EP0370535B1 - Process for applying phosphate coatings - Google Patents
Process for applying phosphate coatings Download PDFInfo
- Publication number
- EP0370535B1 EP0370535B1 EP89201936A EP89201936A EP0370535B1 EP 0370535 B1 EP0370535 B1 EP 0370535B1 EP 89201936 A EP89201936 A EP 89201936A EP 89201936 A EP89201936 A EP 89201936A EP 0370535 B1 EP0370535 B1 EP 0370535B1
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- EP
- European Patent Office
- Prior art keywords
- zinc
- phosphating solution
- contacted
- phosphating
- iron
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
- C23C22/365—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations containing also zinc and nickel cations
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- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
- C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel cations
Definitions
- the invention relates to a method for applying phosphate coatings on surfaces made of aluminum and / or zinc or its or their alloys with the aid of phosphating solutions which operate according to the low zinc technology 0.4 to 1.5 g / l zinc and 10 to 16 g / l P2O5 contain,
- phosphating solutions that work according to the low-zinc technology are those that predominantly contain zinc as a layer-forming cation in a concentration of approx. 0.4 to 1.5 g / l and in which the Zn / PO4 ratio is less than approx. Is 0.08.
- phosphating solutions used for this usually contain zinc, nickel, manganese, magnesium, cadmium, copper, cobalt, alkali and / or ammonium ions, phosphate ions, accelerating additives such as nitrite, chlorate, bromate, peroxide, m -Nitrobenzenesulfonate, nitrophenol or combinations thereof.
- accelerating additives such as nitrite, chlorate, bromate, peroxide, m -Nitrobenzenesulfonate, nitrophenol or combinations thereof.
- aluminum, its alloys and galvanized steel they preferably additionally contain simple and / or complex fluorides.
- the phosphating solutions can also contain layer-refining additives, such as hydroxy carboxylic acids, amino carboxylic acids or condensed phosphates.
- the metal surfaces consist to a large extent of steel in addition to varying amounts of galvanized steel and a small amount of aluminum materials and are treated by spraying and / or immersion.
- the object of the invention is to provide a method for applying phosphate coatings on surfaces made of zinc and / or aluminum or its alloys with phosphating solutions working according to the low zinc technology, in which an increase in the free acid or the acid ratio is prevented and consequently, the disadvantages of the known methods are avoided, which is nevertheless easy to use and economical.
- the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the surface is brought into contact with a phosphating solution which contains a minimum concentration of iron (III) ions of 1 mg / l and which is treated per m2 Surface 50 to 2000 mg of iron III ions can be added.
- the iron ions can be introduced into the phosphating solution in the form of Fe-III ions, but also in the form of Fe-II ions together with an oxidizing agent, such as chlorate, nitrite, peroxide, which oxidizes to Fe-III.
- Suitable compounds are e.g. the nitrates, chlorides and fluorides of divalent or trivalent iron and iron-III complex compounds of hydroxy carboxylic acids, aminocarboxylic acids and the like.
- a preferred embodiment of the invention consists in bringing the surface into contact with a phosphating solution, to which 50 to 1000 mg of iron III ions are added per m2 of treated surface.
- the dosage can take place as mentioned above.
- such solutions are used that up to 1.3 g / l Ni up to 1.3 g / l Mn up to 1.3 g / l Mg contain.
- the weight ratio of Ni, Mn and or Mg to Zn should be set to a value of up to 1.5: 1.
- phosphating solutions which act as accelerators 2 to 25 g / l NO3 1 to 6 g / l ClO3 0.1 to 2 g / l organic nitro compound 0.05 to 0.5 g / l NO2 0.02 to 0.1 g / l peroxide (calculated as H2O2) or mixtures thereof.
- the phosphating solutions can be applied in a conventional manner. Particularly suitable forms of application are spraying and / or dipping, a temperature in the range from 30 to 70 ° C. being preferred.
- the method according to the invention is particularly suitable for the treatment of pure aluminum and alloys, e.g. of the qualities AlMgSi, AlMg and AlMgMn.
- Suitable materials are also solid zinc alloys or steel alloys with e.g. Ni, Fe or Al.
- iron III citrate By adding iron III citrate, the iron III concentration had been adjusted to 2 mg / l when the phosphating solution was started up.
- iron III citrate (calc. As Fe) was added to the phosphating solution of 10 l of 250 mg / m 2 surface.
- the number of free acid points was practically constant.
- the phosphate coating obtained was consistently uniform and closed.
Description
Die Erfindung betrifft ein Verfahren zum Aufbringen von Phosphatüberzügen auf Oberflächen aus Aluminium und/oder Zink bzw. dessen oder deren Legierungen mit Hilfe von gemäß der Niedrigzink-Technologie arbeitenden Phosphatierungslösungen, die
0,4 bis 1,5 g/l Zink und
10 bis 16 g/l P₂O₅
enthalten,
Phosphatierungslösungen, die gemäß der Niedrigzink-Technologie arbeiten, sind begrifflich solche, die als schichtbildendes Kation überwiegend Zink in einer Konzentration von ca. 0,4 bis 1,5 g/l enthalten und in denen das Zn/PO₄-Verhältnis kleiner als ca. 0,08 ist.The invention relates to a method for applying phosphate coatings on surfaces made of aluminum and / or zinc or its or their alloys with the aid of phosphating solutions which operate according to the low zinc technology
0.4 to 1.5 g / l zinc and
10 to 16 g / l P₂O₅
contain,
Conceptually, phosphating solutions that work according to the low-zinc technology are those that predominantly contain zinc as a layer-forming cation in a concentration of approx. 0.4 to 1.5 g / l and in which the Zn / PO₄ ratio is less than approx. Is 0.08.
Es ist bekannt, dünne Phosphatüberzüge auf Metalloberflächen von Stahl, verzinktem Stahl sowie Aluminium aufzubringen, die für eine nachfolgende elektrophoretische Tauchlackierung eine geeignete Lackgrundlage bilden. Die hierfür eingesetzten Phosphatierungslösungen enthalten üblicherweise Zink-, Nickel-, Mangan-, -Magnesium-, Kadmium-, Kupfer-, Kobalt-, Alkali- und/oder Ammoniumionen, Phosphationen, beschleunigend wirkende Zusätze wie Nitrit, Chlorat, Bromat, Peroxid, m-Nitrobenzolsulfonat, Nitrophenol oder Kombinationen hiervon. Für die Behandlung von Aluminium, dessen Legierungen und galvanisch verzinktem Stahl enthalten sie vorzugsweise zusätzlich einfache und/oder komplexe Fluoride. Zusätzliche Anionen, wie Chlorid, Nitrat und Sulfat, dienen der Wahrung der Elektroneutralität. Gegebenenfalls können die Phosphatierungslösungen noch schichtverfeinernde Zusätze, wie hydroxicarbonsäuren, Aminocarbonsäuren oder kondensierte Phosphate, enthalten.It is known to apply thin phosphate coatings to metal surfaces of steel, galvanized steel and aluminum, which form a suitable coating base for a subsequent electrophoretic dip coating. The phosphating solutions used for this usually contain zinc, nickel, manganese, magnesium, cadmium, copper, cobalt, alkali and / or ammonium ions, phosphate ions, accelerating additives such as nitrite, chlorate, bromate, peroxide, m -Nitrobenzenesulfonate, nitrophenol or combinations thereof. For the treatment of aluminum, its alloys and galvanized steel, they preferably additionally contain simple and / or complex fluorides. Additional anions, such as chloride, nitrate and sulfate, serve to maintain electroneutrality. Optionally, the phosphating solutions can also contain layer-refining additives, such as hydroxy carboxylic acids, amino carboxylic acids or condensed phosphates.
Die Metalloberflächen bestehen dabei zu einem erheblichen Anteil aus Stahl neben wechselnden Mengen verzinktem Stahl sowie einem geringen Anteil an Aluminiumwerkstoffen und werden im Spritz- und/oder Tauchverfahren behandelt.The metal surfaces consist to a large extent of steel in addition to varying amounts of galvanized steel and a small amount of aluminum materials and are treated by spraying and / or immersion.
Werden ausschließlich Zinkoberflächen und/oder Aluminiumoberflächen mit der Phosphatierungslösung in Berührung gebracht, stellt man fest, daß die Freie Säure bzw. das Verhältnis Freie Säure zu Gesamtsäure der arbeitenden Phosphatierungslösung ansteigt und die Phosphatierungslösung außerhalb des Gleichgewichtes gerät. Die Folge ist, daß mit zunehmendem Durchsatz die Überzugsausbildung verschlechtert wird und schließlich ganz unterbleibt. Ein Abstumpfen der überschüssigen Säure mit Natriumhydroxid, Ammoniumhydroxid oder anderen Alkalien ist nicht durchführbar, da dann ein Teil der Badkomponente Zink mitausgefällt wird.If only zinc surfaces and / or aluminum surfaces are brought into contact with the phosphating solution, it is found that the free acid or the ratio of free acid to total acid of the working phosphating solution increases and the phosphating solution becomes out of equilibrium. The result is that with increasing throughput the coating formation deteriorates and ultimately does not occur. The excess acid cannot be blunted with sodium hydroxide, ammonium hydroxide or other alkalis, since part of the bath component zinc is then also precipitated.
Aufgabe der Erfindung ist es, ein Verfahren zum Aufbringen von Phosphatüberzügen auf Oberflächen aus Zink und/oder Aluminium bzw. dessen oder deren Legierungen mit gemäß der Niedrigzink-Technologie arbeitenden Phosphatierungslösungen bereitzustellen, bei dem ein Anstieg der Freien Säure bzw. des Säureverhältnisses verhindert wird und mithin die Nachteile der bekannten Verfahren vermieden werden, das aber dennoch einfach in der Handhabung sowie wirtschaftlich ist.The object of the invention is to provide a method for applying phosphate coatings on surfaces made of zinc and / or aluminum or its alloys with phosphating solutions working according to the low zinc technology, in which an increase in the free acid or the acid ratio is prevented and consequently, the disadvantages of the known methods are avoided, which is nevertheless easy to use and economical.
Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man die Oberfläche mit einer Phosphatierungslösung in Kontakt bringt, die eine Mindestkonzentration an Eisen-III-ionen von 1 mg/l enthält und der pro m² behandelter Oberfläche 50 bis 2000 mg Eisen-III-ionen zugesetzt werden.The object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the surface is brought into contact with a phosphating solution which contains a minimum concentration of iron (III) ions of 1 mg / l and which is treated per m² Surface 50 to 2000 mg of iron III ions can be added.
Zwar ist es aus EP-A-0 264 811 bekannt, bei der Erzeugung von Phosphatüberzügen auf Oberflächen von kaltgewalztem Stahl sowie ein- oder zweiseitig verzinktem Stahl im Tauchen in Phosphatierungslösungen, die u.a. 10 bis 20 g/l Phosphat (ber. als PO₄) und 1,5 bis 2,5 g/l Zink (ber. als Zn) enthalten, einen Eisen-III-Gehalt (ber. als Fe) von 2 bis 20 mg/l und das Gewichtsverhältnis von Zn:PO₄ auf (0,08 bis 0.21):1 einzustellen. Hierbei handelt es sich jedoch nicht um Phosphatierungslösungen, die entsprechend der Niedrigzink-Technologie arbeiten und von denen sich das Dokument in der Einleitung klar abgrenzt. Zum andern ist darauf hingewiesen, daß beim Verlassen der Zinkkonzentration von 1,5 bis 2,5 g/l unerwünscht schwere, bzw. zu dünne Schichten entstehen und beim Unterschreiten eines Gewichtsverhältnisses von Zn/PO₄ unter einen Wert von 0.08 die Phosphatschichtbildung beeinträchtig wird.It is known from EP-A-0 264 811, when producing phosphate coatings on surfaces of cold-rolled steel and one- or two-sided galvanized steel when immersed in phosphating solutions, which among other things. Contain 10 to 20 g / l phosphate (calc. As PO₄) and 1.5 to 2.5 g / l zinc (calc. As Zn), an iron III content (calc. As Fe) of 2 to 20 mg / l and the weight ratio of Zn: PO₄ to (0.08 to 0.21): 1. However, these are not phosphating solutions that work according to the low-zinc technology and from which the document is clearly distinguished in the introduction. On the other hand, it is pointed out that when leaving the zinc concentration of 1.5 to 2.5 g / l, undesirably heavy or too thin layers are formed and if the weight ratio of Zn / PO₄ falls below a value of 0.08, the formation of the phosphate layer is impaired.
Weiterhin ergibt sich aus FR-A-2 401 234, daß den Phosphatierungslösungen, die nach konventionellen Verfahren arbeiten und hohe Zinkkonzentrationen von z.B. 2,85 bzw. 3,7 g/l bei einem hohen Zn/P₂O₅-Verhältnis von 0,40 und 0,51 aufweisen, von Zeit zu Zeit oder kontinuierlich Eisenhydroxid zugesetzt werden soll. Diese Arbeitsweise beseitig Ausfällung von tertiärem Zinkphosphat, bzw. Schlammbildung und Verschlechterung der auflagequalität.Furthermore, it follows from FR-A-2 401 234 that the phosphating solutions which work according to conventional processes and high zinc concentrations of e.g. 2.85 or 3.7 g / l at a high Zn / P₂O₅ ratio of 0.40 and 0.51, iron hydroxide should be added from time to time or continuously. This procedure eliminates precipitation of tertiary zinc phosphate or sludge formation and deterioration in the quality of the coating.
Das Dokument EP-A 0 111 246 schließlich beschreibt weder Phosphatierverfahren, die der Niedrigzink-Technologie angehören, noch offenbart es einen Zusatz von Eisen zu Phosphatierungslösungen. Die genannte Zinkkonzentration von 1 bis 2,5 g/l läßt zwar eine gewisse Überlappung mit Niedrigzinkverfahren vermuten. Jedoch verdeutlicht das einzige Beispiel (Beispiel 1) mit einem "niedrigen" Zinkgehalt von 1,1 g/l und einer PO₄-Konzentration von 7,4 g/l entsprechend einem Zn/P₂O₅-Verhältnis von 1 : 5, daß es sich tatsächlich um Lösungen handelt, die nicht bei der Niedrigzink Technologie zum Einsatz kommen.Finally, document EP-A 0 111 246 neither describes phosphating processes which belong to the low-zinc technology, nor does it disclose the addition of iron to phosphating solutions. The zinc concentration of 1 to 2.5 g / l mentioned suggests a certain overlap with low-zinc processes. However, the only example (example 1) with a "low" zinc content of 1.1 g / l and a PO₄ concentration of 7.4 g / l corresponding to a Zn / P₂O₅ ratio of 1: 5 illustrates that it is actually are solutions that are not used in low-zinc technology.
Die Eisenionen können in Form von Fe-III-Ionen, aber auch in Form von Fe-II-Ionen zusammen mit einem Fe-II zu Fe-III oxidierenden Oxidationsmittel, wie Chlorat, Nitrit, Peroxid, in die Phosphatierungslösung eingebracht werden. Geeignete Verbindungen sind z.B. die Nitrate, Chloride und Fluoride von zwei oder dreiwertigem Eisen sowie Eisen-III-komplexverbindungen von Hydroxicarbonsäuren, Aminocarbonsäuren und dergleichen.The iron ions can be introduced into the phosphating solution in the form of Fe-III ions, but also in the form of Fe-II ions together with an oxidizing agent, such as chlorate, nitrite, peroxide, which oxidizes to Fe-III. Suitable compounds are e.g. the nitrates, chlorides and fluorides of divalent or trivalent iron and iron-III complex compounds of hydroxy carboxylic acids, aminocarboxylic acids and the like.
Es ist besonders zweckmäßig, die Eisenionen in in Wasser vorgelöster Form in die Phosphatierungslösung einzubringen.It is particularly expedient to introduce the iron ions into the phosphating solution in a form predissolved in water.
Eine bevorzugte Ausgestaltung der Erfindung besteht darin, die Oberfläche mit einer Phosphatierungslösung in Kontakt zu bringen, der pro m² behandelter Oberfläche 50 bis 1000 mg Eisen-III-ionen zugesetzt werden. Auch hierbei kann die Dosierung wie oben erwähnt erfolgen.A preferred embodiment of the invention consists in bringing the surface into contact with a phosphating solution, to which 50 to 1000 mg of iron III ions are added per m² of treated surface. Here, too, the dosage can take place as mentioned above.
Gemäß einer weiteren bevorzugten Ausgestaltung werden solche Lösungen eingesetzt, die
bis 1,3 g/l Ni
bis 1,3 g/l Mn
bis 1,3 g/l Mg
enthalten. Bei diesen Lösungen sollte das Gewichtsverhältnis von Ni, Mn und oder Mg zu Zn auf einen Wert bis 1,5 : 1 eingestellt sein.According to a further preferred embodiment, such solutions are used that
up to 1.3 g / l Ni
up to 1.3 g / l Mn
up to 1.3 g / l Mg
contain. With these solutions, the weight ratio of Ni, Mn and or Mg to Zn should be set to a value of up to 1.5: 1.
Gemäß einer weiteren vorteilhaften Ausgestaltung der Erfindung kommen Phosphatierungslösungen zum Einsatz, die als Beschleuniger
2 bis 25 g/l NO₃
1 bis 6 g/l ClO₃
0,1 bis 2 g/l organische Nitroverbindung
0,05 bis 0,5 g/l NO₂
0,02 bis 0,1 g/l Peroxid (ber. als H₂O₂)
oder Mischungen hiervon enthalten.According to a further advantageous embodiment of the invention, phosphating solutions are used which act as accelerators
2 to 25 g / l NO₃
1 to 6 g / l ClO₃
0.1 to 2 g / l organic nitro compound
0.05 to 0.5 g / l NO₂
0.02 to 0.1 g / l peroxide (calculated as H₂O₂)
or mixtures thereof.
Die Phosphatierungslösungen können auf herkömmliche Weise appliziert werden. Besonders geeignete Applikationsformen sind Spritzen und/oder Tauchen, wobei eine Temperatur im Bereich von 30 bis 70°C bevorzugt ist.The phosphating solutions can be applied in a conventional manner. Particularly suitable forms of application are spraying and / or dipping, a temperature in the range from 30 to 70 ° C. being preferred.
Während Arbeitspausen ist durch Zugabe von Eisen-III-ionen dafür Sorge zu tragen, daß die Mindestkonzentration von 1 mg/l aufrechterhalten wird.During work breaks, the addition of iron III ions must ensure that the minimum concentration of 1 mg / l is maintained.
Das erfindungsgemäße Verfahren eignet sich insbesondere zur Behandlung von Reinaluminium und Legierungen, z.B. der Qualitäten AlMgSi, AlMg und AlMgMn.The method according to the invention is particularly suitable for the treatment of pure aluminum and alloys, e.g. of the qualities AlMgSi, AlMg and AlMgMn.
Hinsichtlich der Überzugsbildung auf Zinkoberflächen können Werkstücke aus massivem Zink, insbesondere aber aus schmelztauch- oder elektrolytisch verzinktem Stahl, behandelt werden. Geeignete Werkstoffe sind weiterhin massive oder auf Stahl aufgebrachte Zinklegierungen mit z.B. Ni, Fe oder Al.With regard to the formation of a coating on zinc surfaces, workpieces made of solid zinc, but especially of hot-dip or electrolytically galvanized steel, can be treated. Suitable materials are also solid zinc alloys or steel alloys with e.g. Ni, Fe or Al.
Mit Hilfe des erfindungsgemäßen Verfahrens gelingt es, selbst über einen längeren Zeitpunkt hinweg Phosphatüberzüge zu erzeugen, die durchweg gleichmäßig und geschlossen sind. Diese Überzüge eignen sich in besonderer Weise für eine nachfolgende elektrophoretische Tauchlackierung.With the aid of the method according to the invention, it is possible to produce phosphate coatings which are uniform and uniform even over a longer period of time are closed. These coatings are particularly suitable for subsequent electrophoretic dip coating.
Die Erfindung wird anhand der nachfolgenden Beispiele beispielsweise und näher erläutert.The invention is illustrated by the following examples, for example and in more detail.
In einem 10 l Phosphatierungsbehälter wurden alternierend zuvor entfettete und gebeizte Bleche aus Aluminium (70 %) der Qualität AlMgSi und AlMg3 und elektrolytisch verzinktem Stahl (30 %) mit einer Phosphatierungslösung behandelt, die
0,7 g/l Zn
0,7 g/l Ni
1,0 g/l Mn
3,4 g/l Na
11,5 g/l P₂O₅
3,0 g/l NO₃
0,5 g/l F
0,1 g/l NO₂
enthielt. Die Temperatur der Lösung betrug 55 bis 60°C. Die Behandlung erfolgte im Spritzen für die Dauer von 3 min. Die Freie Säure der Phosphatierungslösung lag bei 1,0.Alternately previously degreased and pickled aluminum (70%) sheets of AlMgSi and AlMg3 quality and electrolytically galvanized steel (30%) were treated with a phosphating solution in a 10 liter phosphating container
0.7 g / l Zn
0.7 g / l Ni
1.0 g / l Mn
3.4 g / l Na
11.5 g / l P₂O₅
3.0 g / l NO₃
0.5 g / l F
0.1 g / l NO₂
contained. The temperature of the solution was 55 to 60 ° C. The treatment was carried out by spraying for 3 minutes. The free acidity of the phosphating solution was 1.0.
Durch Zugabe von Eisen III-Zitrat war die Eisen-III-konzentration bei Inbetriebnahme der Phosphatierungslösung auf 2 mg/l eingestellt worden.By adding iron III citrate, the iron III concentration had been adjusted to 2 mg / l when the phosphating solution was started up.
Im Verlauf des Durchsatzes wurden der Phosphatierungslösung von 10 l 250 mg/m² Oberfläche Eisen III-Zitrat (ber. als Fe) zugegeben. Wie die nachfolgende Tabelle zeigt, war die Zahl der Freie-Säure-Punkte praktisch konstant. Der erhaltene Phosphatüberzug war durchweg gleichmäßig und geschlossen.
Als Vergleichsbeispiel wurden Bleche gleicher Qualität und in gleicher Weise durch die vorgenannte Phosphatierungslösung, die jedoch keine Eisen-III-ionen enthielt und nicht mit Eisen-III-ionen ergänzt worden war, durchgesetzt. Entsprechend zunehmendem Durchsatz veränderte sich die Zahl der Freie-Säure-Punkte wie unten angegeben. Während anfänglich hochwertige Phosphatüberzüge erhalten wurden, war mit steigender Punktzahl eine Verschlechterung der Qualität festzustellen. Ab einer Zahl Freie-Säure-Punkte von 1,50 war überhaupt keine Überzugsausbildung zu beobachten.
Claims (6)
- A process of applying phosphate coatings to surfaces consisting of aluminium and/or zinc and/or its or their alloys by means of phosphating solutions operating according to the low-zinc technology, which contain
0.4 to 1.5 g/l zinc and
10 to 26 g/l P₂O₅
and in which the weight ratio of Zn to P₂O₅ is adjusted to a value in the range of (0.075 to 0.015) : 1, characterized in that the surface is contacted with a phosphating solution which contains iron-III-ions in a minimum concentration of 1 mg/l and to which 50 to 2000 mg iron-III-ions are added per square meter of treated area. - A process according to claim 1, characterized in that the metal surface is contacted with a phosphating solution to which 50 to 1000 mg iron-III-ions are added per square meter of treated area.
- A process according to claim 1 or 2, characterized in that the surface is contacted with a phosphating solution which contains
up to 1.3 g/l Ni
up to 1.3 g/l Mn
up to 1.3 g/l Mg. - A process according to claim 3, characterised in that the surface is contacted with a phosphating solution in which the weight ratio of Ni, Mn and/or Mg to Zn is adjusted to a value up to 1.5 : 1.
- A process according to any of claims 1 to 4, characterized in that the surface is contacted with a phosphating solution which additionally contains
2 to 25 g/l NO₃
1 to 6 g/l ClO₃
0.1 to 2 g/l organic nitro compound
0.05 to 0.5 g/l NO₂
0.02 to 0.1 g/l peroxide (calculated as H₂O₂)
or mixtures thereof. - A process according to any of claims 1 to 5, characterized in that the surface is contacted with a phosphating solution at a temperature in the range from 30 to 70°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3839802 | 1988-11-25 | ||
| DE3839802 | 1988-11-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0370535A1 EP0370535A1 (en) | 1990-05-30 |
| EP0370535B1 true EP0370535B1 (en) | 1992-11-11 |
Family
ID=6367867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89201936A Expired - Lifetime EP0370535B1 (en) | 1988-11-25 | 1989-07-22 | Process for applying phosphate coatings |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0370535B1 (en) |
| JP (1) | JP2845246B2 (en) |
| CA (1) | CA1334371C (en) |
| DD (1) | DD299968A5 (en) |
| DE (1) | DE58902702D1 (en) |
| ES (1) | ES2036023T3 (en) |
| GB (1) | GB2226829B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5238506A (en) * | 1986-09-26 | 1993-08-24 | Chemfil Corporation | Phosphate coating composition and method of applying a zinc-nickel-manganese phosphate coating |
| DE3828676A1 (en) * | 1988-08-24 | 1990-03-01 | Metallgesellschaft Ag | PHOSPHATING PROCESS |
| DE3918136A1 (en) * | 1989-06-03 | 1990-12-06 | Henkel Kgaa | METHOD FOR PRODUCING MANAGE-CONTAINING PHOSPHATE COATINGS ON METAL SURFACES |
| CA2035048A1 (en) * | 1990-01-26 | 1991-07-27 | Thomas W. Cape | Phosphate coating composition and method of applying a zinc-nickel-manganese phosphate coating |
| US5261973A (en) * | 1991-07-29 | 1993-11-16 | Henkel Corporation | Zinc phosphate conversion coating and process |
| US5645706A (en) * | 1992-04-30 | 1997-07-08 | Nippondenso Co., Ltd. | Phosphate chemical treatment method |
| JPH05306497A (en) | 1992-04-30 | 1993-11-19 | Nippondenso Co Ltd | Phophatizing chemical conversion treatment |
| DE4228470A1 (en) * | 1992-08-27 | 1994-03-03 | Henkel Kgaa | Process for phosphating steel strips galvanized on one side |
| DE4243214A1 (en) * | 1992-12-19 | 1994-06-23 | Metallgesellschaft Ag | Process for the production of phosphate coatings |
| US5797987A (en) * | 1995-12-14 | 1998-08-25 | Ppg Industries, Inc. | Zinc phosphate conversion coating compositions and process |
| US5900073A (en) * | 1996-12-04 | 1999-05-04 | Henkel Corporation | Sludge reducing zinc phosphating process and composition |
| JP3366826B2 (en) * | 1997-04-30 | 2003-01-14 | 本田技研工業株式会社 | Zinc phosphate treatment agent for aluminum alloy |
| JP4019723B2 (en) * | 2001-02-23 | 2007-12-12 | 株式会社デンソー | Electrolytic phosphate chemical treatment method |
| RU2560891C1 (en) * | 2014-05-05 | 2015-08-20 | Федеральное государственное унитарное предприятие федеральный научно-производственный центр "Производственное объединение "Старт" им. М.В. Проценко" (ФГУП ФНПЦ "ПО "Старт" им. М.В. Проценко") | Method of iron-cobalt alloy phosphating |
| KR20170133480A (en) * | 2015-04-07 | 2017-12-05 | 케메탈 게엠베하 | How to tailor the electrical conductivity of the conversion coating |
| RU2624566C1 (en) * | 2016-02-15 | 2017-07-04 | Федеральное государственное унитарное предприятие федеральный научно-производственный центр "Производственное объединение "Старт" им. М.В. Проценко" (ФГУП ФНПЦ "ПО "Старт" им. М.В. Проценко") | Method of phosphatory of magnetic-aluminium alloys of type permalloy (versions) |
| US11124880B2 (en) | 2016-04-07 | 2021-09-21 | Chemetall Gmbh | Method for nickel-free phosphating metal surfaces |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2738281A1 (en) * | 1977-08-25 | 1979-03-01 | Metallgesellschaft Ag | METHOD FOR PHOSPHATING METALS |
| DE2738282A1 (en) * | 1977-08-25 | 1979-03-01 | Metallgesellschaft Ag | METHOD FOR APPLYING PHOSPHATE |
| DE2738283A1 (en) * | 1977-08-25 | 1979-03-01 | Metallgesellschaft Ag | METHOD FOR PHOSPHATING METALS |
| US4278477A (en) * | 1980-03-19 | 1981-07-14 | Amchem Products, Inc. | Metal treatment |
| US4486241A (en) * | 1981-09-17 | 1984-12-04 | Amchem Products, Inc. | Composition and process for treating steel |
| DE3245411A1 (en) * | 1982-12-08 | 1984-07-05 | Gerhard Collardin GmbH, 5000 Köln | METHOD FOR PHOSPHATING ELECTROLYTICALLY GALVANIZED METAL GOODS |
| FR2569203B1 (en) * | 1984-08-16 | 1989-12-22 | Produits Ind Cie Fse | PROCESS FOR THE TREATMENT BY CHEMICAL CONVERSION OF SUBSTRATES IN ZINC OR IN ONE OF ITS ALLOYS, CONCENTRATE AND BATH USED FOR THE IMPLEMENTATION OF THIS PROCESS |
| JPS63100185A (en) * | 1986-10-16 | 1988-05-02 | Nippon Parkerizing Co Ltd | Phosphating method |
-
1989
- 1989-07-22 EP EP89201936A patent/EP0370535B1/en not_active Expired - Lifetime
- 1989-07-22 DE DE8989201936T patent/DE58902702D1/en not_active Expired - Lifetime
- 1989-07-22 ES ES198989201936T patent/ES2036023T3/en not_active Expired - Lifetime
- 1989-08-02 CA CA000607371A patent/CA1334371C/en not_active Expired - Fee Related
- 1989-08-04 GB GB8917936A patent/GB2226829B/en not_active Expired - Fee Related
- 1989-11-21 JP JP1300984A patent/JP2845246B2/en not_active Expired - Lifetime
-
1990
- 1990-04-19 DD DD339887A patent/DD299968A5/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE58902702D1 (en) | 1992-12-17 |
| GB8917936D0 (en) | 1989-09-20 |
| DD299968A5 (en) | 1992-05-14 |
| JPH02190478A (en) | 1990-07-26 |
| ES2036023T3 (en) | 1993-05-01 |
| GB2226829B (en) | 1993-01-20 |
| EP0370535A1 (en) | 1990-05-30 |
| JP2845246B2 (en) | 1999-01-13 |
| GB2226829A (en) | 1990-07-11 |
| CA1334371C (en) | 1995-02-14 |
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