EP0359296A1 - Phosphating process - Google Patents

Phosphating process Download PDF

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Publication number
EP0359296A1
EP0359296A1 EP89201935A EP89201935A EP0359296A1 EP 0359296 A1 EP0359296 A1 EP 0359296A1 EP 89201935 A EP89201935 A EP 89201935A EP 89201935 A EP89201935 A EP 89201935A EP 0359296 A1 EP0359296 A1 EP 0359296A1
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EP
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Prior art keywords
zinc
phosphating
phosphating solution
brought
contact
Prior art date
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EP89201935A
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German (de)
French (fr)
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EP0359296B1 (en
Inventor
Klaus Bittner
Gerhard Müller
Werner Dr. Rausch
Klaus Dr. Wittel
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GEA Group AG
Continentale Parker SA
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Metallgesellschaft AG
Continentale Parker SA
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Priority to AT89201935T priority Critical patent/ATE85817T1/en
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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
    • 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
    • C23C22/12—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
    • C23C22/34—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
    • C23C22/368—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 magnesium cations

Definitions

  • the invention relates to a method for phosphating galvanized surfaces, in particular galvanized steel, by means of aqueous zinc ions, phosphate ions, further layer-forming cations and phosphating solutions containing accelerators, and its use for the treatment of galvanized steel strip, optionally with subsequent application of lacquer or organic foils.
  • DE-OS 32 45 411 describes a process for the formation of zinc phosphate layers on electrolytically galvanized steel.
  • the area-related mass of less than 2 g / m2 hopeit which can be achieved within a short time and which is achieved with this method is advantageous, since this is the later welding of the galvanized and phosphated strip allowed.
  • the disadvantage is the restriction to electrolytically galvanized surfaces. Bands galvanized in the hot-dip process, on the other hand, show a low reactivity towards the phosphating solution, so that the desired layer formation cannot usually be achieved in the desired short treatment time.
  • the object of the invention is to provide a process for the phosphating of galvanized surfaces, which is equally suitable for zinc coatings which have been applied electrolytically or in the hot-dip process and leads to bright, almost white coatings, phosphate layers with less than 2 g / m2 of area-related mass, which are suitable for protection against bright corrosion and as a primer for paint and organic foils, and which forms closed coatings in a short time.
  • Zinc coatings are understood to be those made from pure zinc, but also from zinc alloys with zinc as the main component. These include e.g. Galfan (approx. 5% Al, less than 1% mixed metal, balance zinc), zinc / nickel alloys (approx. 10% Ni, balance Zn) zinc / iron and zinc / cobalt alloys.
  • the accelerators used in the aforementioned phosphating solution are common.
  • the phosphating solution used in the process according to the invention works with a comparatively high S value, so that it is highly aggressive towards the zinc surface.
  • the addition of the phosphating solution, which is essential to the invention, is therefore carried out with a concentrate which, measured on conventional concentrates, contains little or no zinc.
  • An S value in the range from 0.2 to 0.3 is particularly advantageous.
  • the S value is the ratio of "free acid” - calculated as P2O5 - and the so-called “total acid Fischer", ie the total amount of P2O5, expressed as consumption of 0.1 n NaOH when titrating a 10 ml bath sample (cf. W. Rausch: "The Phosphating of Metals", Eugen G. Leuze Verlag, Saulgau 1974, pages 274 to 277).
  • Phosphate layers with particularly favorable properties are obtained if, according to an advantageous development of the invention, the surfaces are brought into contact with a phosphating solution which contains a maximum of 1.5 g / l zinc, preferably 0.5 to 1 g / l zinc, at a weight ratio of Magnesium: contains zinc from (0.5 to 3): 1.
  • the surfaces are brought into contact with a phosphating solution which additionally contains nickel ions in an amount of at most 1.5 g / l, preferably in an amount of at most 0.5 g / l.
  • a phosphating solution which additionally contains nickel ions in an amount of at most 1.5 g / l, preferably in an amount of at most 0.5 g / l.
  • the surface is brought into contact with a phosphating solution which additionally contains simple or complex fluoride in an amount of at most 3 g / l, preferably from 0.1 to 1.5 g / l, (each calculated as F).
  • a phosphating solution which additionally contains simple or complex fluoride in an amount of at most 3 g / l, preferably from 0.1 to 1.5 g / l, (each calculated as F).
  • simple or complex fluoride in an amount of at most 3 g / l, preferably from 0.1 to 1.5 g / l, (each calculated as F).
  • complex fluoride compounds are BF4 ⁇ , SiF6 ⁇ , PF6 ⁇ , ZrF6 ⁇ or TiF6 ⁇ .
  • the chemical consumption occurring in the treatment of the surfaces is taken into account by supplementing the phosphating solution with a concentrate. Because of the high aggressiveness of the phosphating solution, the zinc ions required for the layer formation mainly come from the treated surface, which leads to favorable layer properties.
  • the phosphating solution is preferably supplemented with a zinc-free concentrate.
  • nitrate is used as an accelerator, it is advisable to supplement it with a concentrate in which the weight ratio of NO3: P2O5 is in the range from (0.15 to 0.7): 1, preferably from (0.3 to 0.5) : 1, lies.
  • the surface to be phosphated must be free of organic and inorganic contaminants. This is ensured when using the method according to the invention in an electrolytic strip galvanizing line. In other cases, cleaning with cleaning solutions, which usually work in an alkaline but also in an acidic environment, is common, followed by a one- or multi-stage rinsing with water.
  • activating agent contain finely ground zinc phosphate or specially prepared compounds from titanium and phosphate ions.
  • the activating agent is applied by dipping or flooding, preferably by spraying. If the method according to the invention is used to treat strip material, the treatment is carried out for 0.5 to 3 s.
  • the phosphating according to the invention follows the activation. This is done by diving or flooding, preferably by spraying.
  • the spray pressure is expediently 0.5 to 2 bar, and 0.5 to 0.8 bar is particularly favorable.
  • the temperature of the treatment solution is usually in the range of 40 to 65 ° C. During this treatment, a light gray layer of zinc and magnesium phosphates forms.
  • the mass per unit area of the layer is below 2 g / m2, usually below 1.5 g / m2.
  • the phosphating treatment is followed by rinsing with water in order to remove unreacted treatment solution from the surface of the treated workpiece.
  • this rinsing can be dispensed with.
  • the phosphate layers produced can be rinsed with rinsing agents before drying.
  • Weakly acidic solutions containing chromium (VI) and / or chromium (III) ions are mostly used.
  • the method according to the invention is suitable for all galvanized surfaces, taking into account the definition given above for "galvanized”.
  • a particularly advantageous application is the treatment of galvanized, in particular electrolytically galvanized steel strip.
  • phosphating can take place directly after the galvanizing in the galvanizing line.
  • the phosphating is a final treatment, if necessary with rinsing, it serves as bearing protection against the formation of white rust and to improve the forming properties of the galvanized strip, in particular to reduce the zinc abrasion during pressing and deep drawing as well as to reduce tool wear.
  • Another application of the method according to the invention is the pretreatment of steel strip, which is coated with zinc electrolytically or in the hot-dip process, before the subsequent coating with lacquer or films made of organic polymers.
  • the phosphating according to the invention takes place here to improve the adhesion and the corrosion protection of the subsequently applied organic coatings.
  • This process is known in the art under the term "coil coating”.
  • varnishes include, for example, alkyl, acrylate, epoxy, polyester, silicone-modified acrylate and polyester paints, as well as polyvinyl chloride organosols and plastisols, polyvinyl fluoride and polyvinylidene fluoride systems.
  • the films come in particular from polyvinyl chloride, Polyvinyl fluoride or thermoplastic acrylates.
  • Freshly galvanized steel sheets of quality RSt 1405 were treated as follows: - Activation with a commercially available activating agent based on titanium phosphate, 1 g / l in deionized water, 3 s spraying at 1.0 bar and 35 ° C. - Phosphating with solutions of the concentrations given in the table, preparation in deionized water, 5 s spraying at 0.8 bar and 55 °.
  • the phosphating solution was supplemented with a zinc-free concentrate with a NO3: P2O5 ratio of 0.4: 1 to constant acidity. NO2 and - if available - Ni, Mg and F were added to maintain a constant concentration.
  • the table shows that the methods according to the invention offer advantages with regard to the mass per unit area and the appearance of the layer.
  • Galvanized steel sheets were treated as follows: - cleaning with a strongly alkaline, commercially available cleaner, batch 10 g / l in tap water, 10 s spraying at 1.2 bar for 10 s. - rinsing with tap water, 3 s spraying at 1.5 bar and 25 ° C. - Activation with the above-mentioned commercial activating agent, batch 1.3 g / l in deionized water, 3 s spraying at 1.0 bar at 35 ° C. - Phosphating with solutions of the concentrations given in the table, preparation in deionized water, 8 s spraying at 1.2 bar at 55 ° C.
  • the phosphating solution was supplemented with a zinc-free concentrate with a NO3: P2O5 ratio of 0.4: 1 to constant acidity. NO2 and - if available - Ni, Mg and F were added to ensure that the concentrations were constant. - rinsing with tap water, 2 s spraying at 1.5 bar at 25 ° C. - rinsing with the above-mentioned commercial passivating agent, preparation in deionized water, 2 s spraying at 0.8 bar and 55 ° C. - Drying in a convection oven, 20 s at 120 °.

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Abstract

Disclosed is a process for phosphating a galvanized surface, particularly of galvanized steel wherein the surface is contacted for up to 10 seconds with a phosphating solution which contains accelerator, particularly nitrate, 0.5 to 5.0 g/l zinc, 3 to 20 g/l phosphate (calculated as P2O5), 0.3 to 3 g/l magnesium at a weight ratio of magnesium: zinc=(0.5 to 10):1 and has an S value in the range from 0.2 to 0.4 preferably in the range from 0.2 to 0.3, and is replenished with a concentrate in which the weight ratio of zinc to phosphate (calculated as P2O5) is in the range from (0 to 1):8. It is particularly desirable to use a phosphating solution which contains up to 1.5 g/l zinc, preferably 0.5 to 1 g/l zinc, at a weight ratio of magnesium: zinc of (0.5 to 3:1, nickel ions in an amount of up to 1.5 g/l, preferably in an amount of up to 0.5 g/l and simple or complex fluoride in an amount of up to 3 g/l, preferable 0.1 to 1.5 g/l (calculated as F in each case). A special advantage is afforded by the use of the process to treat galvanized steel strip which is subsequently painted or coated with a preformed organic film.

Description

Die Erfindung betrifft ein Verfahren zur Phosphatierung von verzinkten Oberflächen, insbesondere von verzinktem Stahl, mittels wässriger Zinkionen, Phosphationen, weitere schichtbildende Kationen sowie Beschleuniger enthaltenden Phosphatierungslösungen sowie dessen Anwendung zur Behandlung von verzinktem Stahlband ggf. mit anschließender Aufbringung von Lack oder organischen Folien.The invention relates to a method for phosphating galvanized surfaces, in particular galvanized steel, by means of aqueous zinc ions, phosphate ions, further layer-forming cations and phosphating solutions containing accelerators, and its use for the treatment of galvanized steel strip, optionally with subsequent application of lacquer or organic foils.

Es ist aus der DE-OS 21 00 021 bekannt, Metalloberflächen mit Phosphatierungslösungen zu behandeln, die als wesentliches Kation Nickel enthalten. Es bilden sich auf Zinkoberflächen Phosphatschichten, die neben Zink beträchtliche Mengen Nickel als Kation enthalten. Der Korrosionsschutz solcher Schichten ist sehr gut, vor allem, wenn sie mit den üblichen Cr(VI)-Cr(III)-haltigen Nachspülmitteln nachgespült werden. Die Schichten eignen sich auch in hervorragender Weise als Lackuntergrund bei der Bandbeschichtung. Ein Nachteil dieses Verfahrens ist die relativ dunkle, bis ins Schwarze reichende Färbung der erzeugten Konversionsschicht, was optisch nicht anspricht und zudem zu Farbproblemen bei der Lackierung mit hellen und mit weißen Lacken führt.It is known from DE-OS 21 00 021 to treat metal surfaces with phosphating solutions which contain nickel as an essential cation. Phosphate layers are formed on zinc surfaces, which contain zinc as a cation in addition to zinc. The corrosion protection of such layers is very good, especially if they are rinsed with the usual rinse agents containing Cr (VI) -Cr (III). The layers are also excellently suited as a lacquer substrate for coil coating. A disadvantage of this process is the relatively dark coloration of the conversion layer that reaches into the black, which is not visually appealing and also leads to color problems when painting with light and white paints.

Die DE-OS 32 45 411 beschreibt ein Verfahren zur Bildung von Zinkphosphat-Schichten auf elektrolytisch verzinktem Stahl. Vorteilhaft ist die innerhalb kurzer Zeit erreichbare flächenbezogene Masse von kleiner 2 g/m² Hopeit, die mit diesem Verfahren erzielt wird, da dies das spätere Schweißen des verzinkten und phosphatierten Bandes erlaubt. Nachteilig ist die Einschränkung auf elektrolytisch verzinkte Oberflächen. Im Schmelztauch-Verfahren verzinkte Bänder zeigen hingegen eine geringe Reaktivität gegenüber der Phosphatierungslösung, so daß die erwünschte Schichtausbildung in der angestrebten kurzen Behandlungsdauer meist nicht erreichbar ist.DE-OS 32 45 411 describes a process for the formation of zinc phosphate layers on electrolytically galvanized steel. The area-related mass of less than 2 g / m² hopeit which can be achieved within a short time and which is achieved with this method is advantageous, since this is the later welding of the galvanized and phosphated strip allowed. The disadvantage is the restriction to electrolytically galvanized surfaces. Bands galvanized in the hot-dip process, on the other hand, show a low reactivity towards the phosphating solution, so that the desired layer formation cannot usually be achieved in the desired short treatment time.

Weiterhin ist es bekannt, daß Phosphatschichten, die vorwiegend aus Hopeit (Zn₃(PO₄)₂ . 4 H₂O) bestehen, in ihren Anwendungseigenschaften solchen unterlegen sind, die überwiegend aus Phosphophyllit (Zn₂Fe(PO₄)₂ . 4 H₂O) gebildet sind (K. Wittel: "Moderne Zinkphosphatier-Verfahren-Niedrig-Zink-Technik", Industrie-Lackierbetrieb, 5/83, Seite 169 und 6/83, Seite 210). Für Zinkoberflächen sind jedoch noch keine praktikablen Verfahren zur Erzeugung von Phosphophyllit-Schichten bekannt.Furthermore, it is known that phosphate layers which predominantly consist of hopeit (Zn₃ (PO₄) ₂. 4 H₂O) are inferior in their application properties to those which are predominantly formed from phosphophyllite (Zn₂Fe (PO₄) ₂. 4 H₂O) (K. Wittel: "Modern Zinc Phosphating Process-Low-Zinc Technology", Industrie-Lackierbetrieb, 5/83, pages 169 and 6/83, page 210). However, no practical methods for producing phosphophyllite layers are known for zinc surfaces.

Aufgabe der Erfindung ist es, ein Verfahren für die Phosphatierung verzinkter Oberflächen bereitzustellen, das für Zinküberzüge, die elektrolytisch oder im Schmelztauch-Verfahren aufgebracht worden sind, gleichermaßen geeignet ist, zu hellen, fast weißen Überzügen führt, Phosphat-Schichten mit weniger als 2 g/m² flächenbezogener Masse erzeugt, die sich zum Blankkorrosionsschutz und als Haftgrund für Lack und organische Folien eignen, und in kurzen Zeiten geschlossene Überzüge bildet.The object of the invention is to provide a process for the phosphating of galvanized surfaces, which is equally suitable for zinc coatings which have been applied electrolytically or in the hot-dip process and leads to bright, almost white coatings, phosphate layers with less than 2 g / m² of area-related mass, which are suitable for protection against bright corrosion and as a primer for paint and organic foils, and which forms closed coatings in a short time.

Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man die Oberflächen für die Dauer von maximal 10 s mit einer Phosphatierungslösung in Kontakt bringt, die
0,5 bis 5,0 g/l Zink
3 bis 20 g/l Phosphat (ber. als P₂O₅)
0,3 bis 3 g/l Magnesium
bei einem Gewichtsverhältnis von Magnesium : Zink = (0,5 bis 10) : 1 enthält, einen S-Wert im Bereich von 0,1 bis 0,4 aufweist und mit einem Konzentrat, in dem das Gewichtsverhältnis von Zink zu Phosphat (ber. als P₂O₅) im Bereich von (0 bis 1) : 8 liegt, ergänzt wird.The object is achieved by the method of the type mentioned in the introduction according to the invention is designed such that the surfaces are brought into contact with a phosphating solution for a maximum of 10 s
0.5 to 5.0 g / l zinc
3 to 20 g / l phosphate (calculated as P₂O₅)
0.3 to 3 g / l magnesium
at a weight ratio of magnesium: zinc = (0.5 to 10): 1, has an S value in the range from 0.1 to 0.4 and with a concentrate in which the weight ratio of zinc to phosphate (calc. as P₂O₅) is in the range from (0 to 1): 8, is added.

Unter Zinküberzügen sind solche aus reinem Zink, aber auch aus Zinklegierungen mit Zink als Hauptbestandteil verstanden. Hierzu zählen z.B. Galfan (ca. 5 % Al, weniger als 1 % Mischmetall, Rest Zink), Zink/Nickel-Legierungen (ca. 10 % Ni, Rest Zn) Zink/Eisen- und Zink/Kobalt-Legierungen.Zinc coatings are understood to be those made from pure zinc, but also from zinc alloys with zinc as the main component. These include e.g. Galfan (approx. 5% Al, less than 1% mixed metal, balance zinc), zinc / nickel alloys (approx. 10% Ni, balance Zn) zinc / iron and zinc / cobalt alloys.

Die in der vorgenannten Phosphatierungslösung verwendeten Beschleuniger sind allgemein üblich. Es kommen z.B. Nitrit, Chlorat, Peroxid, organische Nitro- oder Peroxidverbindungen, insbesondere aber Nitrat in Betracht.The accelerators used in the aforementioned phosphating solution are common. For example, Nitrite, chlorate, peroxide, organic nitro or peroxide compounds, but especially nitrate.

Die im erfindungsgemäßen Verfahren eingesetzte Phosphatierungslösung arbeitet mit einem vergleichsweise hohen S-Wert, so daß sie von hoher Aggressivität gegenüber der Zinkoberfläche ist. Die erfindungswesentliche Ergänzung der Phosphatierungslösung erfolgt daher mit einem Konzentrat, das - gemessen an herkömmlichen Konzentraten - wenig bis kein Zink enthält. Ein S-Wert im Bereich von 0,2 bis 0,3 ist besonders vorteilhaft. Der S-Wert ist das Verhältnis aus "Freier Säure" - gerechnet als P₂O₅ - und der sogenannten "Gesamtsäure Fischer", d.h. der Gesamtmenge P₂O₅, ausgedrückt als Verbrauch an 0,1 n NaOH bei Titration einer 10 ml Badprobe (vgl. W. Rausch: "Die Phosphatierung von Metallen", Eugen G. Leuze Verlag, Saulgau 1974, Seiten 274 bis 277).The phosphating solution used in the process according to the invention works with a comparatively high S value, so that it is highly aggressive towards the zinc surface. The addition of the phosphating solution, which is essential to the invention, is therefore carried out with a concentrate which, measured on conventional concentrates, contains little or no zinc. An S value in the range from 0.2 to 0.3 is particularly advantageous. The S value is the ratio of "free acid" - calculated as P₂O₅ - and the so-called "total acid Fischer", ie the total amount of P₂O₅, expressed as consumption of 0.1 n NaOH when titrating a 10 ml bath sample (cf. W. Rausch: "The Phosphating of Metals", Eugen G. Leuze Verlag, Saulgau 1974, pages 274 to 277).

Phosphatschichten mit besonders günstigen Eigenschaften werden erhalten, wenn man entsprechend einer vorteilhaften Weiterbildung der Erfindung die Oberflächen mit einer Phosphatierungslösung in Kontakt bringt, die maximal 1,5 g/l Zink, vorzugsweise 0,5 bis 1 g/l Zink, bei einem Gewichtsverhältnis von Magnesium : Zink von (0,5 bis 3) : 1 enthält.Phosphate layers with particularly favorable properties are obtained if, according to an advantageous development of the invention, the surfaces are brought into contact with a phosphating solution which contains a maximum of 1.5 g / l zinc, preferably 0.5 to 1 g / l zinc, at a weight ratio of Magnesium: contains zinc from (0.5 to 3): 1.

Gemäß einer weiteren vorteilhaften Ausgestaltung der Erfindung bringt man die Oberflächen mit einer Phosphatierungslösung in Kontakt, die zusätzlich Nickelionen in einer Menge von maximal 1,5 g/l, vorzugsweise in einer Menge von maximal 0,5 g/l enthält. Durch den dadurch erzielten partiellen Einbau von Nickel in die Phosphatschicht wird deren Qualität weiterhin verbessert. Bei höheren Nickelkonzentrationen besteht die Gefahr, daß der Nickelanteil zu hoch und damit der Magnesiumanteil zu niedrig wird.According to a further advantageous embodiment of the invention, the surfaces are brought into contact with a phosphating solution which additionally contains nickel ions in an amount of at most 1.5 g / l, preferably in an amount of at most 0.5 g / l. The partial incorporation of nickel into the phosphate layer thus achieved further improves its quality. At higher nickel concentrations there is a risk that the nickel content will be too high and the magnesium content will be too low.

Für besonders kurze Behandlungszeiten, sowie zur Behandlung von gealterten verzinkten Oberflächen oder von im Schmelztauch-Verfahren verzinkten Oberflächen, wird gemäß einer vorteilhaften Weiterbildung der Erfindung die Oberfläche mit einer Phosphatierungslösung in Kontakt gebracht, die zusätzlich einfaches oder komplexes Fluorid in einer Menge von maximal 3 g/l, vorzugsweise von 0,1 bis 1,5 g/l, (jeweils ber. als F) enthält. Es können dazu z.B. Flußsäure, Alkali-, Ammonium- oder Zinkfluorid oder die entsprechenden Bifluoride, sowie komplexe Fluoridverbindungen in Form der Säuren oder der Salze mit Alkali-, Ammonium- oder Zinkionen eingesetzt werden. Beispiele für komplexe Fluoridverbindungen sind BF₄⁻, SiF₆⁻⁻, PF₆⁻, ZrF₆⁻⁻ oder TiF₆⁻⁻.For particularly short treatment times, as well as for the treatment of aged galvanized surfaces or of surfaces galvanized using the hot-dip method, according to an advantageous development of the invention, the surface is brought into contact with a phosphating solution which additionally contains simple or complex fluoride in an amount of at most 3 g / l, preferably from 0.1 to 1.5 g / l, (each calculated as F). For example, hydrofluoric acid, alkali, ammonium or zinc fluoride or the corresponding bifluorides, as well as complex fluoride compounds in the form of acids or salts with alkali, ammonium or zinc ions. Examples of complex fluoride compounds are BF₄⁻, SiF₆⁻⁻, PF₆⁻, ZrF₆⁻⁻ or TiF₆⁻⁻.

Dem bei der Behandlung der Oberflächen auftretenden Chemikalienverbrauch wird dadurch Rechnung getragen, daß man die Phosphatierungslösung mit einem Konzentrat ergänzt. Wegen der hohen Aggressivität der Phosphatierungslösung stammen die zur Schichtbildung benötigten Zinkionen überwiegend aus der behandelten Oberfläche, was zu günstigen Schichteigenschaften führt. Vorzugsweise wird die Phosphatierungslösung mit einem zinkfreien Konzentrat ergänzt.The chemical consumption occurring in the treatment of the surfaces is taken into account by supplementing the phosphating solution with a concentrate. Because of the high aggressiveness of the phosphating solution, the zinc ions required for the layer formation mainly come from the treated surface, which leads to favorable layer properties. The phosphating solution is preferably supplemented with a zinc-free concentrate.

Im Fall der Verwendung von Nitrat als Beschleuniger sollte zweckmäßigerweise mit einem Konzentrat ergänzt werden, in dem das Gewichtsverhältnis von NO₃ : P₂O₅ im Bereich von (0,15 bis 0,7) : 1, vorzugsweise von (0,3 bis 0,5) : 1, liegt.If nitrate is used as an accelerator, it is advisable to supplement it with a concentrate in which the weight ratio of NO₃: P₂O₅ is in the range from (0.15 to 0.7): 1, preferably from (0.3 to 0.5) : 1, lies.

Die zu phosphatierende Oberfläche muß frei sein von organischen und anorganischen Verunreinigungen. Dies ist beim Einsatz des erfindungsgemäßen Verfahren in einer elektrolytischen Bandverzinkungslinie gewährleistet. In anderen Fällen ist eine Reinigung mit Reinigungslösungen, die meist im alkalischen, aber auch im sauren Milieu arbeiten, üblich, gefolgt von einer ein- oder mehrstufigen Spülung mit Wasser.The surface to be phosphated must be free of organic and inorganic contaminants. This is ensured when using the method according to the invention in an electrolytic strip galvanizing line. In other cases, cleaning with cleaning solutions, which usually work in an alkaline but also in an acidic environment, is common, followed by a one- or multi-stage rinsing with water.

Zur Erzeugung einer feinkristallinen, fest haftenden Phosphatschicht ist es zweckmäßig, die zu behandelnde Oberfläche anschließend mit einem sogenannten Aktivierungsmittel in Berührung zu bringen. Diese enthalten feingemahlenes Zinkphosphat oder aber speziell hergestellte Verbindungen aus Titan- und Phosphationen. Das Aktivierungsmittel wird im Tauchen oder Fluten, vorzugsweise im Spritzen, aufgebracht. Dient das erfindungsgemäße Verfahren zur Behandlung von Bandmaterial, erfolgt die Behandlung für 0,5 bis 3 s.To produce a fine crystalline, firmly adhering phosphate layer, it is expedient to subsequently bring the surface to be treated into contact with a so-called activating agent. These contain finely ground zinc phosphate or specially prepared compounds from titanium and phosphate ions. The activating agent is applied by dipping or flooding, preferably by spraying. If the method according to the invention is used to treat strip material, the treatment is carried out for 0.5 to 3 s.

An die Aktivierung schließt sich die erfindungsgemäße Phosphatierung an. Diese erfolgt im Tauchen oder Fluten, vorzugsweise im Spritzen. Der Spritzdruck beträgt zweckmäßig 0,5 bis 2 bar, besonders günstig sind 0,5 bis 0,8 bar. Die Temperatur der Behandlungslösung liegt meist im Bereich von 40 bis 65°C. Während dieser Behandlung bildet sich eine hellgraue Schicht aus Phosphaten des Zinks und Magnesiums. Die flächenbezogene Masse der Schicht liegt unter 2 g/m², meist unter 1,5 g/m².The phosphating according to the invention follows the activation. This is done by diving or flooding, preferably by spraying. The spray pressure is expediently 0.5 to 2 bar, and 0.5 to 0.8 bar is particularly favorable. The temperature of the treatment solution is usually in the range of 40 to 65 ° C. During this treatment, a light gray layer of zinc and magnesium phosphates forms. The mass per unit area of the layer is below 2 g / m², usually below 1.5 g / m².

Nach der Phosphatierungsbehandlung folgt ein Spülen mit Wasser, um nicht ausreagierte Behandlungslösung von der Oberfläche des behandelten Werkstücks zu entfernen. Bei besonders eingestellten Behandlungslösungen kann auf dieses Spülen verzichtet werden.The phosphating treatment is followed by rinsing with water in order to remove unreacted treatment solution from the surface of the treated workpiece. With specially adjusted treatment solutions, this rinsing can be dispensed with.

Abschließend können die erzeugten Phosphatschichten vor dem Trocknen mit Nachspülmitteln nachgespült werden. Zum Einsatz gelangen meist schwach saure Lösungen, die Chrom(VI)- und/oder Chrom(III)-Ionen enthalten.Finally, the phosphate layers produced can be rinsed with rinsing agents before drying. Weakly acidic solutions containing chromium (VI) and / or chromium (III) ions are mostly used.

Das erfindungsgemäße Verfahren ist im Prinzip für alle verzinkten Oberflächen unter Berücksichtigung der oben gegebenen Definition für "verzinkt" geeignet. Ein besonders vorteilhafter Anwendungsfall ist die Behandlung von verzinktem, insbesondere von elektrolytisch verzinktem Stahlband. Bei Anwendung auf elektrolytisch verzinktes Stahlband kann die Phosphatierung direkt nach der Verzinkung in der Verzinkungslinie erfolgen.In principle, the method according to the invention is suitable for all galvanized surfaces, taking into account the definition given above for "galvanized". A particularly advantageous application is the treatment of galvanized, in particular electrolytically galvanized steel strip. When used on electrolytically galvanized steel strip, phosphating can take place directly after the galvanizing in the galvanizing line.

Soweit die Phosphatierung ggf. mit Nachspülung Endbehandlung ist, dient sie als Lagerschutz gegen die Bildung von Weißrost und zur Verbesserung der Umformeigenschaften des verzinkten Bandes, insbesondere zur Verminderung des Zinkabriebs beim Pressen und Tiefziehen sowie zur Verminderung des Werkzeugverschleißes.Insofar as the phosphating is a final treatment, if necessary with rinsing, it serves as bearing protection against the formation of white rust and to improve the forming properties of the galvanized strip, in particular to reduce the zinc abrasion during pressing and deep drawing as well as to reduce tool wear.

Ein weiterer Anwendungsfall des erfindungsgemäßen Verfahrens liegt in der Vorbehandlung von Stahlband, das elektrolytisch oder im Schmelztauch-Verfahren mit Zink beschichtet ist, vor der sich anschließenden Beschichtung mit Lack oder Folien aus organischen Polymeren. Die erfindungsgemäße Phosphatierung erfolgt hier zur Verbesserung der Haftung und des Korrosionsschutzes der anschließend aufgebrachten organischen Überzüge. In der Technik ist dieses Verfahren unter dem Begriff "coil-coating" bekannt. Als Lacke kommen solche hoher Flexibilität zum Einsatz. Hierzu zählen beispielsweise Alkyl-, Acrylat-, Epoxid-, Polyester-, silikonmodifizierte Acrylate- und Polyester-Lacke sowie Polyvinylchlorid-Organosole und -Plastisole, Polyvinylfluorid- und Polyvinylidenfluorid-Systeme. Als Folien kommen insbesondere solche aus Polyvinylchlorid, Polyvinylfluorid oder thermoplastischen Acrylaten in Betracht.Another application of the method according to the invention is the pretreatment of steel strip, which is coated with zinc electrolytically or in the hot-dip process, before the subsequent coating with lacquer or films made of organic polymers. The phosphating according to the invention takes place here to improve the adhesion and the corrosion protection of the subsequently applied organic coatings. This process is known in the art under the term "coil coating". Such high flexibility is used as varnishes. These include, for example, alkyl, acrylate, epoxy, polyester, silicone-modified acrylate and polyester paints, as well as polyvinyl chloride organosols and plastisols, polyvinyl fluoride and polyvinylidene fluoride systems. The films come in particular from polyvinyl chloride, Polyvinyl fluoride or thermoplastic acrylates.

Die Erfindung wird anhand der folgenden Beispiele beispielsweise und näher erläutert:The invention is illustrated by the following examples, for example and in more detail:

Vergleichsbeispiel a, erfindungsgemäße Beispiele 1 und 2Comparative Example a, Examples 1 and 2 according to the invention

Frisch elektrolytisch verzinkte Stahlbleche der Qualität RSt 1405 wurden wie folgt behandelt:
- Aktivierung mit einem handelsüblichen Aktivierungsmittel auf Basis Titanphosphat,
1 g/l in vollentsalztem Wasser,
3 s Spritzen bei 1,0 bar und 35°C.
- Phosphatierung mit Lösungen der in der Tabelle angegebenen Konzentrationen, Ansatz in vollentsalztem Wasser, 5 s Spritzen bei 0,8 bar und 55°. Die Ergänzung der Phosphatierungslösung erfolgte mit einem zinkfreien Konzentrat mit einem NO₃:P₂O₅-Verhältnis von 0,4:1 auf Gesamtsäurekonstanz. NO₂ und - soweit vorhanden - Ni, Mg und F wurden auf Konstanz der Konzentration ergänzt.
- Spülen mit Leitungswasser,
2 s Spritzen bei 1,5 bar und 25°C.
- Nachspülen mit einem handelsüblichen Passivierungsmittel auf Basis Cr/VI)/Cr(III),
Ansatz in vollentsalztem Wasser,
2 s Spritzen bei 0,8 bar und 55°C.
- Trocknen im Umluftofen, 20 s bei 120°C.Freshly galvanized steel sheets of quality RSt 1405 were treated as follows:
- Activation with a commercially available activating agent based on titanium phosphate,
1 g / l in deionized water,
3 s spraying at 1.0 bar and 35 ° C.
- Phosphating with solutions of the concentrations given in the table, preparation in deionized water, 5 s spraying at 0.8 bar and 55 °. The phosphating solution was supplemented with a zinc-free concentrate with a NO₃: P₂O₅ ratio of 0.4: 1 to constant acidity. NO₂ and - if available - Ni, Mg and F were added to maintain a constant concentration.
- rinsing with tap water,
2 s spraying at 1.5 bar and 25 ° C.
- rinsing with a commercially available passivating agent based on Cr / VI) / Cr (III),
Preparation in deionized water,
2 s spraying at 0.8 bar and 55 ° C.
- Drying in a forced air oven, 20 s at 120 ° C.

Anschließend wurde die Farbe im Vergleich beurteilt, die flächenbezogene Masse durch Ablösen nach DIN 50 942 und das Blankkorrosionsschutz-Vermögen im Kondenswasser-Feuchte-Wechselklima-Test nach DIN 50 017 bestimmt. Als Kriterium für ausreichend gutes Verhalten wurden 6 Runden ohne sichtbare Korrosion gewählt.The color was then assessed in a comparison, the mass per unit area determined by detachment according to DIN 50 942 and the bright corrosion protection capacity in the condensation-moisture-alternating climate test according to DIN 50 017. 6 rounds without visible corrosion were chosen as criteria for good behavior.

In allen Beispielen wurde eine geschlossene Schicht erzielt.A closed layer was achieved in all examples.

Die Tabelle zeigt, daß die erfindungsgemäßen Verfahren Vorteile in Bezug auf die flächenbezogene Masse und das Aussehen der Schicht bieten.The table shows that the methods according to the invention offer advantages with regard to the mass per unit area and the appearance of the layer.

Vergleichsbeispiel b, erfindungsgemäße Beispiele 3 und 4Comparative Example b, Examples 3 and 4 according to the invention

Verzinkte Stahlbleche wurden wie folgt behandelt:
- Reinigung mit einem starkalkalischen, handelsüblichen Reiniger, Ansatz 10 g/l in Leitungswasser,
10 s Spritzen mit 1,2 bar für 10 s.
- Spülen mit Leitungswasser,
3 s Spritzen bei 1,5 bar und 25°C.
- Aktivierung mit dem oben genannten handelsüblichen Aktivierungsmittel, Ansatz 1,3 g/l in vollentsalztem Wasser, 3 s Spritzen mit 1,0 bar bei 35°C.
- Phosphatierung mit Lösungen der in der Tabelle angegebenen Konzentrationen, Ansatz in vollentsalztem Wasser, 8 s Spritzen mit 1,2 bar bei 55°C. Die Ergänzung der Phosphatierungslösung erfolgte mit einem zinkfreien Konzentrat mit einem NO₃:P₂O₅-­Verhältnis von 0,4:1 auf Gesamtsäurekonstanz. NO₂ und - soweit vorhanden - Ni, Mg und F wurden auf Konstanz der Konzentrationen ergänzt.
- Spülen mit Leitungswasser,
2 s Spritzen mit 1,5 bar bei 25°C.
- Nachspülen mit dem oben genannten handelsüblichen Passivierungsmittel, Ansatz in vollentsalztem Wasser,
2 s Spritzen mit 0,8 bar und 55°C.
- Trocknen im Umluftofen, 20 s bei 120°.Galvanized steel sheets were treated as follows:
- cleaning with a strongly alkaline, commercially available cleaner, batch 10 g / l in tap water,
10 s spraying at 1.2 bar for 10 s.
- rinsing with tap water,
3 s spraying at 1.5 bar and 25 ° C.
- Activation with the above-mentioned commercial activating agent, batch 1.3 g / l in deionized water, 3 s spraying at 1.0 bar at 35 ° C.
- Phosphating with solutions of the concentrations given in the table, preparation in deionized water, 8 s spraying at 1.2 bar at 55 ° C. The phosphating solution was supplemented with a zinc-free concentrate with a NO₃: P₂O₅ ratio of 0.4: 1 to constant acidity. NO₂ and - if available - Ni, Mg and F were added to ensure that the concentrations were constant.
- rinsing with tap water,
2 s spraying at 1.5 bar at 25 ° C.
- rinsing with the above-mentioned commercial passivating agent, preparation in deionized water,
2 s spraying at 0.8 bar and 55 ° C.
- Drying in a convection oven, 20 s at 120 °.

Farbe und flächenbezogene Masse wurden bestimmt (Tabelle). Ein Teil der Bleche wurden mit einem handelsüblichen coil-coating Lacksystem Epoxy-Primer + Acrylat-Deckschicht versehen. Je zwei Bleche wurden nach Anritzen im Salzsprühnebeltest, je zwei Bleche im T-Bend-Test auf Haftung geprüft. Die Tabelle zeigt die Haftungsverbesserung durch das erfindungsgemäße Verfahren, sowie den Vorteil der deutlich helleren Färbung, was erlaubt, auch helle Einschichtlacke, z.B. für die Hausgeräte-Industrie, einzusetzen. Tabelle Beispiel a 1 2 b 3 4 Materiala) E-Zn E-Zn E-Zn F-Zn F-Zn E-Zn S-Wert 0,20 0,20 0,25 0,13 0,20 0,24 P₂O₅ (g/l) 5,5 4,0 8,0 6,0 6,0 5,5 Zn (g/l) 2,0 1,0 0,8 3,0 1,0 0,9 Ni (g/l) 0,08 0,05 - 0,8 0,02 - Mg (g/l) - 1,0 2,0 - 1,0 1,5 NO₃ (g/l) 2,5 2,5 4,0 6,0 3,0 2,9 NO₂⁻ (mg/l) 50 50 50 80 80 60 F⁻ (g/l) - - 0,01 0,08 0,08 - Farbe dunkelgrau hellgrau hellgrau dunkelgrau hellgrau hellgrau SG (g/m²)b) 1,8 1,4 1,5 3,1 1,3 1,2 Korrosionsschutz c) i.O. i.O. i.O. i.O. i.O. i.O. Haftung d) - - - n.i.O. i.O. i.O. a) E-Zn: Elektrolytisch verzinkter Stahl F-Zn: Schmelztauchverzinkter Stahl b) Flächenbezogene Masse, vgl. DIN 50 941 c) für Beispiel a, 1 + 2: 6 Runden Kondenswasser-Feuchte-Wechselklima-Test gemäß DIN 50 017; i.O.: ohne Korrosion für Beispiel b, 3 + 4: 480 h Salzsprühnebel gemäß DIN 50 021 mit Anritzen; i.O.: kleiner 3 mm Unterwanderung d) für Beispiel b, 3 + 4: T-Bend-Test nach ECCA-T 7 (1985) i.O.: kein Abplatzen bei T 2-Test; n.i.O.: Applatzen bei T 2-Test. Color and mass per unit area were determined (table). Some of the sheets were coated with a commercially available coil-coating lacquer system, epoxy primer + acrylate top layer. After scoring, two sheets were tested for adhesion in the salt spray test, and two sheets in the T-Bend test. The table shows the improvement in adhesion by the process according to the invention, as well as the advantage of the significantly lighter color, which also makes it possible to use light single-layer paints, for example for the household appliance industry. table example a 1 2nd b 3rd 4th Material a) E-Zn E-Zn E-Zn F-Zn F-Zn E-Zn S value 0.20 0.20 0.25 0.13 0.20 0.24 P₂O₅ (g / l) 5.5 4.0 8.0 6.0 6.0 5.5 Zn (g / l) 2.0 1.0 0.8 3.0 1.0 0.9 Ni (g / l) 0.08 0.05 - 0.8 0.02 - Mg (g / l) - 1.0 2.0 - 1.0 1.5 NO₃ (g / l) 2.5 2.5 4.0 6.0 3.0 2.9 NO₂⁻ (mg / l) 50 50 50 80 80 60 F⁻ (g / l) - - 0.01 0.08 0.08 - colour dark gray light gray light gray dark gray light gray light gray SG (g / m²) b) 1.8 1.4 1.5 3.1 1.3 1.2 Corrosion protection c) OK OK OK OK OK OK Liability d) - - - not ok OK OK a) E-Zn: electrolytically galvanized steel F-Zn: hot-dip galvanized steel b) mass per unit area, cf. DIN 50 941 c) for example a, 1 + 2: 6 rounds of condensation-moisture alternating climate test according to DIN 50 017; OK: without corrosion for example b, 3 + 4: 480 h salt spray according to DIN 50 021 with scoring; OK: less than 3 mm infiltration d) for example b, 3 + 4: T-bend test according to ECCA-T 7 (1985) OK: no flaking in the T 2 test; not ok: Applatzen at T 2 test.

Claims (10)

1. Verfahren zur Phosphatierung von verzinkten Oberflächen, insbesondere von verzinktem Stahl, mittels wäßriger Zinkionen, Phosphationen, weitere schichtbildende Kationen sowie Beschleuniger enthaltenden Phosphatierungslösungen, dadurch gekennzeichnet, daß man die Oberflächen für die Dauer von maximal 10 s mit einer Phosphatierungslösung in Kontakt bringt, die
0,5 bis 5,0 g/l Zink
3 bis 20 g/l Phosphat (ber. als P₂O₅)
0,3 bis 3 g/l Magnesium
bei einem Gewichtsverhältnis von Magnesium : Zink = (0,5 bis 10) : 1 enthält, einen S-Wert im Bereich von 0,1 bis 0,4 aufweist und mit einem Konzentrat, in dem das Gewichtsverhältnis von Zink zu Phosphat (ber. als P₂O₅) im Bereich von (0 bis 1) : 8 liegt, ergänzt wird.1. Process for the phosphating of galvanized surfaces, in particular of galvanized steel, by means of aqueous zinc ions, phosphate ions, further layer-forming cations and accelerating phosphating solutions, characterized in that the surfaces are brought into contact with a phosphating solution for a maximum of 10 s which
0.5 to 5.0 g / l zinc
3 to 20 g / l phosphate (calculated as P₂O₅)
0.3 to 3 g / l magnesium
at a weight ratio of magnesium: zinc = (0.5 to 10): 1, has an S value in the range from 0.1 to 0.4 and with a concentrate in which the weight ratio of zinc to phosphate (calc. as P₂O₅) is in the range from (0 to 1): 8, is added. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Oberflächen mit einer Phosphatierungslösung in Kontakt bringt, die als Beschleuniger Nitrat enthält.2. The method according to claim 1, characterized in that the surfaces are brought into contact with a phosphating solution which contains nitrate as an accelerator. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man die Oberflächen mit einer Phosphatierungslösung in Kontakt bringt, die einen S-Wert im Bereich von 0,2 bis 0,3 aufweist.3. The method according to claim 1 or 2, characterized in that the surfaces are brought into contact with a phosphating solution which has an S value in the range from 0.2 to 0.3. 4. Verfahren nach Anspruch 1, 2 oder 3, dadurch gekennzeichnet, daß man die Oberflächen mit einer Phosphatierungslösung in Kontakt bringt, die maximal 1,5 g/l Zink, vorzugsweise 0,5 bis 1 g/l Zink, bei einem Gewichtsverhältnis von Magnesium : Zink von (0,5 bis 3) : 1 enthält.4. The method according to claim 1, 2 or 3, characterized in that the surfaces are brought into contact with a phosphating solution which contains a maximum of 1.5 g / l zinc, preferably 0.5 to 1 g / l zinc, at a weight ratio of Magnesium: contains zinc from (0.5 to 3): 1. 5. Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man die Oberflächen mit einer Phosphatierungslösung in Kontakt bringt, die zusätzlich Nickelionen in einer Menge von maximal 1,5 g/l, vorzugsweise in einer Menge von maximal 0,5 g/l enthält.5. The method according to one or more of claims 1 to 4, characterized in that the surfaces are brought into contact with a phosphating solution which additionally contains nickel ions in an amount of at most 1.5 g / l, preferably in an amount of at most 0, Contains 5 g / l. 6. Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man die Oberflächen mit einer Phosphatierungslösung in Kontakt bringt, die zusätzlich einfaches oder komplexes Fluorid in einer Menge von maximal 3 g/l, vorzugsweise von 0,1 bis 1,5 g/l, (jeweils ber. als F) enthält.6. The method according to one or more of claims 1 to 5, characterized in that the surfaces are brought into contact with a phosphating solution which additionally contains simple or complex fluoride in an amount of at most 3 g / l, preferably from 0.1 to 1 , 5 g / l, (each calculated as F) contains. 7. Verfahren nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man die Oberflächen mit einer Phosphatierungslösung in Kontakt bringt, die mit einem zinkfreien Konzentrat ergänzt wird.7. The method according to one or more of claims 1 to 6, characterized in that the surfaces are brought into contact with a phosphating solution which is supplemented with a zinc-free concentrate. 8. Verfahren nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß man die Oberflächen mit einer Phosphatierungslösung in Kontakt bringt, die mit einem Konzentrat, in dem das Gewichtsverhältnis von NO₃:P₂O₅ im Bereich von (0,15 bis 0,7):1, vorzugsweise im Bereich von (0,3 bis 0,5):1, liegt, ergänzt wird.8. The method according to one or more of claims 1 to 7, characterized in that the surfaces are brought into contact with a phosphating solution containing a concentrate in which the weight ratio of NO₃: P₂O₅ in the range from (0.15 to 0, 7): 1, preferably in the range from (0.3 to 0.5): 1, is added. 9. Anwendung des Verfahrens nach einem oder mehreren der Ansprüche 1 bis 8 auf die Behandlung von verzinktem Stahlband, vorzugsweise elektrolytisch verzinktem Stahlband.9. Application of the method according to one or more of claims 1 to 8 to the treatment of galvanized steel strip, preferably electrolytically galvanized steel strip. 10. Anwendung gemäß Anspruch 9 mit der Maßgabe, daß anschließend eine Lackierung oder Beschichtung mit organischen Folien erfolgt.10. Application according to claim 9 with the proviso that subsequently painting or coating with organic foils.
EP89201935A 1988-08-24 1989-07-22 Phosphating process Expired - Lifetime EP0359296B1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991004354A1 (en) * 1989-09-21 1991-04-04 Henkel Corporation Articles with zinciferous surfaces with improved unpainted corrosion resistance, and processes for making and using the same
WO1995004842A1 (en) * 1993-08-06 1995-02-16 Metallgesellschaft Aktiengesellschaft Phosphate treatment process for steel strip with one galvanised surface

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JP4267213B2 (en) 2001-03-27 2009-05-27 新日本製鐵株式会社 Zinc phosphate-treated zinc-coated steel sheet with excellent corrosion resistance and color tone
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WO1991004354A1 (en) * 1989-09-21 1991-04-04 Henkel Corporation Articles with zinciferous surfaces with improved unpainted corrosion resistance, and processes for making and using the same
WO1995004842A1 (en) * 1993-08-06 1995-02-16 Metallgesellschaft Aktiengesellschaft Phosphate treatment process for steel strip with one galvanised surface

Also Published As

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GB8919200D0 (en) 1989-10-04
EP0359296B1 (en) 1993-02-17
DE3828676A1 (en) 1990-03-01
ATE85817T1 (en) 1993-03-15
GB2223239A (en) 1990-04-04
US5152849A (en) 1992-10-06
JPH02101175A (en) 1990-04-12
ES2038400T3 (en) 1993-07-16
JP2770860B2 (en) 1998-07-02
CA1332560C (en) 1994-10-18
DE58903562D1 (en) 1993-03-25
GB2223239B (en) 1992-09-23

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