EP0186823A2 - Process for facilitating cold-forming - Google Patents

Process for facilitating cold-forming Download PDF

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Publication number
EP0186823A2
EP0186823A2 EP85115775A EP85115775A EP0186823A2 EP 0186823 A2 EP0186823 A2 EP 0186823A2 EP 85115775 A EP85115775 A EP 85115775A EP 85115775 A EP85115775 A EP 85115775A EP 0186823 A2 EP0186823 A2 EP 0186823A2
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EP
European Patent Office
Prior art keywords
phosphating solution
phosphate
contact
brought
iron materials
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EP85115775A
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German (de)
French (fr)
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EP0186823A3 (en
EP0186823B1 (en
Inventor
Thomas Ward Tull
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Henkel Corp
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Henkel Corp
Parker Chemical Co
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Priority to AT85115775T priority Critical patent/ATE63575T1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—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

Definitions

  • the invention relates to a method for facilitating the cold forming of iron materials by applying a phosphate coating by means of an aqueous, acidic phosphating solution which contains zinc ions and hydroxylamine as accelerators.
  • Phosphate coatings are usually applied to metal surfaces in order to improve their corrosion resistance and to increase the adhesion of the subsequently applied paint. Phosphate coatings also serve to facilitate cold forming, where they themselves act as a "lubricant" by helping to avoid seizing or welding of material and tools, or by binding a subsequently applied lubricant so that it is practically not removed during the forming process. In particular, the latter ability is of particular importance because only the combination of phosphate coating and lubricant enables multiple or severe cold working, possibly without renewed intermediate treatment with lubricant.
  • Layer-forming here means the formation of phosphate coatings by means of phosphating solutions which, in addition to the phosphate ions, also supply the majority of the cations for coating formation.
  • the cations of the phosphate coating usually come from the treated metal itself, i.e. the phosphating solution essentially only provides the phosphate ions.
  • US Pat. No. 2,298,280 describes a coating solution which contains an acidic phosphate, such as zinc or manganese phosphate, and hydroxylamine as an accelerator.
  • an acidic phosphate such as zinc or manganese phosphate
  • hydroxylamine as an accelerator
  • the phosphate layer formation aims to improve the corrosion resistance and the paint adhesion.
  • the patent does not contain any reference to the layer thickness of the phosphate layer produced or to the suitability of this layer for facilitating the cold deformation.
  • the zinc and manganese concentrations mentioned, for example are so low that the usability of these phosphating solutions for the relief of cold working is extremely doubtful.
  • a disadvantage of the known, especially the aforementioned The method is that the phosphate coatings produced do not have the thickness required to facilitate cold working and the adhesion is too low.
  • the object of the invention is to provide a process for facilitating the cold forming of ferrous materials which does not have the disadvantages of the known processes and which leads to thick, adherent phosphate coatings with simple process control.
  • 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 iron materials are brought into contact with a phosphating solution which contains 7.5 to 75 g / 1 zinc ions and 0.1 to 10 g / 1 hydroxylamine contains.
  • layer-forming phosphating is used to produce phosphate coatings, which among other things is also intended to facilitate cold forming, known from US Pat. No. 2,743,204. It describes phosphating solutions for the treatment of iron, steel, zinc and aluminum with zinc or manganese as layer-forming cations, which can contain a wide variety of accelerators. Nitrite, chlorate, bromate, sulfite, nitro organic compounds such as nitrobenzenesulfonate, picric acid, and iodate, hydroxylamine and nitrate are mentioned. With regard to the achievable layer weights, chlorate is particularly emphasized. It has obviously not been recognized that hydroxylamine is particularly important in this regard.
  • Phosphating solutions with hydroxylamine as an accelerator in combination with comparatively high concentrations of zinc are particularly suitable for the production of Phosphate coatings designed to facilitate cold working. Thanks to their excellent adhesion to the iron material as such, but especially in combination with conventional lubricants, the phosphate coatings are effective even with the most severe deformations. In addition, the process is not adversely affected even in the presence of ferrous or ferric ions in the solution.
  • An additional advantage of the method according to the invention therefore lies in being able to bring the iron materials into contact with a phosphating solution, the iron ion content of which can be up to 25 g / l.
  • Cold deformation in the sense of the present method are all deformation processes into which the workpiece is introduced at a temperature ranging from approximately ambient temperature to approximately 100 ° C. and in which an increase in temperature of the workpiece is the result of the deformation work performed.
  • Such methods are, for example, extrusion, upsetting, wire or tube drawing.
  • the method is particularly suitable for workpieces made of steel with a carbon content below 1% by weight, especially with a carbon content of approximately 0.05 to 0.6% by weight. Compared to known processes, it is also suitable for higher-alloy steels, which generally also have a higher hardness.
  • the hydroxylamine to be added to the phosphating solution can be of any commercial type. Storage-stable salts or complex compounds, which are predominantly in the form of hydrate, are preferred. Hydroxylamine sulfate, also called hydroxylammonium sulfate [(NH Z OH) 2 . H 2 SO 4 ] is a particularly suitable compound.
  • the assumption about the particularly advantageous effect of the hydroxylamine as an accelerator is that the zinc content incorporated in the phosphate coatings is particularly high.
  • This high zinc content increases the lubricating properties of the phosphate crystals themselves.
  • it is particularly important that the increased zinc content greatly increases the reactivity to a subsequently applied lubricant, especially when it comes to fatty acids or soaps.
  • the preferred zinc content of the phosphating solution is 7.5 to 55 g / l and is preferably in the range of 10 to 30 g / l.
  • a preferred embodiment of the invention provides for the use of a phosphating solution which additionally contains manganese ions in an amount of up to 20 g / l.
  • the phosphate content of the phosphating solution must be based on the content of the layer-forming cations. It is generally 5 to 80 g / l, preferably 10 to 70 g / 1 (calculated as P0 4 ).
  • a phosphating solution which contains nitrate as an additional accelerator.
  • the nitrate content should be 5 to 75 g / l, preferably 30 to 70 g / l (calculated as NO 3 ). If nitrate is used as an additional accelerator, it is recommended that the weight ratio of nitrate to phosphate be in the range from 0.3 to 6, preferably 0.5 to 5, but in particular 0.9 to 4.5 (calculated as the weight ratio NO 3 : P0 4 ).
  • the phosphating solution used in the process according to the invention has the ability to form phosphate coatings with a high zinc content and yet to tolerate comparatively high iron contents.
  • the concentration of iron ions in the form of ferrous or ferric ions can be up to 25 g / l, so that the process can also be carried out on the iron side without any loss.
  • a further advantageous embodiment of the invention provides for the iron materials to be brought into contact with a phosphating solution which additionally contains nickel ions, preferably in an amount of 0.05 to 1 g / l, in particular 0.1 to 0.5 g / l. contains.
  • the phosphating solutions can expediently be used at a temperature of 54.4 to 96.1, in particular 71.1 to 87.8 ° C. Their pH is about 1.8 to 2.5 at the above temperatures.
  • the application of the phosphating solution is carried out in the usual way, preference is given to immersion or flooding, in particular immersion.
  • the contact time during the immersion treatment is about 0.5 to 30 minutes, preferably 5 to 15 minutes.
  • the workpieces are pretreated before phosphating in the usual way, such as cleaning, pickling, rinsing or activating.
  • a water rinse or a rinse with a weakly alkaline solution e.g. Contains borax, nitrite, triethanolamine or mixtures thereof.
  • the iron material can then be subjected to cold working.
  • a lubricant that is customary in cold-forming processes is preferably also applied. This can be done immediately after coating or after rinsing.
  • the lubricant can also be applied immediately before the deformation, if necessary also between the deformation steps. If the purpose of the formation of zinc soaps is with the application of lubricant, care must be taken to ensure that the phosphate coating is sufficiently moist for the reaction.
  • Soaps, oils and other auxiliaries for cold working or emulsions of fatty acids or soaps, in particular with 8 to 18 carbon atoms in the acid anion, can be applied as lubricants.
  • fatty acids and soaps an emulsion containing 3 to 15% by weight should be used. Because of the reaction with the cation of the phosphate coating already mentioned above, sodium and / or Potassium soaps, especially stearates, are particularly advantageous.
  • drying can be carried out in a conventional manner after the final treatment or between individual treatment stages - with the aforementioned limitation in the formation of zinc soap.
  • a pickling step can be inserted into the pretreatment.
  • the iron material can then be subjected to cold working immediately or after intermediate storage.
  • a phosphating solution was prepared which contained and had 60 total acid points in a 5.0 ml sample (total acid points equal to consumption of 0.1 N NaOH in ml when titrated against phenolphthalein as an indicator).
  • the solution was heated to 82.2 ° C and 5 g / 1 hydroxylamine sulfate was added.
  • the materials treated as above were then rinsed with a weakly alkaline solution and provided with a lubricant containing sodium stearate. It was then dried and the excess soap left on the workpiece.
  • the workpiece was then subjected to conventional cold forming, for example an extrusion treatment.
  • the results were excellent and far superior to those achieved using standard phosphating processes.
  • a concentrate A was formulated for the preparation of a phosphating solution 210 g of this concentrate were then diluted to 1 1 ready-to-use phosphating solution.
  • This supplemental concentrate can be used if the ratio of total acid to free acid in the working phosphating solution rises above the desired value. If the ratio in the working phosphating solution falls below the desired value, concentrate A can be added.

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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Lubricants (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Mounting, Exchange, And Manufacturing Of Dies (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
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  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
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Abstract

A heavy phosphate coating suitable as a base for a lubricant, prior to cold deformation of a ferrous surface, is formed by application of an aqueous acidic phosphating solution containing phosphate, organic nitro compound or nitrate (introduced as an inorganic nitrate), zinc, manganese or iron and, to increase the coating weight, hydroxylamine, is an amount of at least 0.01% by weight.

Description

Die Erfindung betrifft ein Verfahren zur Erleichterung der Kaltverformung von Eisenwerkstoffen durch Aufbringen eines Phosphatüberzuges mittels einer wäßrigen, sauren Phosphatierungslösung, die Zinkionen und Hydroxylamin als Beschleuniger enthält.The invention relates to a method for facilitating the cold forming of iron materials by applying a phosphate coating by means of an aqueous, acidic phosphating solution which contains zinc ions and hydroxylamine as accelerators.

Phosphatüberzüge werden üblicherweise auf Metalloberflächen aufgebracht, um deren Korrosionsbeständigkeit zu verbessern und die Haftung des anschließend aufgebrachten Lackes zu erhöhen. Phosphatüberzüge dienen auch der Erleichterung der Kaltverformung, wobei sie selbst wie ein "Schmiermittel" wirken, indem sie ein Fressen oder Verschweißen von Werkstoff und Werkzeug vermeiden helfen, oder aber ein anschließend aufgebrachtes Schmiermittel so stark binden, daß es beim Verformungsvorgang praktisch nicht entfernt wird. Insbesondere die letztgenannte Fähigkeit ist von besonderer Bedeutung, weil erst die Verbindung von Phosphatüberzug und Schmiermittel eine mehrfache oder starke Kaltverformung, gegebenenfalls ohne erneute Zwischenbehandlung mit Schmiermittel, ermöglicht.Phosphate coatings are usually applied to metal surfaces in order to improve their corrosion resistance and to increase the adhesion of the subsequently applied paint. Phosphate coatings also serve to facilitate cold forming, where they themselves act as a "lubricant" by helping to avoid seizing or welding of material and tools, or by binding a subsequently applied lubricant so that it is practically not removed during the forming process. In particular, the latter ability is of particular importance because only the combination of phosphate coating and lubricant enables multiple or severe cold working, possibly without renewed intermediate treatment with lubricant.

Es sind zahlreiche Verfahren zur Erleichterung der Kaltverformung durch Aufbringen von Phosphatüberzügen bekannt. Sie können sowohl der Kategorie der "schichtbildenden" als auch - allerdings mit erheblich geringerer Bedeutung - der Kategorie der "nichtschichtbildenden" Verfahren angehören.Numerous methods are known to facilitate cold working by applying phosphate coatings. They can belong to the category of "layer-forming" as well as - albeit with considerably less importance - the category of "non-layer-forming" processes.

Unter "schichtbildend" versteht man hierbei die Ausbildung von Phosphatüberzügen mittels Phosphatierungslösungen, die neben den Phosphationen auch den überwiegenden Teil der Kationen zur Überzugsbildung liefern. Bei den sogenannten "nichtschichtbildenden" Verfahren stammen demgegenüber die Kationen des Phosphatüberzuges üblicherweise aus dem behandelten Metall selbst, d.h. die Phosphatierungslösung liefert im wesentlichen nur die Phosphationen."Layer-forming" here means the formation of phosphate coatings by means of phosphating solutions which, in addition to the phosphate ions, also supply the majority of the cations for coating formation. In contrast, in the so-called "non-layer-forming" processes, the cations of the phosphate coating usually come from the treated metal itself, i.e. the phosphating solution essentially only provides the phosphate ions.

So beschreibt die US-PS 2 298 280 eine Überzugslösung, die ein saures Phosphat, wie Zink- oder Manganphosphat, und Hydroxylamin als Beschleuniger enthält. Die Phosphatschichtausbildung bezweckt gemäß den einleitenden Bemerkungen die Verbesserung des Korrosionswiderstandes und der Lackhaftung. Irgendein Hinweis auf die Schichtdicke der erzeugten Phosphatschicht oder auf die Eignung dieser Schicht zur Erleichterung der Kaltverformung findet sich in der Patentschrift nicht. Außerdem sind die beispielsweise genannten Zink- und Mangankonzentrationen so gering, daß die Brauchbarkeit dieser Phosphatierungslösungen für die Erleichterung der Kaltverformung äußerst zweifelhaft ist.For example, US Pat. No. 2,298,280 describes a coating solution which contains an acidic phosphate, such as zinc or manganese phosphate, and hydroxylamine as an accelerator. According to the introductory remarks, the phosphate layer formation aims to improve the corrosion resistance and the paint adhesion. The patent does not contain any reference to the layer thickness of the phosphate layer produced or to the suitability of this layer for facilitating the cold deformation. In addition, the zinc and manganese concentrations mentioned, for example, are so low that the usability of these phosphating solutions for the relief of cold working is extremely doubtful.

Die US-PS 2 702 768 erwähnt den Einsatz von Hydroxylamin als Beschleuniger in "nichtschichtbildenden" Phosphatierungslösungen. Derartige Systeme sind jedoch - wie bereits vorstehend angedeutet - von untergeordneter Bedeutung und für schwere Verformungen unbrauchbar. Im wesentlichen das gleiche gilt für die Verfahren gemäß den US-PSs 3 615 912 und 4 149 909, die auf die Erzeugung von Eisenphosphatüberzügen abgestellt sind und daher mit Alkali- bzw. Ammoniumphosphatlösungen arbeiten.US Pat. No. 2,702,768 mentions the use of hydroxylamine as an accelerator in "non-layer-forming" phosphating solutions. Such systems are - as already indicated above - of minor importance and unusable for severe deformations. Essentially the same applies to the processes according to US Pat. Nos. 3,615,912 and 4,149,909, which are based on the production of iron phosphate coatings and therefore work with alkali or ammonium phosphate solutions.

Nachteilig bei den bekannten, insbesondere den vorgenannten Verfahren ist, daß die erzeugten Phosphatüberzüge nicht die zur Erleichterung der Kaltverformung erforderliche Dicke aufweisen und ein zu geringes Haftvermögen besitzen.A disadvantage of the known, especially the aforementioned The method is that the phosphate coatings produced do not have the thickness required to facilitate cold working and the adhesion is too low.

Aufgabe der Erfindung ist es, ein Verfahren zur Erleichterung der Kaltverformung von Eisenwerkstoffen bereitzustellen, das die Nachteile der bekannten Verfahren nicht aufweist und bei einfacher Verfahrensführung zu dicken, haftfesten Phosphatüberzügen führt.The object of the invention is to provide a process for facilitating the cold forming of ferrous materials which does not have the disadvantages of the known processes and which leads to thick, adherent phosphate coatings with simple process control.

Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man die Eisenwerkstoffe mit einer Phosphatierungslösung in Kontakt bringt, die 7,5 bis 75 g/1 Zinkionen und 0,1 bis 10 g/1 Hydroxylamin enthält.The object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the iron materials are brought into contact with a phosphating solution which contains 7.5 to 75 g / 1 zinc ions and 0.1 to 10 g / 1 hydroxylamine contains.

Zwar ist eine "schichtbildende" Phosphatierung zur Erzeugung von Phosphatüberzügen, die u.a. auch der Erleichterung der Kaltverformung dienen soll, aus der US-PS 2 743 204 bekannt. Sie beschreibt Phosphatierungslösungen zur Behandlung von Eisen, Stahl, Zink und Aluminium mit Zink- oder Mangan als schichtbildende Kationen, die die unterschiedlichsten Beschleuniger enthalten können. Genannt sind Nitrit, Chlorat, Bromat, Sulfit, nitroorganische Verbindungen, wie Nitrobenzolsulfonat, Pikrinsäure, sowie Jodat, Hydroxylamin und Nitrat. Hinsichtlich der erreichbaren Schichtgewichte ist Chlorat besonders herausgestellt. Daß gerade Hydroxylamin insoweit eine besondere Bedeutung zukommt, ist offensichtlich nicht erkannt worden.It is true that "layer-forming" phosphating is used to produce phosphate coatings, which among other things is also intended to facilitate cold forming, known from US Pat. No. 2,743,204. It describes phosphating solutions for the treatment of iron, steel, zinc and aluminum with zinc or manganese as layer-forming cations, which can contain a wide variety of accelerators. Nitrite, chlorate, bromate, sulfite, nitro organic compounds such as nitrobenzenesulfonate, picric acid, and iodate, hydroxylamine and nitrate are mentioned. With regard to the achievable layer weights, chlorate is particularly emphasized. It has obviously not been recognized that hydroxylamine is particularly important in this regard.

Phosphatierungslösungen mit Hydroxylamin als Beschleuniger in Verbindung mit vergleichsweise hohen Konzentrationen an Zink eignen sich in besonderer Weise zur Erzeugung von Phosphatüberzügen, die für die Erleichterung der Kaltverformung bestimmt sind. Die Phosphatüberzüge sind dabei dank ihrer hervorragenden Haftung auf dem Eisenwerkstoff als solche, insbesondere aber in Kombination mit herkömmlichen Schmiermitteln, selbst bei schwersten Verformungen wirksam. Außerdem erfährt das Verfahren auch in Gegenwart von Ferro- oder Ferriionen in der Lösung keine Beeinträchtigung. Ein zusätzlicher Vorteil des erfindungsgemäßen Verfahrens liegt daher darin, die Eisenwerkstoffe mit einer Phosphatierungslösung in Kontakt bringen zu können, deren Gehalt an Eisenionen bis 25 g/1 betragen kann.Phosphating solutions with hydroxylamine as an accelerator in combination with comparatively high concentrations of zinc are particularly suitable for the production of Phosphate coatings designed to facilitate cold working. Thanks to their excellent adhesion to the iron material as such, but especially in combination with conventional lubricants, the phosphate coatings are effective even with the most severe deformations. In addition, the process is not adversely affected even in the presence of ferrous or ferric ions in the solution. An additional advantage of the method according to the invention therefore lies in being able to bring the iron materials into contact with a phosphating solution, the iron ion content of which can be up to 25 g / l.

Kaltverformung im Sinne des vorliegenden Verfahrens sind alle Verformungsvorgänge, in die das Werkstück mit einer etwa von Umgebungstemperatur bis ca. 100°C reichenden Temperatur eingeführt wird und bei dem eine Temperaturerhöhung des Werkstückes das Ergebnis der geleisteten Verformungsarbeit ist. Derartige Verfahren sind beispielsweise Extrudieren, Stauchen, Draht-oder Rohrzug.Cold deformation in the sense of the present method are all deformation processes into which the workpiece is introduced at a temperature ranging from approximately ambient temperature to approximately 100 ° C. and in which an increase in temperature of the workpiece is the result of the deformation work performed. Such methods are, for example, extrusion, upsetting, wire or tube drawing.

Das Verfahren eignet sich insbesondere für Werkstücke aus Stahl mit einem Kohlenstoffgehalt unterhalb 1 Gew.-%, vor allem mit einem solchen von etwa 0,05 bis 0,6 Gew.-% Kohlenstoff. Gegenüber bekannten Verfahren eignet es sich zudem für höherlegierte Stähle, die in der Regel auch eine größere Härte besitzen.The method is particularly suitable for workpieces made of steel with a carbon content below 1% by weight, especially with a carbon content of approximately 0.05 to 0.6% by weight. Compared to known processes, it is also suitable for higher-alloy steels, which generally also have a higher hardness.

Das der Phosphatierungslösung zuzugebende Hydroxylamin kann von jeder handelsüblichen Art sein. Bevorzugt sind lagerstabile Salze oder Komplexverbindungen, die häufig in Hydratform voriegen. Hydroxylaminsulfat, auch Hydroxylammoniumsulfat genannt [(NHZOH)2 . H2SO4], ist eine besonders geeignete Verbindung.The hydroxylamine to be added to the phosphating solution can be of any commercial type. Storage-stable salts or complex compounds, which are predominantly in the form of hydrate, are preferred. Hydroxylamine sulfate, also called hydroxylammonium sulfate [(NH Z OH) 2 . H 2 SO 4 ] is a particularly suitable compound.

Die Vermutung über die besonders vorteilhafte Wirkung des Hydroxylamins als Beschleuniger geht dahin, daß der in den Phosphatüberzügen eingebaute Zinkanteil besonders hoch ist. Dieser hohe Zinkanteil erhöht die Schmiereigenschaften der Phosphatkristalle selbst. Besonders wichtig ist jedoch, daß der erhöhte Zinkanteil die Reaktivität gegenüber einem nachträglich aufgebrachten Schmiermittel, insbesondere wenn es sich um Fettsäuren oder Seifen handelt, stark erhöht. Es findet dabei nämlich eine Umsetzung zwischen dem Zink der Phosphatschicht und dem Fettsäureanion unter Bildung von beispielsweise Zinkstearat statt, das wesentlich bessere Schmiereigenschaften als Natriumstearat besitzt. Das heißt, je höher der Zinkanteil im Phosphatüberzug ist, desto stärker ist die Umsetzung zu Zinkseifen und desto besser ist die Schmiereigenschaft der aus dem Phosphatüberzug und der Seife gebildeten Schmierschicht.The assumption about the particularly advantageous effect of the hydroxylamine as an accelerator is that the zinc content incorporated in the phosphate coatings is particularly high. This high zinc content increases the lubricating properties of the phosphate crystals themselves. However, it is particularly important that the increased zinc content greatly increases the reactivity to a subsequently applied lubricant, especially when it comes to fatty acids or soaps. This is because there is a reaction between the zinc of the phosphate layer and the fatty acid anion with the formation of, for example, zinc stearate, which has significantly better lubricating properties than sodium stearate. That is, the higher the zinc content in the phosphate coating, the stronger the conversion to zinc soaps and the better the lubricating properties of the lubricating layer formed from the phosphate coating and the soap.

Der bevorzugte Zinkgehalt der Phosphatierungslösung beträgt 7,5 bis 55 g/1 und liegt vorzugsweise im Bereich von 10 bis 30 g/l.The preferred zinc content of the phosphating solution is 7.5 to 55 g / l and is preferably in the range of 10 to 30 g / l.

Eine bevorzugte Ausgestaltung der Erfindung sieht vor, eine Phosphatierungslösung einzusetzen, die zusätzlich Manganionen in einer Menge bis 20 g/1 enthält.A preferred embodiment of the invention provides for the use of a phosphating solution which additionally contains manganese ions in an amount of up to 20 g / l.

Der Phosphatgehalt der Phosphatierungslösung hat sich am Gehalt der schichtbildenden Kationen zu orientieren. Er beträgt im allgemeinen 5 bis 80 g/l, vorzugsweise 10 bis 70 g/1 (berechnet als P04).The phosphate content of the phosphating solution must be based on the content of the layer-forming cations. It is generally 5 to 80 g / l, preferably 10 to 70 g / 1 (calculated as P0 4 ).

Eine weitere bevorzugte Ausgestaltung der Erfindung sieht vor, eine Phosphatierungslösung einzusetzen, die als zusätzlichen Beschleuniger Nitrat enthält. Der Nitratgehalt sollte 5 bis 75 g/l, vorzugsweise 30 bis 70 g/l (berechnet als NO3), betragen. Sofern Nitrat als zusätzlicher Beschleuniger eingesetzt wird, empfiehlt es sich, das Gewichtsverhältnis Nitrat zu Phosphat auf einen Wert im Bereich von 0,3 bis 6, vorzugsweise 0,5 bis 5, insbesondere aber 0,9 bis 4,5 (berechnet als Gewichtsverhältnis NO3 : P04), einzustellen.Another preferred embodiment of the invention provides for the use of a phosphating solution which contains nitrate as an additional accelerator. The nitrate content should be 5 to 75 g / l, preferably 30 to 70 g / l (calculated as NO 3 ). If nitrate is used as an additional accelerator, it is recommended that the weight ratio of nitrate to phosphate be in the range from 0.3 to 6, preferably 0.5 to 5, but in particular 0.9 to 4.5 (calculated as the weight ratio NO 3 : P0 4 ).

Wie bereits angedeutet, besitzt die im erfindungsgemäßen Verfahren zum Einsatz kommende Phosphatierungslösung die Fähigkeit, Phosphatüberzüge mit hohem Zinkanteil zu bilden und dennoch vergleichsweise hohe Eisenanteile zu tolerieren. Beispielsweise kann die Konzentration an Eisenionen sowohl in Form von Ferro- oder Ferriionen bis 25 g/1 betragen, so daß sich das Verfahren auch ohne jede Einbuße auf der Eisenseite fahren läßt.As already indicated, the phosphating solution used in the process according to the invention has the ability to form phosphate coatings with a high zinc content and yet to tolerate comparatively high iron contents. For example, the concentration of iron ions in the form of ferrous or ferric ions can be up to 25 g / l, so that the process can also be carried out on the iron side without any loss.

Eine weitere vorteilhafte Ausführungsform der Erfindung sieht vor, die Eisenwerkstoffe mit einer Phosphatierungslösung in Kontakt zu bringen, die zusätzlich Nickelionen, vorzugsweise in einer Menge von 0,05 bis 1 g/l, insbesondere von 0,1 bis 0,5 g/l, enthält.A further advantageous embodiment of the invention provides for the iron materials to be brought into contact with a phosphating solution which additionally contains nickel ions, preferably in an amount of 0.05 to 1 g / l, in particular 0.1 to 0.5 g / l. contains.

Die Phosphatierungslösungen können zweckmäßigerweise bei einer Temperatur von 54,4 bis 96,1, insbesondere von 71,1 bis 87,8°C, zum Einsatz kommen. Ihr pH-Wert beträgt etwa 1,8 bis 2,5 bei den vorgenannten Temperaturen.The phosphating solutions can expediently be used at a temperature of 54.4 to 96.1, in particular 71.1 to 87.8 ° C. Their pH is about 1.8 to 2.5 at the above temperatures.

Die Applikation der Phosphatierungslösung wird in üblicher Weise vorgenommen, bevorzugt sind Tauchen oder Fluten, insbesondere Tauchen. Die Kontaktdauer bei der Tauchbehandlung beträgt etwa 0,5 bis 30 min, vorzugsweise 5 bis 15 min.The application of the phosphating solution is carried out in the usual way, preference is given to immersion or flooding, in particular immersion. The contact time during the immersion treatment is about 0.5 to 30 minutes, preferably 5 to 15 minutes.

Mit Hilfe des erfindungsgemäßen Verfahrens gelingt es, Phosphatüberzüge mit einem Schichtgewicht von 2,7 bis 64,6 g/m2 zu erzeugen. Dadurch ist die Möglichkeit gegeben, das Schichtgewicht an die Schwere der vorgesehenen Kaltverformung, die Größe des Werkstückes und dergl. anzupassen. Schließlich wird die Wahl des Schichtgewichtes auch zu berücksichtigen haben, ob anschließend ein Schmiermittel aufgebracht wird oder nicht. In der Regel werden Schichtgewichte von 3,8 bis 48,4 bzw. von 5,4 bis 37,7 g/m2 den üblichen Anforderungen genügen.With the aid of the method according to the invention, To produce phosphate coatings with a layer weight of 2.7 to 64.6 g / m 2 . This gives the possibility of adapting the layer weight to the severity of the intended cold forming, the size of the workpiece and the like. Finally, the choice of layer weight will also have to take into account whether a lubricant is subsequently applied or not. As a rule, layer weights of 3.8 to 48.4 or 5.4 to 37.7 g / m 2 will meet the usual requirements.

Die Vorbehandlung der Werkstücke vor der Phosphatierung erfolgt auf übliche Weise, wie durch Reinigen, Beizen, Spülen bzw. Aktivieren. Als Nachbehandlung kann eine Wasserspülung bzw. eine Spülung mit einer schwachalkalischen Lösung, die z.B. Borax, Nitrit, Triäthanolamin oder Mischungen hiervon enthält, erfolgen. Danach kann der Eisenwerkstoff der Kaltverformung unterworfen werden. Vorzugsweise wird jedoch noch ein bei Kaltverformungsprozessen übliches Schmiermittel aufgebracht. Dies kann unmittelbar nach der Überzugsbildung oder nach der Spülung geschehen. Der Schmiermittelauftrag kann aber auch unmittelbar vor der Verformung, gegebenenfalls auch zwischen den Verformungsschritten geschehen. Sofern mit der Schmiermittelaufbringung die Bildung von Zinkseifen bezweckt ist, ist auf eine für die Reaktion erforderliche ausreichende Feuchtigkeit des Phosphatüberzuges zu achten.The workpieces are pretreated before phosphating in the usual way, such as cleaning, pickling, rinsing or activating. A water rinse or a rinse with a weakly alkaline solution, e.g. Contains borax, nitrite, triethanolamine or mixtures thereof. The iron material can then be subjected to cold working. However, a lubricant that is customary in cold-forming processes is preferably also applied. This can be done immediately after coating or after rinsing. The lubricant can also be applied immediately before the deformation, if necessary also between the deformation steps. If the purpose of the formation of zinc soaps is with the application of lubricant, care must be taken to ensure that the phosphate coating is sufficiently moist for the reaction.

Als Schmiermittel können Seifen, Öle und andere Hilfsmittel für die Kaltverformung bzw. Emulsionen von Fettsäuren oder Seifen, insbesondere mit 8 bis 18 C-Atomen im Säureanion, aufgebracht werden. Bei Verwendung von Fettsäuren und Seifen sollte eine Emulsion mit einem Gehalt an 3 bis 15 Gew.-% verwendet werden. Wegen der bereits oben erwähnten Umsetzung mit dem Kation des Phosphatüberzuges sind Natrium- und/oder Kaliumseifen, insbesondere Stearate, besonders vorteilhaft.Soaps, oils and other auxiliaries for cold working or emulsions of fatty acids or soaps, in particular with 8 to 18 carbon atoms in the acid anion, can be applied as lubricants. When using fatty acids and soaps, an emulsion containing 3 to 15% by weight should be used. Because of the reaction with the cation of the phosphate coating already mentioned above, sodium and / or Potassium soaps, especially stearates, are particularly advantageous.

Im Bedarfsfall kann nach der Endbehandlung oder auch zwischen einzelnen Behandlungsstufen - mit der vorgenannten Einschränkung bei der Zinkseifenbildung - in herkömmlicher Weise getrocknet werden.If necessary, drying can be carried out in a conventional manner after the final treatment or between individual treatment stages - with the aforementioned limitation in the formation of zinc soap.

Eine besonders bevorzugte Verfahrensfolge besteht in

  • 1. Reinigen
  • 2. Heißwasserspülung
  • 3. Behandeln mit der Phosphatierungslösung
  • 4. Kaltwasserspülung
  • 5. Spülung mit schwachalkalischer Lösung
  • 6. Kontaktieren mit einem Überschuß eines Schmiermittels auf Basis Natriumstearat
  • 7. Trocknen (Entspannungstrocknen)
A particularly preferred sequence of procedures consists in
  • 1. Clean
  • 2. Hot water rinse
  • 3. Treat with the phosphating solution
  • 4. Cold water rinse
  • 5. Rinse with weakly alkaline solution
  • 6. Contact with an excess of a lubricant based on sodium stearate
  • 7. Drying (flash drying)

Gegebenenfalls kann eine Beizstufe in die Vorbehandlung eingeschoben werden.If necessary, a pickling step can be inserted into the pretreatment.

Der Eisenwerkstoff kann dann sofort oder nach Zwischenlagerung der Kaltverformung zugeführt werden.The iron material can then be subjected to cold working immediately or after intermediate storage.

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

Es wurde eine Phosphatierungslösung hergestellt die,

Figure imgb0001
enthielt und 60 Gesamtsäurepunkte bei einer 5,0 ml-Probe aufwies (Gesamtsäurepunkte gleich Verbrauch von 0,1 n NaOH in ml bei Titration gegen Phenolphthalein als Indikator).A phosphating solution was prepared which
Figure imgb0001
 contained and had 60 total acid points in a 5.0 ml sample (total acid points equal to consumption of 0.1 N NaOH in ml when titrated against phenolphthalein as an indicator).

Die Lösung wurde auf 82,2°C erwärmt und mit 5 g/1 Hydroxylaminsulfat versetzt.The solution was heated to 82.2 ° C and 5 g / 1 hydroxylamine sulfate was added.

Nach 5 min Dauer zur Einstellung des Gleichgewichtes wurden 0,07 g/1 Natriumnitrit (berechnet als NaN02) zugesetzt.After 5 minutes to adjust the equilibrium, 0.07 g / 1 sodium nitrite (calculated as NaN0 2 ) was added.

Nach weiteren 5 min wurden jeweils 2 Bleche aus kaltgewalztem und gebeiztem Stahl - Abmessungen 10,2 . 15,2 . 0,23 cm) 5 min im Tauchen phosphatiert. Der Einsatz derartiger Bleche erfolgte jeweils im Abstand von 10 min, so daß die Badbelastung 1,34 m . 2 h-1 . 1-1 betrug.After a further 5 minutes, 2 sheets of cold-rolled and pickled steel - dimensions 10.2. 15.2. 0.23 cm) phosphated for 5 min while diving. Such sheets were used at intervals of 10 minutes, so that the bath load was 1.34 m . 2 h -1 . Was 1 -1 .

Es wurde analytisch ermittelt, daß - gegenüber der Verwendung einer Phosphatierungslösung ohne Hydroxylamingehalt - nicht nur eine Verdoppelung des Schichtgewichtes erzielt wurde, sondern auch der Abfall des Schichtgewichtes bei Verwendung der gleichen Lösung weit weniger schnell erfolgte als sonst. Dabei bleibt die durch Röntgenstrahluntersuchung ermittelte Morphologie bzw. Zusammensetzung der Kristalle die gleiche. Das Gewichtsverhältnis von Phosphophyllit zur Summe von Phosphophyllit und Hopeit betrug 1,05 gegenüber 1,65, wenn die oben genannte Phosphatierungslösung, jedoch ohne Hydroxylamin, eingesetzt wurde.It was determined analytically that - compared to the use of a phosphating solution without hydroxylamine content - not only a doubling of the layer weight was achieved, but also a decrease in the layer weight when using the same solution was far less rapid than usual Composition of crystals the same. The weight ratio of phosphophyllite to the sum of phosphophyllite and hopeit was 1.05 compared to 1.65 when the above-mentioned phosphating solution was used, but without hydroxylamine.

Die wie vorstehend behandelten Werkstoffe wurden dann mit einer schwachalkalischen Lösung gespült und mit einem Natriumstearat enthaltenden Schmiermittel versehen. Danach wurde getrocknet und die überschüssige Seife auf dem Werkstück belassen.The materials treated as above were then rinsed with a weakly alkaline solution and provided with a lubricant containing sodium stearate. It was then dried and the excess soap left on the workpiece.

Anschließend wurde das Werkstück einer konventionellen Kaltverformung, beispielsweise einer Extrudierbehandlung, unterworfen. Die Ergebnisse waren ausgezeichnet und denen, die unter Einsatz der üblichen Phosphatierverfahren erzielt wurden, weit überlegen.The workpiece was then subjected to conventional cold forming, for example an extrusion treatment. The results were excellent and far superior to those achieved using standard phosphating processes.

Beispiel 2Example 2

Es wurde ein Konzentrat A zur Herstellung einer Phosphatierungslösung formuliert aus

Figure imgb0002
210 g dieses Konzentrats wurden dann auf 1 1 gebrauchsfertige Phosphatierungslösung verdünnt.A concentrate A was formulated for the preparation of a phosphating solution
Figure imgb0002
 210 g of this concentrate were then diluted to 1 1 ready-to-use phosphating solution.

Während der Verwendung der Lösung kann mit einem Konzentrat B ergänzt bzw. aufgefrischt werden, das aus folgenden Bestandteilen gewonnen wurde:

Figure imgb0003
While using the solution, it can be supplemented or refreshed with a concentrate B, which was obtained from the following components:
Figure imgb0003

Dieses Ergänzungskonzentrat kann verwendet werden, wenn in der arbeitenden Phosphatierungslösung das Verhältnis von Gesamtsäure zu Freier Säure über den erwünschten Wert ansteigt. Sofern in der arbeitenden Phosphatierungslösung das genannte Verhältnis unter den erwünschten Wert fällt, kann mit Konzentrat A ergänzt werden.This supplemental concentrate can be used if the ratio of total acid to free acid in the working phosphating solution rises above the desired value. If the ratio in the working phosphating solution falls below the desired value, concentrate A can be added.

Claims (9)

1. Verfahren zur Erleichterung der Kaltverformung von Eisenwerkstoffen durch Aufbringen eines Phosphatüberzuges mittels einer wäßrigen, sauren Phosphatierungslösung, die Zinkionen und Hydroxylamin als Beschleuniger enthält, dadurch gekennzeichnet, daß man die Eisenwerkstoffe mit einer Phosphatierungslösung in Kontakt bringt, die 7,5 bis 75 g/1 Zinkionen und 0,1 bis 10 g/1 Hydroxylamin enthält.1. A process for facilitating the cold forming of iron materials by applying a phosphate coating using an aqueous, acid phosphating solution which contains zinc ions and hydroxylamine as accelerators, characterized in that the iron materials are brought into contact with a phosphating solution which is 7.5 to 75 g / 1 contains zinc ions and 0.1 to 10 g / 1 hydroxylamine. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Eisenwerkstoffe mit einer Phosphatierungslösung in Kontakt bringt, deren Gehalt an Eisenionen bis 25 g/1 beträgt.2. The method according to claim 1, characterized in that the iron materials are brought into contact with a phosphating solution whose iron ion content is up to 25 g / 1. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man die Eisenwerkstoffe mit einer Phosphatierungslösung in Kontakt bringt, die 7,5 bis 55, insbesondere 10 bis 30 g/1 Zink enthält.3. The method according to claim 1 or 2, characterized in that the iron materials are brought into contact with a phosphating solution which contains 7.5 to 55, in particular 10 to 30 g / 1 zinc. 4. Verfahren nach einem oder mehreren der Ansprüche 1, 2 oder 3, dadurch gekennzeichnet, daß man die Eisenwerkstoffe mit einer Phosphatierungslösung in Kontakt bringt, die zusätzlich bis 20 g/1 Manganionen enthält.4. The method according to one or more of claims 1, 2 or 3, characterized in that the iron materials are brought into contact with a phosphating solution which additionally contains up to 20 g / 1 manganese ions. 5. Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man die Eisenwerkstoffe mit einer Phosphatierungslösung in Kontakt bringt, die 5 bis 80 g/l, vorzugsweise 10 bis 70 g/l, Phosphat (als PO4 berechnet) enthält.5. The method according to one or more of claims 1 to 4, characterized in that the iron materials are brought into contact with a phosphating solution containing 5 to 80 g / l, preferably 10 to 70 g / l, of phosphate (calculated as PO 4 ) contains. 6. Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man die Eisenwerkstoffe mit einer Phosphatierungslösung in Kontakt bringt, die zusätzlich 5 bis 75 g/l, vorzugsweise 30 bis 70 g/l, Nitrat (jeweils als N03 berechnet) enthält.6. The method according to one or more of claims 1 to 5, characterized in that the iron materials are brought into contact with a phosphating solution which additionally contains 5 to 75 g / l, preferably 30 to 70 g / l, nitrate (in each case as N0 3 calculated) contains. 7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß man die Eisenwerkstoffe mit einer Phosphatierungslösung in Kontakt bringt, in der das Gewichtsverhältnis von Nitrat zu Phosphat 0,3 bis 6,0, vorzugsweise 0,5 bis 5, insbesondere 0,9 bis 4,5, beträgt.7. The method according to claim 6, characterized in that the iron materials are brought into contact with a phosphating solution in which the weight ratio of nitrate to phosphate is 0.3 to 6.0, preferably 0.5 to 5, in particular 0.9 to 4 , 5, is. 8. Verfahren nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß man die Eisenwerkstoffe mit einer Phosphatierungslösung in Kontakt bringt, die zusätzlich Nickelionen, vorzugsweise in einer Menge von 0,05 bis 1,0 g/l, insbesondere von 0,1 bis 0,5 g/l, enthält.8. The method according to one or more of claims 1 to 7, characterized in that the iron materials are brought into contact with a phosphating solution which additionally contains nickel ions, preferably in an amount of 0.05 to 1.0 g / l, in particular 0 , 1 to 0.5 g / l, contains. 9. Verfahren nach einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß man die Eisenwerkstoffe mit einer Phosphatierungslösung in Kontakt bringt, die einen pH-Wert von 1,8 bis 2,5 aufweist.9. The method according to one or more of claims 1 to 8, characterized in that the ferrous materials are brought into contact with a phosphating solution which has a pH of 1.8 to 2.5.
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US3923554A (en) * 1974-02-07 1975-12-02 Detrex Chem Ind Phosphate coating composition and method
EP0042631A1 (en) * 1980-06-24 1981-12-30 Metallgesellschaft Ag Method of phosphating metallic surfaces

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0287133A1 (en) * 1987-04-11 1988-10-19 Metallgesellschaft Ag Phosphating treatment before electrophoretic dip painting
EP0315059A1 (en) * 1987-10-30 1989-05-10 HENKEL CORPORATION (a Delaware corp.) Process and composition for zinc phosphate coating
EP0327153A2 (en) * 1988-02-03 1989-08-09 Metallgesellschaft Ag Process for applying phosphate coatings to metals
EP0327153A3 (en) * 1988-02-03 1990-04-25 Metallgesellschaft Ag Process for applying phosphate coatings to metals
WO1993020259A1 (en) * 1992-03-31 1993-10-14 Henkel Kommanditgesellschaft Auf Aktien Nickel-free phosphatization process
WO1998048076A1 (en) * 1997-04-17 1998-10-29 Henkel Kommanditgesellschaft Auf Aktien Phosphatising process accelerated with hydroxylamine and chlorate

Also Published As

Publication number Publication date
AU5052285A (en) 1986-06-26
JPS61157684A (en) 1986-07-17
GB8531408D0 (en) 1986-02-05
JPH0465151B2 (en) 1992-10-19
CA1257527A (en) 1989-07-18
DE3582873D1 (en) 1991-06-20
AU577424B2 (en) 1988-09-22
EP0186823A3 (en) 1988-04-27
ATE63575T1 (en) 1991-06-15
GB2169620B (en) 1988-05-11
ES8703943A1 (en) 1987-03-16
EP0186823B1 (en) 1991-05-15
ZA859171B (en) 1986-08-27
GB2169620A (en) 1986-07-16
ES550112A0 (en) 1987-03-16
DE3543733A1 (en) 1986-07-03

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