EP0154367A2 - Process for phosphatizing metals - Google Patents

Process for phosphatizing metals Download PDF

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Publication number
EP0154367A2
EP0154367A2 EP85200192A EP85200192A EP0154367A2 EP 0154367 A2 EP0154367 A2 EP 0154367A2 EP 85200192 A EP85200192 A EP 85200192A EP 85200192 A EP85200192 A EP 85200192A EP 0154367 A2 EP0154367 A2 EP 0154367A2
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EP
European Patent Office
Prior art keywords
phosphating
activator
steel
phosphating solution
contact
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP85200192A
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German (de)
French (fr)
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EP0154367A3 (en
EP0154367B1 (en
Inventor
Gerhard Müller
Werner Dr. Rausch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GEA Group AG
Continentale Parker Ste
Continentale Parker SA
Original Assignee
Metallgesellschaft AG
Continentale Parker Ste
Continentale Parker SA
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Application filed by Metallgesellschaft AG, Continentale Parker Ste, Continentale Parker SA filed Critical Metallgesellschaft AG
Priority to AT85200192T priority Critical patent/ATE37203T1/en
Publication of EP0154367A2 publication Critical patent/EP0154367A2/en
Publication of EP0154367A3 publication Critical patent/EP0154367A3/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
    • C23C22/23—Condensed phosphates
    • 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
    • C23C22/17—Orthophosphates containing zinc cations containing also organic acids
    • 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 method for phosphating metals, in particular steel and galvanized steel, by spraying using an aqueous, acid accelerator, zinc and optionally nickel-containing phosphating solution and its use before 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.
  • PCT publication WO 84/00386 discloses phosphating solutions with 0.2 to 0.6 g / 1 Zn and Ni in a ratio of 5.2 to 16 mol Ni to 1 mol Zn, the phosphate layers with a particularly high resistance to Have resolution in alkali.
  • the Japanese patent publication (according to Chemical Abstracts 99/216843 u) 58 144 477 describes spray phosphating solutions for steel containing 0.1 to 0.5 g / 1 Zn, 15 to 30 g / 1 phosphate and 0.01 to 0.2 g / 1 nitrite.
  • the phosphate layers thus produced are particularly suitable for pretreatment subsequent cathodic electrodeposition coating is well suited.
  • the object of the invention is to provide a process which does not have the disadvantages of the known processes and which forms uniform, uniform phosphate layers with improved paint adhesion.
  • 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 an aqueous acidic phosphating solution which and contains at least one activator from the group formate, nitrilotriacetate, trichloroacetate and ethylenediaminetetraacetate.
  • the method according to the invention is intended in particular for the treatment of iron, steel and galvanized steel. However, it is also suitable for the phosphating of zinc alloys, Aluminum and aluminum alloys.
  • the treatment is carried out by spraying, the contact times for iron, steel and aluminum being 90 to 240 seconds, for example, and zinc 5 to 240 seconds.
  • the method according to the invention is mostly used at bath temperatures between 30 and 60 ° C.
  • the addition of nickel to the phosphating bath generally has a favorable effect on the phosphating speed, 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 phosphating solutions to be used in the process according to the invention preferably contain alkali ions, for example Na, K, Li, NH 4 and, if necessary, further anions, for example N0 3 , Cl, 8 ° 4.
  • the baths can also contain other cations known in phosphating technology, such as Co, Cu, Mn, Ca, Mg and Fe.
  • nitrite and / or nitrobenzenesulfonate are used as oxidation accelerators.
  • further oxidation accelerators e.g. Chlorate is possible and can be beneficial.
  • An advantageous embodiment of the method according to the invention is to bring the metal surface into contact with a phosphating solution which contains at least one further activator from the group consisting of fluoride, hexafluorosilicate, tetrafluoroborate, glycolate, citrate, tartrate and condensed phosphate.
  • the activators to be used in the method according to the invention have an accelerating and comparative effect on the layer formation and control the weight per unit area of the phosphate layers.
  • the addition can e.g. over the corresponding acids or alkali salts.
  • concentrations in the phosphating solution apply to the activators: 0.5 to 3 g / 1 fluoride; 1 to 5 g / 1 hexafluorosilicate; 3 to 10 g / 1 tetrafluoroborate; 5 to 15 g / 1 formate; 0.3 to 5 g / 1 glycolate; 0.3 to 3 g / 1 nitrilotriacetate; 2 to 15 g / 1 trichloroacetate; 0.1 to 3 g / 1 ethylenediaminetetraacetate; 0.01 to 0.5 g / 1 citrate; 0.03 to 0.8 g / 1 tartrate; 0.03 to 0.3 g / 1 condensed phosphate such as pyro-, tripo
  • the weight per unit area of the phosphate layers produced on steel using the method according to the invention is usually between 0.8 and 2.5 g / m 2 .
  • activating agents for example based on titanium phosphate, in the pre-rinse bath or in the last cleaning stage is recommended.
  • the phosphate layers produced with the method according to the invention are suitable in principle for all purposes for which phosphate layers are suitable.
  • 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 as well as a considerable increase in the adhesion of the coating to the metallic substrate in the event of scratching, impact and bending stress.
  • 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. for the phosphating of car bodies.
  • Body steel sheets degreased with mildly alkaline, activating cleaner in the spray process and then rinsed with water were sprayed with the following phosphating solutions for 2 min at 55 ° C., then rinsed with water, passively rinsed with dilute Cr (VI) / Cr (III) solution, rinsed with demineralized water and partly dried and partly cathodically electro-coated.
  • the phosphating solutions according to 1 to 7 contained identical as well as the zinc contents indicated in the table.
  • the phosphating solutions according to 8 to 11 contained as well as the activator levels listed in the table.
  • the phosphating solutions mentioned were adjusted to the phosphating equilibrium with alkali.
  • Examples 8 to 11 show clearly the advantages of the procedure according to the invention in comparison with Examples 1 to 6 according to the prior art. Due to the different chemical surface activity of steel sheets from different rolled batches, the absolute value of the visual assessment is subject to certain fluctuations, but without significantly influencing the relative differences.
  • a portion of the cathodically coated panels was about / tested with an automobile paint system of a total of 100 micrometers and provided by various methods.
  • the results of the sheets treated according to the invention with regard to VW stone chips with a salt spray test, cross-cut after exposure to condensation and bending over the conical mandrel are very good and behave significantly better than Examples 4 and 7 of the prior art.

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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)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Catalysts (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Paints Or Removers (AREA)
  • Secondary Cells (AREA)
  • Materials For Medical Uses (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Glass Compositions (AREA)

Abstract

The quality of coatings in a low zinc phosphating process is improved by including an activator of formate, nitrilotriacetate, trichloroacetate or ethylenediamenetetraacetate to produce more uniform coatings particularly desirable in advance of electrocoating.

Description

Die Erfindung betrifft ein Verfahren zur Phosphatierung von Metallen, insbesondere von Stahl und verzinktem Stahl, im Spritzverfahren mittels einer wäßrigen, sauren Beschleuniger, Zink und gegebenenfalls Nickel enthaltenden Phosphatierungslösung und dessen Anwendung vor der Elektrotauchlackierung.The invention relates to a method for phosphating metals, in particular steel and galvanized steel, by spraying using an aqueous, acid accelerator, zinc and optionally nickel-containing phosphating solution and its use before electrocoating.

In der DE-OS 22 32 067 werden wäßrige saure Phosphatierungslösungen 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.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.

Aus der PCT-Publikation WO 84/00386 sind Phosphatierungslösungen mit 0,2 bis 0,6 g/1 Zn und Ni in einem Verhältnis von 5,2 bis 16 Mol Ni zu 1 Mol Zn bekannt, die Phosphatschichten mit einer besonders hohen Beständigkeit gegen Auflösung in Alkali aufweisen.PCT publication WO 84/00386 discloses phosphating solutions with 0.2 to 0.6 g / 1 Zn and Ni in a ratio of 5.2 to 16 mol Ni to 1 mol Zn, the phosphate layers with a particularly high resistance to Have resolution in alkali.

Die japanische Patentpublikation (gemäß Chemical Abstracts 99/216843 u) 58 144 477 beschreibt Spritzphosphatierlösungen für Stahl mit einem Gehalt an 0,1 bis 0,5 g/1 Zn, 15 bis 30 g/1 Phosphat und 0,01 bis 0,2 g/1 Nitrit. Die damit erzeugten Phosphatschichten sind insbesondere als Vorbehandlung für eine anschließende kathodische Elektrotauchlackieung gut geeignet.The Japanese patent publication (according to Chemical Abstracts 99/216843 u) 58 144 477 describes spray phosphating solutions for steel containing 0.1 to 0.5 g / 1 Zn, 15 to 30 g / 1 phosphate and 0.01 to 0.2 g / 1 nitrite. The phosphate layers thus produced are particularly suitable for pretreatment subsequent cathodic electrodeposition coating is well suited.

Nachteilig an den bekannten Verfahren mit Zinkkonzentrationen im Phosphatierbad von 0,1 bis 0,6 g/1 ist, daß sie bei der Anwendung im Spritzen auf Stahl häufig zu ungleichmäßigen Phosphatschichten mit teils grauer, teils.grünlich-bläulich irisierender Farbe führen. Diese Ungleichmäßigkeiten können sich im anschließend aufgebrachten Elektrotauchlack markieren und teure Nacharbeiten verursachen. Ferner genügt die Lackhaftung bei Beanspruchung durch z.B. Biegung oder durch längeren Kontakt mit Wasser nicht immer den gestellten Anforderungen./ A disadvantage of the known processes with zinc concentrations in the P hosphatierbad of 0.1 to 0.6 g of 1, that they often result in the application by spraying to steel in uneven phosphate layers with partly gray, bluish-teils.grünlich iridescent color. These irregularities can mark themselves in the subsequently applied electro-dip lacquer and cause expensive rework. Furthermore, the paint adhesion does not always meet the requirements in the case of stress caused by, for example, bending or prolonged contact with water.

Aufgabe der Erfindung ist es, ein Verfahren bereitzustellen, das die Nachteile der bekannten Verfahren nicht aufweist und gleichmäßige, einheitliche Phosphatschichten mit verbesserter Lackhaftung ausbildet.The object of the invention is to provide a process which does not have the disadvantages of the known processes and which forms uniform, uniform phosphate layers with improved paint adhesion.

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

Figure imgb0001
und mindestens einen Aktivator aus der Gruppe Formiat, Nitrilotriacetat, Trichloracetat und Ethylendiamintetraacetat enthält.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 an aqueous acidic phosphating solution which
Figure imgb0001
 and contains at least one activator from the group formate, nitrilotriacetate, trichloroacetate and ethylenediaminetetraacetate.

Das erfindungsgemäße Verfahren ist insbesondere für die Behandlung von Eisen, Stahl und verzinktem Stahl gedacht. Es eignet sich jedoch außerdem für die Phosphatierung von Zinklegierungen, Aluminium und Aluminiumlegierungen.The method according to the invention is intended in particular for the treatment of iron, steel and galvanized steel. However, it is also suitable for the phosphating of zinc alloys, Aluminum and aluminum alloys.

Die Behandlung erfolgt im Spritzverfahren, wobei die Kontaktzeiten für Eisen, Stahl und Aluminium beispielsweise 90 bis 240 sec, die für Zink beispielsweise 5 bis 240 sec betragen.The treatment is carried out by spraying, the contact times for iron, steel and aluminum being 90 to 240 seconds, for example, and zinc 5 to 240 seconds.

Das erfindungsgemäße Verfahren wird meist bei Badtemperaturen zwischen 30 und 60 °C eingesetzt.The method according to the invention is mostly used at bath temperatures between 30 and 60 ° C.

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

Zur Einstellung des Phosphatiergleichgewichtes enthalten die im erfindungsgemäßen Verfahren einzusetzenden Phosphatierungslösungen vorzugsweise Alkaliionen, z.B. Na, K, Li, NH4 und erforderlichenfalls weitere Anionen, z.B. N03, Cl, 8°4. Die Bäder können ferner weitere in der Phosphatiertechnik bekannte Kationen, wie Co, Cu, Mn, Ca, Mg und Fe enthalten.To adjust the phosphating equilibrium, the phosphating solutions to be used in the process according to the invention preferably contain alkali ions, for example Na, K, Li, NH 4 and, if necessary, further anions, for example N0 3 , Cl, 8 ° 4. The baths can also contain other cations known in phosphating technology, such as Co, Cu, Mn, Ca, Mg and Fe.

Als Oxidationsbeschleuniger werden beim erfindungsgemäßen Verfahren Nitrit und/oder Nitrobenzolsulfonat verwendet. Die Mitverwendung weiterer Oxidationsbeschleuniger, z.B. Chlorat, ist möglich und kann vorteilhaft sein.In the process according to the invention, nitrite and / or nitrobenzenesulfonate are used as oxidation accelerators. The use of further oxidation accelerators, e.g. Chlorate is possible and can be beneficial.

Eine vorteilhafte Ausgestaltung des erfindungsgemäßen Verfahrens besteht darin, die Metalloberfläche mit einer Phosphatierungslösung in Berührung zu bringen, die mindestens einen weiteren Aktivator aus der Gruppe Fluorid, Hexafluorosilikat, Tetrafluoroborat, Glykolat, Citrat, Tartrat und kondensiertes Phosphat enthält.An advantageous embodiment of the method according to the invention is to bring the metal surface into contact with a phosphating solution which contains at least one further activator from the group consisting of fluoride, hexafluorosilicate, tetrafluoroborate, glycolate, citrate, tartrate and condensed phosphate.

Die beim erfindungsgemäßen Verfahren einzusetzenden Aktivatoren wirken beschleunigend und vergleichmäßigend auf die Schichtbildung und steuern das Flächengewicht der Phosphatschichten. Die Zugabe kann z.B. über die entsprechenden Säuren oder auch Alkalisalze erfolgen. Für die Aktivatoren gelten folgende vorzugsweise Konzentrationen in der Phosphatierungslösung: 0,5 bis 3 g/1 Flüorid; 1 bis 5 g/1 Hexafluorosilikat; 3 bis 10 g/1 Tetrafluoroborat; 5 bis 15 g/1 Formiat; 0,3 bis 5 g/1 Glykolat; 0,3 bis 3 g/1 Nitrilotriacetat; 2 bis 15 g/1 Trichloracetat; 0,1 bis 3 g/1 Ethylendiamintetraacetat; 0,01 bis 0,5 g/1 Citrat; 0,03 bis 0,8 g/1 Tartrat; 0,03 bis 0,3 g/1 kondensiertes Phosphat, wie Pyro-, Tripoly- und Hexametaphosphat.The activators to be used in the method according to the invention have an accelerating and comparative effect on the layer formation and control the weight per unit area of the phosphate layers. The addition can e.g. over the corresponding acids or alkali salts. The following preferably concentrations in the phosphating solution apply to the activators: 0.5 to 3 g / 1 fluoride; 1 to 5 g / 1 hexafluorosilicate; 3 to 10 g / 1 tetrafluoroborate; 5 to 15 g / 1 formate; 0.3 to 5 g / 1 glycolate; 0.3 to 3 g / 1 nitrilotriacetate; 2 to 15 g / 1 trichloroacetate; 0.1 to 3 g / 1 ethylenediaminetetraacetate; 0.01 to 0.5 g / 1 citrate; 0.03 to 0.8 g / 1 tartrate; 0.03 to 0.3 g / 1 condensed phosphate such as pyro-, tripoly- and hexametaphosphate.

Das Flächengewicht der mit dem erfindungsgemäBen Verfahren auf Stahl erzeugten Phosphatschichten liegt meist zwischen 0,8 und 2,5 g/m2. Um die Ausbildung besonders dünner feinkristalliner Phosphatschichten weiter zu_unterstützen, empfiehlt sich die Anwendung von Aktivierungsmitteln, z.B. auf Titanphosphatbasis, im Vorspülbad oder der letzten Reinigerstufe.The weight per unit area of the phosphate layers produced on steel using the method according to the invention is usually between 0.8 and 2.5 g / m 2 . In order to further support the formation of particularly thin, fine-crystalline phosphate layers, the use of activating agents, for example based on titanium phosphate, in the pre-rinse bath or in the last cleaning stage is recommended.

Die mit dem erfindungsgemäßen Verfahren erzeugten Phosphatschichten eignen sich prinzipiell für alle Zwecke, für die Phosphatschichten geeignet sind. 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 bei Kratz-, Schlag- und Biegebeanspruchung. 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 with the method according to the invention are suitable in principle for all purposes for which phosphate layers are suitable. 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 as well as a considerable increase in the adhesion of the coating to the metallic substrate in the event of scratching, impact and bending stress. 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. 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 im Spritzverfahren entfettete und anschließend mit Wasser gespülte Karosseriestahlbleche wurden mit den nachstehenden Phosphatierungslösungen 2 min bei 55 °C im Spritzen behandelt, danach mit Wasser gespült, mit verdünnter Cr(VI)/Cr(III)-Lösung passivierend nachgespült, mit vollentsalztem Wasser abgebraust und zum Teil getrocknet und zum Teil kathodisch elektrotauchlackiert. Die Phosphatierungslösungen gemäß 1 bis 7 enthielten übereinstimmend

Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
sowie die tabellarisch angegebenen zinkgehalte.Body steel sheets degreased with mildly alkaline, activating cleaner in the spray process and then rinsed with water were sprayed with the following phosphating solutions for 2 min at 55 ° C., then rinsed with water, passively rinsed with dilute Cr (VI) / Cr (III) solution, rinsed with demineralized water and partly dried and partly cathodically electro-coated. The phosphating solutions according to 1 to 7 contained identical
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
 as well as the zinc contents indicated in the table.

Die Phosphatierungslösungen gemäß 8 bis 11 enthielten

Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
sowie zusätzlich die tabellarisch genannten Aktivatorgehalte. Die genannten Phosphatierungslösungen waren jeweils mit Alkali auf das Phosphatiergleichgewicht eingestellt.The phosphating solutions according to 8 to 11 contained
Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
 as well as the activator levels listed in the table. The phosphating solutions mentioned were adjusted to the phosphating equilibrium with alkali.

Die Ergebnisse der Phosphatierbehandlung sind in Form der Schichtbeurteilung nachfolgend zusammengestellt.

Figure imgb0011
Figure imgb0012
 The results of the phosphating treatment are summarized below in the form of the layer assessment.
Figure imgb0011
Figure imgb0012

Die Schichtbeurteilung zeigt an den Beispielen 8 bis 11 deutlich die Vorteile der erfindungsgemäßen Arbeitsweise im Vergleich zu den Beispielen 1 bis 6 nach dem Stand der Technik. Aufgrund unterschiedlicher chemischer Oberflächenaktivität von Stahlblechen aus verschiedenen Walzchargen unterliegt der Absolutwert der visuellen Beurteilung gewissen Schwankungen, ohne jedoch die relativen Unterschiede wesentlich zu beeinflussen.Examples 8 to 11 show clearly the advantages of the procedure according to the invention in comparison with Examples 1 to 6 according to the prior art. Due to the different chemical surface activity of steel sheets from different rolled batches, the absolute value of the visual assessment is subject to certain fluctuations, but without significantly influencing the relative differences.

Auch in nitrithaltigen chloratfreien Phosphatierungslösungen sowie solchen mit Nitrobenzolsulfonat, gegebenenfalls zusammen mit Nitrit, ergaben sich ähnliche Schichtbeurteilungen.Similar layer assessments were also obtained in nitrate-containing chlorate-free phosphating solutions and those with nitrobenzenesulfonate, possibly together with nitrite.

Die gemäß Beispiel 1 bis 6 phosphatierten Stahlbleche führten nach der kathodischen Elektrotauchlackierung zu einem Lackfilm mit unruhiger Oberflächenstruktur, während auf den gemäß Beispiel 7 bis 11 phosphatierten Stahlblechen gleichmäßige Lackfilme abzuscheiden waren.The steel sheets phosphated according to Examples 1 to 6 led after the cathodic electrocoating to a paint film with an uneven surface structure, while uniform paint films had to be deposited on the steel sheets phosphated according to Examples 7 to 11.

Ein Teil der kathodisch lackierten Bleche wurde mit einem Automobillackaufbau von insgesamt etwa 100 /um versehen und nach verschiedenen Methoden geprüft. Die Ergebnisse der erfindungsgemäß behandelten Bleche hinsichtlich VW-Steinschlag mit Salzsprühtest, Gitterschnitt nach Schwitzwasserbeanspruchung und Biegung über den konischen Dorn sind sehr gut und verhalten sich deutlich besser als die Beispiele 4 und 7 des Standes der Technik.A portion of the cathodically coated panels was about / tested with an automobile paint system of a total of 100 micrometers and provided by various methods. The results of the sheets treated according to the invention with regard to VW stone chips with a salt spray test, cross-cut after exposure to condensation and bending over the conical mandrel are very good and behave significantly better than Examples 4 and 7 of the prior art.

Claims (4)

.1:. Verfahren zur Phosphatierung von Metallen, insbesondere von Stahl und verzinktem Stahl, im Spritzverfahren mittels einer wäßrigen, sauren Beschleuniger, Zink und gegebenenfalls Nickel enthaltenden Phosphatierungslösung, dadurch gekennzeichnet, daß die Metalloberfläche mit einer Phosphatierungslösung in Berührung gebracht wird, die
Figure imgb0013
und mindestens einen Aktivator aus der Gruppe Formiat, Nitrilotriacetat, Trichloracetat und Ethylendiamintetraacetat enthält..1 :. Process for phosphating metals, in particular steel and galvanized steel, by spraying using an aqueous, acid accelerator, zinc and, if appropriate, nickel-containing phosphating solution, characterized in that the metal surface is brought into contact with a phosphating solution which
Figure imgb0013
 and contains at least one activator from the group formate, nitrilotriacetate, trichloroacetate and ethylenediaminetetraacetate. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Metalloberfläche mit einer Phosphatierungslösung in Berührung gebracht wird, die mindestens einen weiteren Aktivator aus der Gruppe Fluorid, Hexafluorosilikat, Tetrafluoroborat, Glykolat, Citrat, Tartrat und kondensiertes Phosphat enthält.2. The method according to claim 1, characterized in that the metal surface is brought into contact with a phosphating solution which contains at least one further activator from the group fluoride, hexafluorosilicate, tetrafluoroborate, glycolate, citrate, tartrate and condensed phosphate. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Metalloberfläche mit einer Phosphatierungslösung in Berührung gebracht wird, die den Aktivator in einer Menge von
Figure imgb0014
enthält.3. The method according to claim 1 or 2, characterized in that the metal surface is brought into contact with a phosphating solution which the activator in an amount of
Figure imgb0014
 contains. 4. Anwendung des Verfahrens nach einem oder mehreren der Ansprüche 1 bis 3 auf die Vorbereitung von Metalloberflächen für die Elektrotauchlackierung, insbesondere die kathodische Elektrotauchlackierung.4. Application of the method according to one or more of claims 1 to 3 to the preparation of metal surfaces for electrocoating, in particular cathodic electrocoating.
EP85200192A 1984-03-09 1985-02-15 Process for phosphatizing metals Expired EP0154367B1 (en)

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AT85200192T ATE37203T1 (en) 1984-03-09 1985-02-15 PROCESSES FOR THE PHOSPHATION OF METALS.

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DE19843408577 DE3408577A1 (en) 1984-03-09 1984-03-09 METHOD FOR PHOSPHATING METALS
DE3408577 1984-03-09

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GB2196024A (en) * 1986-09-05 1988-04-20 Pyrene Chemical Services Ltd Process for producing phosphate coatings
GB2208876A (en) * 1987-08-19 1989-04-19 Ardrox Pyrene Ltd Process for forming phosphate coatings on metals
EP0361375A1 (en) * 1988-09-27 1990-04-04 Nihon Parkerizing Co., Ltd. Phosphate-coating process
EP0369616A2 (en) * 1988-10-20 1990-05-23 Nippon Paint Co., Ltd. Metal surface treatment composition and process
EP0399425A1 (en) * 1989-05-20 1990-11-28 KOLBENSCHMIDT Aktiengesellschaft Process for applying a phosphate running layer on a bearing metal layer
WO1995032319A1 (en) * 1994-05-21 1995-11-30 Henkel Kommanditgesellschaft Auf Aktien Iron phosphatisation using substituted monocarboxilic acids

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GB8527833D0 (en) * 1985-11-12 1985-12-18 Pyrene Chemicals Services Ltd Phosphate coating of metals
JPH01100281A (en) * 1987-10-13 1989-04-18 Nippon Parkerizing Co Ltd Chemical conversion coating liquid for surface of metal
JP2636919B2 (en) * 1989-01-26 1997-08-06 日本パーカライジング株式会社 Lubrication treatment method for cold plastic working of steel
DE4409306A1 (en) * 1994-03-18 1995-09-21 Basf Ag Process for modifying metal surfaces
US6716192B1 (en) * 1997-09-30 2004-04-06 Charles F. Schroeder Medical needle having a visibly marked tip
US6551417B1 (en) 2000-09-20 2003-04-22 Ge Betz, Inc. Tri-cation zinc phosphate conversion coating and process of making the same
DE102005047424A1 (en) * 2005-09-30 2007-04-05 Henkel Kgaa Phosphating solution used as a pre-treatment for metal surfaces contains zinc irons, phosphate ions, hydrogen peroxide or an equivalent amount of a hydrogen peroxide-splitting substance and aliphatic chelate-forming carboxylic acid
CN102839374A (en) * 2012-09-05 2012-12-26 业纮企业股份有限公司 Surface treatment method of carbon steel sphere for ball valve
CN103668149B (en) * 2013-12-19 2016-08-24 湖南金裕化工有限公司 Ordinary-temp fast bonderizing liquor and preparation method thereof
CN103695881B (en) * 2013-12-19 2016-08-24 湖南金裕化工有限公司 Room temperature is without slag fast bonderizing liquor and preparation method thereof

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GB2196024A (en) * 1986-09-05 1988-04-20 Pyrene Chemical Services Ltd Process for producing phosphate coatings
GB2208876A (en) * 1987-08-19 1989-04-19 Ardrox Pyrene Ltd Process for forming phosphate coatings on metals
GB2208876B (en) * 1987-08-19 1991-08-14 Ardrox Pyrene Ltd Processes for forming phosphate coatings on metals
EP0361375A1 (en) * 1988-09-27 1990-04-04 Nihon Parkerizing Co., Ltd. Phosphate-coating process
AU617870B2 (en) * 1988-09-27 1991-12-05 Nihon Parkerizing Company Limited Zinc-nickel phosphate conversion coating composition and process
EP0369616A2 (en) * 1988-10-20 1990-05-23 Nippon Paint Co., Ltd. Metal surface treatment composition and process
EP0369616A3 (en) * 1988-10-20 1990-07-18 Nippon Paint Co., Ltd. Metal surface treatment composition and process
US5039563A (en) * 1988-10-20 1991-08-13 Nippon Paint Co., Ltd. Surface treating agent before coating
EP0399425A1 (en) * 1989-05-20 1990-11-28 KOLBENSCHMIDT Aktiengesellschaft Process for applying a phosphate running layer on a bearing metal layer
WO1995032319A1 (en) * 1994-05-21 1995-11-30 Henkel Kommanditgesellschaft Auf Aktien Iron phosphatisation using substituted monocarboxilic acids
US5919318A (en) * 1994-05-21 1999-07-06 Henkel Kommanditgesellschaft Auf Aktien Iron phosphating using substituted monocarboxylic acids

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AU3957485A (en) 1985-09-12
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GB8506049D0 (en) 1985-04-11
ATE37203T1 (en) 1988-09-15
DE3408577A1 (en) 1985-09-12
CN85101297A (en) 1987-01-24
EP0154367A3 (en) 1986-08-20
ES8602152A1 (en) 1985-12-01
US4637838A (en) 1987-01-20
CA1224121A (en) 1987-07-14
ZA851761B (en) 1985-11-27
EP0154367B1 (en) 1988-09-14

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