EP0042631A1 - Method of phosphating metallic surfaces - Google Patents

Method of phosphating metallic surfaces Download PDF

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Publication number
EP0042631A1
EP0042631A1 EP81200442A EP81200442A EP0042631A1 EP 0042631 A1 EP0042631 A1 EP 0042631A1 EP 81200442 A EP81200442 A EP 81200442A EP 81200442 A EP81200442 A EP 81200442A EP 0042631 A1 EP0042631 A1 EP 0042631A1
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EP
European Patent Office
Prior art keywords
phosphating
metal surfaces
bath
manganese
phosphating solution
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EP81200442A
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German (de)
French (fr)
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EP0042631B1 (en
Inventor
Han Yong Dr. Dipl.-Chem. Oei
Günter Ing. grad. Siemund
Rudolf Vey
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GEA Group AG
Continentale Parker Ste
Continentale Parker SA
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Metallgesellschaft AG
Continentale Parker Ste
Continentale Parker SA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/364—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
    • 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 process for the production of phosphate coatings on metal surfaces of iron and steel using an acidic nitrate-accelerated zinc and manganese ion-containing phosphating solution at elevated temperatures in the immersion process.
  • z. B. in the range between 8 to 30 g / m 2 required.
  • particularly high demands are placed on corrosion protection. This can be achieved by increasing the layer weight.
  • An increase in the layer weight would also allow higher degrees of deformation in cold forming.
  • the deposition of thick zinc phosphate layers can according to DE-AS 12 87 412 and US Pat. No. 3,268,367 by bringing iron and steel into contact with a nitrate-accelerated acidic zinc phosphating solution with the addition of polycarboxylic acids in which the carbon atom adjacent to at least one carboxyl group is a hydroxy -, Amino or carboxyl group can be achieved.
  • This phosphating solution can also contain additives such as nickel, cobalt, lithium, bismuth and manganese in small concentrations of less than 0.5 g / l. They activate the metal surface to be phosphated and promote the deposition of zinc phosphate layers.
  • the object of the invention is to provide a phosphating process which does not have the disadvantages described, in particular is universally applicable, requires little chemicals and leads to higher-quality phosphate layers.
  • the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the metal surfaces are brought into contact with a phosphating solution which contains at least 0.6 g / l of manganese ions at treatment temperatures of 50 to 98 ° C. in which the weight ratio is and which has a total acid score of at least 20 points when incorporated.
  • Such a method leads to zinc-manganese-phosphate layers which, with comparable layer thicknesses, are superior to zinc phosphate layers with regard to corrosion protection and cold-forming properties.
  • the metal surfaces are preferably brought into contact with a phosphating solution in which the manganese ion content is at least 1 g / l.
  • the metal surfaces are brought into contact with a phosphating solution in which the weight ratio of Mn: Zn is 1: (0.8 to 12).
  • Manganese ion contents in the phosphating solution above the range of 1: 0.2 lead to non-closed, perforated layers.
  • baths with e.g. 80 total acid points can be composed as follows:
  • the total acid number can be determined by titration of a 10 ml bath sample with 0.1 N NaOH against phenolphthalein as an indicator until the color changes from colorless to pink.
  • nickel and / or cobalt and / or copper ions and the like can be added to the bath.
  • these metal ions in a concentration of z. B. 0.02 to 0.10 g / l added to the bath.
  • the anion belonging to the metal ions can e.g. B. nitrate or sulfate.
  • a phosphating solution which contains simple and / or complex fluorides, such as NaF, NaHF 2 and / or Na 2 SiF 6 .
  • a certain reduction in the layer weight can be brought about if condensed phosphates are added to the phosphating bath.
  • the workpieces to be phosphated should be free of grease, scale and rust.
  • the degreasing can e.g. B. by means of aqueous, alkaline, surface-active substances containing cleaners.
  • Descaling is advantageously carried out using sulfuric acid or hydrochloric acid.
  • the workpieces After cleaning and / or pickling, the workpieces should be rinsed well with water.
  • the workpieces can be formed in a manner known per se, e.g. B. with titanium orthophosphate or manganese orthophosphate suspensions in water. It has been found in practice that in some cases a pre-rinse with water at 50 to 98 ° C activates the surface.
  • the phosphating bath is operated between 50 and 98 ° C depending on the type of workpiece, the alloy and the type of application. It has been shown that a diving time of 5 to 15 minutes is sufficient for most applications.
  • iron II will accumulate in the phosphating bath in the course of the throughput. This does not affect the way the bath works. In special cases, e.g. B. at high nitrate concentrations or at high bath temperatures, it can also happen that the bath remains iron-II-free due to the oxidation of FeII to FeIII. This also does not affect the way the bath works.
  • the addition of the bath is expediently carried out on a constant total acid number.
  • the layer weight of the zinc-manganese-phosphate layers obtained is normally between about 5 and about 30 g / m 2, depending on the composition of the phosphating bath and the alloy of the workpiece to be treated.
  • z. B. be treated with chromic acid solutions, followed by treatment with anti-corrosion oil emulsions.
  • the workpieces can e.g. B. be treated with soap solutions.
  • the workpieces treated in this way are superior to the workpieces treated with conventional nitrate accelerated zinc phosphating systems in terms of corrosion protection and cold forming properties.
  • baths F and G The composition of baths F and G is shown in the following table.
  • the total acid number of baths was 90 points each.
  • sample sheets became branched off to determine the layer weight and for the corrosion test in the salt spray test according to DIN 50021 SS.
  • the sheets for the corrosion test were previously treated with a 15% emulsion of an anti-corrosion oil and then dried in an oven at 70 ° C. It can be clearly seen that the preferred configuration of the supplement means that the phosphating baths, even after a throughput of 4 m 2 / l, lead to layers which have retained their good properties.

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

Abstract

Coatings are formed on iron or steel surfaces by immersing them in a hot acidic solution comprising zinc, phosphate and nitrate and a relatively high content of manganese of at least 0.6 g/l.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von Phosphatüberzügen auf Metalloberflächen von Eisen und Stahl unter Verwendung einer sauren nitratbeschleunigten Zink- und Manganionen enthaltenden Phosphatierungslösung bei erhöhten Temperaturen im Tauchverfahren.The invention relates to a process for the production of phosphate coatings on metal surfaces of iron and steel using an acidic nitrate-accelerated zinc and manganese ion-containing phosphating solution at elevated temperatures in the immersion process.

Es ist bekannt, Eisen und Stahl zwecks Ausbildung einer Phosphatschicht mit Phosphatierlösungen im Tauchen zu behandeln, die Zink-, Wasserstoff-, Nitrat- sowie Phosphationen enthalten. Die Phosphatschichten, die auf diese Weise erzeugt worden sind, eignen sich besonders als Schmiermittelträger bei der Kaltumformung. Mit einer Rostschutzölnachbehandlung führen sie zu Korrosionsbeständigkeiten, die galvanisch aufgebrachten Metallüberzügen aus Zink, Kadmium etc. entsprechen.It is known to treat iron and steel for the purpose of forming a phosphate layer with phosphating solutions in diving which contain zinc, hydrogen, nitrate and phosphate ions. The phosphate layers that have been produced in this way are particularly suitable as lubricants for cold forming. With anti-rust oil aftertreatment, they lead to corrosion resistance that corresponds to galvanically applied metal coatings made of zinc, cadmium, etc.

Insbesondere für den Korrosionsschutz mit Ölen und die Erleichterung der Kaltumformung, wie z. B. das Kaltfließpressen, werden Schichten mit höherem Auflagegewicht, z. B. im Bereich zwischen 8 bis 30 g/m2, benötigt. In manchen Fällen werden besonders hohe Ansprüche an den Korrosionsschutz gestellt. Dies kann erreicht werden durch eine Erhöhung des Schichtgewichtes. Eine Erhöhung des Schichtgewichtes würde auch in der Kaltumformung höhere Umformgrade zulassen.In particular for corrosion protection with oils and to facilitate cold forming, e.g. B. cold extrusion, layers with a higher coating weight, z. B. in the range between 8 to 30 g / m 2 required. In some cases, particularly high demands are placed on corrosion protection. This can be achieved by increasing the layer weight. An increase in the layer weight would also allow higher degrees of deformation in cold forming.

Die Abscheidung von dicken Zinkphosphatschichten kann gemäß DE-AS 12 87 412 sowie US-PS 32 68 367 durch in-Berührung-bringen von Eisen und Stahl mit einer nitratbeschleunigten sauren Zinkphosphatierlösung unter Zusatz von Polycarbonsäuren, in der das wenigstens einer Carboxylgruppe benachbarte Kohlenstoffatom eine Hydroxy-, Amino- oder Carboxylgruppe trägt, erreicht werden. Diese Phosphatierlösung kann weiterhin Zusätze wie Nickel, Kobalt, Lithium, Wismut und Mangan in geringen Konzentrationen von kleiner als 0,5 g/l enthalten. Sie aktivieren die zu phosphatierende Metalloberfläche und begünstigen die Abscheidung von Zinkphosphatschichten.The deposition of thick zinc phosphate layers can according to DE-AS 12 87 412 and US Pat. No. 3,268,367 by bringing iron and steel into contact with a nitrate-accelerated acidic zinc phosphating solution with the addition of polycarboxylic acids in which the carbon atom adjacent to at least one carboxyl group is a hydroxy -, Amino or carboxyl group can be achieved. This phosphating solution can also contain additives such as nickel, cobalt, lithium, bismuth and manganese in small concentrations of less than 0.5 g / l. They activate the metal surface to be phosphated and promote the deposition of zinc phosphate layers.

Die Abscheidung derart dicker Phosphatschichten zur Lösung des geschilderten Problems hat den Nachteil, daß der Chemikalienverbrauch vergleichsweise hoch ist. Weiterhin kann in manchen Fällen, z. B. je nach Art der Legierung des zu phosphatierenden Werkstückes, der Erzeugung von dickeren Schichten Grenzen gesetzt sein.The deposition of such thick phosphate layers to solve the problem described has the disadvantage that the chemical consumption is comparatively high. Furthermore, in some cases, e.g. B. depending on the type of alloy of the workpiece to be phosphated, the production of thicker layers.

Aufgabe der Erfindung ist, ein Phosphatierverfahren bereitzustellen, das die geschilderten Nachteile nicht aufweist, insbesondere universell anwendbar ist, mit einem geringen Chemikalienbedarf auskommt und zu hochwertigeren Phosphatschichten führt.The object of the invention is to provide a phosphating process which does not have the disadvantages described, in particular is universally applicable, requires little chemicals and leads to higher-quality phosphate layers.

Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man die Metalloberflächen bei Behandlungstemperaturen von 50 bis 98 °C mit einer Phosphatierungslösung in Berührung bringt, die mindestens 0,6 g/1 Manganionen enthält, in der das Gewichtsverhältnis

Figure imgb0001
Figure imgb0002
Figure imgb0003
beträgt und
die im eingearbeiteten Zustand eine Gesamtsäurepunktzahl von mindestens 20 Punkten aufweist.The object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the metal surfaces are brought into contact with a phosphating solution which contains at least 0.6 g / l of manganese ions at treatment temperatures of 50 to 98 ° C. in which the weight ratio
Figure imgb0001
Figure imgb0002
Figure imgb0003
 is and
which has a total acid score of at least 20 points when incorporated.

Ein derartiges Verfahren führt zu Zink-Mangan-Phosphatschichten, die bei vergleichbaren Schichtdicken Zinkphosphatschichten bezüglich Korrosionsschutz und Kaltumformeigenschaften überlegen sind.Such a method leads to zinc-manganese-phosphate layers which, with comparable layer thicknesses, are superior to zinc phosphate layers with regard to corrosion protection and cold-forming properties.

Vorzugsweise werden die Metalloberflächen mit einer Phosphatierungslösung in Berührung gebracht, in der der Gehalt an Manganionen mindestens 1 g/l beträgt. Hierdurch wird ein höherer, die vorgenannten Eigenschaften noch verbessernder Manganphosphat-Anteil in der Schicht erzielt.The metal surfaces are preferably brought into contact with a phosphating solution in which the manganese ion content is at least 1 g / l. As a result, a higher manganese phosphate content in the layer, which improves the aforementioned properties, is achieved.

Optimale Ergebnisse hinsichtlich der Schichtqualität werden erzielt, wenn in einer weiteren bevorzugten Ausgestaltung der Erfindung die Metalloberflächen mit einer Phosphatierungslösung in Berührung gebracht werden, in der das Gewichtsverhältnis von Mn : Zn gleich 1 : (0,8 bis 12) beträgt.Optimal results with regard to the layer quality are achieved if, in a further preferred embodiment of the invention, the metal surfaces are brought into contact with a phosphating solution in which the weight ratio of Mn: Zn is 1: (0.8 to 12).

Weiterhin wurde gefunden, daß mit steigendem Manganphosphat-Anteil in der Schicht sich deren Eignung speziell zur Vorbereitung für die Kaltumformung verbessert. Über dem Bereich von 1 : 0,2 liegende Manganionen-Gehalte in der Phosphatierungslosung führen zu nicht geschlossenen, löcherigen Schichten.Furthermore, it was found that with increasing manganese phosphate content in the layer, its suitability especially for preparation for cold forming improves. Manganese ion contents in the phosphating solution above the range of 1: 0.2 lead to non-closed, perforated layers.

Innerhalb der geforderten Grenzen können Bäder mit z.B. 80 Gesamtsäurepunkten wie folgt zusammengesetzt sein:

Figure imgb0004
Within the required limits, baths with e.g. 80 total acid points can be composed as follows:
Figure imgb0004

Die Gesamtsäurepunktzahl läßt sich durch Titration einer 10 ml Badprobe mit 0,1 n NaOH gegen Phenolphthalein als Indikator bis zum Umschlag von farblos nach rosa ermitteln.The total acid number can be determined by titration of a 10 ml bath sample with 0.1 N NaOH against phenolphthalein as an indicator until the color changes from colorless to pink.

Zur Aktivierung der zu phosphatierenden Stahl- oder Eisenoberflächen können dem Bad Nickel- und/oder Kobalt- und/ oder Kupferionen und dergleichen zugesetzt werden. Zweckmäßigerweise werden diese Metallionen in einer Konzentration von z. B. 0,02 bis 0,10 g/l dem Bad zugesetzt. Das zu den Metallionen gehörige Anion kann z. B. Nitrat oder Sulfat sein.To activate the steel or iron surfaces to be phosphated, nickel and / or cobalt and / or copper ions and the like can be added to the bath. Advantageously, these metal ions in a concentration of z. B. 0.02 to 0.10 g / l added to the bath. The anion belonging to the metal ions can e.g. B. nitrate or sulfate.

Falls eine weitere Erhöhung des Schichtgewichtes erwünscht ist, empfiehlt es sich, die Metalloberflächen mit einer Phosphatierungslösung in Berührung zu bringen, die einfache und/oder komplexe Fluoride, wie NaF, NaHF2 und/oder Na2SiF6, enthalten.If a further increase in the layer weight is desired, it is advisable to bring the metal surfaces into contact with a phosphating solution which contains simple and / or complex fluorides, such as NaF, NaHF 2 and / or Na 2 SiF 6 .

Falls erwünscht, kann eine gewisse Erniedrigung des Schichtgewichtes herbeigeführt werden, wenn dem Phosphatierungsbad kondensierte Phosphate zugesetzt werden.If desired, a certain reduction in the layer weight can be brought about if condensed phosphates are added to the phosphating bath.

Es liegt in der Natur eines nitratbeschleunigten Phosphatierbades, daß sich infolge des Durchsatzes von Metalloberflächen Eisen-II-Ionen im Bad anreichern und die Gesamtsäure-Punktzahl abnimmt. Um einer Verschlechterung des Phosphatierergebnisses zu begegnen, ist eine Ergänzung des Phosphatierungsbades erforderlich.It is in the nature of a nitrate-accelerated phosphating bath that iron II ions accumulate in the bath due to the throughput of metal surfaces and the Total acid score decreases. To counteract a deterioration in the phosphating result, an addition of the phosphating bath is necessary.

Besonders vorteilhafte Ergebnisse werden erzielt, wenn man das Phosphatierungsbad hinsichtlich der Komponenten Zink-, Mangan-, Phosphat- und Nitrationen im Gewichtsverhältnis

Figure imgb0005
Figure imgb0006
Figure imgb0007
ergänzt.Particularly advantageous results are obtained if the phosphating bath with respect to the components zinc, manganese, phosphate and nitrate ions in a weight ratio
Figure imgb0005
Figure imgb0006
Figure imgb0007
 added.

Die zu phosphatierenden Werkstücke sollen fett- und zunder- bzw. rostfrei sein. Die Entfettung kann z. B. mittels wäßriger, alkalischer, oberflächenaktive Substanzen enthaltender Reiniger erfolgen.The workpieces to be phosphated should be free of grease, scale and rust. The degreasing can e.g. B. by means of aqueous, alkaline, surface-active substances containing cleaners.

Die Entzunderung erfolgt zweckmäßigerweise mittels Schwefelsäure oder Salzsäure.Descaling is advantageously carried out using sulfuric acid or hydrochloric acid.

Nach der Reinigung und/oder Beizung sollten die Werkstücke gut mit Wasser gespült werden.After cleaning and / or pickling, the workpieces should be rinsed well with water.

Die Werkstücke können vor der Phosphatierung zur Ausbildung von feinkristallinen Schichten in an sich bekannter Weise, z. B. mit Titanorthophosphat- bzw. Manganorthophosphatsuspensionen in Wasser, vorgespült werden. Es hat sich in der Praxis erwiesen, daß in manchen Fällen auch schon eine Vorspülung mit 50 bis 98 °C heißem Wasser die Oberfläche aktiviert.The workpieces can be formed in a manner known per se, e.g. B. with titanium orthophosphate or manganese orthophosphate suspensions in water. It has been found in practice that in some cases a pre-rinse with water at 50 to 98 ° C activates the surface.

Das Phosphatierbad wird je nach Werkstückart, je nach Legierung und je nach Anwendungsart zwischen 50 und 98 °C betrieben. Es hat sich erwiesen, daß eine Tauchzeit von 5 bis 15 Minuten für die meisten Anwendungsfälle ausreichend ist.The phosphating bath is operated between 50 and 98 ° C depending on the type of workpiece, the alloy and the type of application. It has been shown that a diving time of 5 to 15 minutes is sufficient for most applications.

Wie erwähnt, wird sich - bedingt durch die Nitratbeschleunigung - im Laufe des Durchsatzes Eisen-II im Phosphatierbad anreichern. Die Wirkungsweise des Bades wird hierdurch nicht beeinträchtigt. In Sonderfällen, z. B. bei hohen Nitratkonzentrationen oder bei hohen Badtemperaturen, kann es jedoch auch vorkommen, daß das Bad infolge der Oxidation von FeII zu FeIII Eisen-II-frei bleibt. Auch dies beeinträchtigt die Wirkungsweise des Bades nicht. Die Ergänzung des Bades erfolgt zweckmäßigerweise auf Konstanz der Gesamtsäurepunktzahl.As mentioned, due to the acceleration of nitrate, iron II will accumulate in the phosphating bath in the course of the throughput. This does not affect the way the bath works. In special cases, e.g. B. at high nitrate concentrations or at high bath temperatures, it can also happen that the bath remains iron-II-free due to the oxidation of FeII to FeIII. This also does not affect the way the bath works. The addition of the bath is expediently carried out on a constant total acid number.

Das Schichtgewicht der erzielten Zink-Mangan-Phosphatschichten liegt je nach Phosphatierbadzusammensetzung und Legierung des zu behandelnden Werkstückes normalerweise zwischen ca. 5 und ca. 30 g/m2.The layer weight of the zinc-manganese-phosphate layers obtained is normally between about 5 and about 30 g / m 2, depending on the composition of the phosphating bath and the alloy of the workpiece to be treated.

Nach der Phosphatierung wird mit Wasser gespült, gegebenenfalls nachbehandelt und bei Bedarf getrocknet.After phosphating, it is rinsed with water, optionally aftertreated and dried if necessary.

Für den Korrosionsschutz kann z. B. nachbehandelt werden mit Chromsäurelösungen, gefolgt von einer Behandlung mit Korrosionsschutzölemulsionen. Für die Kaltumformung können die Werkstücke z. B. mit Seifenlösungen nachbehandelt werden.For corrosion protection z. B. be treated with chromic acid solutions, followed by treatment with anti-corrosion oil emulsions. For cold forming, the workpieces can e.g. B. be treated with soap solutions.

Die auf diese Weise behandelten Werkstücke sind den mit üblichen nitratbeschleunigten Zinkphosphatiersystemen behandelten Werkstücken bezüglich Korrosionsschutz und Kaltumformeigenschaften überlegen.The workpieces treated in this way are superior to the workpieces treated with conventional nitrate accelerated zinc phosphating systems in terms of corrosion protection and cold forming properties.

Die Erfindung wird anhand der folgenden Beispiele beispielsweise und näher erläutert.The invention is illustrated by the following examples, for example and in more detail.

Beispiel 1example 1

Stahlschrauben wurden wie folgt behandelt:

  • a) Beizen in 15 %iger Schwefelsäure mit einem Zusatz eines Beizinhibitors bei 60 °C und einer Tauchzeit von 10 Minuten
  • b) Spülen mit kaltem Wasser
  • c) Spülen mit 60 °C heißem Wasser
  • d) jeweils 10 Schrauben wurden 10 min im Tauchen im Phosphatierbad A, B und C phosphatiert.
    Figure imgb0008
  • e) Spülen mit kaltem Wasser
  • f) Nachspülen in vollentsalztem Wasser mit Zusatz von 0,5 g/l Natriumbichromat bei 80 °C
  • g) Behandeln mit einer 13 %igen Emulsion eines Korrosionsschutzöles bei 60 °C
  • h) Ofentrocknen bei 70 °C.
Steel screws were treated as follows:
  • a) Pickling in 15% sulfuric acid with the addition of a pickling inhibitor at 60 ° C and a dipping time of 10 minutes
  • b) Rinse with cold water
  • c) Rinse with hot water at 60 ° C
  • d) 10 screws in each case were phosphatized for 10 minutes while immersed in the phosphating bath A, B and C.
    Figure imgb0008
  • e) Rinse with cold water
  • f) rinsing in deionized water with the addition of 0.5 g / l sodium bichromate at 80 ° C.
  • g) Treatment with a 13% emulsion of an anti-corrosion oil at 60 ° C
  • h) oven drying at 70 ° C.

Die Schrauben wurden dann im Salzsprühtest nach DIN 50021 SS geprüft, für jedes der drei Verfahren A, B und C wurden 10 Schrauben geprüft. Nach 72 Stunden Prüfzeit waren bei den Verfahren A und B 50 % der Schrauben verrostet; bei Verfahren C waren alle 10 Schrauben noch nicht angegriffen, obwohl das Schichtgewicht geringer ist als bei den Verfahren A und B.The screws were then tested in a salt spray test according to DIN 50021 SS, for each of the three methods A, B and C. 10 screws checked. After 72 hours of testing, methods A and B had rusted 50% of the screws; in method C, all 10 screws had not yet been attacked, although the layer weight was lower than in methods A and B.

Beispiel 2Example 2

Kaltfließpressteile wurden wie folgt behandelt:

  • a) Beizen in 15 %iger Salzsäure mit Zusatz eines Beizinhibitors bei Raumtemperatur und einer Behandlungszeit von 10 Minuten
  • b) Spülen mit kaltem Wasser
  • c) Spülen mit 75 °C heißem Wasser
  • d) jeweils 100 Kaltfließpressteile wurden 10 min im Tauchen in Phosphatierbad D und E behandelt.
    Figure imgb0009
  • e) Spülen mit kaltem Wasser
  • f) Behandeln in einer 5 %igen Natronseife bei 73 °C und einer Tauchzeit von 5 min
  • g) Trocknen durch Eigenwärme an der Luft.
Cold extrusion parts were treated as follows:
  • a) Pickling in 15% hydrochloric acid with the addition of a pickling inhibitor at room temperature and a treatment time of 10 minutes
  • b) Rinse with cold water
  • c) Rinse with hot water at 75 ° C
  • d) 100 cold extrusion parts were treated for 10 minutes by immersion in phosphating baths D and E.
    Figure imgb0009
  • e) Rinse with cold water
  • f) treatment in a 5% sodium soap at 73 ° C and a dipping time of 5 min
  • g) Drying in the air by natural heat.

Die Teile wurden rückwärts fließgepreßt zu Hülsen. Bei den Teilen, die in Bad D behandelt worden sind, hatten die Hülsen zu etwa 80 % Riefen und die Oberfläche hatte ein metallisch blankes Aussehen. Bei den Teilen, die in Bad E behandelt worden sind, konnten keine Riefen festgestellt werden und die Oberfläche war grau, was auf eine erhebliche Restphosphatschicht deutet.The parts were extruded back into sleeves. For the parts that were treated in bath D, the sleeves had about 80% grooves and the surface had a shiny metallic appearance. In the parts that were treated in bath E, no marks could be found and the surface was gray, which indicates a significant residual phosphate layer.

Beispiel 3Example 3

Stahlbleche der Qualität USt 1405 m wurden wie folgt behandelt:

  • a) Reinigen in einem stark alkalischen wäßrigen Reiniger bei 95 °C und einer Tauchzeit von 15 min
  • b) Spülen mit kaltem Wasser.
  • c) Beizen in H2S04, 20 %ig mit Zusatz eines Beizinhibitors, bei 65 °C und einer Tauchzeit von 10 min
  • d) Spülen mit kaltem Wasser
  • e) Phosphatieren bei 75 °C und einer Tauchzeit von 10 min in Bad F und G
  • f) Spülen mit kaltem Wasser.
Steel sheets of the VAT 1405 m quality were treated as follows:
  • a) cleaning in a strongly alkaline aqueous cleaner at 95 ° C and a dipping time of 15 min
  • b) Rinse with cold water.
  • c) Pickling in H2S04, 20% with the addition of a pickling inhibitor, at 65 ° C and a dipping time of 10 min
  • d) Rinse with cold water
  • e) Phosphating at 75 ° C and a dipping time of 10 min in bath F and G
  • f) Rinse with cold water.

Die Zusammensetzung der Bäder F und G ist in der folgenden Tabelle aufgeführt. Die Gesamtsäurepunktzahl der Bäder betrug jeweils 90 Punkte.The composition of baths F and G is shown in the following table. The total acid number of baths was 90 points each.

Nach einem Durchsatz von jeweils 0,2 m2 Blechoberfläche pro Liter Badlösung wurden die Bäder auf Punktkonstanz mit den in der Tabelle aufgeführten Ergänzungskonzentraten ergänzt.After a throughput of 0.2 m 2 of sheet metal surface per liter of bath solution, the baths were supplemented to the point constancy with the supplementary concentrates listed in the table.

Bei Beginn des Durchsatzes und nach Durchsatz von 4 m2 Stahloberfläche pro Liter Badlösung wurden Musterbleche abgezweigt zur Schichtgewichtsbestimmung und zur Korrosionsprüfung im Salzsprühtest nach DIN 50021 SS. Die Bleche für die Korrosionsprüfung wurden vorher behandelt mit einer 15 %igen Emulsion eines Korrosionsschutzöles und anschließend bei 70 °C im Ofen getrocknet.

Figure imgb0010
Es ist deutlich erkennbar, daß durch die bevorzugte Ausgestaltung der Ergänzung die Phosphatier-Bäder auch nach Durchsatz von 4 m2/l zu Schichten führen, die ihre guten Eigenschaften beibehalten haben.At the start of the throughput and after the throughput of 4 m 2 of steel surface per liter of bath solution, sample sheets became branched off to determine the layer weight and for the corrosion test in the salt spray test according to DIN 50021 SS. The sheets for the corrosion test were previously treated with a 15% emulsion of an anti-corrosion oil and then dried in an oven at 70 ° C.
Figure imgb0010
 It can be clearly seen that the preferred configuration of the supplement means that the phosphating baths, even after a throughput of 4 m 2 / l, lead to layers which have retained their good properties.

Claims (5)

1. Verfahren zur Herstellung von Phosphatüberzügen auf Metalloberflächen von Eisen und Stahl unter Verwendung einer sauren nitratbeschleunigten Zink- und Manganionen enthaltenden Phosphatierungslösung bei erhöhten Temperaturen im Tauchverfahren, dadurch gekennzeichnet, daß man die Metalloberflächen bei Behandlungstemperaturen von 50 bis 98 °C mit einer Phosphatierungslösung in Berührung bringt, die mindestens 0,6 g/l Manganionen enthält, in der das Gewichtsverhältnis
Figure imgb0011
Figure imgb0012
Figure imgb0013
beträgt und
die im eingearbeiteten Zustand eine Gesamtsäurepunktzahl von mindestens 20 Punkten aufweist.1. A process for the preparation of phosphate coatings on metal surfaces of iron and steel using an acidic nitrate-accelerated zinc and manganese ion-containing phosphating solution at elevated temperatures in the immersion process, characterized in that the metal surfaces are in contact with a phosphating solution at treatment temperatures of 50 to 98 ° C. brings, which contains at least 0.6 g / l of manganese ions, in which the weight ratio
Figure imgb0011
Figure imgb0012
Figure imgb0013
 is and
which has a total acid score of at least 20 points when incorporated. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Metalloberflächen mit einer Phosphatierungslösung in Berührung bringt, in der der Gehalt an Manganionen mindestens 1 g/l beträgt.2. The method according to claim 1, characterized in that the metal surfaces are brought into contact with a phosphating solution in which the manganese ion content is at least 1 g / l. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man die Metalloberflächen mit einer Phosphatierungslösung in Berührung bringt, in der das Gewichtsverhältnis von Mn : Zn = 1 : (0,8 bis 12) beträgt.3. The method according to claim 1 or 2, characterized in that the metal surfaces are brought into contact with a phosphating solution in which the weight ratio of Mn: Zn = 1: (0.8 to 12). 4. Verfahren nach Anspruch 1, 2 oder 3, dadurch gekennzeichnet, daß man die Metalloberflächen mit einer Phosphatierungslösung in Berührung bringt, die einfache und/oder komplexe Fluoride, wie NaF, NaHF2 und/oder Na2SiF6, enthalten.4. The method according to claim 1, 2 or 3, characterized in that the metal surfaces are brought into contact with a phosphating solution which contain simple and / or complex fluorides, such as NaF, NaHF 2 and / or Na 2 SiF 6 . 5. Verfahren nach Anspruch 1, 2, 3 oder 4, dadurch gekennzeichnet, daß man das Phosphatierungsbad hinsichtlich der Komponenten Zink-, Mangan-, Phosphat-und Nitrationen im Gewichtsverhältnis
Figure imgb0014
Figure imgb0015
Figure imgb0016
 5. The method according to claim 1, 2, 3 or 4, characterized in that the phosphating bath with respect to the components zinc, manganese, phosphate and nitrate ions in a weight ratio
Figure imgb0014
Figure imgb0015
Figure imgb0016
EP81200442A 1980-06-24 1981-04-17 Method of phosphating metallic surfaces Expired EP0042631B1 (en)

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DE3023479 1980-06-24
DE19803023479 DE3023479A1 (en) 1980-06-24 1980-06-24 PHOSPHATING PROCESS

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PT (1) PT73117B (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0106459A1 (en) * 1982-08-24 1984-04-25 HENKEL CORPORATION (a Delaware Corp.) Phosphate coating metal surfaces
EP0172806A1 (en) * 1984-01-06 1986-03-05 Ford Motor Company Alkaline resistance phosphate conversion coatings
EP0186823A2 (en) * 1984-12-20 1986-07-09 HENKEL CORPORATION (a Delaware corp.) Process for facilitating cold-forming
US4681641A (en) * 1982-07-12 1987-07-21 Ford Motor Company Alkaline resistant phosphate conversion coatings
EP0298827A1 (en) * 1987-06-25 1989-01-11 Roquette Frˬres Mixed phosphatation solution and process
US5039361A (en) * 1988-12-02 1991-08-13 Metallgesellschaft Aktiengesellschaft Process of phosphating metal surfaces
US5234509A (en) * 1984-12-20 1993-08-10 Henkel Corporation Cold deformation process employing improved lubrication coating
WO1996009422A1 (en) * 1994-09-23 1996-03-28 Henkel Kommanditgesellschaft Auf Aktien No-rinse phosphatising process
WO2001023638A1 (en) * 1999-09-30 2001-04-05 Chemetall Gmbh Method for applying manganese phosphate layers
US9506151B2 (en) 1999-09-30 2016-11-29 Chemetall Gmbh Method for applying manganese phosphate layers

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6342107B1 (en) * 1982-08-24 2002-01-29 Henkel Corporation Phosphate coatings for metal surfaces
DE3636390A1 (en) * 1986-10-25 1988-04-28 Metallgesellschaft Ag METHOD FOR PRODUCING PHOSPHATE COATINGS ON METALS
DE10010355A1 (en) * 2000-03-07 2001-09-13 Chemetall Gmbh Applying phosphate coatings to metallic surfaces comprises wetting with an aqueous acidic phosphatizing solution containing zinc ions, manganese ions and phosphate ions, and drying the solution

Citations (4)

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Publication number Priority date Publication date Assignee Title
DE2716709A1 (en) * 1976-04-19 1977-11-03 Nippon Paint Co Ltd METHOD OF PHOSPHATING IRON AND STEEL
US4086103A (en) * 1975-08-13 1978-04-25 Kevin James Woods Accelerator for phosphating solutions
DE2818426A1 (en) * 1977-05-03 1978-11-09 Metallgesellschaft Ag METHOD FOR APPLYING A PHOSPHATE COATING TO METAL SURFACES
US4180417A (en) * 1977-10-12 1979-12-25 Nippon Paint Co., Ltd. Phosphating of metallic substrate

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DE1287412B (en) * 1963-11-30 1969-01-16 Metallgesellschaft Ag Process to improve the corrosion resistance by producing phosphate coatings of increased layer weight on surfaces made of iron and steel

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4086103A (en) * 1975-08-13 1978-04-25 Kevin James Woods Accelerator for phosphating solutions
DE2716709A1 (en) * 1976-04-19 1977-11-03 Nippon Paint Co Ltd METHOD OF PHOSPHATING IRON AND STEEL
DE2818426A1 (en) * 1977-05-03 1978-11-09 Metallgesellschaft Ag METHOD FOR APPLYING A PHOSPHATE COATING TO METAL SURFACES
US4180417A (en) * 1977-10-12 1979-12-25 Nippon Paint Co., Ltd. Phosphating of metallic substrate

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4681641A (en) * 1982-07-12 1987-07-21 Ford Motor Company Alkaline resistant phosphate conversion coatings
EP0106459A1 (en) * 1982-08-24 1984-04-25 HENKEL CORPORATION (a Delaware Corp.) Phosphate coating metal surfaces
EP0172806A1 (en) * 1984-01-06 1986-03-05 Ford Motor Company Alkaline resistance phosphate conversion coatings
EP0172806A4 (en) * 1984-01-06 1986-05-16 Ford Motor Co Alkaline resistance phosphate conversion coatings.
US5234509A (en) * 1984-12-20 1993-08-10 Henkel Corporation Cold deformation process employing improved lubrication coating
EP0186823A2 (en) * 1984-12-20 1986-07-09 HENKEL CORPORATION (a Delaware corp.) Process for facilitating cold-forming
EP0186823A3 (en) * 1984-12-20 1988-04-27 Parker Chemical Company Process for facilitating cold-forming
EP0298827A1 (en) * 1987-06-25 1989-01-11 Roquette Frˬres Mixed phosphatation solution and process
US5045130A (en) * 1987-06-25 1991-09-03 Compagnie Francaise De Produits Industriels Solution and process for combined phosphatization
FR2618164A1 (en) * 1987-06-25 1989-01-20 Roquette Freres SOLUTION AND METHOD FOR MIXED PHOSPHATION.
US5039361A (en) * 1988-12-02 1991-08-13 Metallgesellschaft Aktiengesellschaft Process of phosphating metal surfaces
WO1996009422A1 (en) * 1994-09-23 1996-03-28 Henkel Kommanditgesellschaft Auf Aktien No-rinse phosphatising process
US5976272A (en) * 1994-09-23 1999-11-02 Henkel Kommanditgesellschaft Auf Aktien No-rinse phosphating process
WO2001023638A1 (en) * 1999-09-30 2001-04-05 Chemetall Gmbh Method for applying manganese phosphate layers
US9506151B2 (en) 1999-09-30 2016-11-29 Chemetall Gmbh Method for applying manganese phosphate layers

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IT1137254B (en) 1986-09-03
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GB2078788A (en) 1982-01-13
EP0042631B1 (en) 1984-10-31
DE3023479A1 (en) 1982-01-14
ES8305052A1 (en) 1983-04-16
PT73117A (en) 1981-07-01
IT8122510A0 (en) 1981-06-23
ES502507A0 (en) 1983-04-16
PT73117B (en) 1982-07-15

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