1 phosphating solution was determined. This corresponds to approx. 0.6 ml of sludge per m 2 of penetrated steel surface. A perfect phosphate layer had formed on the zinc side, the layer weight of which was 1.6 g / m 2 . The steel side was in perfect condition, ie showed practically no layer formation.

    Bei einem Vergleichsversuch ohne Zusatz von Komplexbildner und NO2-abbauender Substanz, aber sonst den gleichen Bedingungen, kam es zu einem Naß-Schlammanfall von 28 ml/1 Phosphatierungslösung. Dies entspricht etwa 8,4 ml Schlamm pro m2 durchgesetzter Stahloberfläche. Das Schichtgewicht auf der Zinkseite betrug auch hier 1,6 g/m2, die Stahlseite hingegen zeigte eine beginnende Phosphatschichtausbildung.In a comparative test without the addition of complexing agent and NO 2 -degrading substance, but otherwise under the same conditions, a wet sludge accumulation of 28 ml / 1 phosphating solution was obtained. This corresponds to approximately 8.4 ml of sludge per m 2 of penetrated steel surface. The layer weight on the zinc side was 1.6 g / m 2 here too, while the steel side, on the other hand, showed a beginning formation of phosphate layers.

    Claims (11)

    1. A method for the phosphating treatment of steel strip or sheet which is zinc-plated or zinc alloy-plated on one side, with the aid of phosphating solutions which contain zinc, nitrate and nitrite, characterised in that the steel strip or sheet which is zinc-plated or zinc alloy-plated on one side is brought into contact for a time of 4 to 20 seconds with a phosphating solution at a temperature of 45 to 80°C which contains
      0.5 to 5 g/l zinc,
      3 to 20 g/l P2O5,
      0.005 to 0.2 g/l NO2,
      3 to 30 g/l NO3,
      0.2 to 2.5 g/l complexing agent for iron,
      has an S value of 0.08 to 0.30 and in the case of the phosphating treatment of hot-dip zinc-plated or hot-dip zinc alloy-plated steel strip or sheet has an additional content of 0.2 to 4 g/l complex and/or simple fluoride (calculated as F).
    2. A method according to Claim 1, characterised in that the steel strip or sheet which is zinc-plated or zinc alloy-plated on one side is brought into contact with a phosphating solution the nitrite concentration of which is kept within the limits from 0.005 to 0.2 g/l by urea and/or amidosulphonic acid.
    3. A method according to Claim 2, characterised in that the steel strip or sheet which is zinc-plated or zinc alloy-plated on one side is brought into contact with a phosphating solution the nitrite concentration of which is kept within the limits from 0.005 to 0.2 g/l by setting a urea concentration of 1 to 3 g/l and/or an amidosulphonic acid concentration of 0.5 to 2 g/l.
    4. A method according to Claim 1, 2 or 3, characterised in that the steel strip or sheet which is zinc-plated or zinc alloy-plated on one side is brought into contact with a phosphating solution which contains
      1 to 2.5 g/l zinc,
      10 to 20 g/l P2O5,
      0.020 to 0.060 g/l NO2,
      5 to 15 g/l NO3,
      0.2 to 2.5 g/l complexing agent for iron, and has an S value of 0.12 to 0.20.
    5. A method according to one or more of Claims 1 to 4, characterised in that the steel strip or sheet which is zinc-plated or zinc alloy-plated on one side is brought into contact with a phosphating solution which contains chelating agents, such as tartaric acid, citric acid, ethylenediamine tetraacetic acid, nitrilo-triacetic acid and/or oxalic acid, as complexing agent.
    6. A method according to Claim 5, characterised in that the steel strip or sheet which is zinc-plated or zinc alloy-plated on one side is brought into contact with a phosphating solution which contains
      0.5 to 2.5 g/l tartaric acid,
      0.2 to 0.4 g/l citric acid,
      0.2 to 2.5 g/l nitrilo-triacetic acid or ethylenediamine tetraacetic acid (calculated as ethylenediamine tetraacetic acid).
    7. A method according to one or more of Claims 1 to 6, characterised in that the steel strip or sheet which is zinc-plated or zinc alloy-plated on one side is brought into contact with a phosphating solution which contains additional divalent cations, in particular manganese and/or nickel ions.
    8. A method according to Claim 7, characterised in that the steel strip or sheet which is zinc-plated or zinc alloy-plated on one side is brought into contact with a phosphating solution which contains 1 to 3 g/l, preferably 1.5 to 2.5 g/l, manganese and/or 0.1 to 2.5 g/l, preferably 0.5 to 1.5 g/l, nickel.
    9. A method according to one or more of Claims 1 to 8, characterised in that the steel strip or sheet which is zinc-plated or zinc alloy-plated on one side is brought into contact with a phosphating solution which contains complex and/or simple fluoride, preferably in quantities of 0.1 to 3 g/l (calculated as F).
    10. A method according to Claim 9, characterised in that the steel strip or sheet which is zinc-plated or zinc alloy-plated on one side is brought into contact with a phosphating solution which contains fluoroborate, fluorosilicate, fluorotitanate and/or fluorozirconate as complex fluoride.
    11. A method according to one or more of Claims 1 to 10, characterised in that the steel strip or sheet which is zinc-plated or zinc alloy-plated on one side is brought into contact with the phosphating solution by spray treatment.
    EP94924298A 1993-08-06 1994-07-29 Phosphate treatment process for steel strip with one galvanised surface Expired - Lifetime EP0713539B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    DE4326388A DE4326388A1 (en) 1993-08-06 1993-08-06 Process for the phosphating treatment of one-sided galvanized steel strip
    DE4326388 1993-08-06
    PCT/EP1994/002510 WO1995004842A1 (en) 1993-08-06 1994-07-29 Phosphate treatment process for steel strip with one galvanised surface

    Publications (2)

    Publication Number Publication Date
    EP0713539A1 EP0713539A1 (en) 1996-05-29
    EP0713539B1 true EP0713539B1 (en) 1998-09-09

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    ID=6494574

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    Application Number Title Priority Date Filing Date
    EP94924298A Expired - Lifetime EP0713539B1 (en) 1993-08-06 1994-07-29 Phosphate treatment process for steel strip with one galvanised surface

    Country Status (9)

    Country Link
    US (1) US5795408A (en)
    EP (1) EP0713539B1 (en)
    JP (1) JP3372954B2 (en)
    CN (1) CN1131444A (en)
    AT (1) ATE170931T1 (en)
    DE (2) DE4326388A1 (en)
    ES (1) ES2122318T3 (en)
    WO (1) WO1995004842A1 (en)
    ZA (1) ZA945881B (en)

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    EP1916317A1 (en) 2006-10-27 2008-04-30 Seppeler Holding und Verwaltungs GmbH & Co. KG Method for preweathering metal parts with a surface consisting primarily of zinc

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    DE19756735A1 (en) * 1997-12-19 1999-06-24 Henkel Kgaa Phosphating one-side galvanized steel strip on the galvanized side only
    US20040221924A1 (en) * 1999-09-30 2004-11-11 Klaus-Dieter Nittel Method for applying manganese phosphate layers
    WO2002046494A1 (en) * 2000-12-04 2002-06-13 Jfe Steel Corporation Zinc-based metal plated steel sheet and method for production thereof
    CN102304709B (en) * 2011-04-25 2013-10-30 大连三达奥克化学股份有限公司 Black phosphating agent for special tool for automobiles and preparation method for black phosphating agent
    CN102677034A (en) * 2012-05-25 2012-09-19 衡阳市金化科技有限公司 Medium-temperature low-sediment zinc phosphorizing solution
    CN103184444B (en) * 2013-03-29 2016-08-03 柳州煜华科技有限公司 A kind of Phosphating Solution being applicable to metal fastenings
    RU2560891C1 (en) * 2014-05-05 2015-08-20 Федеральное государственное унитарное предприятие федеральный научно-производственный центр "Производственное объединение "Старт" им. М.В. Проценко" (ФГУП ФНПЦ "ПО "Старт" им. М.В. Проценко") Method of iron-cobalt alloy phosphating
    CN105369238B (en) * 2015-11-23 2017-11-14 安徽千和新材料科技发展有限公司 Normal temperature is without slag phosphating solution and preparation method thereof before Progress in Automobile Galvanized Steel Sheets electrophoresis
    US10465292B2 (en) * 2016-10-07 2019-11-05 Goodrich Corporation Anti-corrosion and/or passivation composition for metal-containing substrates and methods for making, enhancing, and applying the same
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    US11566330B2 (en) * 2019-04-16 2023-01-31 Ppg Industries Ohio, Inc. Systems and methods for maintaining pretreatment baths
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    Also Published As

    Publication number Publication date
    US5795408A (en) 1998-08-18
    JPH09501202A (en) 1997-02-04
    JP3372954B2 (en) 2003-02-04
    DE4326388A1 (en) 1995-02-09
    EP0713539A1 (en) 1996-05-29
    CN1131444A (en) 1996-09-18
    DE59406893D1 (en) 1998-10-15
    ES2122318T3 (en) 1998-12-16
    ATE170931T1 (en) 1998-09-15
    ZA945881B (en) 1996-02-05
    WO1995004842A1 (en) 1995-02-16

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