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EP0324395A1 - Process for phosphatizing metal surfaces - Google Patents

Process for phosphatizing metal surfaces Download PDF

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Publication number
EP0324395A1
EP0324395A1 EP89100228A EP89100228A EP0324395A1 EP 0324395 A1 EP0324395 A1 EP 0324395A1 EP 89100228 A EP89100228 A EP 89100228A EP 89100228 A EP89100228 A EP 89100228A EP 0324395 A1 EP0324395 A1 EP 0324395A1
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EP
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Prior art keywords
ions
metal surfaces
zinc
phosphating
contact
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Granted
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EP89100228A
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German (de)
French (fr)
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EP0324395B1 (en
Inventor
Kurt Hosemann
Reinhard Opitz
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Gerhard Collardin GmbH
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Gerhard Collardin GmbH
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Priority to AT89100228T priority Critical patent/ATE83509T1/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
    • C23C22/22—Orthophosphates containing alkaline earth metal 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
    • C23C22/34—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
    • C23C22/367—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 alkaline earth metal cations

Definitions

  • the present invention relates to a method for phosphating metal surfaces, in particular the zinc-calcium phosphating of surfaces made of iron, steel, zinc and / or aluminum as a pretreatment for cold forming.
  • Zinc phosphating baths can contain, for example, monozinc phosphate, free phosphoric acid, zinc nitrate and oxidizing agents as main components.
  • the pH of such solutions is usually in the range between 2.8 and 3.4.
  • the process sequence consists of two reactions, the pickling reaction and the formation of a zinc phosphate layer on the surface to be phosphated.
  • the alkali phosphating processes clean and degrease the metal surface and form a corrosion-protective cover layer, which mainly consists of iron phosphate.
  • the layer formation is initiated by a pickling reaction in which a small amount of the base metal is removed.
  • the majority of the dissolved surface material reacts with the phosphate ion of the solution to form poorly soluble phosphates, which deposit as a firmly adhering coating on the surface.
  • the layer-forming cation originates from the base metal itself.
  • iron phosphate layers with a low layer weight of around 0.2 to 0.4 g / m2 and iron phosphate layers with higher basis weights from 0.6 to 1.2 g / m2.
  • the thin phosphate layers are particularly suitable for painting; they ensure excellent paint adhesion, offer good rust protection, electrical insulation, reduction of sliding resistance and facilitate cold forming.
  • phosphate layers with a layer weight of up to 40 g / m2 are usually deposited.
  • the metal soaps are known to be produced.
  • Aluminum, calcium, lithium, zinc and magnesium stearates are water-repellent and, as solid lubricants in wire drawing, result in lower coefficients of friction at higher surface pressures than conventional alkali soaps.
  • Metal soaps have the advantage over alkali soaps that they hardly absorb moisture from the air, remain unchanged in their lubricating effect due to their high compressive strength and allow higher overall cross-sectional decreases, while with alkaline soaps the lubricating effect can decrease significantly due to moisture absorption.
  • EP-PS 0 045 110 describes a process for the production of phosphate coatings on iron or steel surfaces by immersion or flooding with an aqueous acidic zinc phosphate solution, the surfaces being brought into contact with a solution which, in addition to Zn2+, PO43 ⁇ , NO3 ⁇ or contains an equivalent iron (II) non-oxidizing accelerator in which the weight ratio Zn: PO4 is greater than 0.8, the ratio of total acid to free acid is at least 5 and in which one by suitable measurement of ClO3 ⁇ or an equivalent Iron (II) to iron (III) oxidizing accelerator sets an iron (II) content of 0.05 to 1 wt .-%.
  • the object of the present invention was to provide an improved method for phosphating metal surfaces, in particular surfaces made of iron, steel, zinc and their alloys, as well as aluminum as a pretreatment for cold forming.
  • the objects of the present invention are achieved by the improved phosphating process based on zinc-calcium-phosphate layers.
  • the phosphating solution with which the surfaces to be coated are brought into contact can Zn2+ and Ca2+ ions in a weight ratio of 1: 0.5 to 1: 1.5 and preferably in a ratio of 1: 1.
  • preferred embodiments of the present phosphating solution contain further cations of transition metal ions in addition to the above Ca2 und and Zn2+ cations.
  • Ni2+ ions are particularly preferred at this point.
  • the phosphating solutions contain Ni2+ ions, an amount of 0.01 to 10 g / l of Ni2+ ions is preferred.
  • phosphating solutions according to the invention can contain further additional anions.
  • simple and / or complex fluorides can be used as further anions, if appropriate. These can be used in the phosphating solutions in particular in amounts of 0.01 to 10 g / l.
  • a preferred embodiment of the present invention is to set the temperature range in the range from 50 to 70 ° C. and to bring the metal surfaces into contact with the phosphating solutions.
  • phosphating solutions according to the invention can contain 0.1 to 2.0 g of organic nitro compounds.
  • Organic nitro compounds in the sense of the present invention are selected from m-nitrobenzenesulfonates and / or nitroguanidine.
  • the organic nitro compounds can also be present in amounts of 0.1 to 2.0 g / l in addition to 10 to 100 g / l NO3 ⁇ ions in the phosphating solutions.
  • the process for phosphating metal surfaces in particular surfaces made of iron, steel, zinc and their alloys, as well as aluminum, zinc-calcium-phosphate layers (Scholzit) with a basis weight of 3 to 9 g / m2 are produced.
  • Scholzit zinc-calcium-phosphate layers
  • the zinc-calcium-phosphate layers can be created on the metal surfaces by dipping, spraying and flooding as well as by combined processes.
  • the surfaces to be phosphated are degreased according to the methods known in the prior art.
  • Oil, grease and lubricant residues or grinding dust from previous manufacturing processes can be removed by organic solvents or aqueous cleaners.
  • the chlorinated hydrocarbons are the most frequently used organic solvents because they dissolve oils and fats excellently and are not flammable. Solids and inorganic contaminants, however, are only removed inadequate. Water-based cleaners have a very high cleaning ability.
  • the advantage of the present invention is that zinc-calcium-phosphate layers are suitable for producing low layer weights on the order of 3 to 9 g / m 2 on wire.
  • the zinc-calcium-phosphate layers largely contain the mineral scholzite.
  • a mixed soap of zinc-calcium stearate is formed in addition to zinc stearate and calcium stearate.
  • zinc calcium stearate has the advantage that the durability of the drawing dies is increased many times over. Pulling tests in the technical center also showed that the wire surfaces, in particular during a subsequent polishing pull, achieve a substantially brighter and more uniform appearance than can be achieved with conventional methods operated on the accelerator side.
  • Another product advantage is the fact that the new zinc-calcium phosphating process for cold working works in a temperature range of preferably 50 to 70 ° C.
  • the sludge behavior in this process can be classified as particularly favorable, since even after a bath load of 1.5 m2 steel surface per liter of bath solution, only minimal quantities in the order of a few milliliters of bath sludge are produced.
  • Another advantage of the present invention is that the Sales with drawing soap (sodium stearate) resulting zinc-calcium stearate mixed soaps allow a longer service life of the drawing dies due to the improved properties.
  • a phosphating solution was prepared that 10.3 gl ⁇ 1 Ca2+ ions 14.0 gl ⁇ 1 Zn2+ ions 27.8 gl ⁇ 1 PO43 ⁇ ions 46.5 gl ⁇ 1 NO3 ⁇ ions contained.
  • the phosphating solution had the following characteristics: pH: approx.2.6 Acid ratio: approx. 1:21 (free acid to total acid)
  • the pH was 2.5 and the ratio of free Acid to total acid 1: 17.6.
  • the wire coated in this way could easily be reduced to the desired size using several drawing dies connected in series.
  • the result was a bright and shiny surface.

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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)
  • Laminated Bodies (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The present invention relates to a process for phosphating metal surfaces, and more specifically of surfaces of iron, zinc, and aluminum and the alloys thereof as a pretreatment for cold working wherein the surfaces without previous activation are contacted in a temperature range of from 30 DEG C. to 70 DEG C. with an aqueous solution containing (a) from 10 to 40 g/l of Ca2+ ions, (b) from 10 to 40 g/l of Zn2+ ions, (c) from 10 to 100 g/l of OP43- ions and, as accelerator, (d) from 10 to 100 g/l of NO3- ions and/or (e) from 0.1 to 2.0 g/l of organic nitro compounds, said solution exhibiting a pH value in the range of from 2.0 to 3.8 and a ratio of free acid to total acid of from 1:4 to 1:100.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Phosphatierung von Metalloberflächen, insbesondere die Zink-Calcium-Phosphatierung von Oberflächen aus Eisen, Stahl, Zink und/oder Aluminium als Vorbehandlung für die Kaltumformung.The present invention relates to a method for phosphating metal surfaces, in particular the zinc-calcium phosphating of surfaces made of iron, steel, zinc and / or aluminum as a pretreatment for cold forming.

Verfahren zum Phosphatieren von Oberflächen aus Eisen, Stahl, Zink und deren Legierungen sowie Aluminium sind seit langem bekannt (Ullmanns Encyklopädie der techni­schen Chemie, 4. Auflage, Band 15 Seite 686 f). Das Phosphatieren der genannten Oberflächen dient zur Er­höhung der Haftfestigkeit von Lackschichten und zur Verbesserung des Korrosionsschutzes.Processes for phosphating surfaces made of iron, steel, zinc and their alloys as well as aluminum have long been known (Ullmanns Encyklopadie der Technische Chemie, 4th edition, volume 15 page 686 f). The phosphating of the surfaces mentioned serves to increase the adhesive strength of paint layers and to improve corrosion protection.

Die größte Bedeutung der Phosphatierverfahren besitzen das Zink- und das Alkaliphosphatieren. Zinkphospha­tierbäder können beispielsweise Monozinkphosphat, freie Phosphorsäure, Zinknitrat und Oxidationsmittel als Hauptkomponenten enthalten. Der pH-Wert solcher Lösungen liegt üblicherweise im Bereich zwischen 2,8 und 3,4. Der Verfahrensablauf besteht aus zwei Reak­tionen, der Beizreaktion und der Bildung einer Zink­phosphatschicht auf der zu phosphatierenden Oberflä­che.The most important of the phosphating processes are zinc and alkali phosphating. Zinc phosphating baths can contain, for example, monozinc phosphate, free phosphoric acid, zinc nitrate and oxidizing agents as main components. The pH of such solutions is usually in the range between 2.8 and 3.4. The process sequence consists of two reactions, the pickling reaction and the formation of a zinc phosphate layer on the surface to be phosphated.

Im Gegensatz dazu reinigen und entfetten die Alkali­phosphatierverfahren die Metalloberfläche und bilden eine korrosionsschützende Deckschicht aus, die haupt­sächlich aus Eisenphosphat besteht. Die Schichtbildung wird durch eine Beizreaktion eingeleitet, bei der eine geringe Menge des Grundmetalls abgelöst wird. Der überwiegende Teil des gelösten Oberflächenmaterials reagiert mit dem Phosphation der Lösung unter Bildung von schwerlöslichen Phosphaten, die sich als festhaf­tender Überzug auf der Oberfläche abscheiden. Im Ge­gensatz zur Zinkphosphatierung stammt hier das schichtbildende Kation aus dem Grundmetall selbst.In contrast, the alkali phosphating processes clean and degrease the metal surface and form a corrosion-protective cover layer, which mainly consists of iron phosphate. The layer formation is initiated by a pickling reaction in which a small amount of the base metal is removed. The majority of the dissolved surface material reacts with the phosphate ion of the solution to form poorly soluble phosphates, which deposit as a firmly adhering coating on the surface. In contrast to zinc phosphating, the layer-forming cation originates from the base metal itself.

Prinzipiell kann bei der Korrosionsschutzphosphatie­rung zwischen zwei Schichttypen unterschieden werden: Eisenphosphatschichten mit niedrigem Schichtgewicht von etwa 0,2 bis 0,4 g/m² und Eisenphosphatschichten mit höheren Flächengewichten von 0,6 bis 1,2 g/m². Für eine Lackierung sind die dünnen Phosphatschichten be­sonders geeignet; sie gewähren eine vorzügliche Lack­haftung, bieten einen guten Unterrostungsschutz, elek­trische Isolation, Verminderung des Gleitwiderstandes und erleichtern die Kaltumformung.In principle, a distinction can be made between corrosion protection phosphating between two types of layers: iron phosphate layers with a low layer weight of around 0.2 to 0.4 g / m² and iron phosphate layers with higher basis weights from 0.6 to 1.2 g / m². The thin phosphate layers are particularly suitable for painting; they ensure excellent paint adhesion, offer good rust protection, electrical insulation, reduction of sliding resistance and facilitate cold forming.

Für die Kaltumformung werden üblicherweise Phosphat­schichten mit einem Schichtgewicht bis zu 40 g/m² ab­geschieden. Bei Umsetzung der bekannten Phosphat­schichten für die Kaltumformung mit entsprechenden Natriumstearatseifen entstehen bekanntermaßen die Me­tallseifen. Aluminium-, Calcium-, Lithium-, Zink- und Magnesiumstearate sind wasserabweisend und ergeben als Festschmierstoffe im Drahtzug bei höheren Flächenpres­sungen geringere Reibwerte als übliche Alkaliseifen.For cold forming, phosphate layers with a layer weight of up to 40 g / m² are usually deposited. When the known phosphate layers for cold forming are implemented with corresponding sodium stearate soaps, the metal soaps are known to be produced. Aluminum, calcium, lithium, zinc and magnesium stearates are water-repellent and, as solid lubricants in wire drawing, result in lower coefficients of friction at higher surface pressures than conventional alkali soaps.

Da die Schmelzpunkte niedriger sind als bei Natrium­seifen und die Metallstearate für sich alleine zu fett sind, werden in der Praxis Trägerstoffe, wie bei­spielsweise Kalk, eingearbeitet, um die Metallseifen im Schmierspalt zu halten. Metallseifen haben gegen­über Alkaliseifen den Vorteil, daß sie kaum Feuchtig­keit aus der Luft aufnehmen, infolge ihrer hohen Druckfestigkeit in ihrer Schmierwirkung unverändert bleiben und höhere Gesamtquerschnittsabnahmen ermög­lichen, während bei Alkaliseifen die Schmierwirkung durch Feuchtigkeitsaufnahme stark sinken kann.Since the melting points are lower than with sodium soaps and the metal stearates are too fat by themselves, in practice carriers such as lime are incorporated in order to keep the metal soaps in the lubrication gap. Metal soaps have the advantage over alkali soaps that they hardly absorb moisture from the air, remain unchanged in their lubricating effect due to their high compressive strength and allow higher overall cross-sectional decreases, while with alkaline soaps the lubricating effect can decrease significantly due to moisture absorption.

Die EP-PS 0 045 110 beschreibt ein Verfahren zur Her­stellung von Phosphatüberzügen auf Eisen oder Stahl­oberflächen im Tauchverfahren oder Flutverfahren mit einer wäßrigen sauren Zinkphosphatlösung, wobei man die Oberflächen mit einer Lösung in Berührung bringt, die neben Zn²⁺, PO₄³⁻, NO₃⁻ oder eines gleich wirken­den Eisen (II) nicht oxidierenden Beschleunigers ent­hält, in der das Gewichtsverhältnis Zn : PO₄ größer als 0,8 ist, das Verhältnis von Gesamtsäure zu freier Säure mindestens 5 beträgt und in der man durch geeig­nete Bemessung von ClO₃⁻ oder einem gleich wirkenden Eisen (II) zu Eisen (III) oxidierenden Beschleuniger einen Eisen (II) gehalt von 0,05 bis 1 Gew.-% einstellt.EP-PS 0 045 110 describes a process for the production of phosphate coatings on iron or steel surfaces by immersion or flooding with an aqueous acidic zinc phosphate solution, the surfaces being brought into contact with a solution which, in addition to Zn²⁺, PO₄³⁻, NO₃⁻ or contains an equivalent iron (II) non-oxidizing accelerator in which the weight ratio Zn: PO₄ is greater than 0.8, the ratio of total acid to free acid is at least 5 and in which one by suitable measurement of ClO₃⁻ or an equivalent Iron (II) to iron (III) oxidizing accelerator sets an iron (II) content of 0.05 to 1 wt .-%.

Der vorliegenden Erfindung lag die Aufgabe zugrunde, ein verbessertes Verfahren zur Phosphatierung von Me­talloberflächen, insbesondere von Oberflächen aus Eisen, Stahl, Zink und deren Legierungen sowie Alu­minium als Vorbehandlung für die Kaltumformung zur Verfügung zu stellen.The object of the present invention was to provide an improved method for phosphating metal surfaces, in particular surfaces made of iron, steel, zinc and their alloys, as well as aluminum as a pretreatment for cold forming.

Die Aufgaben der vorliegenden Erfindung werden durch das verbesserte Phosphatierungsverfahren auf der Basis von Zink-Calcium-Phosphatschichten gelöst.The objects of the present invention are achieved by the improved phosphating process based on zinc-calcium-phosphate layers.

Gegenstand der vorliegenden Erfindung ist ein Verfah­ren zur Phosphatierung von Metalloberflächen, insbe­sondere von Oberflächen aus Eisen, Stahl, Zink und deren Legierungen sowie Aluminium als Vorbehandlung für die Kaltumformung, wobei man die Oberfläche in an sich bekannter Weise reinigt und/oder beizt, dadurch gekennzeichnet, daß man die Oberflächen ohne vorherige Aktivierung im Temperaturbereich von 30 bis 70 °C mit einer wäßrigen Lösung in Kontakt bringt, die

  • (a) 10 bis 40 g/l Ca²⁺-Ionen,
  • (b) 10 bis 40 g/l Zn²⁺-Ionen,
  • )c) 10 bis 100 g/l PO₄³⁻-Ionen
sowie als Beschleuniger
  • (d) 10 bis 100 g/l NO₃⁻-Ionen und/oder
  • (e) 0,1 bis 2,0 g/l organische Nitroverbindungen,
enthält
wobei die Lösung einen pH-Wert im Bereich von 2,0 bis 3,8 und ein Verhältnis von feier Säure zu Gesamtsäure von 1 : 4 bis 1 : 100 aufweist.The present invention relates to a process for phosphating metal surfaces, in particular surfaces made of iron, steel, zinc and their alloys and aluminum as pretreatment for cold forming, the surface being cleaned and / or pickled in a manner known per se, characterized in that that the surfaces are brought into contact with an aqueous solution in the temperature range from 30 to 70 ° C. without prior activation
  • (a) 10 to 40 g / l Ca²⁺ ions,
  • (b) 10 to 40 g / l Zn²⁺ ions,
  • ) c) 10 to 100 g / l PO₄³⁻ ions
as well as an accelerator
  • (d) 10 to 100 g / l NO₃⁻ ions and / or
  • (e) 0.1 to 2.0 g / l organic nitro compounds,
contains
the solution having a pH in the range of 2.0 to 3.8 and a ratio of acid to total acid of 1: 4 to 1: 100.

Überraschenderweise wurde trotz des gegenüber der EP-PS 0 045 101 verschiedenen Zn : Ca Verhältnisses und den hohen Calcium-Anteilen die nach dem Stand der Technik nicht zu erwartende Schichtausbildung bei der hohen Konzentration des Ca-Ions in der Phosphatie­rungslösung gefunden.Surprisingly, in spite of the different Zn: Ca ratio compared to EP-PS 0 045 101 and the high calcium proportions, the layer formation not to be expected according to the prior art was found at the high concentration of the Ca ion in the phosphating solution.

Gemäß einer bevorzugten Ausführungsform der vorliegen­den Erfindung kann die Phosphatierlösung, mit der man die zu beschichtenden Oberflächen in Kontakt bringt, Zn²⁺- und Ca²⁺-Ionen im Gewichtsverhältnis von 1 : 0,5 bis 1 : 1,5 und vorzugsweise im Verhältnis von 1 : 1 enthalten.According to a preferred embodiment of the present invention, the phosphating solution with which the surfaces to be coated are brought into contact can Zn²⁺ and Ca²⁺ ions in a weight ratio of 1: 0.5 to 1: 1.5 and preferably in a ratio of 1: 1.

Vorteilhafterweise enthalten bevorzugte Ausführungs­formen der vorliegenden Phosphatierlösung zusätzlich zu den oben genannten Ca²⁺- und Zn²⁺-Kationen weitere Kationen von Übergangsmetallionen. Insbesondere bevor­zugt sind an dieser Stelle Ni²⁺-Ionen. In dem Falle, daß die Phosphatierlösungen Ni²⁺-Ionen enthalten, ist eine Menge von 0,01 bis 10 g/l an Ni²⁺-Ionen bevor­zugt.Advantageously, preferred embodiments of the present phosphating solution contain further cations of transition metal ions in addition to the above Ca² und and Zn²⁺ cations. Ni²⁺ ions are particularly preferred at this point. In the case that the phosphating solutions contain Ni²⁺ ions, an amount of 0.01 to 10 g / l of Ni²⁺ ions is preferred.

Zusätzlich zu den genannten Anionen wie PO₄³⁻- und NO₃⁻-Ionen können erfindungsgemäße Phosphatierlösungen weitere zusätzliche Anionen enthalten. Als gegebenen­falls zu verwendende weitere Anionen kommen gemäß einer bevorzugten Ausführungsform einfache und/oder komplexe Fluoride in Frage. Diese können in den Phos­phatierlösungen insbesondere in Mengen von 0,01 bis 10 g/l verwendet werden.In addition to the anions mentioned, such as PO₄³⁻ and NO₃⁻ ions, phosphating solutions according to the invention can contain further additional anions. According to a preferred embodiment, simple and / or complex fluorides can be used as further anions, if appropriate. These can be used in the phosphating solutions in particular in amounts of 0.01 to 10 g / l.

Während üblicherweise das erfindungsgemäße Phosphatie­rungsverfahren im Bereich von 30 bis 70 °C durchge­führt wird, besteht eine bevorzugte Ausführungsform der vorliegenden Erfindung darin, den Temperaturbe­reich im Bereich von 50 bis 70 °C einzustellen und die Metalloberflächen mit den Phosphatierlösungen in Kon­takt zu bringen.While the phosphating process according to the invention is usually carried out in the range from 30 to 70 ° C., a preferred embodiment of the present invention is to set the temperature range in the range from 50 to 70 ° C. and to bring the metal surfaces into contact with the phosphating solutions.

Anstelle von 10 bis 100 g/l NO₃⁻-Ionen können erfin­dungsgemäße Phosphatierungslösungen 0,1 bis 2,0 g or­ganische Nitroverbindungen enthalten. Organische Nitroverbindungen im Sinne der vorliegenden Erfindung sind ausgewählt aus m-Nitrobenzolsulfonaten und/oder Nitroguanidin. Die organischen Nitroverbindungen kön­nen auch in Mengen von 0,1 bis 2,0 g/l neben 10 bis 100 g/l NO₃⁻-Ionen in den Phosphatierungslösungen vor­liegen. Gemäß einer Ausführungsform der vorliegenden Erfindung werden durch das Verfahren zur Phosphatie­rung von Metalloberflächen, insbesondere von Oberflä­chen aus Eisen, Stahl, Zink und deren Legierungen so­wie Aluminium, Zink-Calcium-Phosphatschichten (Schol­zit) mit einem Flächengewicht von 3 bis 9 g/m² er­zeugt.Instead of 10 to 100 g / l of NO₃⁻ ions, phosphating solutions according to the invention can contain 0.1 to 2.0 g of organic nitro compounds. Organic nitro compounds in the sense of the present invention are selected from m-nitrobenzenesulfonates and / or nitroguanidine. The organic nitro compounds can also be present in amounts of 0.1 to 2.0 g / l in addition to 10 to 100 g / l NO₃⁻ ions in the phosphating solutions. According to one embodiment of the present invention, the process for phosphating metal surfaces, in particular surfaces made of iron, steel, zinc and their alloys, as well as aluminum, zinc-calcium-phosphate layers (Scholzit) with a basis weight of 3 to 9 g / m² are produced.

Die Zink-Calcium-Phosphatschichten können auf den Me­talloberflächen durch Tauchen, Spritzen und Fluten sowie durch kombinierte Verfahren erzeugt werden. Vor der Anwendung des erfindungsgemäßen Verfahrens zur Phosphatierung werden die zu phosphatierenden Ober­flächen nach den im Stand der Technik bekannten Ver­fahren entfettet. Von vorangegangenen Fertigungspro­zessen stammende Öl-, Fett- und Schmierstoffreste oder Schleifstaub können durch organische Lösemittel oder wäßrige Reiniger entfernt werden. Die chlorierten Koh­lenwasserstoffe sind die am häufigsten angewendeten organischen Lösungsmittel, da sie Öle und Fette ausge­zeichnet lösen und nicht brennbar sind. Feststoffe und anorganische Verunreinigungen werden jedoch nur man­gelhaft entfernt. Reiniger auf wäßriger Basis haben ein sehr hohes Reinigungsvermögen. Sie enthalten ober­flächenaktive Substanzen, die Öle und Fette im Wasser emulgieren, sowie anorganische Bestandteile, wie Car­bonate, Silikate, Borate und Phosphate, die alkalisch reagieren und natürliche Fette verseifen. Eine weitere Möglichkeit der Vorreinigung vor der Phosphatierung besteht darin, die zu phosphatierenden Metallober­ flächen einer Ultraschallreinigung oder einer mecha­nischen Reinigung zu unterziehen.The zinc-calcium-phosphate layers can be created on the metal surfaces by dipping, spraying and flooding as well as by combined processes. Before the method for phosphating according to the invention is used, the surfaces to be phosphated are degreased according to the methods known in the prior art. Oil, grease and lubricant residues or grinding dust from previous manufacturing processes can be removed by organic solvents or aqueous cleaners. The chlorinated hydrocarbons are the most frequently used organic solvents because they dissolve oils and fats excellently and are not flammable. Solids and inorganic contaminants, however, are only removed inadequate. Water-based cleaners have a very high cleaning ability. They contain surface-active substances that emulsify oils and fats in the water, as well as inorganic components such as carbonates, silicates, borates and phosphates, which have an alkaline reaction and saponify natural fats. A further possibility of pre-cleaning before phosphating is the metal surface to be phosphated surfaces to undergo ultrasonic cleaning or mechanical cleaning.

Der Vorteil der vorliegenden Erfindung besteht darin, daß Zink-Calcium-Phosphatschichten geeignet sind, auf Draht niedrige Schichtgewichte in der Größenordnung von 3 bis 9 g/m² zu erzeugen.The advantage of the present invention is that zinc-calcium-phosphate layers are suitable for producing low layer weights on the order of 3 to 9 g / m 2 on wire.

Die gebildeten Zink-Calcium-Phosphatschichten enthal­ten größtenteils das Mineral Scholzit. Beim Umsetzen der Zink-Calcium-Phosphatschichten mit den in der Technik verwendeten Natriumstearatseifen entsteht ne­ben Zinkstearat und Calciumstearat auch eine Misch­seife aus Zink-Calciumstearat.The zinc-calcium-phosphate layers largely contain the mineral scholzite. When the zinc-calcium-phosphate layers are reacted with the sodium stearate soaps used in the technology, a mixed soap of zinc-calcium stearate is formed in addition to zinc stearate and calcium stearate.

Zink-Calciumstearat hat ziehtechnisch den Vorteil, daß die Haltbarkeit der Ziehsteine um ein vielfaches er­höht wird. Ziehversuche im Technikum ergaben weiter­hin, daß die Drahtoberflächen, insbesondere bei einem nachfolgenden Polierzug, eine wesentliche hellere und gleichmäßigere Optik erzielen, als dies bei herkömm­liche, auf der Beschleunigerseite gefahrenen Verfah­ren erreicht werden kann.In terms of drawing technology, zinc calcium stearate has the advantage that the durability of the drawing dies is increased many times over. Pulling tests in the technical center also showed that the wire surfaces, in particular during a subsequent polishing pull, achieve a substantially brighter and more uniform appearance than can be achieved with conventional methods operated on the accelerator side.

Ein weiterer Produktvorteil ist darin zu sehen, daß das neue Zink-Calcium-Phosphatierungsverfahren für die Kaltverformung in einem Temperaturbereich von vorzugs­weise 50 bis 70 °C arbeitet. Das Schlammverhalten ist bei diesem Verfahren als besonders günstig einzustu­fen, da selbst nach einer Badbelastung von 1,5 m² Stahloberfläche pro Liter Badlösung nur minimale Men­gen in der Größenordnung von wenigen Millilitern an Badschlamm entstehen. Ein weiterer Vorteil der vor­liegenden Erfindung besteht darin, daß die durch den Umsatz mit Ziehseife (Natriumstearat) entstehenden Zink-Calciumstearat-Mischseifen wegen der verbesserten Eigenschaften eine längere Standzeit der Ziehsteine ermöglichen.Another product advantage is the fact that the new zinc-calcium phosphating process for cold working works in a temperature range of preferably 50 to 70 ° C. The sludge behavior in this process can be classified as particularly favorable, since even after a bath load of 1.5 m² steel surface per liter of bath solution, only minimal quantities in the order of a few milliliters of bath sludge are produced. Another advantage of the present invention is that the Sales with drawing soap (sodium stearate) resulting zinc-calcium stearate mixed soaps allow a longer service life of the drawing dies due to the improved properties.

BeispieleExamples Beispiel 1example 1

Es wurde eine Phosphatierungslösung hergestellt, die
10,3 g l⁻¹ Ca²⁺-Ionen
14,0 g l⁻¹ Zn²⁺-Ionen
27,8 g l⁻¹ PO₄³⁻-Ionen
46,5 g l⁻¹ NO₃⁻-Ionen
enthielt.A phosphating solution was prepared that
10.3 gl⁻¹ Ca²⁺ ions
14.0 gl⁻¹ Zn²⁺ ions
27.8 gl⁻¹ PO₄³⁻ ions
46.5 gl⁻¹ NO₃⁻ ions
contained.

Die Phosphatierlösung hatte folgende Kenndaten:
pH-Wert: ca. 2,6
Säureverhältnis: ca. 1 : 21 (freie Säure zu Gesamt­säure)The phosphating solution had the following characteristics:
pH: approx.2.6
Acid ratio: approx. 1:21 (free acid to total acid)

Stahldrähte, die zuvor mit einer alkalischen Reini­gungslösung bei 80 °C während 10 Minuten durch Tauch­behandlung gereinigt und mit Wasser gespült worden waren, wurden mit der vorgenannten Phosphatierlösung 7 min bei 50 °C im Tauchen behandelt. Anschließend wurde mit Wasser gespült und eine reaktive Seife auf­getragen. Danach wurden die Drähte über Ziehsteine gezogen. Das Ergebnis war eine sehr helle und glän­zende Oberfläche, die mit anderen erfindungsgemäßen Phosphatierlösungen nicht erreicht werden konnte.Steel wires which had previously been immersed in an alkaline cleaning solution at 80 ° C. for 10 minutes and rinsed with water were treated with the aforementioned phosphating solution for 7 minutes at 50 ° C. in immersion. It was then rinsed with water and a reactive soap was applied. Then the wires were drawn over drawing dies. The result was a very bright and shiny surface that could not be achieved with other phosphating solutions according to the invention.

Beispiel 2Example 2

Es wurde eine Lösung hergestellt, die
18,0 g/l Ca²⁺-Ionen
12,0 g/l Zn²⁺-Ionen
2,8 g/l Ni²⁺-Ionen
87,2 g/l PO₄³⁻-Ionen
27,5 g/l NO₃⁻-Ionen
enthielt.A solution was made that
18.0 g / l Ca²⁺ ions
12.0 g / l Zn²⁺ ions
2.8 g / l Ni²⁺ ions
87.2 g / l PO₄³⁻ ions
27.5 g / l NO₃⁻ ions
contained.

Der pH-Wert betrug 2,5 und das Verhältnis von freier
Säure zu Gesamtsäure 1 : 17,6.The pH was 2.5 and the ratio of free
Acid to total acid 1: 17.6.

Stahldraht, der vorher bei 80°C 10 Minuten lang im Tauchbad alkalisch gereinigt und anschließend kalt gespült wurde, ist mit der vorgenannten Phosphatie­rungslösung 10 Minuten lang bei 55°C im Tauchen be­handelt worden.Steel wire, which had previously been alkaline cleaned in an immersion bath at 80 ° C. for 10 minutes and then rinsed cold, was immersed in the aforementioned phosphating solution for 10 minutes at 55 ° C.

Anschließend wurde mit Wasser gespült und im Tauchbad bei 80°C eine reaktive Ziehseife aufgebracht.It was then rinsed with water and a reactive drawing soap was applied in the immersion bath at 80 ° C.

Der so beschichtete Draht ließ sich über mehrere hin­tereinandergeschaltete Ziehsteine problemlos auf das Sollmaß reduzieren. Es entstand dabei eine helle und glänzende Oberfläche.The wire coated in this way could easily be reduced to the desired size using several drawing dies connected in series. The result was a bright and shiny surface.

Claims (9)

1. Verfahren zur Phosphatierung von Metalloberflächen, insbesondere von Oberflächen aus Eisen, Stahl, Zink und deren Legierungen sowie Aluminium als Vorbehand­lung für die Kaltumformung, wobei man die Oberflächen in an sich bekannter Weise reinigt und/oder beizt, dadurch gekennzeichnet, daß man die Oberflächen ohne Aktivierung im Temperaturbereich von 30 bis 70 °C mit einer wäßrigen Lösung in Kontakt bringt, die
(a) 10 bis 40 g/l Ca²⁺-Ionen
(b) 10 bis 40 g/l Zn²⁺-Ionen
(c) 10 bis 100 g/l PO₄³⁻-Ionen
sowie als Beschleuniger
(d) 10 bis 100 g/l NO₃⁻-Ionen und/oder
(e) 0,1 bis 2,0 g/l organische Nitroverbindungen,
enthält,
wobei die Lösung einen pH-Wert im Bereich von 2,0 bis 3,8 und ein Verhältnis von feier Säure zu Gesamtsäure von 1 : 4 bis 1 : 100 aufweist.1. Process for phosphating metal surfaces, in particular surfaces made of iron, steel, zinc and their alloys and aluminum as a pretreatment for cold forming, the surfaces being cleaned and / or pickled in a manner known per se, characterized in that the surfaces without activation in the temperature range of 30 to 70 ° C in contact with an aqueous solution that
(a) 10 to 40 g / l Ca²⁺ ions
(b) 10 to 40 g / l Zn²⁺ ions
(c) 10 to 100 g / l PO₄³⁻ ions
as well as an accelerator
(d) 10 to 100 g / l NO₃⁻ ions and / or
(e) 0.1 to 2.0 g / l organic nitro compounds,
contains
the solution having a pH in the range of 2.0 to 3.8 and a ratio of acid to total acid of 1: 4 to 1: 100. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Metalloberfläche mit einer Lösung in Kon­takt bringt, die Zn²⁺- und Ca²⁺-Ionen im Gewichtsver­hältnis von 1 : 0,5 bis 1 : 1,5 und vorzugsweise im Verhältnis 1 : 1 enthalten.2. The method according to claim 1, characterized in that the metal surface is brought into contact with a solution containing Zn²⁺ and Ca²⁺ ions in a weight ratio of 1: 0.5 to 1: 1.5 and preferably in a ratio of 1: 1 included. 3. Verfahren nach Ansprüchen 1 und 2, dadurch gekenn­zeichnet, daß man die Metalloberflächen mit Lösungen in Kontakt bringt, die Ni²⁺-Ionen in einer Menge von 0,01 bis 10 g/l enthalten.3. Process according to Claims 1 and 2, characterized in that the metal surfaces are brought into contact with solutions which contain Ni²⁺ ions in an amount of 0.01 to 10 g / l. 4. Verfahren nach Ansprüchen 1 bis 3, dadurch gekenn­zeichnet, daß man die Metalloberflächen mit Lösungen in Kontakt bringt, die einfache und/oder komplexe Fluoride in Mengen von 0,01 bis 10 g/l enthalten.4. Process according to claims 1 to 3, characterized in that the metal surfaces with solutions in contact that contain simple and / or complex fluorides in amounts of 0.01 to 10 g / l. 5. Verfahren nach Ansprüchen bis 4, dadurch gekenn­zeichnet, daß man die Metalloberflächen bei 50 bis 70°C mit den Lösungen in Kontakt bringt.5. Process according to Claims 4, characterized in that the metal surfaces are brought into contact with the solutions at 50 to 70 ° C. 6. Verfahren nach Ansprüchen 1 bis 5, dadurch gekenn­zeichnet, daß man die Metalloberflächen mit Lösungen in Kontakt bringt, die organische Nitroverbindungen enthalten, die ausgewählt sind aus m-Nitrobenzolsul­fonaten und/oder Nitroguanidin.6. Process according to Claims 1 to 5, characterized in that the metal surfaces are brought into contact with solutions which contain organic nitro compounds which are selected from m-nitrobenzenesulfonates and / or nitroguanidine. 7. Verfahren nach Ansprüchen 1 bis 6, dadurch gekenn­zeichnet, daß Phosphatschichten erzeugt werden, die Schichtgewichte in der Größenordnung von 3 bis 9 g/m² aufweisen.7. The method according to claims 1 to 6, characterized in that phosphate layers are produced which have layer weights in the order of 3 to 9 g / m². 8. Verfahren nach Ansprüchen 1 bis 7, dadurch gekenn­zeichnet, daß man die Metalloberflächen mit den Lösun­gen durch Tauchen, Spritzen und Fluten oder kombinier­te Verfahren behandelt.8. Process according to Claims 1 to 7, characterized in that the metal surfaces are treated with the solutions by dipping, spraying and flooding or combined processes. 9. Verwendung des Verfahrens nach Ansprüchen 1 bis 8 zur Vorbehandlung von Metalloberflächen, insbesondere aus Eisen, Stahl, Zink und deren Legierungen sowie Aluminium in der kaltumformenden Industrie.9. Use of the method according to claims 1 to 8 for the pretreatment of metal surfaces, in particular of iron, steel, zinc and their alloys as well as aluminum in the cold-forming industry.
EP89100228A 1988-01-14 1989-01-07 Process for phosphatizing metal surfaces Expired - Lifetime EP0324395B1 (en)

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DE3800835A DE3800835A1 (en) 1988-01-14 1988-01-14 METHOD FOR PHOSPHATING METAL SURFACES
DE3800835 1988-01-14

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TR26644A (en) 1994-05-25
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DE3800835A1 (en) 1989-07-27
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