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EP0370535A1 - Process for applying phosphate coatings - Google Patents

Process for applying phosphate coatings Download PDF

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Publication number
EP0370535A1
EP0370535A1 EP89201936A EP89201936A EP0370535A1 EP 0370535 A1 EP0370535 A1 EP 0370535A1 EP 89201936 A EP89201936 A EP 89201936A EP 89201936 A EP89201936 A EP 89201936A EP 0370535 A1 EP0370535 A1 EP 0370535A1
Authority
EP
European Patent Office
Prior art keywords
phosphating solution
zinc
iron
ions
phosphating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP89201936A
Other languages
German (de)
French (fr)
Other versions
EP0370535B1 (en
Inventor
Horst Dr. Gehmecker
Dieter Hauffe
Gerhard Müller
Werner Dr. Rausch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GEA Group AG
Continentale Parker SA
Original Assignee
Metallgesellschaft AG
Continentale Parker SA
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Publication of EP0370535A1 publication Critical patent/EP0370535A1/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
    • C23C22/364—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 manganese cations
    • C23C22/365—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 manganese cations containing also zinc and 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
    • 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

Definitions

  • the invention relates to a method for applying phosphate coatings on surfaces made of aluminum and / or zinc or their alloys with the aid of phosphating solutions working according to the low zinc technology.
  • phosphating solutions that work according to the low-zinc technology are those that predominantly contain zinc as a layer-forming cation in a concentration of approx. 0.4 to 1.5 g / l and in which the Zn / PO4 ratio is less than approx. Is 0.08.
  • the phosphating solutions used for this usually contain zinc, nickel, manganese, magnesium, cadmium, copper, cobalt, alkali and / or ammonium ions, phosphate ions, accelerating additives such as nitrite, chlorate, bromate, peroxide, m- Nitrobenzenesulfonate, nitrophenol or combinations thereof.
  • phosphating solutions can also contain layer-refining additives such as hydroxycarboxylic acids, aminocarboxylic acids or condensed phosphates.
  • the metal surfaces consist to a large extent of steel in addition to varying amounts of galvanized steel and a small amount of aluminum materials and are treated by spraying and / or immersion.
  • the object of the invention is to provide a method for applying phosphate coatings on surfaces made of zinc and / or aluminum or its alloys with phosphating solutions working according to the low zinc technology, in which an increase in the free acid or the acid ratio is prevented and consequently, the disadvantages of the known methods are avoided, which is nevertheless easy to use and economical.
  • 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 surface is brought into contact with a phosphating solution which contains a minimum concentration of iron (III) ions of 1 mg / l and which is treated per m2 Surface 50 to 2000 mg of iron III ions can be added.
  • the iron ions can be introduced into the phosphating solution in the form of Fe-III ions, but also in the form of Fe-II ions together with an oxidizing agent, such as chlorate, nitrite, peroxide, which oxidizes to Fe-III.
  • Suitable compounds are e.g. the nitrates, chlorides and fluorides of divalent or trivalent iron and iron-III complex compounds of hydroxycarboxylic acids, aminocarboxylic acids and the like.
  • a preferred embodiment of the invention consists in bringing the surface into contact with a phosphating solution, to which 50 to 1000 mg of iron III ions are added per m2 of treated surface.
  • the dosage can take place as mentioned above.
  • the method according to the invention can be used for all known phosphating solutions working according to the low zinc technology.
  • such solutions are used that 0.4 to 1.5 g / l Zn 10 to 26 g / l P2O5 as well 0 to 1.3 g / l Ni 0 to 1.3 g / l Mn 0 to 1.3 g / l Mg contain.
  • the weight ratio of Zn to P2O5 should be set to a value in the range of (0.075 to 0.015): 1 and - if available - the weight ratio of Ni, Mn and or Mg to Zn to a value of up to 1.5: 1 .
  • phosphating solutions which act as accelerators 2 nos 25 g / l NO3 1 to 6 g / l ClO3 0.1 to 2 g / l organic nitro compound 0.05 to 0.5 g / l NO2 0.02 to 0.1 g / l peroxide (calculated as H2O2) or mixtures thereof.
  • the phosphating solutions can be applied in a conventional manner. Particularly suitable forms of application are spraying and / or dipping, a temperature in the range from 30 to 70 ° C. being preferred.
  • the method according to the invention is particularly suitable for the treatment of pure aluminum and alloys, e.g. of the qualities AlMgSi, AlMg and AlMgMn.
  • Suitable materials are also solid or steel alloys with e.g. Ni, Fe or Al.
  • iron III citrate By adding iron III citrate, the iron III concentration had been adjusted to 2 mg / l when the phosphating solution was started up.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

In a process of applying phosphate coatings to surfaces consisting of aluminium and/or zinc and/or alloys thereof by means of phosphating solutions used in low-zinc technology, the number of points of free acid is maintained constant in that the surface is contacted with a phosphating solution which contains iron-III-ions in a concentration of at least 1 mg/1 and to which 50 to 2000 mg iron-III-ions, preferably up to 1000 mg iron-III-ions, are added per square metre of treated surface area. The phosphating solution suitably contains 0.4 to 1.5 g/l zinc 10 to 26 g/l P2O5 and 0 to 1.3 g/l Ni 0 to 1.3 g/l Mn and/or 0 to 1.3 g/l Mg and the weight ratio of Zn to P2O5 is in the range from (0.075 to 0.015): 1 and - is applicable - the weight ratio of Ni, Mn and/or Mg to Zn is up to 1.5:1. The phosphating solution may additionally contain as an accelerator 2 to 25 g/l NO3 1 to 6 g/l ClO3 0.1 to 2 g/l organic nitro compound 0.05 to 0.5 g/l NO2 0.02 to 0.1 g/l peroxide (calculated as H2O2) or mixtures thereof. It is used at a temperature in the range from 30 to 70 DEG C.

Description

Die Erfindung betrifft ein Verfahren zum Aufbringen von Phosphatüberzügen auf Oberflächen aus Aluminium und/oder Zink bzw. dessen oder deren Legierungen mit Hilfe von gemäß der Niedrigzink-Technologie arbeitenden Phosphatierungslösungen.The invention relates to a method for applying phosphate coatings on surfaces made of aluminum and / or zinc or their alloys with the aid of phosphating solutions working according to the low zinc technology.

Phosphatierungslösungen, die gemäß der Niedrigzink-Technologie arbeiten, sind begrifflich solche, die als schichtbildendes Kation überwiegend Zink in einer Konzentration von ca. 0,4 bis 1,5 g/l enthalten und in denen das Zn/PO₄-Verhältnis kleiner als ca. 0,08 ist.Conceptually, phosphating solutions that work according to the low-zinc technology are those that predominantly contain zinc as a layer-forming cation in a concentration of approx. 0.4 to 1.5 g / l and in which the Zn / PO₄ ratio is less than approx. Is 0.08.

Es ist bekannt, dünne Phosphatüberzüge auf Metalloberflächen von Stahl, verzinktem Stahl sowie Aluminium aufzubringen, die für eine nachfolgende elektrophoretische Tauchlackierung eine geeignete Lackgrundlage bilden. Die hierfür eingesetzten Phosphatierungslösungen enthalten üblicherweise Zink-, Nickel-, Mangan-, Magnesium-, Kadmium-, Kupfer-, Kobalt-, Alkali- und/oder Ammoniumionen, Phosphationen, beschleunigend wirkende Zusätze wie Nitrit, Chlorat, Bromat, Peroxid, m-Nitrobenzolsulfonat, Nitrophenol oder Kombinationen hiervon. Für die Behandlung von Aluminium, dessen Legierungen und galvanisch verzinktem Stahl enthalten sie vorzugsweise zusätzlich einfache und/oder komplexe Fluoride. Zusätzliche Anionen, wie Chlorid, Nitrat und Sulfat, dienen der Wahrung der Elektroneutralität. Gegebenenfalls können die Phosphatierungslösungen noch schichtverfeinernde Zusätze, wie Hydroxicarbonsäuren, Aminocarbonsäuren oder kondensierte Phosphate, enthalten.It is known to apply thin phosphate coatings to metal surfaces of steel, galvanized steel and aluminum, which form a suitable coating base for a subsequent electrophoretic dip coating. The phosphating solutions used for this usually contain zinc, nickel, manganese, magnesium, cadmium, copper, cobalt, alkali and / or ammonium ions, phosphate ions, accelerating additives such as nitrite, chlorate, bromate, peroxide, m- Nitrobenzenesulfonate, nitrophenol or combinations thereof. For the treatment of aluminum, its alloys and galvanized steel, they preferably additionally contain simple and / or complex fluorides. Additional anions, such as chloride, nitrate and sulfate, serve to maintain electroneutrality. If appropriate, the phosphating solutions can also contain layer-refining additives such as hydroxycarboxylic acids, aminocarboxylic acids or condensed phosphates.

Die Metalloberflächen bestehen dabei zu einem erheblichen Anteil aus Stahl neben wechselnden Mengen verzinktem Stahl sowie einem geringen Anteil an Aluminiumwerkstoffen und werden im Spritz- und/oder Tauchverfahren behandelt.The metal surfaces consist to a large extent of steel in addition to varying amounts of galvanized steel and a small amount of aluminum materials and are treated by spraying and / or immersion.

Werden ausschließlich Zinkoberflächen und/oder Aluminiumoberflächen mit der Phosphatierungslösung in Berührung gebracht, stellt man fest, daß die Freie Säure bzw. das Verhältnis Freie Säure zu Gesamtsäure der arbeitenden Phosphatierungslösung ansteigt und die Phosphatierungslösung außerhalb des Gleichgewichtes gerät. Die Folge ist, daß mit zunehmendem Durchsatz die Überzugsausbildung verschlechtert wird und schließlich ganz unterbleibt. Ein Abstumpfen der überschüssigen Säure mit Natriumhydroxid, Ammoniumhydroxid oder anderen Alkalien ist nicht durchführbar, da dann ein Teil der Badkomponente Zink mitausgefällt wird.If only zinc surfaces and / or aluminum surfaces are brought into contact with the phosphating solution, it is found that the free acid or the ratio of free acid to total acid of the working phosphating solution increases and the phosphating solution becomes out of equilibrium. The result is that with increasing throughput the coating formation deteriorates and ultimately does not occur. The excess acid cannot be blunted with sodium hydroxide, ammonium hydroxide or other alkalis, since part of the bath component zinc is then also precipitated.

Aufgabe der Erfindung ist es, ein Verfahren zum Aufbringen von Phosphatüberzügen auf Oberflächen aus Zink und/oder Aluminium bzw. dessen oder deren Legierungen mit gemäß der Niedrigzink-Technologie arbeitenden Phosphatierungslösungen bereitzustellen, bei dem ein Anstieg der Freien Säure bzw. des Säureverhältnisses verhindert wird und mithin die Nachteile der bekannten Verfahren vermieden werden, das aber dennoch einfach in der Handhabung sowie wirtschaftlich ist.The object of the invention is to provide a method for applying phosphate coatings on surfaces made of zinc and / or aluminum or its alloys with phosphating solutions working according to the low zinc technology, in which an increase in the free acid or the acid ratio is prevented and consequently, the disadvantages of the known methods are avoided, which is nevertheless easy to use and economical.

Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man die Oberfläche mit einer Phosphatierungslösung in Kontakt bringt, die eine Mindestkonzentration an Eisen-III-ionen von 1 mg/l enthält und der pro m² behandelter Oberfläche 50 bis 2000 mg Eisen-III-ionen zugesetzt werden.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 surface is brought into contact with a phosphating solution which contains a minimum concentration of iron (III) ions of 1 mg / l and which is treated per m² Surface 50 to 2000 mg of iron III ions can be added.

Die Eisenionen können in Form von Fe-III-Ionen, aber auch in Form von Fe-II-Ionen zusammen mit einem Fe-II zu Fe-III oxidierenden Oxidationsmittel, wie Chlorat, Nitrit, Peroxid, in die Phosphatierungslösung eingebracht werden. Geeignete Verbindungen sind z.B. die Nitrate, Chloride und Fluoride von zwei oder dreiwertigem Eisen sowie Eisen-III-Komplexverbindungen von Hydroxicarbonsäuren, Aminocarbonsäuren und dergleichen.The iron ions can be introduced into the phosphating solution in the form of Fe-III ions, but also in the form of Fe-II ions together with an oxidizing agent, such as chlorate, nitrite, peroxide, which oxidizes to Fe-III. Suitable compounds are e.g. the nitrates, chlorides and fluorides of divalent or trivalent iron and iron-III complex compounds of hydroxycarboxylic acids, aminocarboxylic acids and the like.

Es ist besonders zweckmäßig, die Eisenionen in in Wasser vorgelöster Form in die Phosphatierungslösung einzubringen.It is particularly expedient to introduce the iron ions into the phosphating solution in a form predissolved in water.

Eine bevorzugte Ausgestaltung der Erfindung besteht darin, die Oberfläche mit einer Phosphatierungslösung in Kontakt zu bringen, der pro m² behandelter Oberfläche 50 bis 1000 mg Eisen-III-ionen zugesetzt werden. Auch hierbei kann die Dosierung wie oben erwähnt erfolgen.A preferred embodiment of the invention consists in bringing the surface into contact with a phosphating solution, to which 50 to 1000 mg of iron III ions are added per m² of treated surface. Here, too, the dosage can take place as mentioned above.

Das erfindungsgemäße Verfahren ist für alle bekannten gemäß der Niedrigzink-Technologie arbeitenden Phosphatierunglösungen anwendbar.The method according to the invention can be used for all known phosphating solutions working according to the low zinc technology.

Gemäß einer weiteren bevorzugten Ausgestaltung werden solche Lösungen eingesetzt, die
0,4 bis 1,5 g/l Zn
10 bis 26 g/l P₂O₅ sowie
0 bis 1,3 g/l Ni
0 bis 1,3 g/l Mn
0 bis 1,3 g/l Mg
enthalten. Bei diesen Lösungen sollte das Gewichtsverhältnis von Zn zu P₂O₅ auf einen Wert im Bereich von (0,075 bis 0,015) : 1 und - sofern vorhanden - das Gewichtsverhältnis von Ni, Mn und oder Mg zu Zn auf einen Wert bis 1,5 : 1 eingestellt sein.According to a further preferred embodiment, such solutions are used that
0.4 to 1.5 g / l Zn
10 to 26 g / l P₂O₅ as well
0 to 1.3 g / l Ni
0 to 1.3 g / l Mn
0 to 1.3 g / l Mg
contain. In these solutions, the weight ratio of Zn to P₂O₅ should be set to a value in the range of (0.075 to 0.015): 1 and - if available - the weight ratio of Ni, Mn and or Mg to Zn to a value of up to 1.5: 1 .

Gemäß einer weiteren vorteilhaften Ausgestaltung der Erfindung kommen Phosphatierungslösungen zum Einsatz, die als Beschleuniger
2 nos 25 g/l NO₃
1 bis 6 g/l ClO₃
0,1 bis 2 g/l organische Nitroverbindung 0,05 bis 0,5 g/l NO₂
0,02 bis 0,1 g/l Peroxid (ber. als H₂O₂)
oder Mischungen hiervon enthalten.According to a further advantageous embodiment of the invention, phosphating solutions are used which act as accelerators
2 nos 25 g / l NO₃
1 to 6 g / l ClO₃
0.1 to 2 g / l organic nitro compound 0.05 to 0.5 g / l NO₂
0.02 to 0.1 g / l peroxide (calculated as H₂O₂)
or mixtures thereof.

Die Phosphatierungslösungen können auf herkömmliche Weise appliziert werden. Besonders geeignete Applikationsformen sind Spritzen und/oder Tauchen, wobei eine Temperatur im Bereich von 30 bis 70°C bevorzugt ist.The phosphating solutions can be applied in a conventional manner. Particularly suitable forms of application are spraying and / or dipping, a temperature in the range from 30 to 70 ° C. being preferred.

Während Arbeitspausen ist durch Zugabe von Eisen-III-ionen dafür Sorge zu tragen, daß die Mindestkonzentration von 1 mg/l aufrechterhalten wird.During work breaks, the addition of iron III ions must ensure that the minimum concentration of 1 mg / l is maintained.

Das erfindungsgemäße Verfahren eignet sich insbesondere zur Behandlung von Reinaluminium und Legierungen, z.B. der Qualitäten AlMgSi, AlMg und AlMgMn.The method according to the invention is particularly suitable for the treatment of pure aluminum and alloys, e.g. of the qualities AlMgSi, AlMg and AlMgMn.

Hinsichtlich der Überzugsbildung auf Zinkoberflächen können Werkstücke aus massivem Zink, insbesondere aber aus schmelztauch- oder elektrolytisch verzinktem Stahl, behandelt werden. Geeignete Werkstoffe sind weiterhin massive oder auf Stahl aufgebrachte Zinklegierungen mit z.B. Ni, Fe oder Al.With regard to the formation of a coating on zinc surfaces, workpieces made of solid zinc, but especially of hot-dip or electrolytically galvanized steel, can be treated. Suitable materials are also solid or steel alloys with e.g. Ni, Fe or Al.

Mit Hilfe des erfindungsgemäßen Verfahrens gelingt es, selbst über einen längeren Zeitpunkt hinweg Phosphatüberzüge zu erzeugen, die durchweg gleichmäßig und geschlossen sind. Diese Überzüge eignen sich in besonderer Weise für eine nachfolgende elektrophoretische Tauchlackierung.With the aid of the method according to the invention, it is possible to produce phosphate coatings which are uniform and uniform even over a longer period of time are closed. These coatings are particularly suitable for subsequent electrophoretic dip coating.

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

Beispielexample

In einem 10 l Phosphatierungsbehälter wurden alternierend zuvor entfettete und gebeizte Bleche aus Aluminium (70 %) der Qualität AlMgSi und AlMg3 und elektrolytisch verzinktem Stahl (30 %) mit einer Phosphatierungslösung behandelt, die
0,7 g/l Zn
0,7 g/l Ni
1,0 g/l Mn
3,4 g/l Na
11,5 g/l P₂O₅
3,0 g/l NO₃
0,5 g/l F
0,1 g/l NO₂
enthielt. Die Temperatur der Lösung betrug 55 bis 60°C. Die Behandlung erfolgte im Spritzen für die Dauer von 3 min. Die Freie Säure der Phosphatierungslösung lag bei 1,0.Alternately previously degreased and pickled aluminum (70%) sheets of AlMgSi and AlMg3 quality and electrolytically galvanized steel (30%) were treated with a phosphating solution in a 10 liter phosphating container
0.7 g / l Zn
0.7 g / l Ni
1.0 g / l Mn
3.4 g / l Na
11.5 g / l P₂O₅
3.0 g / l NO₃
0.5 g / l F
0.1 g / l NO₂
contained. The temperature of the solution was 55 to 60 ° C. The treatment was carried out by spraying for 3 minutes. The free acidity of the phosphating solution was 1.0.

Durch Zugabe von Eisen III-Zitrat war die Eisen-III-konzentration bei Inbetriebnahme der Phosphatierungslösung auf 2 mg/l eingestellt worden.By adding iron III citrate, the iron III concentration had been adjusted to 2 mg / l when the phosphating solution was started up.

Im Verlauf des Durchsatzes wurden der Phosphatierungslösung von 10 l 250 mg/m² Oberfläche Eisen III-Zitrat (ber. als Fe) zugegeben. Wie die nachfolgende Tabelle zeigt, war die Zahl der Freie-Säure-Punkte praktisch konstant. Der erhaltene Phosphatüberzug war durchweg gleichmäßig und geschlossen. Durchsatz (m²) 0,4 0,8 1,2 1,6 2,4 2,8 3,2 Freie-Säure-Punkte 1,0 1,1 1,1 1,0 1,0 1,1 1,0 In the course of the throughput, iron III citrate (calc. As Fe) was added to the phosphating solution of 10 l of 250 mg / m 2 surface. As the table below shows, the number of free acid points was practically constant. The phosphate coating obtained was consistently uniform and closed. Throughput (m²) 0.4 0.8 1.2 1.6 2.4 2.8 3.2 Free acid points 1.0 1.1 1.1 1.0 1.0 1.1 1.0

VergleichsbeispielComparative example

Als Vergleichsbeispiel wurden Bleche gleicher Qualität und in gleicher Weise durch die vorgenannte Phosphatierungslösung, die jedoch keine Eisen-III-ionen enthielt und nicht mit Eisen-III-ionen ergänzt worden war, durchgesetzt. Entsprechend zunehmendem Durchsatz veränderte sich die Zahl der Freie-Säure-Punkte wie unten angegeben. Während anfänglich hochwertige Phosphatüberzüge erhalten wurden, war mit steigender Punktzahl eine Verschlechterung der Qualität festzustellen. Ab einer Zahl Freie-Säure-Punkte von 1,50 war überhaupt keine Überzugsausbildung zu beobachten. Durchsatz (m²) 0,4 0,8 1,2 1,6 2,0 2,4 2,8 3,2 Freie-Säure-Punkte 1,0 1,15 1,25 1,35 1,45 1,50 1,55 1,6 As a comparative example, sheets of the same quality and in the same way were enforced by the aforementioned phosphating solution, which, however, contained no iron III ions and had not been supplemented with iron III ions. As the throughput increased, the number of free acid points changed as indicated below. While high quality phosphate coatings were initially obtained, the quality deteriorated as the score increased. From a number of free acid points of 1.50, no coating formation was observed at all. Throughput (m²) 0.4 0.8 1.2 1.6 2.0 2.4 2.8 3.2 Free acid points 1.0 1.15 1.25 1.35 1.45 1.50 1.55 1.6

Claims (6)

1. Verfahren zum Aufbringen von Phosphatüberzügen auf Oberflächen aus Aluminium und/oder Zink bzw. dessen oder deren Legierungen mit Hilfe von gemäß der Niedrigzink-Technologie arbeitenden Phosphatierungslösungen, dadurch gekennzeichnet, daß man die Oberfläche mit einer Phosphatierungslösung in Kontakt bringt, die eine Mindestkonzentration an Eisen-III-ionen von 1 mg/l enthält und der pro m² behandelter Oberfläche 50 bis 2000 mg Eisen-III-ionen zugesetzt werden.1. A method for applying phosphate coatings on surfaces made of aluminum and / or zinc or its alloys with the aid of phosphating solutions working according to the low zinc technology, characterized in that the surface is brought into contact with a phosphating solution which has a minimum concentration Contains iron III ions of 1 mg / l and 50 to 2000 mg iron III ions are added to the surface treated per m². 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Metalloberfläche mit einer Phosphatierungslösung in Kontakt bringt, der pro m² behandelter Oberfläche 50 bis 1000 mg Eisen-III-ionen zugesetzt werden.2. The method according to claim 1, characterized in that the metal surface is brought into contact with a phosphating solution, 50 to 1000 mg of iron-III ions are added per m² of treated surface. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man die Oberfläche mit einer Phosphatierungslösung in Kontakt bringt, die
0,4 bis 1,5 g/l Zink
10 bis 26 g/l P₂O₅ sowie
0 bis 1,3 g/l Ni
0 bis 1,3 g/l Mn
0 bis 1,3 g/l Mg
enthält.3. The method according to claim 1 or 2, characterized in that the surface is brought into contact with a phosphating solution which
0.4 to 1.5 g / l zinc
10 to 26 g / l P₂O₅ as well
0 to 1.3 g / l Ni
0 to 1.3 g / l Mn
0 to 1.3 g / l Mg
contains. 4. Verfahren nach Anspruch 1, 2 oder 3, dadurch gekennzeichnet, daß man die Oberfläche mit einer Phosphatierungslösung in Kontakt bringt, in der das Gewichtsverhältnis von Zn zu P₂O₅ auf einen Wert im Bereich von (0,075 bis 0,015) : 1 und - sofern vorhanden - das Gewichtsverhältnis von Ni, Mn und oder Mg zu Zn auf einen Wert bis 1,5 : 1 eingestellt ist.4. The method according to claim 1, 2 or 3, characterized in that the surface is brought into contact with a phosphating solution in which the weight ratio of Zn to P₂O₅ to a value in the range from (0.075 to 0.015): 1 and - if present - The weight ratio of Ni, Mn and or Mg to Zn is set to a value up to 1.5: 1. 5. Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man die Oberfläche mit einer Phosphatierungslösung in Kontakt bringt, die zusätzlich
2 bis 25 g/l NO₃
1 bis 6 g/l ClO₃
0,1 bis 2 g/l organische Nitroverbindung 0,05 bis 0,5 g/l NO₂
0,02 bis 0,1 g/l Peroxid (ber. als H₂O₂)
oder Mischungen hiervon enthält.5. The method according to one or more of claims 1 to 4, characterized in that the surface is brought into contact with a phosphating solution, the additional
2 to 25 g / l NO₃
1 to 6 g / l ClO₃
0.1 to 2 g / l organic nitro compound 0.05 to 0.5 g / l NO₂
0.02 to 0.1 g / l peroxide (calculated as H₂O₂)
or mixtures thereof. 6. Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man die Oberfläche mit der Phosphatierungslösung bei einer Temperatur im Bereich von 30 bis 70°C in Kontakt bringt.6. The method according to one or more of claims 1 to 5, characterized in that the surface is brought into contact with the phosphating solution at a temperature in the range from 30 to 70 ° C.
EP89201936A 1988-11-25 1989-07-22 Process for applying phosphate coatings Expired - Lifetime EP0370535B1 (en)

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DE3839802 1988-11-25
DE3839802 1988-11-25

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EP0370535B1 EP0370535B1 (en) 1992-11-11

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EP (1) EP0370535B1 (en)
JP (1) JP2845246B2 (en)
CA (1) CA1334371C (en)
DD (1) DD299968A5 (en)
DE (1) DE58902702D1 (en)
ES (1) ES2036023T3 (en)
GB (1) GB2226829B (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0401616A1 (en) * 1989-06-03 1990-12-12 Henkel Kommanditgesellschaft auf Aktien Process for applying manganese containing phosphate coatings on metallic surfaces
EP0439377A1 (en) * 1990-01-26 1991-07-31 Ppg Industries, Inc. Method of applying a zinc-nickel-manganese phosphate coating.
WO1993003198A1 (en) * 1991-07-29 1993-02-18 Henkel Corporation Zinc phosphate conversion coating composition and process
WO1994005826A1 (en) * 1992-08-27 1994-03-17 Henkel Kommanditgesellschaft Auf Aktien Process for phosphatizing steel zinc-coated on one side only
EP0603921A1 (en) * 1992-12-19 1994-06-29 Metallgesellschaft Ag Process for forming phosphate coatings
EP1012355A4 (en) * 1996-12-04 2000-06-28 Henkel Corp Sludge reducing zinc phosphating process and composition
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
RU2624566C1 (en) * 2016-02-15 2017-07-04 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 phosphatory of magnetic-aluminium alloys of type permalloy (versions)
WO2017174222A1 (en) * 2015-04-07 2017-10-12 Chemetall Gmbh Improved method for nickel-free phosphating metal surfaces
US11124880B2 (en) 2016-04-07 2021-09-21 Chemetall Gmbh Method for nickel-free phosphating metal surfaces

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5238506A (en) * 1986-09-26 1993-08-24 Chemfil Corporation Phosphate coating composition and method of applying a zinc-nickel-manganese phosphate coating
DE3828676A1 (en) * 1988-08-24 1990-03-01 Metallgesellschaft Ag PHOSPHATING PROCESS
US5645706A (en) * 1992-04-30 1997-07-08 Nippondenso Co., Ltd. Phosphate chemical treatment method
JPH05306497A (en) 1992-04-30 1993-11-19 Nippondenso Co Ltd Phophatizing chemical conversion treatment
US5797987A (en) * 1995-12-14 1998-08-25 Ppg Industries, Inc. Zinc phosphate conversion coating compositions and process
JP3366826B2 (en) * 1997-04-30 2003-01-14 本田技研工業株式会社 Zinc phosphate treatment agent for aluminum alloy
JP4019723B2 (en) * 2001-02-23 2007-12-12 株式会社デンソー Electrolytic phosphate chemical treatment method

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2401236A1 (en) * 1977-08-25 1979-03-23 Parker Ste Continentale ZINC PHOSPHATION PROCESS WITH PRENEUTRALIZATION
FR2401234A1 (en) * 1977-08-25 1979-03-23 Parker Ste Continentale ZINC PHOSPHATION PROCESS WITH THE ADDITION OF IRON
FR2512840A1 (en) * 1981-09-17 1983-03-18 Amchem Prod AQUEOUS ACID SOLUTIONS FOR ZINC PHOSPHATE COATINGS AND CONCENTRATES, METHODS OF COATING THEM USING THEM AND METAL ACTIVATION SOLUTIONS USED IN SUCH PROCESSES
EP0111246A2 (en) * 1982-12-08 1984-06-20 Gerhard Collardin GmbH Process for phosphatizing zinc-electroplated metal objects
EP0175606A1 (en) * 1984-08-16 1986-03-26 Compagnie Francaise De Produits Industriels Process for the chemical-conversion treatment of zinc or its alloys, concentrate and bath for performing this process
EP0264811A1 (en) * 1986-10-16 1988-04-27 Nihon Parkerizing Co., Ltd. Process for producing phosphate coatings

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2738282A1 (en) * 1977-08-25 1979-03-01 Metallgesellschaft Ag METHOD FOR APPLYING PHOSPHATE
US4278477A (en) * 1980-03-19 1981-07-14 Amchem Products, Inc. Metal treatment

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2401236A1 (en) * 1977-08-25 1979-03-23 Parker Ste Continentale ZINC PHOSPHATION PROCESS WITH PRENEUTRALIZATION
FR2401234A1 (en) * 1977-08-25 1979-03-23 Parker Ste Continentale ZINC PHOSPHATION PROCESS WITH THE ADDITION OF IRON
FR2512840A1 (en) * 1981-09-17 1983-03-18 Amchem Prod AQUEOUS ACID SOLUTIONS FOR ZINC PHOSPHATE COATINGS AND CONCENTRATES, METHODS OF COATING THEM USING THEM AND METAL ACTIVATION SOLUTIONS USED IN SUCH PROCESSES
EP0111246A2 (en) * 1982-12-08 1984-06-20 Gerhard Collardin GmbH Process for phosphatizing zinc-electroplated metal objects
EP0175606A1 (en) * 1984-08-16 1986-03-26 Compagnie Francaise De Produits Industriels Process for the chemical-conversion treatment of zinc or its alloys, concentrate and bath for performing this process
EP0264811A1 (en) * 1986-10-16 1988-04-27 Nihon Parkerizing Co., Ltd. Process for producing phosphate coatings

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0401616A1 (en) * 1989-06-03 1990-12-12 Henkel Kommanditgesellschaft auf Aktien Process for applying manganese containing phosphate coatings on metallic surfaces
WO1990015167A1 (en) * 1989-06-03 1990-12-13 Henkel Kommanditgesellschaft Auf Aktien Process for producing manganese-containing phosphate coatings on metal surfaces
EP0439377A1 (en) * 1990-01-26 1991-07-31 Ppg Industries, Inc. Method of applying a zinc-nickel-manganese phosphate coating.
WO1993003198A1 (en) * 1991-07-29 1993-02-18 Henkel Corporation Zinc phosphate conversion coating composition and process
US5261973A (en) * 1991-07-29 1993-11-16 Henkel Corporation Zinc phosphate conversion coating and process
CN1038949C (en) * 1991-07-29 1998-07-01 亨凯尔公司 Zinc Phosphate conversion coating and process
TR28730A (en) * 1991-07-29 1997-02-20 Henkel Corp Chemical coating process with zinc phosphate.
US5516372A (en) * 1992-08-27 1996-05-14 Henkel Kommanditgesellschaft Auf Aktien Process for phosphating steel strip galvanized on one side
WO1994005826A1 (en) * 1992-08-27 1994-03-17 Henkel Kommanditgesellschaft Auf Aktien Process for phosphatizing steel zinc-coated on one side only
US5383982A (en) * 1992-12-19 1995-01-24 Metallgesellschaft Aktiengesellschaft Process of producing phosphate coatings
EP0603921A1 (en) * 1992-12-19 1994-06-29 Metallgesellschaft Ag Process for forming phosphate coatings
EP1012355A4 (en) * 1996-12-04 2000-06-28 Henkel Corp Sludge reducing zinc phosphating process and composition
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
WO2017174222A1 (en) * 2015-04-07 2017-10-12 Chemetall Gmbh Improved method for nickel-free phosphating metal surfaces
CN109312466A (en) * 2015-04-07 2019-02-05 凯密特尔有限责任公司 Improved method for nickel-free phosphating metal surfaces
RU2624566C1 (en) * 2016-02-15 2017-07-04 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 phosphatory of magnetic-aluminium alloys of type permalloy (versions)
US11124880B2 (en) 2016-04-07 2021-09-21 Chemetall Gmbh Method for nickel-free phosphating metal surfaces

Also Published As

Publication number Publication date
EP0370535B1 (en) 1992-11-11
GB2226829A (en) 1990-07-11
JP2845246B2 (en) 1999-01-13
JPH02190478A (en) 1990-07-26
CA1334371C (en) 1995-02-14
GB8917936D0 (en) 1989-09-20
GB2226829B (en) 1993-01-20
DE58902702D1 (en) 1992-12-17
DD299968A5 (en) 1992-05-14
ES2036023T3 (en) 1993-05-01

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