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EP0039093A1 - Method of phosphating the surfaces of metals, and its use - Google Patents

Method of phosphating the surfaces of metals, and its use Download PDF

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Publication number
EP0039093A1
EP0039093A1 EP81200286A EP81200286A EP0039093A1 EP 0039093 A1 EP0039093 A1 EP 0039093A1 EP 81200286 A EP81200286 A EP 81200286A EP 81200286 A EP81200286 A EP 81200286A EP 0039093 A1 EP0039093 A1 EP 0039093A1
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Prior art keywords
solutions
phosphating
metal surfaces
brought
ratio
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EP81200286A
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German (de)
French (fr)
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EP0039093B1 (en
Inventor
Dieter Hauffe
Gerhard Müller
Werner Dr. Dipl.-Chem. Rausch
Gudrun Volling
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GEA Group AG
Continentale Parker Ste
Continentale Parker SA
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Metallgesellschaft AG
Continentale Parker Ste
Continentale Parker SA
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Application filed by Metallgesellschaft AG, Continentale Parker Ste, Continentale Parker SA filed Critical Metallgesellschaft AG
Priority to AT81200286T priority Critical patent/ATE5332T1/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
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/362—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also zinc cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/14—Orthophosphates containing zinc cations containing also chlorate anions

Definitions

  • the invention relates to a process for phosphating metals, in particular iron and steel, with aqueous acidic oxidizing agent-containing zinc phosphate solutions, and to the use thereof for preparing the metal surfaces for electrocoating.
  • the reduced zinc content compared to the usual phosphating baths leads to improved thin and uniform phosphate coatings on metal surfaces, especially on iron and steel. These coatings are very adhesive and durable and are particularly suitable as a basis for the subsequent electrocoating.
  • the object of the invention is to provide a process which avoids the known disadvantages, in particular those mentioned with reference to DE-OS 22 32 067, and leads to phosphate layers which, while maintaining the very good properties of the layers, e.g. as the basis for a subsequent painting, which shows the desired wet corrosion resistance of the phosphate layers.
  • iron and steel are treated with the method according to the invention.
  • it is also suitable for the phosphating of zinc and aluminum materials and for steel with coatings made of zinc, zinc alloys, Aluminum and aluminum alloys.
  • the metal surfaces can be treated by spraying, flooding and also immersion. However, it is also possible with combined working methods, e.g. Spray-dive-spray, flood-dive and the like are applicable.
  • the contact times for the phosphating solution with the metal surface are in the usual range and can e.g. for spraying 45 seconds to 3 minutes, for diving 2 to 5 minutes and for spray-immersion spraying 20 seconds spraying, 3 minutes diving, 20 seconds spraying.
  • the bath temperatures are usually 40 to 70 ° C, preferably 50 to 60 ° C. If the contact times are extended, however, they can also be reduced to 30 ° C and below.
  • the phosphating bath essentially only contains alkali metal ions, in such an amount as is necessary to adjust the ratio of free to total P 2 0 5 required for the phosphating.
  • This acid ratio is usually between 0.04 and 0.09, and it increases with increasing bath temperature, increasing total concentration and increasing amount of zinc in relation to P 2 0 5 .
  • small quantities may also be present; these include in particular ammonium, calcium, manganese, copper and cobalt.
  • nickel to the bath has a favorable effect on the rate of phosphating, the formation of layers on steel surfaces that are difficult to phosphate and on the phosphating of zinc surfaces.
  • the nickel concentration is no more than 1.5 times the zinc concentration.
  • the known advantage of the weight ratio of Zn to P 2 0 5 should lie in particular in the fact that, compared to phosphating processes based on zinc phosphate, in which the ratio of Zn to P 2 0 5 is higher, a zinc phosphate coating with a higher iron content is formed, which is more acid-resistant is. This reduces the amount of phosphate coating detachment that occurs, for example, when the pH value at the interface decreases during electrocoating. As a result, smaller amounts of layers get into the lacquer film, so that the associated disadvantageous influence on the film is significantly reduced. Since the solutions according to the invention lead to uniformly fine coatings with a low layer weight, the electrical resistance at the interface is lower, so that the lacquer film is deposited in a particularly adhesive manner.
  • the concentration is between 50 and 500 mg / l, with the low to medium concentrations preferably at work temperatures of 50 to 60 0 C are used, while the higher contents are used at lower bath temperatures.
  • nitrobenzenesulfonate e.g. is used in concentrations between 200 and 2000 mg / l. The best results are generally found at levels of 300 to 700 mg / l.
  • the baths can contain SiF 6 - , for example in amounts up to 1.5 g / l, and / or F - , for example in amounts up to 0.8 g / l. It is also possible to use other complex fluorides, eg BF 4 - .
  • the phosphate layers produced with the method according to the invention are in principle suitable for all types of use of the phosphate layers known to date. In particular, however, they have proven themselves as a preparation for electrocoating, the best results being achieved in connection with cathodic electrocoating.
  • the method according to the invention finds practical application e.g. for the phosphating of car bodies.
  • Sheet steel test specimens degreased with mildly alkaline aqueous spray and dip cleaner at 60 ° C. and for 3 minutes were rinsed in water, then firstly sprayed for 20 seconds and then treated with the following phosphating bath at 55 ° C. for 180 seconds:
  • This bath has the following titration data:
  • test specimens were then rinsed with water, rinsed with a rinse solution containing chromium and dried.
  • the phosphate layers were uniformly gray opaque, extremely fine crystalline and had a weight per unit area of 1.8 g / m 2 . This also applied to the surfaces of the test specimen, which were not hit by the spray jet due to the special form of treatment, but were only treated in diving. The test specimens could be exposed to the nitrous gas-containing vapor space above the phosphating bath significantly more than 1 min after the phosphating, without rusting the surface. Test specimens which had been phosphated in the claimed amounts without the addition of N0 3 and C10 3 proved to be particularly sensitive to rust, particularly in the places accessible only by immersion treatment.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Catalysts (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Saccharide Compounds (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Glass Compositions (AREA)
  • Secondary Cells (AREA)
  • Materials For Medical Uses (AREA)
  • Laminated Bodies (AREA)

Abstract

Phosphate coatings are formed on metal surfaces e.g. sheet steel by use of a zinc phosphate composition having a low ratio Zn:P2O5 but containing relatively high contacts of CIO3 and NO3. The process results in coatings having a fine grain and high wet corrosion resistance and which are particularly suitable for immersion electro-lacquering. Solutions contain (in g/l) 0.3-1.3 Zn, 10-26 P2O5, 0.1-3 Ni, 1-6 CIO3 and 5-25 NO3. The ratio of P2O5/Zn is in the range 9-85 and the ratio of Ni/Zn in the range 0-1.5. Solutions may also include sodium nitrite or nitrobenzene sulphonate, BF<->4 or SiF<2->6 and small amounts (e.g. up to 0.5 g/l) of other cations e.g. NH<+>4, Ca, Mn, Cu, Co.

Description

Die Erfindung betrifft ein Verfahren zur Phosphatierung von Metallen, insbesondere Eisen und Stahl, mit wäßrigen sauren oxidationsmittelhaltigen Zinkphosphatlösungen sowie dessen Anwendung zur Vorbereitung der Metalloberflächen für die Elektrotauchlackierung.The invention relates to a process for phosphating metals, in particular iron and steel, with aqueous acidic oxidizing agent-containing zinc phosphate solutions, and to the use thereof for preparing the metal surfaces for electrocoating.

In der deutschen Offenlegungsschrift 22 32 067 werden wäßrige saure Phosphatierlösungen mit einem Gewichtsverhältnis von Zn : P04 = 1 : (12 bis 110) entsprechend Zn : P205 = 1 : (8,96 bis 82) zur Oberflächenbehandlung von Metallen beschrieben.German laid-open specification 22 32 067 describes aqueous acid phosphating solutions with a weight ratio of Zn: P0 4 = 1 : (12 to 110) corresponding to Zn: P 2 0 5 = 1: (8.96 to 82) for the surface treatment of metals.

Der gegenüber den üblichen Phosphatierbädern verringerte Zinkgehalt führt zu verbesserten dünnen und gleichmäßigen Phosphatüberzügen auf Metalloberflächen, insbesondere auf Eisen und Stahl. Diese Überzüge sind sehr haftfest und beständig und als Grundlage für die anschließende Elektrotauchlackierung besonders geeignet.The reduced zinc content compared to the usual phosphating baths leads to improved thin and uniform phosphate coatings on metal surfaces, especially on iron and steel. These coatings are very adhesive and durable and are particularly suitable as a basis for the subsequent electrocoating.

Bei der praktischen Anwendung dieses Verfahrens wurde jedoch gefunden, daß unter bestimmten Bedingungen die "Naßkorrosionsbeständigkeit" der Phosphatschichten im Übergang von der Phosphatierzone zur anschließenden Wasserspülzone nicht ausreichend ist. Insbesondere an unvollkommen vom Spritzstrahl der Phosphatierlösung getroffenen Oberflächenpartien kann sich im Übergang Rost bilden, der zu Beanstandungen führt. Ähnliches kann beobachtet werden, wenn bei der Tauchanwendung der Phosphatierlösung zu kurze Behandlungszeiten eingehalten werden.In the practical application of this method, however, it was found that the "wet corrosion resistance" of the phosphate layers in the transition from the phosphating zone to the subsequent water rinsing zone is not sufficient under certain conditions. In particular, rust may form in the transition on surface areas that are imperfectly hit by the spray jet of the phosphating solution, which leads to complaints. Similar things can are observed if treatment times are too short when the phosphating solution is immersed.

Aufgabe der Erfindung ist es, ein Verfahren bereitzustellen, das die bekannten, insbesondere mit Bezug auf die DE-OS 22 32 067 genannten Nachteile vermeidet und zu Phosphatschichten führt, die unter Beibehaltung der sehr guten Eigenschaften der Schichten, z.B. als Basis für eine nachfolgende Lackierung, die erwünschte Naßkorrosionsbeständigkeit der Phosphatschichten ausweisen.The object of the invention is to provide a process which avoids the known disadvantages, in particular those mentioned with reference to DE-OS 22 32 067, and leads to phosphate layers which, while maintaining the very good properties of the layers, e.g. as the basis for a subsequent painting, which shows the desired wet corrosion resistance of the phosphate layers.

Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß die Metalloberflächen mit Lösungen in Berührung gebracht werden, die

  • 0,3 bis 1,3, vorzugsweise 0,5 bis 1,1 g/1 Zn 0 bis 1,3 g/1 Ni
  • 10 bis 26 g/l P 2 0 5
  • 1 bis 6, vorzugsweise 1,5 bis 3 g/l ClO3 und 5 bis 25, vorzugsweise 10 bis 20 g/1 N03

enthalten, in denen das Gewichtsverhältnis von Zn zu Ni zwischen 1 : (0 bis 1,5) und das Gewichtsverhältnis von Zn zu P205 zwischen 1 : (9 bis 85) eingestellt ist und in denen das für die Phosphatierung geforderte Verhältnis von Freiem- zu Gesamt-P205 im wesentlichen durch Alkalimetallionen eingestellt ist.The object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the metal surfaces are brought into contact with solutions which
  • 0.3 to 1.3, preferably 0.5 to 1.1 g / 1 Zn 0 to 1.3 g / 1 Ni
  • 1 0 to 26 g / l P 2 0 5
  • 1 to 6, preferably 1.5 to 3 g / l ClO 3 and 5 to 25, preferably 10 to 20 g / 1 NO 3

included, in which the weight ratio of Zn to Ni between 1: (0 to 1.5) and the weight ratio of Zn to P 2 0 5 between 1: (9 to 85) is set and in which the ratio required for phosphating of Free to total P 2 0 5 is essentially adjusted by alkali metal ions.

Mit dem erfindungsgemäßen Verfahren werden insbesondere Eisen und Stahl behandelt. Es eignet sich jedoch auch für die Phosphatierung von Zink- und Aluminiumwerkstoffen sowie für Stahl mit nach den verschiedensten Verfahren erzeugten Überzügen aus Zink, Zinklegierungen, Aluminium und Aluminiumlegierungen.In particular, iron and steel are treated with the method according to the invention. However, it is also suitable for the phosphating of zinc and aluminum materials and for steel with coatings made of zinc, zinc alloys, Aluminum and aluminum alloys.

Die Behandlung der Metaloberflächen kann im Spritzverfahren, im Flutverfahren und auch im Tauchverfahren erfolgen. Es ist jedoch auch bei kombinierten Arbeitsweisen, z.B. Spritzen-Tauchen-Spritzen, Fluten-Tauchen und dergleichen anwendbar.The metal surfaces can be treated by spraying, flooding and also immersion. However, it is also possible with combined working methods, e.g. Spray-dive-spray, flood-dive and the like are applicable.

Die Kontaktzeiten für die Phosphatierungslösung mit der Metalloberfläche liegen im üblichen Rahmen und können z.B. für das Spritzen 45 sec bis 3 min, für das Tauchen 2 bis 5 min und für das Spritzen-Tauchen-Spritzen 20 sec Spritzen, 3 min Tauchen, 20 sec Spritzen betragen.The contact times for the phosphating solution with the metal surface are in the usual range and can e.g. for spraying 45 seconds to 3 minutes, for diving 2 to 5 minutes and for spray-immersion spraying 20 seconds spraying, 3 minutes diving, 20 seconds spraying.

Die Badtemperaturen betragen üblicherweise 40 bis 70 °C, vorzugsweise 50 bis 60 °C. Bei Verlängerung der Kontaktzeiten können sie jedoch auch auf 30 °C und darunter gesenkt werden.The bath temperatures are usually 40 to 70 ° C, preferably 50 to 60 ° C. If the contact times are extended, however, they can also be reduced to 30 ° C and below.

Außer Zink und gegebenenfalls Nickel enthält das Phosphatierbad im wesentlichen nur noch Alkalimetallionen, und zwar in einer solchen Menge, wie zur Einstellung des für die Phosphatierung geforderten Verhältnisses von Freiem- zu Gesamt-P205 notwendig. Dieses Säureverhältnis liegt in der Regel zwischen 0,04 und 0,09, und zwar steigt es mit zunehmender Badtemperatur, zunehmender Gesamtkonzentration und steigender Menge von Zink im Verhältnis zu P205. Neben den genannten Kationen können jedoch noch weitere in geringen Mengen vorhanden sein; hierzu zählen insbesondere Ammonium, Calcium, Mangan, Kupfer und Kobalt.In addition to zinc and possibly nickel, the phosphating bath essentially only contains alkali metal ions, in such an amount as is necessary to adjust the ratio of free to total P 2 0 5 required for the phosphating. This acid ratio is usually between 0.04 and 0.09, and it increases with increasing bath temperature, increasing total concentration and increasing amount of zinc in relation to P 2 0 5 . In addition to the cations mentioned, small quantities may also be present; these include in particular ammonium, calcium, manganese, copper and cobalt.

Die Zugabe von Nickel zum Bad wirkt sich günstig auf die Phosphatiergeschwindigkeit, die Schichtausbildung auf schwerer phosphatierbaren Stahloberflächen und auf die Phosphatierung von Zinkoberflächen aus. Aus Gründen der Wirtschaftlichkeit und der zunehmend schwierigeren Badführung beträgt jedoch die Nickelkonzentration nicht mehr als das 1,5-fache der Zinkkonzentration.The addition of nickel to the bath has a favorable effect on the rate of phosphating, the formation of layers on steel surfaces that are difficult to phosphate and on the phosphating of zinc surfaces. For reasons of economy and the increasingly difficult bathroom However, the nickel concentration is no more than 1.5 times the zinc concentration.

Verantwortlich für die bessere Naßkorrosionsbeständigkeit und das z.T. deutlich verbesserte Verhalten im lackierten Zustand ist die Gegenwart von NO3 und CI03 in den angegebenen Konzentrationen im Phosphatierungsbad. Die Anwendung derartig hoher Oxidationsmittelgehalte bei gleichzeitig sehr niedrigen Gehalten an Zink ist neu und in seiner Wirkung nicht voraussehbar gewesen. An dieser Stelle sei darauf hingewiesen, daß das ClO3 durch die . Phosphatierreaktion zu Cl reduziert wird, so daß sich in den Bädern diese Komponente bis zu einer stationären Konzentration anreichert.The presence of NO 3 and CI03 in the specified concentrations in the phosphating bath is responsible for the better wet corrosion resistance and the sometimes significantly improved behavior in the painted state. The use of such high levels of oxidizing agents and at the same time very low levels of zinc is new and its effect was not predictable. At this point it should be noted that the ClO 3 by. Phosphating reaction is reduced to Cl, so that this component accumulates in the baths up to a stationary concentration.

Der an sich bekannte Vorteil des Gewichtsverhältnisses von Zn zu P205 dürfte insbesondere darin liegen, daß gegenüber Phosphatierverfahren auf Basis Zinkphosphat, in denen das Verhältnis Zn zu P205 höher ist, ein Zinkphosphatüberzug mit einem höheren Eisengehalt ausgebildet wird, der säurebeständiger ist. Hierdurch nimmt das Ausmaß der Phosphatüberzug-Ablösung ab, die z.B. eintritt, wenn der pH-Wert bei der Elektrotauchlackierung an der Grenzfläche abnimmt. Dadurch gelangen geringere Schichtmengen in den Lackfilm, so daß der damit verbundene nachteilige Einfluß auf den Film wesentlich vermindert ist. Da die erfindungsgemäßenLösungen zu gleichmäßig feinen Überzügen mit niedrigem Schichtgewicht führen, ist der elektrische Widerstand an der Grenzfläche niedriger, so daß der Lackfilm besonders haftfest abgeschieden wird.The known advantage of the weight ratio of Zn to P 2 0 5 should lie in particular in the fact that, compared to phosphating processes based on zinc phosphate, in which the ratio of Zn to P 2 0 5 is higher, a zinc phosphate coating with a higher iron content is formed, which is more acid-resistant is. This reduces the amount of phosphate coating detachment that occurs, for example, when the pH value at the interface decreases during electrocoating. As a result, smaller amounts of layers get into the lacquer film, so that the associated disadvantageous influence on the film is significantly reduced. Since the solutions according to the invention lead to uniformly fine coatings with a low layer weight, the electrical resistance at the interface is lower, so that the lacquer film is deposited in a particularly adhesive manner.

Es hat sich als nützlich erwiesen, die erfindungsgemäßen Bäder mit Alkalinitrit als Zusatzbeschleuniger zu fahren. Üblicherweise liegt die Konzentration, ausgedrückt als NaN02, zwischen 50 und 500 mg/l, wobei die niedrigen bis mittleren Konzentrationen vorzugsweise bei Arbeitstemperaturen von 50 bis 60 0C eingesetzt werden, während die höheren Gehalte bei niedrigeren Badtemperaturen zur Anwendung kommen.It has proven useful to run the baths according to the invention with alkali nitrite as an additional accelerator. Usually, the concentration, expressed as NaN0 2 , is between 50 and 500 mg / l, with the low to medium concentrations preferably at work temperatures of 50 to 60 0 C are used, while the higher contents are used at lower bath temperatures.

Das Arbeiten mit nitritfreien Bädern gelingt dann besonders einfach, wenn organische Nitrobeschleuniger als Zusatz verwendet werden. Eine bevorzugte Substanz ist Nitrobenzolsulfonat, das z.B. in Konzentrationen zwischen 200 und 2000 mg/l eingesetzt wird. Die günstigsten Ergebnisse findet man im allgemeinen bei Gehalten von 300 bis 700 mg/l.Working with nitrite-free baths is particularly easy when organic nitro accelerators are used as additives. A preferred substance is nitrobenzenesulfonate, e.g. is used in concentrations between 200 and 2000 mg / l. The best results are generally found at levels of 300 to 700 mg / l.

Insbesondere bei der Mitbehandlung von Zink- und/oder Aluminiumoberflächen, aber auch bei der alleinigen Behandlung von Eisen und Stahl kann durch Zusätze von einfachen und/oder komplexen Fluoriden die Schichtbildung verbessert werden. So können die Bäder SiF6 --, z.B. in Mengen bis zu 1,5 g/l, und/oder F-, z.B. in Mengen bis zu 0,8 g/l, enthalten. Auch die Verwendung anderer komplexer Fluoride, z.B. BF4 -, ist möglich.In particular when treating zinc and / or aluminum surfaces, but also when treating iron and steel alone, the addition of simple and / or complex fluorides can improve the layer formation. For example, the baths can contain SiF 6 - , for example in amounts up to 1.5 g / l, and / or F - , for example in amounts up to 0.8 g / l. It is also possible to use other complex fluorides, eg BF 4 - .

Die mit dem erfindungsgemäßen Verfahren erzeugten Phosphatschichten eignen sich im Prinzip für alle Anwendungsarten der bis heute bekannten Phosphatschichten.-Insbesondere haben sie sich jedoch als Vorbereitung für die Elektrotauchlackierung bewährt, wobei die besten Ergebnisse in Verbindung mit der kathodischen Elektrotauchlackierung erzielt wurden. Praktische Anwendung findet das erfindungsgemäße Verfahren z.B. für die Phosphatierung von Autokarosserien.The phosphate layers produced with the method according to the invention are in principle suitable for all types of use of the phosphate layers known to date. In particular, however, they have proven themselves as a preparation for electrocoating, the best results being achieved in connection with cathodic electrocoating. The method according to the invention finds practical application e.g. for the phosphating of car bodies.

Neben der mit dem erfindungsgemäßen Verfahren erzielten Verbesserung der Naßkorrosionsbeständigkeit konnten in Verbindung mit bestimmten Lacktypen noch weitere Verbesserungen in Bezug auf Lackhaftung und Lackfilmbeständigkeit erzielt werden. Dies gilt insbesondere für Kombinationstests, so z.B. den Steinschlagtest unter zusätzlicher Korrosionsbeanspruchung mit wäßriger Natriumchloridlösung.In addition to the improvement in wet corrosion resistance achieved with the method according to the invention, further improvements in relation to paint adhesion and paint film resistance could be achieved in connection with certain types of paint. This applies in particular to Combination tests, such as the stone chip test with additional corrosion stress with aqueous sodium chloride solution.

Das erfindungsgemäße Verfahren sei anhand einiger Beispiele näher erläutert:The process according to the invention will be explained in more detail using a few examples:

Beispiel 1example 1

Mit mildalkalischem wäßrigem Spritz- und Tauchreiniger bei 60 °C und 3 min entfettete Stahlblechprobekörper wurden in Wasser gespült, anschließend zunächst 20 sec im Spritzen und danach 180 sec im Tauchen bei 55 °C mit folgendem Phosphatierbad behandelt:

Figure imgb0001
Sheet steel test specimens degreased with mildly alkaline aqueous spray and dip cleaner at 60 ° C. and for 3 minutes were rinsed in water, then firstly sprayed for 20 seconds and then treated with the following phosphating bath at 55 ° C. for 180 seconds:
Figure imgb0001

Dieses Bad weist folgende Titrationsdaten auf:

Figure imgb0002
This bath has the following titration data:
Figure imgb0002

Die Probekörper wurden danach mit Wasser gespült, mit chromhaltiger Nachspüllösung nachgespült und getrocknet.The test specimens were then rinsed with water, rinsed with a rinse solution containing chromium and dried.

Die Phosphatschichten waren gleichmäßig grau deckend, außerordentlich feinkristallin und wiesen ein Flächengewicht von 1,8 g/m2 auf. Dies galt auch für die Flächen des Probekörpers, die durch die spezielle Behandlungsform nicht vom Spritzstrahl getroffen, sondern nur im Tauchen behandelt wurden. Die Probekörper konnten wesentlich über 1 min nach der Phosphatierung dem Nitrose-Gase-haltigen Dampfraum oberhalb des Phosphatierbades ausgesetzt werden, ohne daß eine Anrostung der Oberfläche erfolgte. Probekörper, die ohne den Zusatz an N03 und C103 in den beanspruchten Mengen phosphatiert wurden, erwiesen sich insbesondere in den nur der Tauchbehandlung zugänglichen Stellen als besonders rostempfindlich.The phosphate layers were uniformly gray opaque, extremely fine crystalline and had a weight per unit area of 1.8 g / m 2 . This also applied to the surfaces of the test specimen, which were not hit by the spray jet due to the special form of treatment, but were only treated in diving. The test specimens could be exposed to the nitrous gas-containing vapor space above the phosphating bath significantly more than 1 min after the phosphating, without rusting the surface. Test specimens which had been phosphated in the claimed amounts without the addition of N0 3 and C10 3 proved to be particularly sensitive to rust, particularly in the places accessible only by immersion treatment.

Beispiel 2Example 2

Nachfolgend sind einige weitere Badzusammensetzungen des erfindungsgemäßen Verfahrens aufgeführt:

Figure imgb0003
Auch mit diesem Verfahren wurden die in Beispiel 1 genannten Ergebnisse erzielt.Some further bath compositions of the process according to the invention are listed below:
Figure imgb0003
 The results mentioned in Example 1 were also achieved with this process.

Claims (6)

1. Verfahren zur Phosphatierung von Metallen, insbesondere Eisen und Stahl, mit wäßrigen sauren oxidationsmittelhaltigen Zinkphosphatlösungen, dadurch gekennzeichnet, daß die Metalloberflächen mit Lösungen in Berührung gebracht werden, die 0,3 bis 1,3, vorzugsweise 0,5 bis 1,1 g/l Zn 0 bis 1,3 g/l Ni 10 bis 26 g/l P 2 0 5 1 bis 6, vorzugsweise 1,5 bis 3 g/1 ClO3 5 bis 25, vorzugsweise 10 bis 20 g/1 N03
enthalten, in denen das Gewichtsverhältnis von Zn zu Ni zwischen 1 : (0 bis 1,5) und das Gewichtsverhältnis von Zn zu P205 zwischen 1 : (9 bis 85) eingestellt ist und in denen das für die Phosphatierung geforderte Verhältnis von Freiem- zu Gesamt-P205 im wesentlichen durch Alkalimetallionen eingestellt ist.1. A process for phosphating metals, in particular iron and steel, with aqueous acidic oxidizing agent-containing zinc phosphate solutions, characterized in that the metal surfaces are brought into contact with solutions which 0.3 to 1.3, preferably 0.5 to 1.1 g / l Zn 0 to 1.3 g / l Ni 1 0 to 26 g / l P 2 0 5 1 to 6, preferably 1.5 to 3 g / 1 ClO 3 5 to 25, preferably 10 to 20 g / 1 NO 3
included, in which the weight ratio of Zn to Ni between 1: (0 to 1.5) and the weight ratio of Zn to P 2 0 5 between 1: (9 to 85) is set and in which the ratio required for phosphating of Free to total P 2 0 5 is essentially adjusted by alkali metal ions. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Metalloberflächen mit Lösungen in Berührung gebracht werden, die zusätzlich Alkalinitrit, vorzugsweise in Mengen von 50 bis 500 mg/1 (berechnet als NaN02), enthalten.2. The method according to claim 1, characterized in that the metal surfaces are brought into contact with solutions which additionally contain alkali nitrite, preferably in amounts of 50 to 500 mg / 1 (calculated as NaN0 2 ). 3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Metalloberflächen mit Lösungen in Berührung gebracht werden, die zusätzlich organische Nitroverbindungen, insbesondere Nitrobenzolsulfonat in Mengen von vorzugsweise 200 bis 2000 mg/l, enthalten.3. The method according to claim 1, characterized in that the metal surfaces are brought into contact with solutions which additionally contain organic nitro compounds, in particular nitrobenzenesulfonate in amounts of preferably 200 to 2000 mg / l. 4. Verfahren nach Anspruch 1 und 2, dadurch gekennzeichnet, daß die Metalloberflächen mit Lösungen in Berührung gebracht werden, die zusätzlich einfache und/oder komplexe Fluoride, z.B. bis zu 1,5 g/l SiF6 und/oder bis zu 0,8 g/l F, enthalten.4. The method according to claim 1 and 2, characterized in that the metal surfaces are brought into contact with solutions that are additionally simple and / or complex fluorides, for example up to 1.5 g / l SiF 6 and / or up to 0.8 g / l F, contain. 5. Anwendung des Verfahrens nach Anspruch 1, 2, 3 oder5. Application of the method according to claim 1, 2, 3 or 4..zur Vorbereitung der Metalloberflächen für die Elektrotauchlackierung, insbesondere für die kathodische Elektrotauchlackierung.4.. to prepare the metal surfaces for electrocoating, especially for cathodic electrocoating.
EP81200286A 1980-04-30 1981-03-13 Method of phosphating the surfaces of metals, and its use Expired EP0039093B1 (en)

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AT81200286T ATE5332T1 (en) 1980-04-30 1981-03-13 METAL SURFACES PHOSPHATION PROCESS AND APPLICATION.

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DE19803016576 DE3016576A1 (en) 1980-04-30 1980-04-30 METHOD FOR PHOSPHATING METAL SURFACES AND THE USE THEREOF
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Cited By (3)

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EP0452638A1 (en) * 1990-03-16 1991-10-23 Mazda Motor Corporation Method for phosphating metal surfaces
EP0659906A1 (en) * 1993-12-21 1995-06-28 Mazda Motor Corporation Method of phosphating metal surfaces and treatment solution
WO1996017977A1 (en) * 1994-12-09 1996-06-13 Metallgesellschaft Aktiengesellschaft Method of applying phosphate coatings to metal surfaces

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US4498935A (en) * 1981-07-13 1985-02-12 Parker Chemical Company Zinc phosphate conversion coating composition
US4486241A (en) * 1981-09-17 1984-12-04 Amchem Products, Inc. Composition and process for treating steel
DE3311738A1 (en) * 1983-03-31 1984-10-04 Metallgesellschaft Ag, 6000 Frankfurt METHOD FOR PHOSPHATING METAL SURFACES
DE3325974A1 (en) * 1983-07-19 1985-01-31 Gerhard Collardin GmbH, 5000 Köln METHODS AND UNIVERSALLY APPLICABLE MEANS FOR THE ACCELERATED APPLICATION OF PHOSPHATE COATINGS ON METAL SURFACES
GB2148950B (en) * 1983-10-26 1987-02-04 Pyrene Chemical Services Ltd Phosphating composition and processes
GB8329250D0 (en) * 1983-11-02 1983-12-07 Pyrene Chemical Services Ltd Phosphating processes
DE3408577A1 (en) * 1984-03-09 1985-09-12 Metallgesellschaft Ag, 6000 Frankfurt METHOD FOR PHOSPHATING METALS
RU2159299C2 (en) * 1999-01-18 2000-11-20 Закрытое акционерное общество "ФК" Solution for phosphating of metal surface
RU2190038C2 (en) * 1999-12-20 2002-09-27 Левичев Александр Николаевич Composition for anticorrosive treatment of ferrous metals' surfaces
WO2005028887A1 (en) 2003-09-16 2005-03-31 Ntn Corporation Shell-type needle roller bearing, supporting structure for compressor main shaft, and supporting structure for piston pump drive section

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AT211625B (en) * 1956-01-25 1960-10-25 Metallgesellschaft Ag Process for treating steel strip for cold rolling by applying a zinc phosphate coating
AT342383B (en) * 1975-09-12 1978-03-28 Metallgesellschaft Ag PROCESS FOR THE PRODUCTION OF PHOSPHATE COATINGS ON METAL SURFACES

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AT211625B (en) * 1956-01-25 1960-10-25 Metallgesellschaft Ag Process for treating steel strip for cold rolling by applying a zinc phosphate coating
AT342383B (en) * 1975-09-12 1978-03-28 Metallgesellschaft Ag PROCESS FOR THE PRODUCTION OF PHOSPHATE COATINGS ON METAL SURFACES

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0452638A1 (en) * 1990-03-16 1991-10-23 Mazda Motor Corporation Method for phosphating metal surfaces
EP0659906A1 (en) * 1993-12-21 1995-06-28 Mazda Motor Corporation Method of phosphating metal surfaces and treatment solution
US5536336A (en) * 1993-12-21 1996-07-16 Nippon Paint Co., Ltd. Method of phosphating metal surfaces and treatment solution
WO1996017977A1 (en) * 1994-12-09 1996-06-13 Metallgesellschaft Aktiengesellschaft Method of applying phosphate coatings to metal surfaces
US5904786A (en) * 1994-12-09 1999-05-18 Metallgesellschaft Aktiengesellschaft Method of applying phosphate coatings to metal surfaces
CN1066207C (en) * 1994-12-09 2001-05-23 金属股份有限公司 Method for applying phosphate coating on metal surface

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ATE5332T1 (en) 1983-12-15
ES8207233A1 (en) 1982-09-16
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ES501701A0 (en) 1982-09-16
EP0039093B1 (en) 1983-11-16
DE3161398D1 (en) 1983-12-22
IT8121425A0 (en) 1981-04-29
PT72944B (en) 1982-03-26
GB2074611A (en) 1981-11-04
BR8102619A (en) 1982-01-19
PT72944A (en) 1981-05-01
IT1207959B (en) 1989-06-01
DE3016576A1 (en) 1981-11-05

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