EP0069950B1 - Process for phosphating metal surfaces - Google Patents

Process for phosphating metal surfaces Download PDF

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Publication number
EP0069950B1
EP0069950B1 EP82105960A EP82105960A EP0069950B1 EP 0069950 B1 EP0069950 B1 EP 0069950B1 EP 82105960 A EP82105960 A EP 82105960A EP 82105960 A EP82105960 A EP 82105960A EP 0069950 B1 EP0069950 B1 EP 0069950B1
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EP
European Patent Office
Prior art keywords
metal surfaces
contact
brought
phosphating solution
process according
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EP82105960A
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German (de)
French (fr)
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EP0069950A1 (en
Inventor
Hugh Thomas Springstead
Gary Dennis Kent
Bernhard Norbert Intorp
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Henkel Corp
Original Assignee
Metallgesellschaft AG
Continentale Parker Ste
Continentale Parker SA
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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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/16—Sulfur-containing compounds
    • 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 method for applying phosphate coatings on metal surfaces by means of phosphating solutions based on zinc phosphate as an essential layer-forming component, which are accelerated with chlorate and water-soluble aromatic nitro compound.
  • Oxidizing agents such as chlorate, nitrate, nitrite, hydrogen peroxide or peroxy compounds in general and organic nitro compounds in particular play an important role as accelerators.
  • DE-OS 3 016 576 describes a phosphating process based on zinc phosphate solution which contains nitrate and chlorate as accelerators. In a process based on zinc phosphate solution, it is also intended to use chlorate, nitrite, nitrate, organic nitro compounds or mixtures thereof (AT-PS 314 931).
  • GB-PS 1 542 222 provides for the use of chlorate and nitrobenzenesulfonate as accelerators in zinc phosphate processes.
  • the weight ratio of chlorate to nitrobenzenesulfonate should be 3: 1 to 5: 1.
  • DE-OS 3 004927 also describes a process for phosphating metal surfaces with zinc phosphate solutions, which may contain nitrite and / or organic nitro compound and optionally additionally chlorate.
  • the amounts of nitrite should be 0.01 to 0.2 g / l
  • the amounts of organic nitro compound and optionally chlorate should be in the range of 0.05 to 2 g / l.
  • the object of the invention is to provide a method for applying phosphate layers on metal surfaces which does not have the known, in particular the aforementioned disadvantages, is simple to carry out and can do without the use of expensive chemicals.
  • the method according to the invention is particularly suitable for producing phosphate coatings on steel, galvanized steel and aluminum or on surfaces which contain several of these metals.
  • the active bath components can be introduced in the form of water-soluble or acid-soluble salts or compounds or as acids in water.
  • the water-soluble aromatic nitro compound should have no more than two nitro groups.
  • nitrobenzoic acid is suitable.
  • nitrobenzenesulfonate in particular m-nitrobenzenesulfonate, is used as the water-soluble aromatic nitro compound.
  • solutions used to produce the phosphate coating can have further components if necessary. So it is z. B. advantageous to bring solutions with the metal surfaces in contact, which additionally contain 2 to 9 g / I NOa.
  • phosphating solutions that additionally contain 0.2 to 4 g / 1 fluoride ions.
  • the fluoride can be present in the phosphating solution as free or as a complex-bound fluorine ion.
  • Suitable complex fluorides are e.g. B. fluoborates and / or fluosilicates.
  • phosphating solutions which contain an additional content of Ni, Co and / or Fe ions are advantageous. These ions should preferably be present in a total amount of 0.1 to 2.5 g / l. Such additives can expediently be used in conjunction with 0.2 to 4 g / l of the aforementioned simple or complex fluorides. Such phosphating solutions with contents of Ni, Co and / or Fe ions as well as simple and / or complex fluorine ions are also suitable for the treatment of several metals existing surfaces an advantage. Fluorine contents of up to 1 g / l are generally sufficient. When measuring the addition of Ni, Co and / or Fe ions, the total of these should not exceed the Zn ion content of the phosphating solution.
  • a phosphating solution which has a pH of 2 to 3.5, preferably 2.9 to 3.2.
  • the phosphating solution should have 5 to 30 points total acid and 0.3 to 2.5 points free acid.
  • the number of points is defined in the usual way. For example, the amount of 0.1 n sodium hydroxide solution (in ml) consumed before the bromphenol blue is handled is equal to the number of free acid and the consumption when handling phenolphthalein is equal to the total acid score. The number of points can also be determined by potentiometric titration.
  • the phosphating solution can be applied in any manner. Dip and spray treatments as well as combined dip / spray treatments are particularly suitable.
  • the duration of exposure depends on the desired phosphate layer formation and on the process conditions, but also on the nature of the metal surface and the preceding treatment.
  • the treatment times are generally in the range from 0.5 to 3 minutes.
  • layer weights of about 0.86 to 1.60 g / m 2 (for steel), from 1.30 to 2.15 g / m 2 (for galvanized steel) and up to 0.43 g / m 2 (with aluminum) adjustable.
  • the respective value results from the accelerator ratio used, the layer weight decreasing as the proportion of aromatic nitro compound increases.
  • the phosphating solution used in carrying out the process according to the invention is usually prepared from a concentrate and diluted accordingly.
  • the free acid content in the concentrate can be set sufficiently high to reliably avoid solid separation during storage or transport.
  • the appropriate pH or the free acid content is then set.
  • the working phosphating solution can be supplemented using a supplementary solution which contains all the active ingredients or using several supplementary solutions which contain all of the active ingredients in their entirety.
  • a supplemental solution may contain zinc and phosphate ions and optionally nitrate and / or fluoride and / or nickel ions and another supplementary solution may contain alkali ions, nitrobenzenesulfonate and chlorate ions.
  • the process according to the invention is used within a customary process which consists of cleaning, water rinsing, formation of a phosphate layer, water rinsing, post-treatment and rinsing with demineralized water. This can be followed by a painting treatment or another type of coating.
  • the process according to the invention is particularly advantageous as a pretreatment before electrocoating, especially cathodic electrocoating.
  • the layers produced by the process according to the invention are very fine-grained and permit excellent anchoring of a lacquer coating applied subsequently.
  • the phosphate coatings obtained offer good corrosion protection and show good physical properties, in particular if the subsequent painting is carried out by electrocoating, in particular by cathodic electrocoating, and steel surfaces, galvanized surfaces or aluminum are treated in the process.
  • the method according to the invention is also characterized by reduced sludge and crust formation in the phosphating device.
  • By changing the accelerator ratio it is finally possible to adapt the quality of the phosphate layer with regard to layer weight and fine grain to the respective requirements.
  • Concentrate A was first prepared by mixing the following ingredients in a stainless steel container: In a second container, B mixed while stirring.
  • the sheets treated in this way were cathodically dip-coated with an electrocoat material (ED 3002 R) from PPG Industries and subjected to the tests for determining the corrosion resistance and various physical properties.
  • the properties determined in each case were excellent.
  • Example 2 The procedure according to Example 2 was repeated, but hot-dip galvanized, re-rolled sheets were used instead of steel sheets. Similar test results as in Example 2 were obtained.
  • Example 2 The procedure according to Example 2 was repeated. Instead of the steel sheets, aluminum sheets were treated. Test results similar to those of Example 2 were obtained.
  • Examples 2 to 4 were carried out again, with the difference that the phosphating in stage 3.) according to Example 2 was carried out by immersion treatment at 49 ° C. for 1 minute.
  • the sheet qualities treated in this way also showed test results similar to those in Examples 2 to 4.

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

Description

Die Erfindung betrifft ein Verfahren zum Aufbringen von Phosphatüberzügen auf Metalloberflächen mittels Phosphatierungslösungen auf Basis Zinkphosphat als wesentliche schichtbildende Komponente, die mit Chlorat und wasserlöslicher aromatischer Nitroverbindung beschleunigt sind.The invention relates to a method for applying phosphate coatings on metal surfaces by means of phosphating solutions based on zinc phosphate as an essential layer-forming component, which are accelerated with chlorate and water-soluble aromatic nitro compound.

Es ist bekannt, Metalloberflächen mit Zinkphosphatüberzügen zu versehen. Diese Überzüge verbessern den Korrosionsschutz und die Lackhaftung. Gegenüber älteren Verfahren, die für die Überzugsausbildung eine beträchtliche Behandlungsdauer erforderten, ist durch den Zusatz einer Vielzahl von Beschleunigern die Möglichkeit gegeben, den Bildungsprozeß des Überzuges zu verkürzen. Insbesondere Oxidationsmittel, wie Chlorat, Nitrat, Nitrit, Wasserstoffperoxid bzw. Peroxyverbindungen generell und organische Nitroverbindungen, spielen als Beschleuniger eine wichtige Rolle.It is known to provide zinc phosphate coatings on metal surfaces. These coatings improve corrosion protection and paint adhesion. Compared to older processes, which required a considerable treatment time for coating formation, the addition of a large number of accelerators offers the possibility of shortening the coating formation process. Oxidizing agents such as chlorate, nitrate, nitrite, hydrogen peroxide or peroxy compounds in general and organic nitro compounds in particular play an important role as accelerators.

Schließlich sind auch Phosphatiersysteme mit bestimmten Beschleunigerkombinationen entwickelt worden. So beschreibt die DE-OS 3 016 576 ein Phosphatierverfahren auf Basis Zinkphosphatlösung, das als Beschleuniger Nitrat und Chlorat enthält. Ebenfalls bei einem Verfahren auf Basis Zinkphosphatlösung ist vorgesehen, Chlorat, Nitrit, Nitrat, organische Nitroverbindungen oder Gemische hiervon einzusetzen (AT-PS 314 931).Finally, phosphating systems with certain accelerator combinations have also been developed. DE-OS 3 016 576 describes a phosphating process based on zinc phosphate solution which contains nitrate and chlorate as accelerators. In a process based on zinc phosphate solution, it is also intended to use chlorate, nitrite, nitrate, organic nitro compounds or mixtures thereof (AT-PS 314 931).

Die GB-PS 1 542 222 sieht vor, bei Zinkphosphatverfahren Chlorat und Nitrobenzolsulfonat als Beschleuniger einzusetzen. Dabei soll das Gewichtsverhältnis von Chlorat zu Nitrobenzolsulfonat 3 : 1 bis 5 : 1 sein.GB-PS 1 542 222 provides for the use of chlorate and nitrobenzenesulfonate as accelerators in zinc phosphate processes. The weight ratio of chlorate to nitrobenzenesulfonate should be 3: 1 to 5: 1.

Auch die DE-OS 3 004927 beschreibt ein Verfahren zur Phosphatierung von Metalloberflächen mit Zinkphosphatlösungen, die Nitrit und/oder organische Nitroverbindung sowie gegebenenfalls zusätzlich Chlorat enthalten können. Die Nitritmengen sollen 0,01 bis 0,2 g/I betragen, die Mengen an organischer Nitroverbindung und gegebenenfalls Chlorat sollen im Bereich von 0,05 bis 2 g/1 liegen. Obgleich die vorgenannten Verfahren mit gewissen Vorteilen verbunden sind, haftet ihnen der Nachteil an, daß die erzielbaren Schichtgewichte über den angestrebten Werten liegen, daß die Phosphatschichten häufig nicht die erwünschte Feinkörnigkeit aufweisen und daß es insbesondere an der Flexibilität bei der Erzeugung von Phosphatschichten bestimmter Körnigkeit und bestimmter Schichtgewichte fehlt.DE-OS 3 004927 also describes a process for phosphating metal surfaces with zinc phosphate solutions, which may contain nitrite and / or organic nitro compound and optionally additionally chlorate. The amounts of nitrite should be 0.01 to 0.2 g / l, the amounts of organic nitro compound and optionally chlorate should be in the range of 0.05 to 2 g / l. Although the aforementioned processes are associated with certain advantages, they have the disadvantage that the achievable layer weights are above the desired values, that the phosphate layers often do not have the desired fine grain size and that it is particularly due to the flexibility in the production of phosphate layers of certain grain size and certain layer weights are missing.

Aufgabe der Erfindung ist es, ein Verfahren zum Aufbringen von Phosphatschichten auf Metalloberflächen bereitzustellen, das die bekannten, insbesondere vorgenannten Nachteile nicht aufweist, einfach in der Durchführung ist und auf den Einsatz aufwendiger Chemikalien verzichten kann.The object of the invention is to provide a method for applying phosphate layers on metal surfaces which does not have the known, in particular the aforementioned disadvantages, is simple to carry out and can do without the use of expensive chemicals.

Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man die Metalloberflächen mit einer Phosphatierungslösung in Berührung bringt, die

  • 0,5 bis 4 g/I Zn,
  • 3,0 bis 12 g/I P04,
  • 1,5 bis 7 g/I C103 und
  • 2,0 bis 7 g/I aromatische Nitroverbindung

enthält und in der das Verhältnis CIOa : Nitroverbindung (0,5 bis 1,25) : 1 beträgt.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 a phosphating solution which
  • 0.5 to 4 g / l Zn,
  • 3.0 to 12 g / I P0 4 ,
  • 1.5 to 7 g / I C10 3 and
  • 2.0 to 7 g / l aromatic nitro compound

contains and in which the ratio CIO a : nitro compound (0.5 to 1.25): 1.

Das erfindungsgemäße Verfahren ist insbesondere zur Erzeugung von Phosphatüberzügen auf Stahl, verzinktem Stahl und Aluminium bzw. auf Oberflächen, die mehrere dieser Metalle enthalten, geeignet.The method according to the invention is particularly suitable for producing phosphate coatings on steel, galvanized steel and aluminum or on surfaces which contain several of these metals.

Die wirksamen Badbestandteile können in Form wasserlöslicher oder säurelöslicher Salze bzw. Verbindungen oder als Säuren in Wasser eingebracht werden. Geeignet sind z. B. Zinknitrat, Zinkoxid, Zinkcarbonat, saures Zinkphosphat sowie Phosphorsäure, Mono- oder Dinatriumphosphat und Alkalichlorat.The active bath components can be introduced in the form of water-soluble or acid-soluble salts or compounds or as acids in water. Are suitable for. B. zinc nitrate, zinc oxide, zinc carbonate, acidic zinc phosphate and phosphoric acid, mono- or disodium phosphate and alkali chlorate.

Die wasserlösliche aromatische Nitroverbindung sollte nicht mehr als zwei Nitrogruppen aufweisen. Geeignet ist beispielsweise Nitrobenzoesäure.The water-soluble aromatic nitro compound should have no more than two nitro groups. For example, nitrobenzoic acid is suitable.

In einer bevorzugten Ausgestaltung der Erfindung wird als wasserlösliche aromatische Nitroverbindung Nitrobenzolsulfonat, insbesondere m-Nitrobenzolsulfonat, eingesetzt.In a preferred embodiment of the invention, nitrobenzenesulfonate, in particular m-nitrobenzenesulfonate, is used as the water-soluble aromatic nitro compound.

Die zur Erzeugung des Phosphatüberzuges eingesetzten Lösungen können im Bedarfsfall weitere Bestandteile aufweisen. So ist es z. B. vorteilhaft, Lösungen mit den Metalloberflächen in Berührung zu bringen, die zusätzlich 2 bis 9 g/I NOa enthalten.The solutions used to produce the phosphate coating can have further components if necessary. So it is z. B. advantageous to bring solutions with the metal surfaces in contact, which additionally contain 2 to 9 g / I NOa.

Wenn Aluminiumoberflächen behandelt werden sollen, empfiehlt es sich, Phosphatierungslösungen zum Einsatz zu bringen, die zusätzlich 0,2 bis 4 g/1 Fluoridionen enthalten. Das Fluorid kann in der Phosphatierungslösung als freies oder als komplex gebundenes Fluorion vorliegen. Geeignete komplexe Fluoride sind z. B. Fluoborate und/oder Fluosilikate.If aluminum surfaces are to be treated, it is advisable to use phosphating solutions that additionally contain 0.2 to 4 g / 1 fluoride ions. The fluoride can be present in the phosphating solution as free or as a complex-bound fluorine ion. Suitable complex fluorides are e.g. B. fluoborates and / or fluosilicates.

Insbesondere bei der Behandlung von verzinktem Stahl sind Phosphatierungslösungen von Vorteil, die einen zusätzlichen Gehalt von Ni-, Co- und/oder Fe-Ionen enthalten. Vorzugsweise sollten diese Ionen in einer Gesamtmenge von 0,1 bis 2,5 g/I vorliegen. Derartige Zusätze können zweckmäßigerweise in Verbindung mit 0,2 bis 4 g/I der vorgenannten einfachen oder komplexen Fluoride zum Einsatz kommen. Derartige Phosphatierungslösungen mit Gehalten an Ni-, Co- und/oder Fe-Ionen sowie einfachen und/oder komplexen Fluorionen sind auch für die Behandlung von aus mehreren Metallen bestehenden Oberflächen von Vorteil. Hierbei sind im allgemeinen Fluorgehalte bis 1 g/I ausreichend. Bei der Bemessung des Zusatzes von Ni-, Co- und/oder Fe-Ionen sollte deren Gesamtheit den Gehalt der Phosphatierungslösung an Zn-lonen nicht übersteigen.In the treatment of galvanized steel in particular, phosphating solutions which contain an additional content of Ni, Co and / or Fe ions are advantageous. These ions should preferably be present in a total amount of 0.1 to 2.5 g / l. Such additives can expediently be used in conjunction with 0.2 to 4 g / l of the aforementioned simple or complex fluorides. Such phosphating solutions with contents of Ni, Co and / or Fe ions as well as simple and / or complex fluorine ions are also suitable for the treatment of several metals existing surfaces an advantage. Fluorine contents of up to 1 g / l are generally sufficient. When measuring the addition of Ni, Co and / or Fe ions, the total of these should not exceed the Zn ion content of the phosphating solution.

Es ist vorteilhaft, die Metalloberflächen mit einer Phosphatierungslösung in Berührung zu bringen, die einen pH-Wert von 2 bis 3,5, vorzugsweise 2,9 bis 3,2, aufweist.It is advantageous to bring the metal surfaces into contact with a phosphating solution which has a pH of 2 to 3.5, preferably 2.9 to 3.2.

Die Phosphatierungslösung sollte 5 bis 30 Punkte Gesamtsäure und 0,3 bis 2,5 Punkte Freie Säure aufweisen. Dabei ist die Zahl der Punkte in üblicher Weise definiert. So ist die bis zum Umschlag von Bromphenol blau verbrauchte Menge 0,1 n Natronlauge (in ml) gleich der Zahl Freier Säure und der Verbrauch beim Umschlag von Phenolphtalein gleich der Punktezahl Gesamtsäure. Die Punktezahl kann auch durch potentiometrische Titration ermittelt werden.The phosphating solution should have 5 to 30 points total acid and 0.3 to 2.5 points free acid. The number of points is defined in the usual way. For example, the amount of 0.1 n sodium hydroxide solution (in ml) consumed before the bromphenol blue is handled is equal to the number of free acid and the consumption when handling phenolphthalein is equal to the total acid score. The number of points can also be determined by potentiometric titration.

Es ist vorteilhaft, die Metalloberfläche mit einer eine Temperatur von 26,7 bis 71°C aufweisenden Phosphatierungslösung in Berührung zu bringen. Temperaturen im Bereich von 37,8 bis 49° C sind besonders geeignet.It is advantageous to bring the metal surface into contact with a phosphating solution having a temperature of 26.7 to 71 ° C. Temperatures in the range of 37.8 to 49 ° C are particularly suitable.

Die Aufbringung der Phosphatierungslösung kann auf beliebige Weise erfolgen. Insbesondere Tauch- und Spritzbehandlungen sowie kombinierte Tauch/Spritz-Behandlungen sind geeignet. Die Einwirkungsdauer hängt von der erwünschten Phosphatschichtausbildung sowie von den Verfahrensbedingungen, aber auch von der Beschaffenheit der Metalloberfläche wie der vorgeschalteten Behandlung ab. Im allgemeinen liegen die Behandlungszeiten im Bereich von 0,5 bis 3 Minuten.The phosphating solution can be applied in any manner. Dip and spray treatments as well as combined dip / spray treatments are particularly suitable. The duration of exposure depends on the desired phosphate layer formation and on the process conditions, but also on the nature of the metal surface and the preceding treatment. The treatment times are generally in the range from 0.5 to 3 minutes.

Mit dem erfindungsgemäßen Verfahren sind Schichtgewichte von etwa 0,86 bis 1,60 g/m2 (bei Stahl), von 1,30 bis 2,15 g/m2 (bei verzinktem Stahl) und bis 0,43 g/m2 (bei Aluminium) einstellbar. Der jeweilige Wert ergibt sich aus dem verwendeten Beschleunigerverhältnis, wobei mit steigendem Anteil an aromatischer Nitroverbindung das Schichtgewicht sinkt.With the method according to the invention, layer weights of about 0.86 to 1.60 g / m 2 (for steel), from 1.30 to 2.15 g / m 2 (for galvanized steel) and up to 0.43 g / m 2 (with aluminum) adjustable. The respective value results from the accelerator ratio used, the layer weight decreasing as the proportion of aromatic nitro compound increases.

Üblicherweise wird die bei der Durchführung des erfindungsgemäßen Verfahrens zum Einsatz kommende Phosphatierungslösung aus einem Konzentrat angesetzt und entsprechend verdünnt. Im Konzentrat kann der Gehalt an Freier Säure hinreichend hoch eingestellt werden, um eine Feststoffabscheidung während der Lagerung oder beim Transport mit Sicherheit zu vermeiden. Im Gebrauch, d. h. beim Ansatz und bei der Ergänzung des arbeitenden Phosphatierungsbades, wird dann auf den geeigneten pH-Wert bzw. den Gehalt an Freier Säure eingestellt. Die arbeitende Phosphatierungslösung kann unter Verwendung einer Ergänzungslösung, die sämtliche wirksamen Bestandteile enthält, oder unter Verwendung mehrerer Ergänzungslösungen, die in ihrer Gesamtheit alle wirksamen Bestandteile enthalten, ergänzt werden. Beispielsweise kann eine Ergänzungslösung Zink- und Phosphationen sowie gegebenenfalls Nitrat- und/oder Fluorid- und/oder Nickelionen und eine andere Ergänzungslösung Alkaliionen, Nitrobenzolsulfonat und Chlorationen enthalten.The phosphating solution used in carrying out the process according to the invention is usually prepared from a concentrate and diluted accordingly. The free acid content in the concentrate can be set sufficiently high to reliably avoid solid separation during storage or transport. In use, i.e. H. when preparing and supplementing the working phosphating bath, the appropriate pH or the free acid content is then set. The working phosphating solution can be supplemented using a supplementary solution which contains all the active ingredients or using several supplementary solutions which contain all of the active ingredients in their entirety. For example, a supplemental solution may contain zinc and phosphate ions and optionally nitrate and / or fluoride and / or nickel ions and another supplementary solution may contain alkali ions, nitrobenzenesulfonate and chlorate ions.

Das erfindungsgemäße Verfahren findet innerhalb eines üblichen Verfahrensganges, der aus Reinigen, Wasserspülen, Phosphatschichtausbildung, Wasserspülen, Nachbehandeln und Spülen mit vollentsalztem Wasser besteht, Anwendung. Danach kann sich eine Lackierbehandlung oder eine andersartige Beschichtung anschließen.The process according to the invention is used within a customary process which consists of cleaning, water rinsing, formation of a phosphate layer, water rinsing, post-treatment and rinsing with demineralized water. This can be followed by a painting treatment or another type of coating.

Das erfindungsgemäße Verfahren ist insbesondere als Vorbehandlung vor der Elektrotauchlackierung, speziell der kathodischen Elektrotauchlackierung, von Vorteil.The process according to the invention is particularly advantageous as a pretreatment before electrocoating, especially cathodic electrocoating.

Die mit dem erfindungsgemäßen Verfahren hergestellten Schichten sind sehr feinkörnig und gestatten eine hervorragende Verankerung eines nachfolgend aufgebrachten Lacküberzuges. Außerdem bieten die erhaltenen Phosphatüberzüge einen guten Korrosionsschutz und zeigen gute physikalische Eigenschaften, insbesondere wenn die anschließende Lackierung durch Elektrotauchlackierung, speziell durch kathodische Elektrotauchlackierung, erfolgt und dabei Stahloberflächen, verzinkte Oberflächen oder Aluminium behandelt werden.The layers produced by the process according to the invention are very fine-grained and permit excellent anchoring of a lacquer coating applied subsequently. In addition, the phosphate coatings obtained offer good corrosion protection and show good physical properties, in particular if the subsequent painting is carried out by electrocoating, in particular by cathodic electrocoating, and steel surfaces, galvanized surfaces or aluminum are treated in the process.

Das erfindungsgemäße Verfahren zeichnet sich außerdem durch verringerte Schlamm- und Krustenbildung in der Phosphatiervorrichtung aus. Durch Veränderung des Beschleunigerverhältnisses ist schließlich die Möglichkeit gegeben, die Qualität der Phosphatschicht hinsichtlich Schichtgewicht und Feinkörnigkeit den jeweiligen Erfordernissen anzupassen.The method according to the invention is also characterized by reduced sludge and crust formation in the phosphating device. By changing the accelerator ratio, it is finally possible to adapt the quality of the phosphate layer with regard to layer weight and fine grain to the respective requirements.

Die Erfindung wird anhand der Beispiele beispielsweise und näher erläutert.The invention is illustrated by way of example and in more detail.

Beispiel 1example 1

Es wurde zunächst ein Konzentrat A durch Vermischen folgender Bestandteile in einem Behälter aus rostfreiem Stahl hergestellt:

Figure imgb0001
In einem zweiten Behälter wurden zur Bildung eines Konzentrates B
Figure imgb0002
unter Rühren vermischt.Concentrate A was first prepared by mixing the following ingredients in a stainless steel container:
Figure imgb0001
 In a second container, B
Figure imgb0002
 mixed while stirring.

Aus beiden Konzentraten wurde eine für die Spritzbehandlung bestimmte Phosphatierungslösung hergestellt, indem

  • 42,0 g des Konzentrates A und
  • 29,2 g des Konzentrates B zusammen mit
  • 1,2 g Soda

mit Wasser auf 1 I aufgefüllt wurden. Die Gesamtsäurepunktzahl war 13 bei Titration einer 10 ml-Badprobe mit 0,1 n Natriumhydroxidlösung gegen Phenolphthalein.A phosphating solution intended for spray treatment was prepared from both concentrates by
  • 42.0 g of concentrate A and
  • 29.2 g of concentrate B together with
  • 1.2 g soda

were made up to 1 liter with water. The total acid score was 13 when titrating a 10 ml bath sample with 0.1N sodium hydroxide solution against phenolphthalein.

Beispiel 2Example 2

Kaltgewalzte Stahlbleche wurden dem Verfahrensgang

  • 1. Reinigung mit einem alkalischen Reiniger (auf Basis Natrium-o-phosphat, Natriumpyrophosphat, Borax, aktivierend wirkendes Titanphosphat, Tensid) bei 60° C während 1 Minute im Spritzen;
  • 2. Warmwasserspülen während 30 Sekunden;
  • 3. Phosphatieren mit der gemäß Beispiel 1 erhaltenen Lösung bei 49° C durch Spritzbehandlung während 1 Minute;
  • 4. Kaltwasserspülen während 30 Sekunden;
  • 5. Nachbehandeln mit einer CrVI/Crlll-lonen enthaltenden Lösung mit einem pH-Wert von 4 bei Raumtemperatur durch Tauchen während 30 Sekunden;
  • 6. Spülen mit vollentsalztem Wasser im Spritzen während 10 Sekunden;
  • 7. Ofentrocknen bei 177° C während 5 Minuten

unterworfen.Cold rolled steel sheets became the process
  • 1. Cleaning with an alkaline cleaner (based on sodium o-phosphate, sodium pyrophosphate, borax, activating titanium phosphate, surfactant) at 60 ° C for 1 minute in a spray;
  • 2. Warm water rinsing for 30 seconds;
  • 3. Phosphating with the solution obtained according to Example 1 at 49 ° C by spraying for 1 minute;
  • 4. Rinse cold water for 30 seconds;
  • 5. aftertreatment with a solution containing CrVI / Crlll ions with a pH of 4 at room temperature by immersion for 30 seconds;
  • 6. Rinse with deionized water in a spray for 10 seconds;
  • 7. Oven dry at 177 ° C for 5 minutes

subject.

Die so behandelten Bleche wurden mit einem Elektrotauchlack (ED 3002 R) der Firma PPG Industries kathodisch tauchlackiert und den Tests zur Ermittlung des Korrosionswiderstandes und verschiedener physikalischer Eigenschaften unterworfen. Die jeweils ermittelten Eigenschaften waren hervorragend.The sheets treated in this way were cathodically dip-coated with an electrocoat material (ED 3002 R) from PPG Industries and subjected to the tests for determining the corrosion resistance and various physical properties. The properties determined in each case were excellent.

Beispiel 3Example 3

Der Verfahrensgang gemäß Beispiel 2 wurde wiederholt, jedoch wurden anstelle von Stahlblechen feuerverzinkte, nachgewalzte Bleche eingesetzt. Ähnliche Testergebnisse wie in Beispiel 2 wurden erhalten.The procedure according to Example 2 was repeated, but hot-dip galvanized, re-rolled sheets were used instead of steel sheets. Similar test results as in Example 2 were obtained.

Beispiel 4Example 4

Der Verfahrensgang gemäß Beispiel 2 wurde wiederholt. Anstelle der Stahlbleche wurden Aluminiumbleche behandelt. Es wurden ähnliche Testergebnisse wie bei Beispiel 2 erhalten.The procedure according to Example 2 was repeated. Instead of the steel sheets, aluminum sheets were treated. Test results similar to those of Example 2 were obtained.

Beispiel 5Example 5

Die Beispiele 2 bis 4 wurden erneut durchgeführt mit dem Unterschied, daß das Phosphatieren in Stufe 3.) gemäß Beispiel 2 durch Tauchbehandlung bei 49° C während 1 Minute erfolgte. Auch die auf diese Weise behandelten Blechqualitäten zeigten ähnliche Testergebnisse wie im Falle der Beispiele 2 bis 4.Examples 2 to 4 were carried out again, with the difference that the phosphating in stage 3.) according to Example 2 was carried out by immersion treatment at 49 ° C. for 1 minute. The sheet qualities treated in this way also showed test results similar to those in Examples 2 to 4.

Claims (9)

1. Process for applying phosphate coatings on metal surfaces by means of phosphating solutions on the basis of zinc phosphate as essential layer forming constituent, which are accelerated by chlorate and water soluble aromatic nitro-compound, characterized in that the metal surfaces are brought in contact with a phosphating solution, which contains
0,5 to 4 g/I Zn
3,0 to 12 g/I P04
1,5 to 7 g/l ClO3 and
2,0 to 7 g/I aromatic nitro-compound

and in which the ratio of ClO3 to nitro-compound is (0,5 to 1,25) : 1.
2. Process according to claim 1, characterized in that the metal surfaces are brought in contact with a phosphating solution, which contains as nitro-compound nitrobenzene sulfonate, in particular m-nitrobenzene sulfonate.
3. Process according to claim 1 or 2, characterized in that the metal surfaces are brought in contact with a phosphating solution, which contains in addition 2 to 9 g/I N03.
4. Process according to claim 1, or 3, characterized in that the metal surfaces are brought in contact with a phosphating solution, which contains in addition 0,2 to 4 g/I F.
5. Process according to one or more of the claims 1 to 4, characterized in that the metal surfaces are brought in contact with a phosphating solution, which contains in addition Ni-, Co- and/or Fe-ions, preferably in a total amount of 0,1 to 2,5 g/I.
6. Process according to one or more of the claims 1 to 5, characterized in that the metal surfaces are brought in contact with a phosphating solution having a pH-value of 2 to 3,5, in particular of 2,9 to 3,2.
7. Process according to one or more of the claims 1 to 6, characterized in that the metal surfaces are brought in contact with a phosphating solution having 5 to 30 total acid points and 0,3 to 2,5 free acid points.
8. Process according to one or more of the claims 1 to 7, characterized in that the metal surfaces are brought in contact with a phosphating solution having a temperature of 26,7 to 71°C, in particular of 37,8 to 49° C.
9. Process according to one or more of the claims 1 to 8, characterized in that the metal surfaces are brought in contact with a phosphating solution by means of dip, spray or combined dip/spray treatment, in particular with a contact time of 0,5 bis 3 minutes.
EP82105960A 1981-07-13 1982-07-03 Process for phosphating metal surfaces Expired EP0069950B1 (en)

Applications Claiming Priority (2)

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US06/282,480 US4498935A (en) 1981-07-13 1981-07-13 Zinc phosphate conversion coating composition
US282480 1981-07-13

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DE3244715A1 (en) * 1982-12-03 1984-06-07 Gerhard Collardin GmbH, 5000 Köln METHOD FOR PHOSPHATING METAL SURFACES, AND BATH SOLUTIONS SUITABLE FOR THIS
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
DE3407513A1 (en) * 1984-03-01 1985-09-05 Gerhard Collardin GmbH, 5000 Köln METHOD FOR ZINC-CALCIUM PHOSPHATION OF METAL SURFACES AT LOW TREATMENT TEMPERATURE
DE3408577A1 (en) * 1984-03-09 1985-09-12 Metallgesellschaft Ag, 6000 Frankfurt METHOD FOR PHOSPHATING METALS
ES8606528A1 (en) * 1985-02-22 1986-04-01 Henkel Iberica Process for the phosphating of metal surfaces.
WO1986005094A1 (en) * 1985-03-08 1986-09-12 Takeda Chemical Industries, Ltd. Antiobesity agent and composition
WO1986006276A1 (en) * 1985-04-30 1986-11-06 Takeda Chemical Industries, Ltd. Sugar digestion-restraining agent and sugar digestion-restraining composition
GB8523572D0 (en) * 1985-09-24 1985-10-30 Pyrene Chemicals Services Ltd Coating metals
US4673445A (en) * 1986-05-12 1987-06-16 The Lea Manufacturing Company Corrosion resistant coating
DE3630246A1 (en) * 1986-09-05 1988-03-10 Metallgesellschaft Ag METHOD FOR PRODUCING PHOSPHATE COVER AND ITS APPLICATION
DE3631759A1 (en) * 1986-09-18 1988-03-31 Metallgesellschaft Ag METHOD FOR PRODUCING PHOSPHATE COATINGS ON METAL SURFACES
US6551417B1 (en) 2000-09-20 2003-04-22 Ge Betz, Inc. Tri-cation zinc phosphate conversion coating and process of making the same
JP5462467B2 (en) 2008-10-31 2014-04-02 日本パーカライジング株式会社 Chemical treatment solution for metal material and treatment method

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