EP0269138B1 - Process for producing phosphate coatings on metals - Google Patents

Process for producing phosphate coatings on metals Download PDF

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Publication number
EP0269138B1
EP0269138B1 EP87201890A EP87201890A EP0269138B1 EP 0269138 B1 EP0269138 B1 EP 0269138B1 EP 87201890 A EP87201890 A EP 87201890A EP 87201890 A EP87201890 A EP 87201890A EP 0269138 B1 EP0269138 B1 EP 0269138B1
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Prior art keywords
metals
iron
ions
process according
contacted
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German (de)
French (fr)
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EP0269138A1 (en
Inventor
Han Yong Dr. Oei
Günter Siemund
Rudolf Vey
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GEA Group AG
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Metallgesellschaft AG
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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
    • C23C22/34—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

Definitions

  • the invention relates to a process for the production of phosphate coatings on at least partially iron or steel surfaces containing metals by means of aqueous phosphating solutions containing zinc, manganese, P0 4 -, nitrate and - in the incorporated state - iron (11) ions, as well as its Application to the preparation of metals for the subsequent cold forming.
  • phosphate metals in particular iron and steel
  • manganese and iron (II) -containing zinc phosphate solutions at temperatures from 50 to 98 ° C.
  • the phosphate coatings produced here are suitable for all fields of application known in phosphating technology, e.g. Rust protection, primer for paints, electrical insulation as well as facilitating sliding processes and non-cutting cold forming (DE-OS 30 23 479, EP-PS 42 631).
  • the object of the invention is to provide a process for the production of phosphate coatings on at least partially iron or steel surfaces containing metals, which works in the low temperature range and on the iron (II) side, gives uniformly covering phosphate coatings and does not require any unusual procedural effort.
  • the method according to the invention is used in particular to treat iron and steel with alloy additives up to a maximum of about 5%.
  • alloy additives up to a maximum of about 5%.
  • other metals e.g. from zinc and zinc alloys, be it in the form of solid workpieces made of them or workpieces coated with them, successfully treated.
  • the individual components of the phosphating solution e.g. Zinc, manganese, phosphate etc. are usually, as is customary in phosphating technology, pre-dissolved together as an acidic phosphating concentrate and introduced into the phosphating solution in this form.
  • the individual components are dimensioned in such a way that the required concentration ranges result in the phosphating solution.
  • additional cations from the alkali and / or ammonium group may have to be used.
  • Preferred embodiments of the invention provide for the metals to be brought into contact with a phosphating solution which additionally contains 0.05 to 2 g / l Ni and / or 0.001 to 0.1 g / l Cu and / or 0.5 to 2 g / I Ca contains.
  • the nickel content supports the layer formation, especially on materials that are more difficult to attack and on zinc.
  • the addition of copper ions accelerates the phosphating process.
  • the phosphate coating is modified and the bath sludge - albeit low - is conditioned in such a way that it is less disruptive in the phosphating bath and is easier to remove from the system.
  • the phosphating solutions to be used in the process according to the invention do not necessarily contain iron (II) ions from the start. Rather, this component inevitably accumulates in the treatment of iron and steel in the bathroom.
  • the phosphating solutions are preferably used in such a way that the concentration of iron (II) ions does not exceed 10 g / l.
  • the iron (II) removal can e.g. in a separate ventilation tank with a downstream filter.
  • Bath components are consumed during the phosphating process, ie through coating formation, sludge formation and mechanical discharge of phosphating solution. These must be returned to the phosphating solution via the individual components or via supplementary concentrates that contain several or all of the individual components.
  • the supplement is particularly advantageous if the phosphating solution is supplemented with regard to the components zinc, manganese, phosphate and nitrate ions by adding at least one concentrate in which the weight ratios of Zn: P 2 0s to (0.3 to 0, 8): I, from Mn: Zn to (0.01 to 0.05): I and from NOs: P 2 0 5 to (0.2 to I): I.
  • the other components should be in the weight ratio Ca: Zn as (0.005 to 0.1): I, Ni: Zn as (0.005 to 0.05): I, Cu: Zn as (0.001 to 0.03 ): I and the components (tartaric acid and / or citric acid): P 2 0 5 as (0.05 to 0.3): I and BF 4 : P 2 0 5 as (0.008 to 0.04): I are added .
  • Manganese carbonate, zinc oxide and / or zinc carbonate which are added to the phosphating solution in powder form or as an aqueous slurry, are preferably suitable for setting the ratio of free acid to total acid required according to the claims.
  • titrate 10 ml bath samples with n / 10 NaOH against the first or second change in phosphoric acid using e.g. the color change of dimethyl yellow (free acid) or of phenolphthalein (total acid) serves.
  • the ml of n / 10 NaOH consumed correspond to the free acid or the total acid in points.
  • nitrite-interfering substances e.g. Contains urea or amidosulfonic acid. This prevents autocatalytic nitrite formation from the nitrate contained and prevents the bath from "tipping over" from the iron side to the nitrite side.
  • the metals can come into contact with the phosphating solution by dipping, flooding or spraying.
  • the application is usually done in diving, with treatment times of e.g. 5 to 15 minutes should be observed.
  • the phosphate layers produced by the methods according to the invention have a layer weight of approximately 3 to 15 g / m 2 .
  • the pretreatment of the metals before the actual phosphating is done in a conventional manner.
  • degreasing can be carried out using aqueous, alkaline cleaners which advantageously contain surfactant.
  • scale or rust can be removed by pickling treatment, e.g. with sulfuric acid or hydrochloric acid.
  • the workpieces can be formed prior to phosphating to form fine crystalline phosphate coatings in a manner known per se, e.g. with an activation bath containing titanium phosphate.
  • the phosphating treatment After the phosphating treatment, it is usually rinsed with water, optionally aftertreated and dried if necessary.
  • water optionally aftertreated and dried if necessary.
  • e.g. are treated with chromic acid and / or corrosion protection emulsions.
  • an aftertreatment e.g. with a soap bath.
  • the phosphate coatings produced by the process according to the invention can be used advantageously in all fields in which phosphate coatings are used. However, they are preferably suitable for the preparation of metals for the subsequent cold forming.
  • the basis weight of the phosphate coating was 8 to 10 g / m 2 .
  • the phosphate coating was uniformly opaque and fine-crystalline despite the absence of an activating pre-rinse with titanium phosphate.
  • the wires pretreated in this way could easily be formed in up to 10 passes with a maximum cross-sectional decrease of 93.5% with very little wear on the drawing tools.
  • the wire surface still had a uniform layer of residual phosphate after drawing and was free of scoring.

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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)

Description

Die Erfindung betrifft ein Verfahren zur Erzeugung von Phosphatüberzügen auf mindestens teilweise Eisen oder Stahloberflächen aufweisenden Metallen mittels wäßriger Phosphatierungslösungen, die Zink-, Mangan-, P04-, Nitrat- und - in eingearbeitetem Zustand - Eisen(11)-ionen enthalten, sowie dessen Anwendung auf die Vorbereitung von Metallen für die anschließende Kaltumformung.The invention relates to a process for the production of phosphate coatings on at least partially iron or steel surfaces containing metals by means of aqueous phosphating solutions containing zinc, manganese, P0 4 -, nitrate and - in the incorporated state - iron (11) ions, as well as its Application to the preparation of metals for the subsequent cold forming.

Es ist bekannt, Metalle, insbesondere Eisen und Stahl, mit Mangan und Eisen(II)-haltigen Zinkphosphatlösungen bei Temperaturen von 50 bis 98°C zu phosphatieren. Die hierbei erzeugten Phosphatüberzüge eignen sich für alle in der Phosphatiertechnik bekannten Anwendungsgebiete, z.B. Rostschutz, Haftgrund für Lacke, elektrische Isolation sowie Erleichterung von Gleitvorgängen und der spanlosen Kaltumformung (DE-OS 30 23 479, EP-PS 42 631).It is known to phosphate metals, in particular iron and steel, with manganese and iron (II) -containing zinc phosphate solutions at temperatures from 50 to 98 ° C. The phosphate coatings produced here are suitable for all fields of application known in phosphating technology, e.g. Rust protection, primer for paints, electrical insulation as well as facilitating sliding processes and non-cutting cold forming (DE-OS 30 23 479, EP-PS 42 631).

Bei der Anwendung der bekannten Verfahren im Bereich niedriger Temperaturen, z.B. zwischen 30 und 50°C, treten jedoch häufig Schwierigkeiten auf, die sich u.a. in der Ausbildung unvollständig deckender und mit zunehmendem Eisen(11)-Gehalt in der Phosphatierungslösung gröber werdenden Phosphatüberzügen äußern. Durch Anwendung einer aktivierenden Vorspülung, z.B. auf Basis von Titanphosphat, lassen sich zwar gewisse Verbesserungen erzielen, ohne jedoch zu voll befriedigenden Ergebnissen zu gelangen. Andererseits besteht wegen der damit verbundenen Energieersparnis ein dringender Bedarf an Niedrigtemperatur-Verfahren. Ferner bringen die auf der Eisen(II)-Seite betriebenen Verfahren im Vergleich zu den Verfahren, die mit praktisch eisen(II)-freien Phosphatierungslösungen arbeiten, den Vorteil, daß sie wesentlich weniger Badschlamm liefern und günstige Verbrauchswerte aufweisen.When using the known methods in the range of low temperatures, for example between 30 and 50 ° C., difficulties often arise which are manifested, among other things, in the formation of incompletely opaque phosphate coatings which become coarser with increasing iron (11) content in the phosphating solution. By using an activating pre-rinse, for example based on titanium phosphate, certain improvements can be achieved without, however, achieving completely satisfactory results. On the other hand, because of the associated energy savings, there is an urgent need for low-temperature processes. Furthermore, the processes operated on the iron (II) side have the advantage, compared to the processes which work with practically iron (II) -free phosphating solutions, that they deliver significantly less bath sludge and have favorable consumption values.

Aufgabe der Erfindung ist es, ein Verfahren zur Erzeugung von Phosphatüberzügen auf mindestens teilweise Eisen- oder Stahloberflächen aufweisenden Metallen bereitzustellen, das im Niedrigtemperaturbereich und auf der Eisen(II)-Seite arbeitet, gleichmäßig deckende Phosphatüberzüge entstehen läßt und keinen unüblichen verfahrensmäßigen Aufwand erfordert.The object of the invention is to provide a process for the production of phosphate coatings on at least partially iron or steel surfaces containing metals, which works in the low temperature range and on the iron (II) side, gives uniformly covering phosphate coatings and does not require any unusual procedural effort.

Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man die Metalle mit einer Phosphatierungslösung einer Temperatur im Bereich von 30 bis 50°C in Kontakt bringt, die

  • Zink in Mengen von 5 bis 25 g/l
  • Mangan in Mengen von 1 bis 10 g/I
  • Eisen(II) in Mengen von 0,1 bis 13 g/I
  • Phosphat in Mengen von 5 bis 40 g/I
  • (ber. als P20s)
  • Nitrat in Mengen von 5 bis 50 g/I
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 metals are brought into contact with a phosphating solution at a temperature in the range from 30 to 50 ° C.
  • Zinc in amounts of 5 to 25 g / l
  • Manganese in quantities of 1 to 10 g / l
  • Iron (II) in amounts of 0.1 to 13 g / l
  • Phosphate in amounts of 5 to 40 g / l
  • (calculated as P 2 0s)
  • Nitrate in amounts of 5 to 50 g / l

sowie zusätzlich

  • 0,5 bis 5 g/l Fluoroborat (ber. als BF4)
  • 0,05 bis 3 g/I Weinsäure und/oder Zitronensäure enthält, in der die Gewichtsverhältnisse Zn: P20sauf (0,5 bis 3) : I und Mn : Zn auf (0,04 bis 0,5) : I und das Verhältnis von Freier Säure zu Gesamtsäure auf (0,04 bis 0,2) : I eingestellt sind.
as well as additionally
  • 0.5 to 5 g / l fluoroborate (calculated as BF 4 )
  • 0.05 to 3 g / l tartaric acid and / or citric acid, in which the weight ratios Zn: P 2 0sauf (0.5 to 3): I and Mn: Zn auf (0.04 to 0.5): I and the ratio of free acid to total acid is set to (0.04 to 0.2): I.

Das erfindungsgemäße Verfahren dient insbesondere der Behandlung von Eisen und Stahl mit Legierungszusätzen bis maximal etwa 5 %. Außerdem lassen sich zusammen mit Eisen und Stahl auch andere Metalle, z.B. aus Zink und Zinklegierungen, sei es in Form hieraus bestehender massiver Werkstücke oder hiermit beschichteter Werkstücke, mit Erfolg behandeln.The method according to the invention is used in particular to treat iron and steel with alloy additives up to a maximum of about 5%. In addition, together with iron and steel, other metals, e.g. from zinc and zinc alloys, be it in the form of solid workpieces made of them or workpieces coated with them, successfully treated.

Die einzelnen Komponenten der Phosphatierungslösung, z.B. Zink, Mangan, Phosphat etc., werden meist, wie in der Phosphatiertechnik üblich, gemeinsam als saures Phosphatierkonzentrat vorgelöst und in dieser Form in die Phosphatierungslösung eingebracht. Die Bemessung der einzelnen Bestandteile erfolgt in der Weise, daß die geforderten Konzentrationsbereiche in der Phosphatierungslösung resultieren. Um das notwendige Verhältnis von Freier Säure zu Gesamtsäure einzustellen, müssen gegebenenfalls weitere Kationen aus der Alkali- und/oder Ammoniumgruppe mitverwendet werden.The individual components of the phosphating solution, e.g. Zinc, manganese, phosphate etc. are usually, as is customary in phosphating technology, pre-dissolved together as an acidic phosphating concentrate and introduced into the phosphating solution in this form. The individual components are dimensioned in such a way that the required concentration ranges result in the phosphating solution. To set the necessary ratio of free acid to total acid, additional cations from the alkali and / or ammonium group may have to be used.

Bevorzugte Ausführungsformen der Erfindung sehen vor, die Metalle mit einer Phosphatierungslösung in Kontakt zu bringen, die zusätzlich 0,05 bis 2 g/I Ni und/oder 0,001 bis 0,1 g/I Cu und/oder 0,5 bis 2 g/I Ca enthält. Durch den Nickelgehalt wird die Schichtbildung, insbesondere auf schwerer angreifbaren Materialien und auf Zink, unterstützt. Durch die Zugabe von Kupferionen findet eine Beschleunigung des Phosphatierprozesses statt. Mit Hilfe des Zusatzes von Kalziumionen wird der Phosphatüberzug modifizert und der - allerdings geringe - Badschlamm so konditioniert, daß er im Phosphatierungsbad noch weniger stört und sich leichter aus dem System entfernen läßt.Preferred embodiments of the invention provide for the metals to be brought into contact with a phosphating solution which additionally contains 0.05 to 2 g / l Ni and / or 0.001 to 0.1 g / l Cu and / or 0.5 to 2 g / I Ca contains. The nickel content supports the layer formation, especially on materials that are more difficult to attack and on zinc. The addition of copper ions accelerates the phosphating process. With the addition of calcium ions, the phosphate coating is modified and the bath sludge - albeit low - is conditioned in such a way that it is less disruptive in the phosphating bath and is easier to remove from the system.

Die im erfindungsgemäßen Verfahren einzusetzenden Phosphatierungslösungen enthalten nicht notwendigerweise vom Start an Eisen(II)-ionen. Diese Komponente reichert sich vielmehr zwangsläufig bei der Behandlung von Eisen und Stahl im Bad an. Vorzugsweise werden die Phosphatierungslösungen derart eingesetzt, daß die Konzentration von Eisen(II)-ionen 10 g/I nicht übersteigt.The phosphating solutions to be used in the process according to the invention do not necessarily contain iron (II) ions from the start. Rather, this component inevitably accumulates in the treatment of iron and steel in the bathroom. The phosphating solutions are preferably used in such a way that the concentration of iron (II) ions does not exceed 10 g / l.

Um einen Anstieg der Konzentration darüber hinaus zu vermeiden, ist es zweckmäßig, einen Teil des durch Beizangriff in Lösung gegangenen Eisen(II)-ions zu Eisen(lll)-ionen zu oxidieren und damit in Form von schwer löslichem Eisen(III)-phosphat-Schlamm auszufällen. Bevorzugte Ausgestaltungen der Erfindung sehen vor, den überschüssigen Eisen(II)-gehalt durch Kontakt mit sauerstoffhaltigem Gas oder mit Hilfe von Chlorat in die dreiwertige Form zu überführen und als Eisen(III)-phosphat-Schlamm auszufällen. In der ersten Ausführungsform kann die Eisen(II)-Entfernung z.B. in einem separaten Belüftungsbehälter mit nachgeschaltetem Filter erfolgen.In order to avoid an increase in the concentration, it is advisable to oxidize part of the iron (II) ion dissolved in the pickling attack to iron (III) ions and thus in the form of poorly soluble iron (III) phosphate - precipitate sludge. Preferred refinements of the invention provide for the excess iron (II) content to be converted into the trivalent form by contact with oxygen-containing gas or with the aid of chlorate and to be precipitated as iron (III) phosphate sludge. In the first embodiment, the iron (II) removal can e.g. in a separate ventilation tank with a downstream filter.

Während des Phosphatierverfahrens, d.h. durch Überzugsausbildung, Schlammbildung und mechanischen Austrag von Phosphatierungslösung, werden Badkomponenten verbraucht. Diese müssen der Phosphatierungslösung über die Einzelkomponenten oder über Ergänzungskonzentrate, die mehrere oder alle Einzelkomponenten enthalten, wieder zugeführt werden. Besonders vorteilhaft gestaltet sich die Ergänzung, wenn man die Phosphatierungslösung hinsichtlich der Komponenten Zink-, Mangan-, Phosphat- und Nitrationen durch Zugabe von mindestens einem Konzentrat ergänzt, bei dem die Gewichtsverhältnisse von Zn : P20s auf (0,3 bis 0,8) : I, von Mn : Zn auf (0,01 bis 0,05) : I und von NOs : P205 auf (0,2 bis I) : I eingestellt sind. Sofern in der Phosphatierungslösung enthalten, sollten die weiteren Komponenten im Gewichtsverhältnis Ca : Zn wie (0,005 bis 0,1) : I, Ni : Zn wie (0,005 bis 0,05) : I, Cu : Zn wie (0,001 bis 0,03) : I sowie die Bestandteile (Weinsäure und/oder Zitronensäure) : P205 wie (0,05 bis 0,3) : I und BF4: P205 wie (0,008 bis 0,04) : I ergänzt werden.Bath components are consumed during the phosphating process, ie through coating formation, sludge formation and mechanical discharge of phosphating solution. These must be returned to the phosphating solution via the individual components or via supplementary concentrates that contain several or all of the individual components. The supplement is particularly advantageous if the phosphating solution is supplemented with regard to the components zinc, manganese, phosphate and nitrate ions by adding at least one concentrate in which the weight ratios of Zn: P 2 0s to (0.3 to 0, 8): I, from Mn: Zn to (0.01 to 0.05): I and from NOs: P 2 0 5 to (0.2 to I): I. If contained in the phosphating solution, the other components should be in the weight ratio Ca: Zn as (0.005 to 0.1): I, Ni: Zn as (0.005 to 0.05): I, Cu: Zn as (0.001 to 0.03 ): I and the components (tartaric acid and / or citric acid): P 2 0 5 as (0.05 to 0.3): I and BF 4 : P 2 0 5 as (0.008 to 0.04): I are added .

Zur Einstellung des anspruchsgemäß geforderten Verhältnisses an Freier Säure zu Gesamtsäure eignen sich vorzugsweise Mangankarbonat, Zinkoxid und/oder Zinkkarbonat, die der Phosphatierungslösung in Pulverform oder als wäßrige Aufschlemmung zugegeben werden. Zur Ermittlung der Freien bzw. der Gesamtsäure werden je 10 ml Badprobe mit n/10 NaOH gegen den ersten bzw. zweiten Umschlag der Phosphorsäure titriert, wobei als Indikator z.B. der Farbumschlag von Dimethylgelb (Freie Säure) bzw. von Phenolphthalein (Gesamtsäure) dient. Die verbrauchten ml an n/10 NaOH entsprechen der Freien Säure bzw. der Gesamtsäure in Punkten.Manganese carbonate, zinc oxide and / or zinc carbonate, which are added to the phosphating solution in powder form or as an aqueous slurry, are preferably suitable for setting the ratio of free acid to total acid required according to the claims. To determine the free or total acid, titrate 10 ml bath samples with n / 10 NaOH against the first or second change in phosphoric acid, using e.g. the color change of dimethyl yellow (free acid) or of phenolphthalein (total acid) serves. The ml of n / 10 NaOH consumed correspond to the free acid or the total acid in points.

Es hat sich ferner als vorteilhaft erwiesen, die Metalle mit einer Phosphatierungslösung in Kontakt zu bringen, die nitritzerstörende Substanzen, z.B. Harnstoff oder Amidosulfosäure, enthält. Hierdurch wird eine autokatalytische Nitritbildung aus dem enthaltenen Nitrat unterbunden und ein "Umkippen" des Bades von der Eisenseite auf die Nitritseite ausgeschlossen.It has also proven to be advantageous to bring the metals into contact with a phosphating solution which contains nitrite-interfering substances, e.g. Contains urea or amidosulfonic acid. This prevents autocatalytic nitrite formation from the nitrate contained and prevents the bath from "tipping over" from the iron side to the nitrite side.

Der Kontakt der Metalle mit der Phosphatierungslösung kann im Tauchen, Fluten oder Spritzen erfolgen. Meist erfolgt die Applikation jedoch im Tauchen, wobei Behandlungszeiten von z.B. 5 bis 15 min eingehalten werden sollten.The metals can come into contact with the phosphating solution by dipping, flooding or spraying. However, the application is usually done in diving, with treatment times of e.g. 5 to 15 minutes should be observed.

Die mit den erfindungsgemäßen Verfahren erzeugten Phosphatschichten besitzen - je nach spezieller Badzusammensetzung, Behandlungstemperatur, Behandlungszeit und Arbeitsgang - ein Schichtgewicht von etwa 3 bis 15 g/m2.Depending on the particular bath composition, treatment temperature, treatment time and operation, the phosphate layers produced by the methods according to the invention have a layer weight of approximately 3 to 15 g / m 2 .

Die Vorbehandlung der Metalle vor der eigentlichen Phosphatierung geschieht in konventioneller Weise. Beispielsweise kann eine Entfettung mittels wäßriger, alkalischer Reiniger, die zweckmäßigerweise Tensid enthalten, vorgenommen werden. Sofern vorhanden, sind Zunder oder Rost durch eine Beizbehandlung, z.B. mit Schwefelsäure oder Salzsäure, zu entfernen.The pretreatment of the metals before the actual phosphating is done in a conventional manner. For example, degreasing can be carried out using aqueous, alkaline cleaners which advantageously contain surfactant. If present, scale or rust can be removed by pickling treatment, e.g. with sulfuric acid or hydrochloric acid.

Obgleich nicht zwingend notwendig, können die Werkstücke vor der Phosphatierung zur Ausbildung feinkristalliner Phosphatüberzüge in an sich bekannter Weise, z.B. mit einem Titanphosphat enthaltenden Aktivierungsbad, vorgespült werden.Although not absolutely necessary, the workpieces can be formed prior to phosphating to form fine crystalline phosphate coatings in a manner known per se, e.g. with an activation bath containing titanium phosphate.

Nach der Phosphatierbehandlung wird üblicherweise mit Wasser gespült, gegebenenfalls nachbehandelt und bei Bedarf getrocknet. Zum Zweck der Verbesserung des Korrosionsschutzes kann z.B. mit Chromsäure und/oder Korrosionsschutzemulsionen nachbehandelt werden. Für den Fall, daß eine Kaltumformung beabsichtigt ist, kann eine Nachbehandlung z.B. mit einem Beseifungsbad erfolgen.After the phosphating treatment, it is usually rinsed with water, optionally aftertreated and dried if necessary. For the purpose of improving corrosion protection, e.g. are treated with chromic acid and / or corrosion protection emulsions. In the event that cold forming is intended, an aftertreatment e.g. with a soap bath.

Die nach dem erfindungsgemäßen Verfahren erzeugten Phosphatüberzüge sind auf allen Gebieten, auf dem Phosphatüberzüge Verwendung finden, mit Vorteil einsetzbar. Vorzugsweise sind sie jedoch für die Vorbereitung von Metallen für die anschließende Kaltumformung geeignet.The phosphate coatings produced by the process according to the invention can be used advantageously in all fields in which phosphate coatings are used. However, they are preferably suitable for the preparation of metals for the subsequent cold forming.

Die Erfindung wird anhand des Beispiels beispielsweise und näher beschrieben.The invention is described by way of example and in more detail.

Beispielexample

Stahldraht mit einem Kohlenstoffgehalt von 0,5 bis 0,9 Gew.-% wurde im Tauchen durch Behandeln mit Salzsäure von Rost und Zunder befreit und nach gründlichem Wasserspülen 6 bis 10 min bei 45°C in einer Phosphatierungslösung nachstehender Zusammensetzung phosphatiert:

  • 10,9 g/I Zn
  • 2,1 g/I Mn
  • 2,0 g/I Fe(II)
  • 0,5 g/I Ca
  • 0,5 g/I Ni
  • 0,01 g/I Cu
  • 0,3 g/l Na
  • 24,0 g/I N03
  • 10,6 g/I P205
  • 1,6 g/I BF4
  • 1,6 g/I Weinsäure
  • 0,5 g/I Harnstoff
  • Freie Säure: 4,7 Punkte
  • Gesamtsäure: 40,7 Punkte
Steel wire with a carbon content of 0.5 to 0.9% by weight was freed of rust and scale in immersion by treatment with hydrochloric acid and, after thorough water rinsing, phosphated for 6 to 10 minutes at 45 ° C. in a phosphating solution of the following composition:
  • 10.9 g / l Zn
  • 2.1 g / l Mn
  • 2.0 g / I Fe (II)
  • 0.5 g / l approx
  • 0.5 g / l Ni
  • 0.01 g / l Cu
  • 0.3 g / l Na
  • 24.0 g / I N0 3
  • 10.6 g / IP 2 0 5
  • 1.6 g / l BF 4
  • 1.6 g / l tartaric acid
  • 0.5 g / l urea
  • Free acidity: 4.7 points
  • Total acidity: 40.7 points

Im Anschluß daran wurde wiederum mit Wasser gespült, in einer wäßrigen, heißen Borax-Lösung neutralisiert und im Ofen getrocknet. Nach diesem Arbeitsgang ergab sich ein Flächengewicht des Phosphatüberzuges von 8 bis 10 g/m2. Der Phosphatüberzug war trotz des Fehlens einer aktivierenden Vorspülung mit Titanphosphat gleichmäßig deckend und feinkristallin.Subsequently, it was rinsed again with water, neutralized in an aqueous, hot borax solution and dried in the oven. After this operation, the basis weight of the phosphate coating was 8 to 10 g / m 2 . The phosphate coating was uniformly opaque and fine-crystalline despite the absence of an activating pre-rinse with titanium phosphate.

Die so vorbehandelten Drähte ließen sich in bis zu 10 Zügen mit einer maximalen Querschnittsabnahme von 93,5 % einwandfrei bei nur sehr niedrigem Verschleiß der Ziehwerkzeuge umformen. Die Drahtoberfläche wies nach dem Ziehen noch eine gleichmäßige Restphosphatschicht auf und war frei von Riefen.The wires pretreated in this way could easily be formed in up to 10 passes with a maximum cross-sectional decrease of 93.5% with very little wear on the drawing tools. The wire surface still had a uniform layer of residual phosphate after drawing and was free of scoring.

Während des Durchsatzes wurde in das Phosphatierbad Luft eingeblasen und damit der Eisen(11)-ionen-Gehalt unter den gegebenen Durchsatzbedingungen im Bereich von 2 bis 7 g/I gehalten. Die Ergänzung des Bades erfolgte auf Konstanz der Gesamtsäurepunkte mit einem Ergänzungskonzentrat, enthaltend

  • 11,4 Gew.-% Zn
  • 0,26 Gew.-% Mn
  • 0,13 Gew.-% Ca
  • 0,11 Gew.-% Ni
  • 0,025 Gew.% Cu
  • 22,9 Gew.-% P205
  • 10,3 Gew.-% NO3
  • 2,6 Gew.-%Weinsäure
  • 0,38 Gew.-% BF4
  • 0,26 Gew.-% Harnstoff
Air was blown into the phosphating bath during the throughput and the iron (11) ion content was thus kept in the range from 2 to 7 g / l under the given throughput conditions. The bath was replenished with a supplement concentrate containing the total acid points
  • 11.4% by weight Zn
  • 0.26 wt% Mn
  • 0.13% by weight approx
  • 0.11 wt% Ni
  • 0.025 wt% Cu
  • 22.9% by weight of P 2 0 5
  • 10.3% by weight of NO 3
  • 2.6% by weight tartaric acid
  • 0.38 wt% BF 4
  • 0.26% by weight urea

Entsprechend der Verfahrensführung auf der Eisenseite bildete sich nur wenig Badschlamm. Der Verbrauch an Ergänzungskonzentrat betrug etwa 20 g/m2 Metalloberfläche und war damit sehr niedrig.According to the procedure on the iron side, only a little bath sludge was formed. The consumption of supplemental concentrate was about 20 g / m 2 metal surface and was therefore very low.

Claims (11)

1. A process of producing phosphate coatings on metals having surfaces which consist at least in part of iron or steel by a treatment with aqueous phosphatizing solutions, which contain zinc ions, manganese ions, P04 ions, nitrate ions and - if being in working condition - iron II ions, characterized in that the metals are contacted with a phosphatizing solution which is at a temperature in the range from 30 to 50°C and contains
zinc in amounts of 5 to 25 g/I
manganese in amounts of 1 to 10 g/l
iron II in amounts of 0,1 to 13 g/I
phosphate in amounts of 5 to 40 g/I (calculated as P20s)
nitrate in amounts of 5 to 50 g/I
and which also contains
0.5 to 5 g/I fluoroborate (calculated as BF4)
0.05 to 3 g/I tartaric acid or citric acid
and which has been adjusted to weight ratios of Zn : P2O5 = (0.5 to 3) : 1 and of
Mn : Zn = (0.04 to 0.5) : 1 and to a ratio of free acid to total acid of (0.04 to 0.2) : 1.
2. A process according to claim 1, characterized in that the metals are contacted with a phosphatizing solution which also contains 0.05 to 2 g/I Ni and/or 0.001 to 0.1 g/I Cu and/or 0.5 to 2 g/I Ca.
3. A process according to claim 1 or 2, characterized in that the metals are contacted with a phosphatizing solution which has been adjusted to an Fe (II) concentration not in excess of 10 g/I.
4. A process according to claim 1, 2 or 3, characterized in that the metals are contacted with a phosphatizing solution in which surplus iron (II) is reacted with an oxygen containing gas to Fe (III) and precipitated as iron (III) phosphate sludge.
5. A process according to claim 1, 2 or 3, characterized in that the metals are contacted with a phosphatizing solution in which surplus iron (II) is reacted with chlorate to form iron (III) and precipitated as iron (III) phosphate sludge.
6. A process according to any of claims 1 to 5, characterized in that the phosphatizing solution is replenished as regards zinc ions, manganese ions, phosphate ions and nitrate ions by addition of at least one concentrate which has been adjusted to weight ratios of Zn : P2O5 = (0.3 to 0.8) : 1, of Mn : Zn = (0.01 to 0.05) : 1 and of NO3: P205 = (0.2 to 1) : 1.
7. A process according to any of claims 1 to 6, characterized in that the phosphatizing solution is replenished as regards Ni, Cu, Ca, tartaric acid and/or citric acid as well as fluoborate according to weight ratios of Ca : Zn = (0.005 to 0.1) : 1, of Ni : Zn = (0.005 to 0.05) : 1, of Cu : Zn = (0.001 to 0.03) : 1, of (tartaric acid and/or citric acid) : P205 = (0.05 to 0.3) : 1 and of BF4 : P2O5= (0.008 to 0.04) : 1.
8. A process according to any of claims 1 to 7, characterized in that the metals are contacted with a phosphatizing solution in which the free acid content has been adjusted by an addition of manganese carbonate, zinc oxide and/or zinc carbonate.
9. A process according to any of claims 1 to 8, characterized in that the metals are contacted with a phosphatizing solution which contains nitrite-destroying substances, such as urea or sulfaminic acid.
10. The use of the process according to any of claims 1 to 9 to preparing metals for a subsequent cold working.
EP87201890A 1986-10-25 1987-10-03 Process for producing phosphate coatings on metals Expired - Lifetime EP0269138B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863636390 DE3636390A1 (en) 1986-10-25 1986-10-25 METHOD FOR PRODUCING PHOSPHATE COATINGS ON METALS
DE3636390 1986-10-25

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EP0269138A1 EP0269138A1 (en) 1988-06-01
EP0269138B1 true EP0269138B1 (en) 1990-11-28

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US (1) US4824490A (en)
EP (1) EP0269138B1 (en)
JP (1) JP2700061B2 (en)
AU (1) AU8003887A (en)
BR (1) BR8705698A (en)
CA (1) CA1308629C (en)
DE (2) DE3636390A1 (en)
ES (1) ES2018535B3 (en)
GB (1) GB2203453B (en)
ZA (1) ZA877980B (en)

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CN102978598B (en) * 2012-12-06 2015-07-22 三达奥克化学股份有限公司 General phosphate agent for cast iron, hot steel, hot-rolled plate, pickling board and cold-rolled plate and preparation method thereof

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DE3636390A1 (en) 1988-04-28
JP2700061B2 (en) 1998-01-19
US4824490A (en) 1989-04-25
GB2203453B (en) 1990-12-05
JPS63190178A (en) 1988-08-05
CA1308629C (en) 1992-10-13
DE3766477D1 (en) 1991-01-10
ZA877980B (en) 1989-06-28
GB2203453A (en) 1988-10-19
BR8705698A (en) 1988-05-31
EP0269138A1 (en) 1988-06-01
AU8003887A (en) 1988-04-28
ES2018535B3 (en) 1991-04-16
GB8725035D0 (en) 1987-12-02

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