EP0327153A2 - Process for applying phosphate coatings to metals - Google Patents

Process for applying phosphate coatings to metals Download PDF

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Publication number
EP0327153A2
EP0327153A2 EP89200142A EP89200142A EP0327153A2 EP 0327153 A2 EP0327153 A2 EP 0327153A2 EP 89200142 A EP89200142 A EP 89200142A EP 89200142 A EP89200142 A EP 89200142A EP 0327153 A2 EP0327153 A2 EP 0327153A2
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EP
European Patent Office
Prior art keywords
individual parts
solution
phosphate
phosphating
contact
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EP89200142A
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German (de)
French (fr)
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EP0327153B1 (en
EP0327153A3 (en
Inventor
Horst Dr. Gehmecker
Werner Dr. Rausch
Peter Jörns
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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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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
    • C23C22/78—Pretreatment of the material to be coated

Definitions

  • the invention relates to a process for the production of phosphate coatings on at least partially iron or steel surfaces having individual parts made of metal by means of aqueous phosphating solutions which contain zinc, phosphate, nitrate and autocatalytically formed nitrite ions and are practically free of iron II ions.
  • Another type of zinc phosphate process which usually works with high nitrate contents and at higher temperatures, is characterized in that the phosphating solutions used are practically free of iron II ions. In them, nitrite, which contains the iron II ions, forms autocatalytically Iron III ions are transferred, which in turn form poorly soluble iron phosphate with phosphate ions (DE-A-25 40 684).
  • the object of the invention is to provide a method for producing phosphate coatings on at least partially iron or steel surfaces having individual parts, which does not have the disadvantage of the long treatment time, but leads in a short time to phosphate coatings which are nevertheless of high quality.
  • 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 individual parts are in contact with a phosphating solution at a temperature in the range from 60 to 100 ° C. for a period of 3 to 30 seconds brings that 10 to 80 g / l zinc 12 to 80 g / l Phosphate (calculated as P2O5) 40 to 150 g / l Nitrate as well as additional 0.1 to 5 g / l fluoride 0.01 to 10 g / l nickel 0.001 to 0.1 g / l copper contains, in which the ratio of free acid to total acid is set to (0.1 to 0.3): 1 and which has at least 80 points total acid.
  • nitrite is formed autocatalytically, it may be necessary to add nitrite to the phosphating solution, for example in an amount of 0.03 to 0.2 g / l, in the initial phase of the process.
  • the method according to the invention is used in particular for the treatment of individual parts whose iron or steel surface has alloy additions of up to a maximum of 5% by weight.
  • the individual components of the phosphating solution such as zinc, phosphate, nitrate, etc.
  • the individual components are usually, as is customary in phosphating technology, pre-dissolved together as an acidic phosphating concentrate and introduced into the phosphating solution in this form.
  • the individual components are dimensioned in such a way that the required concentration ranges result in the phosphating solution.
  • additional cations from the alkali and / or ammonium group may have to be used.
  • titrate 10 ml bath sample with n / 10 NaOH against the first or second change in phosphoric acid using the color change of dimethyl yellow (free acid) or phenolphthalein (total acid), for example, as an indicator.
  • the ml of n / 10 NaOH consumed correspond to the free acid or the total acid in points.
  • the content of nitrite points is usually determined using the saccharometer method. For this, 50 ml of bath solution are mixed with 2 to 5 g of sulfamic acid. The amount of gas generated in ml is equal to the number of points. A gas point corresponds to a content of 46 mg / l NO2 in the phosphating solution.
  • the contact of the individual parts with the phosphating solution is preferably carried out by dipping or flooding.
  • the phosphate coatings produced by the process according to the invention have a layer weight of 2.0 to 10 g / m2.
  • a preferred embodiment of the invention consists in bringing the individual parts into contact with a phosphating solution 30 to 60 g / l zinc 30 to 50 g / l Phosphate (calculated as P2O5) 65 to 100 g / l nitrate 0.5 to 3.0 g / l Fluoride and 0.02 to 0.5 g / l nickel contains.
  • the rate of formation of the phosphate coating can be increased if, in accordance with a further advantageous embodiment of the invention, the individual parts are brought into contact with a phosphating solution which contains further accelerating additives.
  • accelerating additives can be, for example, chlorate, bromate, peroxide, m-nitrobenzenesulfonate, nitrophenol or combinations thereof.
  • a further improvement in the properties of the phosphate coating can be achieved if, according to a further advantageous embodiment of the invention, the individual parts are brought into contact with a phosphating solution which contains an additional 0.1 to 10 g / l, preferably 1 to 5 g / l, of manganese.
  • a phosphating solution which additionally contains 0.05 to 3 g / l tartaric acid and / or citric acid.
  • Another advantageous embodiment of the invention is to clean the individual parts before phosphating, if necessary to free them of rust, scale and phosphate layer and to activate them, and to passivate them with a rinse solution after phosphating, each of the process steps lasting from 3 to 30 sec is carried out.
  • an alkaline cleaning solution at a temperature in the range between 60 and 100 ° C. and a concentration in the range from 20 to 200 g / l for cleaning.
  • cleaners those based on sodium hydroxide, gluconate, phosphate with an additional content of carbonate, silicate and borate and surfactant.
  • the cleaner is preferably used in spraying.
  • Sulfuric acid or phosphoric acid solutions at a temperature in the range from 60 to 100 ° C. and a concentration in the range from 5 to 50% by weight have proven to be advantageous for the removal of rust, scale and phosphate layers that may be required.
  • a sulfuric or phosphoric acid is used which additionally contains iron II and / or iron III ions in a concentration in the range from 1 to 50 g / l.
  • the phosphating treatment After the phosphating treatment, it is usually rinsed with water, rinsed if necessary and dried if necessary.
  • a further advantageous embodiment of the invention provides for the individual parts to be passivated with a chrome-containing or chrome-free rinse solution. Possibly. can also be treated with an emulsion of an anti-corrosion oil, or it can be painted with or without passivation. In the event that cold forming is intended, an aftertreatment with a soap bath can also be carried out.
  • the phosphate coatings produced by the process according to the invention can be used advantageously in all fields in which phosphate coatings are used.
  • the phosphating process according to the invention is particularly favorable in improving the corrosion protection in the case of a subsequent painting.
  • the phosphate coating produced after this operation had a basis weight of 4 to 5 g / m2.
  • the phosphate coating was uniformly opaque and fine crystalline.

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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

To produce phosphate coatings on metal components having surfaces of at least partially iron or steel, these are treated at a temperature in the range from 60 to 100 DEG C for a period of 3 to 30 seconds with a phosphating solution which contains 10 to 80 g/l of zinc, 12 to 80 g/l of phosphate (calculated as P2O5) and 40 to 150 g/l of nitrate, and also additionally 0.1 to 5 g/l of fluoride, 0.01 to 10 g/l of nickel, 0.001 to 0.1 g/l of copper and, if appropriate, tartaric acid, citric acid and/or manganese, in which solution the free acid/total acid ratio has been adjusted to (0.1 to 0.3):1 and which contains at least 80 points of total acid. <??>The components can be cleaned before the phosphating, if appropriate freed of rust, scale and phosphate layers, activated and, after the phosphating, passivated with a rinsing solution, each of these process steps being carried out for a period of 3 to 30 seconds.

Description

Die Erfindung betrifft ein Verfahren zur Erzeugung von Phosphatüberzügen auf mindestens teilweise Eisen- oder Stahloberflächen aufweisenden Einzelteilen aus Metall mittels wäßriger Phosphatierungslösungen, die Zink-, Phosphat-, Nitrat- und autokatalytisch gebildete Nitritionen enthalten sowie praktisch frei von Eisen II-Ionen sind.The invention relates to a process for the production of phosphate coatings on at least partially iron or steel surfaces having individual parts made of metal by means of aqueous phosphating solutions which contain zinc, phosphate, nitrate and autocatalytically formed nitrite ions and are practically free of iron II ions.

Es ist bekannt, mindestens teilweise Stahl- oder Eisenoberflächen aufweisende Werkstücke, beispielsweise Einzelteile, wie Luftfiltergehäuse, tiefgezogene Bremsenteile, Fahrzeugräder sowie weitere Automobilzubehörteile, mit Zinkphosphatüberzügen zu versehen. Hierzu dienen u.a. Phosphatierungslösungen, die neben Zink- und Phosphationen Nitrationen als Beschleuniger enthalten. Derartige Phosphatierungslösungen arbeiten üblicherweise "auf der Eisenseite", d.h. während des Einsatzes reichert sich durch den Beizangriff von der Eisen- oder Stahloberfläche gelöstes Eisen in der Lösung an. Um den Gehalt an Eisen II-Ionen unterhalb der Grenze zu halten, bei der eine Beeinträchtigung der Qualität des Phosphatüberzuges aufzutreten beginnt, ist es bekannt, beispielsweise gezielt Chlorat zuzudosieren, so daß die Eisen II-Konzentration im Bereich von 0,05 bis 1 Gew.% gehalten wird (EP-B-0 045 110).It is known to provide at least partially steel or iron workpieces, for example individual parts such as air filter housings, deep-drawn brake parts, vehicle wheels and other automotive accessories, with zinc phosphate coatings. Among other things, Phosphating solutions that contain nitrate ions as accelerators in addition to zinc and phosphate ions. Such phosphating solutions usually work "on the iron side", i.e. during use, iron pickling from the iron or steel surface accumulates in the solution due to the pickling attack. In order to keep the content of iron II ions below the limit at which an impairment of the quality of the phosphate coating begins to occur, it is known to meter chlorate in a targeted manner, for example, so that the iron II concentration is in the range from 0.05 to 1% by weight % is kept (EP-B-0 045 110).

Eine andere Art von Zinkphosphatverfahren, die in der Regel mit hohen Nitratgehalten und bei höheren Temperaturen arbeiten, zeichnet sich dadurch aus, daß die im Einsatz befindlichen Phosphatierungslösungen praktisch frei von Eisen II-Ionen sind. Bei ihnen bildet sich autokatalytisch Nitrit, das die Eisen II-Ionen in Eisen III-Ionen überführt, die ihrerseits mit Phosphationen schwerlösliches Eisenphosphat bilden (DE-A-25 40 684).Another type of zinc phosphate process, which usually works with high nitrate contents and at higher temperatures, is characterized in that the phosphating solutions used are practically free of iron II ions. In them, nitrite, which contains the iron II ions, forms autocatalytically Iron III ions are transferred, which in turn form poorly soluble iron phosphate with phosphate ions (DE-A-25 40 684).

Beiden vorgenannten Verfahrensarten ist gemeinsam, daß die Ausbildung des Phosphatüberzuges mit 5 bis 15 min. eine vergleichsweise lange Behandlungsdauer erfordert.Both types of process mentioned have in common that the formation of the phosphate coating with 5 to 15 min. requires a comparatively long treatment period.

In der Praxis sind derartig lange Behandlungszeiten jedoch häufig nur mit vergleichsweise großem apparativen Aufwand realisierbar, d.h. es wäre wünschenswert, Verfahren, die in kürzerer Zeit durchführbar sind, zur Verfügung zu haben. Dies ist insbesondere dann wünschenswert, wenn die Oberflächenbehandlung in vorgegebene Fertigungsabläufe, die bei der Behandlung von Einzelteilen, z.B. der vorgenannten Art, von Bedeutung sind, integriert werden soll.In practice, however, such long treatment times can often only be achieved with a relatively large amount of equipment, i.e. it would be desirable to have procedures that can be performed in a shorter time. This is particularly desirable if the surface treatment is carried out in predetermined manufacturing processes that are used in the treatment of individual parts, e.g. of the aforementioned type, are of importance, should be integrated.

Aufgabe der Erfindung ist es, ein Verfahren zur Erzeugung von Phosphatüberzügen auf mindestens teilweise Eisen- oder Stahloberflächen aufweisenden Einzelteilen bereitzustellen, das den Nachteil der langen Behandlungsdauer nicht aufweist, sondern in kurzer Zeit zu Phosphatüberzügen führt, die dennoch von hoher Qualität sind.The object of the invention is to provide a method for producing phosphate coatings on at least partially iron or steel surfaces having individual parts, which does not have the disadvantage of the long treatment time, but leads in a short time to phosphate coatings which are nevertheless of high quality.

Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung in der Weise ausgestaltet wird, daß man die Einzelteile bei einer Temperatur im Bereich von 60 bis 100°C für die Dauer von 3 bis 30 sec. mit einer Phosphatierungslösung in Kontakt bringt, die 10 bis 80 g/l Zink 12 bis 80 g/l Phosphat (ber. als P₂O₅) 40 bis 150 g/l Nitrat sowie zusätzlich 0,1 bis 5 g/l Fluorid 0,01 bis 10 g/l Nickel 0,001 bis 0,1 g/l Kupfer enthält, in der das Verhältnis von Freier Säure zu Gesamtsäure auf (0,1 bis 0,3):1 eingestellt ist und die mindestens 80 Punkte Gesamtsäure aufweist.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 individual parts are in contact with a phosphating solution at a temperature in the range from 60 to 100 ° C. for a period of 3 to 30 seconds brings that 10 to 80 g / l zinc 12 to 80 g / l Phosphate (calculated as P₂O₅) 40 to 150 g / l Nitrate as well as additional 0.1 to 5 g / l fluoride 0.01 to 10 g / l nickel 0.001 to 0.1 g / l copper contains, in which the ratio of free acid to total acid is set to (0.1 to 0.3): 1 and which has at least 80 points total acid.

Obgleich - wie oben dargelegt - Nitrit autokatalytisch gebildet wird, kann es in der Startphase des Verfahrens erforderlich sein, der Phosphatierungslösung Nitrit, beispielsweise in einer Menge von 0,03 bis 0,2 g/l, zuzusetzen.Although - as explained above - nitrite is formed autocatalytically, it may be necessary to add nitrite to the phosphating solution, for example in an amount of 0.03 to 0.2 g / l, in the initial phase of the process.

Das erfindungsgemäße Verfahren dient insbesondere der Behandlung von Einzelteilen, deren Eisen- oder Stahloberfläche Legierungszusätze bis maximal 5 Gew.% aufweist.The method according to the invention is used in particular for the treatment of individual parts whose iron or steel surface has alloy additions of up to a maximum of 5% by weight.

Die einzelnen Komponenten der Phosphatierungslösung, wie Zink, Phosphat, Nitrat usw., werden meist, wie in der Phosphatiertechnik üblich, gemeinsam als saures Phosphatierkonzentrat vorgelöst und in dieser Form in die Phosphatierungslösung eingebracht. Die Bemessung der einzelnen Bestandteile erfolgt in der Weise, daß die geforderten Konzentrationsbereiche in der Phosphatierungslösung resultieren. Um das notwendige Verhältnis von Freier Säure zu Gesamtsäure einzustellen, müssen ggf. weitere Kationen aus der Alkali- und/oder Ammoniumgruppe mitverwendet werden. Ggf. kann auch Zinkoxid und/oder Zinkcarbonat, die der Phosphatierungslösung in Pulverform oder als wäßrige Aufschlämmung zugegeben werden, verwendet werden. Zur Ermittlung der Freien Säure bzw. Gesamtsäure werden jeweils 10 ml Badprobe mit n/10 NaOH gegen den ersten bzw. zweiten Umschlag der Phosphorsäure titriert, wobei als Indikator z.B. der Farbumschlag von Dimethylgelb (Freie Säure) bzw. Phenolphthalein (Gesamtsäure) dient. Die verbrauchten ml an n/10 NaOH entsprechen der Freien Säure bzw. der Gesamtsäure in Punkten.The individual components of the phosphating solution, such as zinc, phosphate, nitrate, etc., are usually, as is customary in phosphating technology, pre-dissolved together as an acidic phosphating concentrate and introduced into the phosphating solution in this form. The individual components are dimensioned in such a way that the required concentration ranges result in the phosphating solution. To set the necessary ratio of free acid to total acid, additional cations from the alkali and / or ammonium group may have to be used. Possibly. can also zinc oxide and / or zinc carbonate, which the Phosphating solution in powder form or as an aqueous slurry can be used. To determine the free acid or total acid, titrate 10 ml bath sample with n / 10 NaOH against the first or second change in phosphoric acid, using the color change of dimethyl yellow (free acid) or phenolphthalein (total acid), for example, as an indicator. The ml of n / 10 NaOH consumed correspond to the free acid or the total acid in points.

Der Gehalt an Nitritpunkten wird in der Regel nach der Saccharometermethode bestimmt. Hierzu werden 50 ml Badlösung mit 2 bis 5 g Sulfaminsäure versetzt. Die dabei gebildete Gasmenge in ml ist gleich der Punktzahl. Ein Gas-Punkt entspricht einem Gehalt von 46 mg/l NO₂ in der Phosphatierungslösung.The content of nitrite points is usually determined using the saccharometer method. For this, 50 ml of bath solution are mixed with 2 to 5 g of sulfamic acid. The amount of gas generated in ml is equal to the number of points. A gas point corresponds to a content of 46 mg / l NO₂ in the phosphating solution.

Der Kontakt der Einzelteile mit der Phosphatierungslösung erfolgt vorzugsweise im Tauchen oder Fluten.The contact of the individual parts with the phosphating solution is preferably carried out by dipping or flooding.

Die mit dem erfindungsgemäßen Verfahren erzeugten Phosphatüberzüge besitzen - je nach Badzusammensetzung, Behandlungszeit und Behandlungstemperatur - ein Schichtgewicht von 2,0 bis 10 g/m².Depending on the bath composition, treatment time and treatment temperature, the phosphate coatings produced by the process according to the invention have a layer weight of 2.0 to 10 g / m².

Eine bevorzugte Ausgestaltung der Erfindung besteht darin, die Einzelteile mit einer Phosphatierungslösung in Kontakt zu bringen, die 30 bis 60 g/l Zink 30 bis 50 g/l Phosphat (ber. als P₂O₅) 65 bis 100 g/l Nitrat 0,5 bis 3,0 g/l Fluorid und 0,02 bis 0,5 g/l Nickel enthält.A preferred embodiment of the invention consists in bringing the individual parts into contact with a phosphating solution 30 to 60 g / l zinc 30 to 50 g / l Phosphate (calculated as P₂O₅) 65 to 100 g / l nitrate 0.5 to 3.0 g / l Fluoride and 0.02 to 0.5 g / l nickel contains.

Die Bildungsgeschwindigkeit des Phosphatüberzuges kann erhöht werden, wenn entsprechend einer weiteren vorteilhaften Ausbildung der Erfindung die Einzelteile mit einer Phosphatierungslösung in Kontakt gebracht werden, die weitere beschleunigend wirkende Zusätze enthalten. Derartige beschleunigend wirkende Zusätze können beispielsweise Chlorat, Bromat, Peroxid, m-Nitrobenzolsulfonat, Nitrophenol oder Kombinationen hiervon sein.The rate of formation of the phosphate coating can be increased if, in accordance with a further advantageous embodiment of the invention, the individual parts are brought into contact with a phosphating solution which contains further accelerating additives. Such accelerating additives can be, for example, chlorate, bromate, peroxide, m-nitrobenzenesulfonate, nitrophenol or combinations thereof.

Eine weitere Verbesserung der Eigenschaften des Phosphatüberzuges ist erzielbar, wenn entsprechend einer weiteren vorteilhaften Ausgestaltung der Erfindung die Einzelteile mit einer Phosphatierungslösung in Kontakt gebracht werden, die zusätzliche 0,1 bis 10 g/l, vorzugsweise 1 bis 5 g/l, Mangan enthält.A further improvement in the properties of the phosphate coating can be achieved if, according to a further advantageous embodiment of the invention, the individual parts are brought into contact with a phosphating solution which contains an additional 0.1 to 10 g / l, preferably 1 to 5 g / l, of manganese.

Zur Erreichung niedriger Überzugsgewichte ist es entsprechend einer weiteren zweckmäßigen Ausführungsform der Erfindung vorteilhaft, die Einzelteile mit einer Phosphatierungslösung in Kontakt zu bringen, die zusätzlich 0,05 bis 3 g/l Weinsäure und/oder Zitronensäure enthält. Eine weitere vorteilhafte Ausgestaltung der Erfindung besteht darin, die Einzelteile vor der Phosphatierung zu reinigen, ggf. von Rost, Zunder und Phosphatschicht zu befreien und zu aktivieren sowie nach der Phosphatierung mit einer Nachspüllösung zu passivieren, wobei jeder der Verfahrensschritte während einer Dauer von 3 bis 30 sec durchgeführt wird.To achieve low coating weights, it is advantageous according to a further advantageous embodiment of the invention to bring the individual parts into contact with a phosphating solution which additionally contains 0.05 to 3 g / l tartaric acid and / or citric acid. Another advantageous embodiment of the invention is to clean the individual parts before phosphating, if necessary to free them of rust, scale and phosphate layer and to activate them, and to passivate them with a rinse solution after phosphating, each of the process steps lasting from 3 to 30 sec is carried out.

In diesem Zusammenhang hat es sich als vorteilhaft erwiesen, zur Reinigung mit einer alkalischen Reinigerlösung einer Temperatur im Bereich zwischen 60 und 100°C und einer Konzentration im Bereich von 20 bis 200 g/l zu arbeiten. Besonders günstige Reiniger sind solche auf Basis Natriumhydroxid, Glukonat, Phosphat mit einem zusätzlichen Gehalt von Carbonat, Silikat und Borat sowie Tensid. Der Einsatz des Reinigers erfolgt vorzugsweise im Spritzen.In this context, it has proven to be advantageous to work with an alkaline cleaning solution at a temperature in the range between 60 and 100 ° C. and a concentration in the range from 20 to 200 g / l for cleaning. Are particularly cheap cleaners those based on sodium hydroxide, gluconate, phosphate with an additional content of carbonate, silicate and borate and surfactant. The cleaner is preferably used in spraying.

Für die ggf. erforderliche Befreiung der Metalloberfläche von Rost, Zunder und Phosphatschichten haben sich Schwefelsäure- oder Phosphorsäurelösungen einer Temperatur im Bereich von 60 bis 100°C und einer Konzentration im Bereich von 5 bis 50 Gew.% als vorteilhaft erwiesen. Entsprechend einer bevorzugten Weiterbildung der Erfindung wird eine Schwefel- oder Phosphorsäure eingesetzt, die zusätzlich Eisen II- und/oder Eisen III-Ionen in einer Konzentration im Bereich von 1 bis 50 g/l enthält. Bei Anwendung derartiger Beizlösungen ist das erzielte Resultat besonders günstig.Sulfuric acid or phosphoric acid solutions at a temperature in the range from 60 to 100 ° C. and a concentration in the range from 5 to 50% by weight have proven to be advantageous for the removal of rust, scale and phosphate layers that may be required. According to a preferred development of the invention, a sulfuric or phosphoric acid is used which additionally contains iron II and / or iron III ions in a concentration in the range from 1 to 50 g / l. When using such pickling solutions, the result obtained is particularly favorable.

Im Anschluß an eine evtl. Entfernung von Rost, Zunder und Phosphatschichten empfiehlt es sich, die Einzelteile mit einer Lösung in Kontakt zu bringen, die die gleichen Säuren, jedoch in Konzentrationen im Bereich von 0,3 bis 3 Gew.% enthält, und eine Temperatur von lediglich 20 bis 50°C besitzt. Dadurch werden die nach dem Ausheben aus der Beizlösung auf den Metalloberflächen durch Antrocknung gebildeten Metallsalze leicht wieder in Lösung gebracht. Eine erneute Bildung derartiger Antrocknungen aus der sauren Spüllösung wird durch die im Vergleich zum Beizbad deutlich niedrigere Badtemperatur wirksam vermieden.Following a possible removal of rust, scale and phosphate layers, it is advisable to bring the individual parts into contact with a solution which contains the same acids, but in concentrations in the range from 0.3 to 3% by weight, and one Has temperature of only 20 to 50 ° C. As a result, the metal salts formed by drying on the metal surfaces after removal from the pickling solution are easily brought back into solution. A renewed formation of such drying out of the acidic rinsing solution is effectively avoided by the bath temperature, which is significantly lower than in the pickling bath.

Obgleich nicht zwingend erforderlich ist es doch vorteilhaft, die Einzelteile zwecks Ausbildung eines feinkristallinen Phosphatüberzuges in an sich bekannter Weise mit einer Dispersion, die eine wäßrige Aufschlämmung von Titanphosphat darstellt und ggf. zusätzlich kondensierte Phosphate enthält, zu aktivieren.Although not absolutely necessary, it is advantageous to activate the individual parts in order to form a finely crystalline phosphate coating in a manner known per se with a dispersion which is an aqueous slurry of titanium phosphate and, if appropriate, additionally contains condensed phosphates.

Nach der Phosphatierbehandlung wird üblicherweise mit Wasser gespült, ggf. nachgespült und bei Bedarf getrocknet.After the phosphating treatment, it is usually rinsed with water, rinsed if necessary and dried if necessary.

Zum Zweck der Verbesserung des Korrosionsschutzes sieht eine weitere vorteilhafte Ausführungsform der Erfindung vor, die Einzelteile mit einer chromhaltigen oder chromfreien Nachspüllösung zu passivieren. Ggf. kann auch mit einer Emulsion eines Korrosionsschutzöles nachbehandelt werden oder aber mit oder ohne Passivierung eine Lackierung erfolgen. Für den Fall, daß eine Kaltumformung beabsichtigt ist, kann auch eine Nachbehandlung mit einem Seifenbad erfolgen.For the purpose of improving the corrosion protection, a further advantageous embodiment of the invention provides for the individual parts to be passivated with a chrome-containing or chrome-free rinse solution. Possibly. can also be treated with an emulsion of an anti-corrosion oil, or it can be painted with or without passivation. In the event that cold forming is intended, an aftertreatment with a soap bath can also be carried out.

Die nach dem erfindungsgemäßen Verfahren erzeugten Phosphatüberzüge sind auf allen Gebieten, auf denen Phosphatüberzüge Verwendung finden, mit Vorteil einsetzbar. Besonders günstig ist jedoch das erfindungsgemäße Phosphatierverfahren bei der Verbesserung des Korrosionsschutzes im Falle einer anschließenden Lackierung.The phosphate coatings produced by the process according to the invention can be used advantageously in all fields in which phosphate coatings are used. However, the phosphating process according to the invention is particularly favorable in improving the corrosion protection in the case of a subsequent painting.

Die Erfindung wird anhand des nachfolgenden Beispiels beispielsweise und näher erläutert.The invention is illustrated by way of example and in more detail using the example below.

BEISPIELEXAMPLE

Tiefgezogene Automobilzubehörteile aus Stahl der Qualität C15 wurden wie folgt behandelt:
Reinigen: 69 % NaOH 24 % Natriumglukonat 4 % Na-Hexametaphosphat 3 % Tensid 100 g/l, 90 - 95°C, 10 sec Spritzen Spülen: Heißwasser, 80 - 90°C, 10 sec Tauchen
Beizen/Entzundern: 20 % H₃PO₄, 90 - 95°C, 10 sec Tauchen
Spülen: Phosphorsäure 1%, Raumtemperatur, 10 sec Tauchen
Spülen: Frischwasser, Raumtemperatur, 10 sec Tauchen
Aktivieren: 2 g/l Titanphosphat, 40°C, 10 sec Tauchen
Phosphatieren: 44 g/l Zn 6,4 g/l Na 0,05 g/l Ni 0,008 g/l Cu 83 g/l NO₃ 38 g/l P₂O₅ 1,6 g/l F Freie Säure: 29,5 Punkte
Gesamtsäure: 150 Punkte
Nitrit: 5 Punkte
85°C, 10 sec Tauchen
Spülen: Frischwasser, Raumtemperatur, 10 sec Tauchen
Nachspülen: 50°C, 0,1 g/l Cr(VI), 10 sec Tauchen
Spülen: Vollentsalztes Wasser, 10 sec Abbrausen, RaumtemperaturDeep-drawn automotive accessories made of steel of quality C15 were treated as follows:
Clean: 69% NaOH 24% Sodium gluconate 4% Na hexametaphosphate 3% Surfactant 100 g / l, 90 - 95 ° C, 10 sec spraying Rinse: hot water, 80 - 90 ° C, 10 sec immersion
Pickling / descaling: 20% H₃PO₄, 90 - 95 ° C, 10 sec immersion
Rinse: phosphoric acid 1%, room temperature, 10 sec immersion
Rinse: fresh water, room temperature, 10 sec immersion
Activate: 2 g / l titanium phosphate, 40 ° C, 10 sec immersion
Phosphating: 44 g / l Zn 6.4 g / l N / A 0.05 g / l Ni 0.008 g / l Cu 83 g / l NO₃ 38 g / l P₂O₅ 1.6 g / l F Free acid: 29.5 points
Total acidity: 150 points
Nitrite: 5 points
85 ° C, 10 sec diving
Rinse: fresh water, room temperature, 10 sec immersion
Rinse: 50 ° C, 0.1 g / l Cr (VI), 10 sec immersion
Rinse: Demineralized water, 10 sec spray, room temperature

Der nach diesem Arbeitsgang erzeugte Phosphatüberzug besaß ein Flächengewicht von 4 bis 5 g/m². Der Phosphatüberzug war gleichmäßig deckend und feinkristallin.The phosphate coating produced after this operation had a basis weight of 4 to 5 g / m². The phosphate coating was uniformly opaque and fine crystalline.

Claims (12)

1. Verfahren zur Erzeugung von Phosphatüberzügen auf mindestens teilweise Eisen- oder Stahloberflächen aufweisenden Einzelteilen aus Metall mittels wäßriger Phosphatierungslösungen, die Zink-, Phosphat-, Nitrat-und autokatalytisch gebildete Nitritionen enthalten sowie praktisch frei von Eisen II-Ionen sind, dadurch gekennzeichnet, daß man die Einzelteile bei einer Temperatur im Bereich von 60 bis 100°C für die Dauer von 3 bis 30 sec. mit einer Phosphatierungslösung in Kontakt bringt, die 10 bis 80 g/l Zink 12 bis 80 g/l Phosphat (ber. als P₂O₅) 40 bis 150 g/l Nitrat sowie zusätzlich 0,1 bis 5 g/l Fluorid 0,01 bis 10 g/l Nickel 0,001 bis 0,1 g/l Kupfer
enthält, in der das Verhältnis von Freier Säure zu Gesamtsäure auf (0,1 bis 0,3):1 eingestellt ist und die mindestens 80 Punkte Gesamtsäure aufweist.1. Process for the production of phosphate coatings on at least partially iron or steel surfaces having individual parts made of metal by means of aqueous phosphating solutions which contain zinc, phosphate, nitrate and autocatalytically formed nitrite ions and are practically free of iron II ions, characterized in that the individual parts are brought into contact with a phosphating solution at a temperature in the range from 60 to 100 ° C. for a period of 3 to 30 sec 10 to 80 g / l zinc 12 to 80 g / l Phosphate (calculated as P₂O₅) 40 to 150 g / l Nitrate as well as additional 0.1 to 5 g / l fluoride 0.01 to 10 g / l nickel 0.001 to 0.1 g / l copper
contains, in which the ratio of free acid to total acid is set to (0.1 to 0.3): 1 and which has at least 80 points total acid. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Einzelteile mit einer Phosphatierungslösung in Kontakt bringt, die 30 bis 60 g/l Zink 30 bis 50 g/l Phosphat (ber. als P₂O₅) 65 bis 100 g/l Nitrat 0,5 bis 3,0 g/l Fluorid und 0,02 bis 0,5 g/l Nickel
enthält.2. The method according to claim 1, characterized in that the individual parts are brought into contact with a phosphating solution which 30 to 60 g / l zinc 30 to 50 g / l Phosphate (calculated as P₂O₅) 65 to 100 g / l nitrate 0.5 to 3.0 g / l Fluoride and 0.02 to 0.5 g / l nickel
contains. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man die Einzelteile mit einer Phosphatierungslösung in Kontakt bringt, die weitere Beschleuniger enthält.3. The method according to claim 1 or 2, characterized in that the individual parts are brought into contact with a phosphating solution which contains further accelerators. 4. Verfahren nach Anspruch 1, 2 oder 3, dadurch gekennzeichnet, daß man die Einzelteile mit einer Phosphatierungslösung in Kontakt bringt, die zusätzlich 0,1 bis 10 g/l, vorzugsweise 1 bis 5 g/l, Mangan enthält.4. The method according to claim 1, 2 or 3, characterized in that the individual parts are brought into contact with a phosphating solution which additionally contains 0.1 to 10 g / l, preferably 1 to 5 g / l, of manganese. 5. Verfahren nach Anspruch 1, 2, 3 oder 4, dadurch gekennzeichnet, daß man die Einzelteile mit einer Phosphatierungslösung in Kontakt bringt, die zusätzlich 0,05 bis 3 g/l Weinsäure und/oder Zitronensäure enthält.5. The method according to claim 1, 2, 3 or 4, characterized in that the individual parts are brought into contact with a phosphating solution which additionally contains 0.05 to 3 g / l tartaric acid and / or citric acid. 6. Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man die Einzelteile vor der Phosphatierung reinigt, ggf. von Rost, Zunder und Phosphatschichten befreit, aktiviert und nach der Phosphatierung mit einer Nachspüllösung passiviert, wobei jeder dieser Verfahrensschritte während einer Dauer von 3 bis 30 sec. durchgeführt wird.6. The method according to one or more of claims 1 to 5, characterized in that the individual parts are cleaned before phosphating, if necessary freed of rust, scale and phosphate layers, activated and passivated after phosphating with a rinse solution, each of these process steps during a duration of 3 to 30 seconds. 7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß man die Einzelteile zur Reinigung mit einer alkalischen Reinigerlösung einer Temperatur im Bereich zwischen 60 und 100°C und einer Konzentration im Bereich von 20 bis 200 g/l in Kontakt bringt.7. The method according to claim 6, characterized in that the individual parts for cleaning with an alkaline cleaning solution at a temperature in the range between 60 and 100 ° C and a concentration in the range of 20 to 200 g / l in contact. 8. Verfahren nach Anspruch 6 oder 7, dadurch gekennzeichnet, daß man die Einzelteile mit einer Schwefelsäurelösung oder Phosphorsäurelösung einer Temperatur im Bereich von 60 bis 100°C und einer Konzentration im Bereich von 5 bis 50 Gew.% in Kontakt bringt.8. The method according to claim 6 or 7, characterized in that the individual parts are brought into contact with a sulfuric acid solution or phosphoric acid solution at a temperature in the range from 60 to 100 ° C and a concentration in the range from 5 to 50% by weight. 9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß man die Einzelteile mit einer Schwefel- oder Phosphorsäurelösung in Kontakt bringt, die zusätzlich Eisen II- und/oder Eisen III-Ionen einer Konzentration im Bereich von 1 bis 50 g/l enthält.9. The method according to claim 8, characterized in that the individual parts are brought into contact with a sulfuric or phosphoric acid solution which additionally contains iron II and / or iron III ions at a concentration in the range from 1 to 50 g / l. 10. Verfahren nach Anspruch 8 oder 9, dadurch gekennzeichnet, daß man die Einzelteile im Anschluß an die Behandlung mit Schwefel- oder Phosphorsäurelösung mit einer Lösung in Kontakt bringt, die eine der Säuren in einer Konzentration im Bereich von 0,3 bis 3 Gew.% enthält und eine Temperatur von 20 bis 50°C besitzt.10. The method according to claim 8 or 9, characterized in that one brings the individual parts following the treatment with sulfuric or phosphoric acid solution in contact with a solution containing one of the acids in a concentration in the range of 0.3 to 3 wt. % contains and has a temperature of 20 to 50 ° C. 11. Verfahren nach einem oder mehreren der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß man die Einzelteile mit einer Dispersion, die eine wäßrige Aufschlämmung von Titanphosphat darstellt und ggf. zusätzlich kondensierte Phosphate enthält, aktiviert.11. The method according to one or more of claims 1 to 10, characterized in that the individual parts are activated with a dispersion which is an aqueous slurry of titanium phosphate and optionally additionally contains condensed phosphates. 12. Verfahren nach einem oder mehreren der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß man die Einzelteile nach Aufbringung des Phosphatüberzuges mit einer chromhaltigen oder chromfreien Nachspüllösung passiviert.12. The method according to one or more of claims 1 to 11, characterized in that the individual parts are passivated after application of the phosphate coating with a chromium-containing or chromium-free rinse solution.
EP89200142A 1988-02-03 1989-01-24 Process for applying phosphate coatings to metals Expired - Lifetime EP0327153B1 (en)

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DE3803068 1988-02-03

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EP (1) EP0327153B1 (en)
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ES2058464T3 (en) 1994-11-01
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JPH01259180A (en) 1989-10-16
EP0327153A3 (en) 1990-04-25
CA1330515C (en) 1994-07-05
JP2713334B2 (en) 1998-02-16
DE58905074D1 (en) 1993-09-09

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