EP0056881B1 - Method of phosphating metals - Google Patents

Method of phosphating metals Download PDF

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Publication number
EP0056881B1
EP0056881B1 EP81201244A EP81201244A EP0056881B1 EP 0056881 B1 EP0056881 B1 EP 0056881B1 EP 81201244 A EP81201244 A EP 81201244A EP 81201244 A EP81201244 A EP 81201244A EP 0056881 B1 EP0056881 B1 EP 0056881B1
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EP
European Patent Office
Prior art keywords
solutions
metal surfaces
value
contact
brought
Prior art date
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EP81201244A
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German (de)
French (fr)
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EP0056881A1 (en
Inventor
Dieter Hauffe
Gerhard Müller
Werner Dr. Dipl.-Chem. Rausch
Josef Rothkegel
Gudrun Volling
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GEA Group AG
Continentale Parker Ste
Continentale Parker SA
Original Assignee
Metallgesellschaft AG
Continentale Parker Ste
Continentale Parker SA
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Priority to AT81201244T priority Critical patent/ATE17955T1/en
Publication of EP0056881A1 publication Critical patent/EP0056881A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—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
    • 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
    • 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

Definitions

  • the invention relates to a process for phosphating metals, in particular iron and steel, with aqueous acidic, chlorate-containing zinc phosphate solutions at temperatures from 30 to 60 ° C. and to the use thereof for preparing the metal surfaces for electrocoating.
  • the reduced zinc content compared to the usual phosphating baths leads to improved thin and uniform phosphate coatings, which are very adhesive and durable and are particularly suitable as a basis for the subsequent electrocoating. In this process, it has proven to be very advantageous to additionally use nitrite in order to achieve the desired results.
  • DE-OS 30 04 927 discloses a process for phosphating metals which are subsequently electroplated, in which acidic aqueous zinc phosphate solutions are also used.
  • the solutions contain nitrite ions and / or aromatic nitro compounds as accelerators.
  • the phosphating is carried out in a special immersion / spray process.
  • the preferred embodiment of the process also provides for baths containing nitrite to be used.
  • nitrite which is preferably used leads to the formation of nitrous gases which are known to be toxic and have an unpleasant smell. Suction measures are therefore essential to ensure occupational safety.
  • the object of the invention is to provide a method which does not have the disadvantages of the known methods, requires little heating energy because of the low application temperatures and is simple to carry out.
  • the method according to the invention is intended in particular for the treatment of iron and steel. However, it is also suitable for the phosphating of zinc and aluminum materials as well as for steel with coatings made of zinc, zinc alloys, aluminum and aluminum alloys produced using a wide variety of processes.
  • the metal surfaces can be treated by spraying, flooding and also immersion. However, it is also with combined working methods, e.g. B. splash-dip-spray, flood-dive and the like applicable.
  • the contact times for the phosphating solution with the metal surface are in the usual range and can, for. B. for spraying 45 sec to 3 min, for diving 2 to 5 min and for syringe diving 20 sec spraying, 3 min diving.
  • the bath temperatures are 30 to 60 ° C. The lower the bath temperature, the longer i. a. the contact time.
  • the addition of nickel to the bath generally has a favorable effect on the rate of phosphating, the formation of layers on steel surfaces that are difficult to phosphate, on the phosphating of zinc surfaces and on the corrosion protection properties.
  • the ratio of free P 2 O 5 to total P 2 O 5 in the bath must be kept between (0.005 to 0.06): 1 in order to produce uniformly covering phosphate layers.
  • the phosphating rate becomes slower, at the same time the quality of the phosphate layers decreases.
  • a Falling below the specified values leads to excessive precipitation of zinc phosphate sludge and is undesirable for this reason alone.
  • the low values of the ratio of free P 2 O 5 to total P 2 O 5 (acid ratio) in the range according to the invention apply to the lower bath temperatures (low Zn / P 2 0 5 ratio and low total concentration); the higher acid ratios relate to higher bath temperatures (higher Zn / P 2 0 5 ratios and higher total concentrations).
  • the optimal acid ratio for a particular bath of the invention can easily be estimated or determined by experiment.
  • the weight ratio of free P 2 O 5 to total P 2 O 5 is preferably set to (0.005 to 0.03): 1, in particular (0.005 to 0.027): 1 for the temperature range from 30-45 ° C. and to (0, 03 to 0.06): 1 set for the temperature range of 45-60 ° C.
  • One embodiment of the invention consists in bringing the metal surfaces into contact with solutions which contain 0.8 to 1.2 g / l of Zn.
  • phosphating solutions which contain up to 0.7 g / l, in particular 0.2 to 0.5 g / l, of Mn.
  • the use of manganese has proven to be particularly beneficial in phosphating in the low temperature range.
  • the layer formation can be improved by adding simple and / or complex fluorides.
  • the solutions for reducing the phosphate layer weight can also contain compounds known per se, such as hydroxycarboxylic acids (e.g. tartaric acid, citric acid), polyphosphates (e.g. tripolyphosphate, hexametaphosphate).
  • hydroxycarboxylic acids e.g. tartaric acid, citric acid
  • polyphosphates e.g. tripolyphosphate, hexametaphosphate.
  • the necessary acid ratio is essentially set only with alkali metal ions.
  • Other cations e.g. B. calcium, copper and cobalt, however, should only be present in minor amounts.
  • the weight per unit area of the phosphate layers produced by the process according to the invention is generally in the range between 0.8 and 4 g / m 2 .
  • activating agents e.g. B. on titanium phosphate basis, in the pre-rinse bath or in / the last cleaning stage.
  • the phosphate layers produced by the method according to the invention are suitable in principle for all types of use of the phosphate layers known to date.
  • the layers bring about an unusually strong improvement in the resistance of the coating film against the infiltration of the coating in the event of corrosive stress and a significant increase in the adhesion of the coating to the metallic substrate.
  • the sheets were rinsed with water, rinsed with a rinse solution containing chromic acid and then coated with anodic and cathodic electrocoat.
  • the application tests such as salt spray test, condensation test, rockfall text and outdoor exposure, led to very good results.

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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)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Paints Or Removers (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

A composition for the phosphatizing of metals, particularly iron and steel, which comprises an aqueous acidic, chlorate-containing zinc phosphate solution which contains from 0.5 to 1.5 g/liter Zn from 0.4 to 1.3 g/liter Ni from 10 to 26 g/liter P2O5 from 0.8 to 5 g/liter Cl03 and in which no nitrite is added, and in which the weight ratio of Zn to Ni shall be adjusted to a value of 1: (from 0.5 to 1.5), that of Zn to P2O5 to a value of 1: (from 8 to 85) and that of free P2O5 to a value of from (0.005 (at about 30 degrees C.) to 0.06 (at about 60 degrees C.)): 1. The composition is particularly useful in processes for the preparation of metal surfaces for electrophoretic coating, particularly for cathodic immersion coating.

Description

Die Erfindung betrifft ein Verfahren zur Phosphatierung von Metallen, insbesondere Eisen und Stahl, mit wäßrigen sauren, chlorathaltigen Zinkphosphatlösungen bei Temperaturen von 30 bis 60 °C sowie dessen Anwendung zur Vorbereitung der Metalloberflächen für die Elektrotauchlackierung.The invention relates to a process for phosphating metals, in particular iron and steel, with aqueous acidic, chlorate-containing zinc phosphate solutions at temperatures from 30 to 60 ° C. and to the use thereof for preparing the metal surfaces for electrocoating.

In der DE-OS 22 32 067 werden wäßrige saure Phosphatierlösungen mit einem Gewichtsverhältnis von Zn : P04 = 1 : (12 bis 110) zur Oberflächenbehandlung von Metallen, insbesondere Eisen und Stahl, beschrieben. Der gegenüber den üblichen Phosphatierbädern verringerte Zinkgehalt führt zu verbesserten dünnen und gleichmäßigen Phosphatüberzügen, die sehr haftfest und beständig und als Grundlage für die anschließende Elektrotauchlackierung besonders geeignet sind. Bei diesem Verfahren hat es sich zur Erzielung der gewünschten Ergebnisse als sehr vorteilhaft erwiesen, zusätzlich Nitrit zu verwenden.DE-OS 22 32 067 describes aqueous acid phosphating solutions with a weight ratio of Zn: P0 4 = 1: (12 to 110) for the surface treatment of metals, in particular iron and steel. The reduced zinc content compared to the usual phosphating baths leads to improved thin and uniform phosphate coatings, which are very adhesive and durable and are particularly suitable as a basis for the subsequent electrocoating. In this process, it has proven to be very advantageous to additionally use nitrite in order to achieve the desired results.

Aus der DE-OS 30 04 927 ist ein Verfahren zur Phosphatierung von Metallen, die anschließend elektroplattiert werden bekannt, bei dem ebenfalls säure wäßrige Zinkphosphatlösungen eingesetzt werden. Als Beschleuniger enthalten die Lösungen Nitritionen und/oder aromatische Nitroverbindungen. Die Durchführung der Phosphatierung erfolgt in einem speziellen Tauch-/Spritz-Verfahren.DE-OS 30 04 927 discloses a process for phosphating metals which are subsequently electroplated, in which acidic aqueous zinc phosphate solutions are also used. The solutions contain nitrite ions and / or aromatic nitro compounds as accelerators. The phosphating is carried out in a special immersion / spray process.

Schließlich ist es aus dem nach Artikel 54 (3) zu berücksichtigenden Stand der Technik gemäß EP-A1-39093 bekannt, Metalle, insbesondere Eisen und Stahl, mit wäßrigen sauren Zinkphosphatlösungen zu behandeln, die 0,3 bis 1,3 g/l Zn, 0 bis 1,3 g/I Ni, 10 bis 26 g/l P205, 1 bis 6 g/I CIOa und 5 bis 25 g/l N03 enthalten, in denen das Gewichtsverhältnis von Zn zu Ni zwischen 1 : (0 bis 1,5) und das Gewichtsverhältnis von Zn zu P205 zwischen 1 : (9 bis 85) eingestellt ist und in denen das für die Phosphatierung geforderte Verhältnis von Freiem- zu Gesamt-P2O5 im wesentlichen durch Alkalimetallionen eingestellt ist.Finally, it is known from the prior art according to EP-A1-39093 to be taken into account in accordance with Article 54 (3) to treat metals, in particular iron and steel, with aqueous acidic zinc phosphate solutions which contain 0.3 to 1.3 g / l Zn , 0 to 1.3 g / I Ni, 10 to 26 g / l P 2 0 5 , 1 to 6 g / I CIO a and 5 to 25 g / l N0 3 , in which the weight ratio of Zn to Ni between 1: (0 to 1.5) and the weight ratio of Zn to P 2 0 5 is set between 1: (9 to 85) and in which the ratio of free to total P 2 O 5 required for the phosphating is essentially is adjusted by alkali metal ions.

Neben dem vergleichsweise hohen Nitratgehalt sieht auch hier die bevorzugte Ausgestaltung des Verfahrens vor, Nitrit enthaltende Bäder einzusetzen.In addition to the comparatively high nitrate content, the preferred embodiment of the process also provides for baths containing nitrite to be used.

Nachteilig bei den bekannten Verfahren ist, daß vorzugsweise eingesetzte Nitrit zur Bildung von nitrosen Gasen, die bekanntlich toxisch und geruchsbelästigend sind, führt. Es sind daher Absaugemaßnahmen zur Gewährleistung der Arbeitssicherheit unerläßlich.A disadvantage of the known processes is that nitrite which is preferably used leads to the formation of nitrous gases which are known to be toxic and have an unpleasant smell. Suction measures are therefore essential to ensure occupational safety.

Aufgabe der Erfindung ist es, ein Verfahren bereitzustellen, das die Nachteile der bekannten Verfahren nicht aufweist, wegen der niedrigen Anwendungstemperaturen wenig Heizenergie benötigt und einfach durchführbar ist.The object of the invention is to provide a method which does not have the disadvantages of the known methods, requires little heating energy because of the low application temperatures and is simple to carry out.

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

Figure imgb0001
enthalten, denen kein Nitrit zugesetzt wird und in denen das Gewichtsverhältnis von

  • Zn zu Ni auf einen Wert zwischen 1 : (0,5 bis 1,5),
  • Zn zu P205 auf einen Wert von maximal 1 : 8 und
  • Freiem P2O5 zu Gesamt-P2O5 auf einen Wert zwischen (0,005 (bei ca. 30 °C) bis 0,06 (bei ca. 60 °C)) : 1 eingestellt ist.
The object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the metal surfaces are brought into contact with solutions which
Figure imgb0001
 contain, to which no nitrite is added and in which the weight ratio of
  • Zn to Ni to a value between 1: (0.5 to 1.5),
  • Zn to P 2 0 5 to a maximum value of 1: 8 and
  • Free P 2 O 5 to total P 2 O 5 is set to a value between (0.005 (at approx. 30 ° C) to 0.06 (at approx. 60 ° C)): 1.

Das erfindungsgemäße Verfahren ist insbesondere für die Behandlung von Eisen- und Stahl gedacht. Es eignet sich jedoch auch für die Phosphatierung von Zink- und Aluminiumwerkstoffen sowie für Stahl mit nach den verschiedensten Verfahren erzeugten Überzügen aus Zink, Zinklegierungen, Aluminium und Aluminiumlegierungen.The method according to the invention is intended in particular for the treatment of iron and steel. However, it is also suitable for the phosphating of zinc and aluminum materials as well as for steel with coatings made of zinc, zinc alloys, aluminum and aluminum alloys produced using a wide variety of processes.

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

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

Die Badtemperaturen betragen 30 bis 60 °C. Je niedriger die Badtemperatur, um so länger muß auch i. a. die Kontaktzeit sein.The bath temperatures are 30 to 60 ° C. The lower the bath temperature, the longer i. a. the contact time.

Die Zugabe von Nickel zum Bad wirkt sich in der Regel günstig auf die Phosphatiergeschwindigkeit, die Schichtausbildung auf schwerer phosphatierbaren Stahloberflächen, auf die Phosphatierung von Zinkoberflächen und auf die Korrosionsschutzeigenschaften aus.The addition of nickel to the bath generally has a favorable effect on the rate of phosphating, the formation of layers on steel surfaces that are difficult to phosphate, on the phosphating of zinc surfaces and on the corrosion protection properties.

Von ausschlaggebender Bedeutung für die hohe Qualität der nach dem erfindungsgemäßen Verfahren erzeugten Phosphatschichten ist die Einhaltung des Konzentrationsverhältnisses zwischen Zn und P205.Of crucial importance for the high quality of the phosphate layers produced by the process according to the invention is compliance with the concentration ratio between Zn and P 2 0 5 .

Weiterhin muß das Verhältnis von Freiem P2O5 zu Gesamt-P2O5 im Bad zwischen (0,005 bis 0,06): 1 gehalten werden, um gleichmäßig deckende Phosphatschichten zu erzeugen. Bei höheren Werten wird die Phosphatiergeschwindigkeit geringer, gleichzeitig nimmt die Qualität der Phosphatschichten ab. Eine Unterschreitung der angegebenen Werte führt zu übermäßiger Ausfällung von Zinkphosphatschlamm und ist schon aus diesem Grunde unerwünscht.Furthermore, the ratio of free P 2 O 5 to total P 2 O 5 in the bath must be kept between (0.005 to 0.06): 1 in order to produce uniformly covering phosphate layers. At higher values, the phosphating rate becomes slower, at the same time the quality of the phosphate layers decreases. A Falling below the specified values leads to excessive precipitation of zinc phosphate sludge and is undesirable for this reason alone.

Die niedrigen Werte des Verhältnisses von Freiem P2O5 zu Gesamt-P2O5 (Säureverhältnis) im erfindungsgemäßen Bereich gelten für die niedrigeren Badtemperaturen (niedriges Verhältnis Zn/P205 und niedrige Gesamtkonzentration) ; die höheren Säureverhältnisse beziehen sich auf höhere Badtemperaturen (höhere Verhältnisse Zn/P205 und höhere Gesamtkonzentrationen). Anhand dieser allgemeinen Aussagen über die Abhängigkeit des Säureverhältnisses kann das für ein bestimmtes Bad der Erfindung optimale Säureverhältnis leicht abgeschätzt oder durch Versuche ermittelt werden.The low values of the ratio of free P 2 O 5 to total P 2 O 5 (acid ratio) in the range according to the invention apply to the lower bath temperatures (low Zn / P 2 0 5 ratio and low total concentration); the higher acid ratios relate to higher bath temperatures (higher Zn / P 2 0 5 ratios and higher total concentrations). On the basis of these general statements about the dependence of the acid ratio, the optimal acid ratio for a particular bath of the invention can easily be estimated or determined by experiment.

Zur Bestimmung von Freiem- und Gesamt-P2O5 können u. a. folgende Methoden dienen (siehe z. B. Rausch : Die Phosphatierung von Metallen, Leuze-Verlag/Saulgau, 1974, Seite 274-277) :

  • Freies P2O5 :
  • 10 ml Badlösung titrieren bis zum Umschlag der 1. H3PO4-Stufe mit n/10 NaOH.
  • 1 ml verbrauchte n/10 NaOH entspricht 0,71 g Freies P205.
  • Störungen durch hydrolysierendes Zinkphosphat können z. B. durch Zugabe von K3(CO(CN)6), Störungen durch hydrolysierendes SiF6 z. B. durch Zugabe von KCI eliminiert werden.
The following methods can be used to determine free and total P 2 O 5 (see, for example, Rausch: The Phosphating of Metals, Leuze-Verlag / Saulgau, 1974, pages 274-277):
  • Free P 2 O 5 :
  • Titrate 10 ml bath solution until the 1st H 3 PO 4 stage changes with n / 10 NaOH.
  • 1 ml of used n / 10 NaOH corresponds to 0.71 g of free P 2 0 5 .
  • Disruptions caused by hydrolyzing zinc phosphate can e.g. B. by adding K 3 (CO (CN) 6 ), interference by hydrolyzing SiF 6 z. B. can be eliminated by adding KCI.

Gesamt-P2O5:

  • 10 ml Badlösung werden nach Zugabe von neutralem Kaliumoxalat von der 1. bis zur 2. Stufe der H3P04 mit n/10 NaOH titriert.
  • 1 ml verbrauchte n/10 NaOH entspricht 0,71 g/I Gesamt-P205.
  • Mögliche Fehler bei der Einstellung der 1. H3PO4-Stufe können, wie bei dem Freien P2O5 angegeben, z. B. durch Zugabe von K3(Co(CN)6 bzw. KCI vermieden werden.
Total P 2 O 5 :
  • After the addition of neutral potassium oxalate, 10 ml bath solution are titrated from the 1st to the 2nd stage of H 3 PO 4 with n / 10 NaOH.
  • 1 ml of used n / 10 NaOH corresponds to 0.71 g / I total P 2 0 5 .
  • Possible errors in the setting of the 1st H 3 PO 4 stage can, as stated for the free P 2 O 5 , e.g. B. can be avoided by adding K 3 (Co (CN) 6 or KCI.

Vorzugsweise wird das Gewichtsverhältnis von Freiem P2O5 zu Gesamt-P2O5 auf (0,005 bis 0,03) : 1, insbesondere (0,005 bis 0,027) : 1 für den Temperaturbereich von 30-45 °C und auf (0,03 bis 0,06) : 1 für den Temperaturbereich von 45-60 °C eingestellt.The weight ratio of free P 2 O 5 to total P 2 O 5 is preferably set to (0.005 to 0.03): 1, in particular (0.005 to 0.027): 1 for the temperature range from 30-45 ° C. and to (0, 03 to 0.06): 1 set for the temperature range of 45-60 ° C.

Eine Ausgestaltung der Erfindung besteht darin, die Metalloberflächen mit Lösungen in Berührung zu bringen, die 0,8 bis 1,2 g/I Zn enthalten.One embodiment of the invention consists in bringing the metal surfaces into contact with solutions which contain 0.8 to 1.2 g / l of Zn.

Weiterhin ist es vorteilhaft, Phosphatierungslösungen einzusetzen, die bis 0,7 g/I, insbesondere 0,2 bis 0,5 g/l Mn enthalten. Die Mitverwendung von Mangan hat sich insbesondere bei der Phosphatierung im niedrigen Temperaturbereich als günstig erwiesen.It is also advantageous to use phosphating solutions which contain up to 0.7 g / l, in particular 0.2 to 0.5 g / l, of Mn. The use of manganese has proven to be particularly beneficial in phosphating in the low temperature range.

Weitere vorteilhafte Ausgestaltungen der Erfindung bestehen darin, die Metalloberflächen mit Lösungen in Berührung zu bringen, in denen der Chloratgehalt 1 bis 3 g/I beträgt bzw. die als Zusatz bis 2 g/I, vorzugsweise mindestens 0,1 g/I, Nitroverbindungen enthalten. Als zu verwendende organische aromatische Nitroverbindung hat sich insbesondere Na-m-nitrobenzolsulfonat bewährt. Es sind jedoch auch andere Vertreter dieser Stoffklasse, z. B. Nitroresorcin oder Nitrobenzoesäure, einsetzbar.Further advantageous refinements of the invention consist in bringing the metal surfaces into contact with solutions in which the chlorate content is 1 to 3 g / l or which contain up to 2 g / l, preferably at least 0.1 g / l, of nitro compounds . Na-m-nitrobenzenesulfonate has proven particularly useful as the organic aromatic nitro compound to be used. However, there are also other representatives of this class of substances, e.g. B. nitroresorcinol or nitrobenzoic acid can be used.

Insbesondere bei der Mitbehandlung von Zink und/oder Aluminiumflächen, aber auch bei der alleinigen Behandlung von Eisen und Stahl kann die Schichtbildung durch Zusätze von einfachen und/oder komplexen Fluoriden verbessert werden.In particular when treating zinc and / or aluminum surfaces, but also when treating iron and steel alone, the layer formation can be improved by adding simple and / or complex fluorides.

Ferner können die Lösungen zur Reduzierung des Phosphatschichtgewichtes hierfür an sich bekannte Verbindungen, wie Hydroxycarbonsäuren (z. B. Weinsäure, Zitronensäure), Polyphosphate (z. B. Tripolyphosphat, Hexametaphosphat) enthalten.The solutions for reducing the phosphate layer weight can also contain compounds known per se, such as hydroxycarboxylic acids (e.g. tartaric acid, citric acid), polyphosphates (e.g. tripolyphosphate, hexametaphosphate).

Bei gegebener Konzentration an Zn, Ni, P2O5, ClO3, ggf. organischer aromatischer Nitroverbindung und Mn und NO3 erfolgt die Einstellung des notwendigen Säureverhältnisses im wesentlichen nur mit Alkalimetallionen. Andere Kationen, z. B. Calcium, Kupfer und Kobalt, sollen dagegen nur in untergeordneten Mengen vorhanden sein.For a given concentration of Zn, Ni, P 2 O 5 , ClO 3 , possibly organic aromatic nitro compound and Mn and NO 3 , the necessary acid ratio is essentially set only with alkali metal ions. Other cations, e.g. B. calcium, copper and cobalt, however, should only be present in minor amounts.

Das Flächengewicht der nach dem erfindungsgemäßen Verfahren erzeugten Phosphatschichten liegt i. a. im Bereich zwischen 0,8 und 4 g/m2. Um besonders dünne, feinkristalline Schichten zu erzeugen, empfiehlt sich die Anwendung von Aktivierungsmitteln, z. B. auf Titanphosphatbasis, im Vorspülbad oder in/der letzten Reinigerstufe.The weight per unit area of the phosphate layers produced by the process according to the invention is generally in the range between 0.8 and 4 g / m 2 . In order to produce particularly thin, fine crystalline layers, the use of activating agents, e.g. B. on titanium phosphate basis, in the pre-rinse bath or in / the last cleaning stage.

Die mit dem erfindungsgemäßen Verfahren erzeugten Phosphatschichten eignen sich im Prinzip für alle Anwendungsarten der bis heute bekannten Phosphatschichten. In Verbindung mit einer Lackierung bewirken die Schichten eine ungewöhnlich starke Verbesserung der Beständigkeit des Lackfilmes gegen Lackunterwanderung bei korrosiver Beanspruchung sowie eine erhebliche Erhöhung der Lackhaftung zum metallischen Untergrund. Diese Vorteile werden besonders bei der Elektrotauchlackierung, insbesondere bei der kathodischen Elektrotauchlackierung deutlich, weshalb das Verfahren vorzugsweise als Vorbereitung für diese Lackierart angewendet wird. Praktische Anwendung findet das erfindungsgemäße Verfahren z. B. für die Phosphatierung von Autokarosserien.The phosphate layers produced by the method according to the invention are suitable in principle for all types of use of the phosphate layers known to date. In conjunction with a coating, the layers bring about an unusually strong improvement in the resistance of the coating film against the infiltration of the coating in the event of corrosive stress and a significant increase in the adhesion of the coating to the metallic substrate. These advantages are particularly evident in electrocoating, in particular in cathodic electrocoating, which is why the method is preferably used as a preparation for this type of painting. The method according to the invention finds practical application e.g. B. for the phosphating of car bodies.

Das erfindungsgemäße Verfahren wird anhand der folgenden Beispiele beispielsweise und näher erläutert.The process according to the invention is explained, for example and in more detail, using the following examples.

BeispieleExamples

Mit mildalkalischem, aktivierendem Reiniger entfettete Bleche aus Stahl, verzinktem Stahl und Aluminium wurden mit den in der folgenden Tabelle aufgeführten Lösungen behandelt.
(Siehe Tabelle Seite 4 f.)

Figure imgb0002
Steel, galvanized steel and aluminum sheets degreased with mildly alkaline, activating cleaner were treated with the solutions listed in the following table.
(See table on page 4 f.)
Figure imgb0002

Die Bleche wurden mit Wasser gespült, mit chromsäurehaltiger Nachspüllösung nachgespült und danach mit anodischem sowie kathodischem Elektrotauchlack beschichtet. Die anwendungstechnischen Prüfungen, wie Salzsprühtest, Schwitzwassertest, Steinschlagtext und Freibewitterung, führten zu sehr guten Ergebnissen.The sheets were rinsed with water, rinsed with a rinse solution containing chromic acid and then coated with anodic and cathodic electrocoat. The application tests, such as salt spray test, condensation test, rockfall text and outdoor exposure, led to very good results.

Claims (8)

1. Method of phosphating metals, in particular iron and steel, by means of aqueous acidic, chlorate containing zinc phosphate solutions at temperatures of 30 to 60 °C, characterized in that the metal surfaces are brought in contact with solutions containing
Figure imgb0004
to which no nitrite is added and in which the weight ratios are adjusted of Zn : Ni to a value between 1 : (0,5 to 1,5) of Zn : P2O5 to a value of utmost 1 : 8 and of free P2O5 to total P2O5 to a value between [(0,005 (at about 30 °C) to 0,06 (at about 60 °C)] : 1.
2. Method according to claim 1, characterized in that the metal surfaces are brought in contact with solutions, in which the weight ratio of free P205 to total P205 at bath temperatures of 30 to 45 °C is adjusted to a value between (0,005 to 0,03) : 1, preferably to a value between (0,005 to 0,027) : 1, and at bath temperatures of 45 to 60 °C is adjusted to a value between (0,03 to 0,06) : 1.
3. Method according to claim 1 or 2, characterized in that the metal surfaces are brought in contact with solutions, which contain 0,8 to 1,2 g/I Zn.
4. Method according to claim 1, 2 or 3 characterized in that the metal surfaces are brought in contact with solutions, which contain up to 0,7 g/I Mn, preferably 0,2 to 0,4 g/I Mn.
5. Method according to claim 1, 2, 3 or 4, characterized in that the metal surfaces are brought in contact with solutions, which contain 1 to 3 g/l ClO3.
6. Method according to one or more of the claims 1 to 5, characterized in that the metal surfaces are brought in contact with solutions, which contain up to 2 g/l, preferably at least 0,1 g/I, aromatic nitro- compound.
7. Method according to one or more of the claims 1 to 6, characterized in that the metal surfaces are brought in contact with solutions, which contain in addition simple or complex fluorides.
8. Use of the method according to one or more of the claims 1 to 7 for the preparation of metal surfaces prior to electro-immersion-painting, particularly prior to cathodic electro-immersion-painting.
EP81201244A 1981-01-22 1981-11-03 Method of phosphating metals Expired EP0056881B1 (en)

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DE19813101866 DE3101866A1 (en) 1981-01-22 1981-01-22 METHOD FOR PHOSPHATING METALS
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IT8219228A0 (en) 1982-01-21
CA1183430A (en) 1985-03-05
ATE17955T1 (en) 1986-02-15
PT74310B (en) 1983-08-08
GB2093075A (en) 1982-08-25
DE3101866A1 (en) 1982-08-26
EP0056881A1 (en) 1982-08-04
GB2093075B (en) 1985-05-22
IT1190666B (en) 1988-02-24
DE3173781D1 (en) 1986-03-27
US4389260A (en) 1983-06-21
PT74310A (en) 1982-02-01
ES508885A0 (en) 1983-04-01

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