EP0064790A1 - Method of phosphating metals, as well as its use in the electrodip painting pretreatment - Google Patents
Method of phosphating metals, as well as its use in the electrodip painting pretreatment Download PDFInfo
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- EP0064790A1 EP0064790A1 EP82200514A EP82200514A EP0064790A1 EP 0064790 A1 EP0064790 A1 EP 0064790A1 EP 82200514 A EP82200514 A EP 82200514A EP 82200514 A EP82200514 A EP 82200514A EP 0064790 A1 EP0064790 A1 EP 0064790A1
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- Prior art keywords
- phosphating
- zinc
- metal surfaces
- zinc phosphate
- phosphate solutions
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/362—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also zinc cations
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
Definitions
- the invention relates to a method for phosphating.
- Metals especially iron, steel and zinc, with acidic, aqueous oxidizing agent-containing zinc phosphate solutions and its use for pretreating the metal surfaces for electrocoating.
- DE-OS 25 38 347 describes acidic aqueous phosphating solutions which contain at least 0.5% phosphate ions and at least 0.03% Zn and in which the molar weight ratio of phosphate ions to nitrate ions is about 1: (0.7 to 1.3) and the molar weight ratio of zinc ions to phosphate ions is less than 0.116: 1 (converted to weight ratio Zn: P 2 O 5 ⁇ 0.107: 1).
- the object of the invention is to provide a method which does not have the disadvantages of the known methods and which also provides uniform, very corrosion-resistant phosphate layers over large throughputs.
- the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the metal surfaces are brought into contact with zinc phosphate solutions which contain, in which the weight ratio of Zn to P 2 O 5 is set to a value of (0.012 to 0.12): 1 and of Ni to Zn to a value of (0 to 1.5): 1 and which is set with Zn , N i and P 2 0 5 in a weight ratio of (0.18 to 0.33): (0 to 0.06): l can be added.
- the method according to the invention is intended in particular for the treatment of iron, steel and zinc. However, it is also suitable for the phosphating of aluminum.
- the metal surfaces can be treated by spraying, flooding and also immersion. However, it is also possible with combined working methods, e.g. Syringes - Diving - Syringes, Syringes - Diving, Dip-Spraying and the like are applicable.
- the contact times for the phosphating solution with the metal surface are in the usual range and can e.g. for spraying 75 seconds to 3 minutes, for diving 2 to 5 minutes and for spraying - diving 20 seconds spraying, 3 minutes diving.
- the bath temperatures are usually between 30 and 65 ° C.
- nickel is particularly beneficial in the treatment of zinc surfaces. But also with steel it often leads to an improvement in the layer quality.
- the solutions can also contain other cations, for example calcium, copper, manganese, cobalt, magnesium. Usually, however, their content does not exceed 0.5 g / l.
- concentration of divalent iron in the bath is kept low by the use of oxidizing agents that oxidize iron (II) to iron (III) and is usually not more than 50 to 100 mg / l. Divalent iron is often not present at all.
- Iron (III) is normally in the concentration given by the low solubility of iron (III) phosphate. tration present, which can be between 3 and 40 mg / 1 Fe (III) depending on the particular bath composition.
- cations from the alkali metal and / or ammonium group are still present.
- the baths used in the process according to the invention contain one or more oxidizing agents which are capable of oxidizing divalent to trivalent iron.
- oxidizing agents which are capable of oxidizing divalent to trivalent iron.
- Favorable results are achieved, for example, with the following additives: 2 to 25 g / l NO 3 ; 1 to 6 g / l C10 3 ; 0.1 to 2 g / 1 organic nitro compounds, for example Na-m-nitrobenzenesulfonate; 0.05 to 0.5 g / l alkali nitrite; 0.02 to 0.1 g / 1 H 2 0 2 .
- the layer formation can be improved by adding simple and / or complex fluorides.
- solutions for reducing the phosphate layer weight may contain compounds known per se, such as hydroxycarboxylic acids (e.g. tartaric acid, citric acid), polyphosphates (e.g. tripolyphosphate, hexametaphosphate).
- hydroxycarboxylic acids e.g. tartaric acid, citric acid
- polyphosphates e.g. tripolyphosphate, hexametaphosphate
- the cations and anions in the phosphating bath must be present in such a proportion that the acidity of the bath is in or near the phosphating equilibrium.
- the weight per unit area of the phosphate layers produced by the process according to the invention is generally in the range between 0.8 and 5 g / m 2 .
- activating agents eg based on titanium phosphate, in the pre-rinse bath or in the last cleaning stage is recommended.
- the phosphate layers produced with the method according to the invention are suitable in principle for all types of application phosphate layers known until today.
- the layers result in an unusually strong improvement in the resistance of the coating film against infiltration under corrosive stress as well as a significant increase in the paint adhesion to the metallic substrate.
- the baths When supplemented with the specified concentrates according to Examples 1 to 4, the baths could be kept in the optimal range practically indefinitely. The layer formation was flawless in all cases. In the nitrite-containing baths, it was only necessary to add the nitrite accelerator in a manner known per se. From time to time, a little sodium hydroxide solution had to be added to bath 4 in order to keep the free acid at the desired value.
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Bei der Phosphatierung von Metallen, insbesondere Eisen, Stahl und Zink, mit sauren wäßrigen oxidationsmittelhaltigen Zinkphosphatlösungen, die 0,4 bis 1,5 g/l Zn 0 bis 1,3 g/l Ni 10 bis 26 g/l P2O5 enthalten und in denen das Gewichtsverhältnis von Zn zu P2O5 auf einen Wert von (0,012 bis 0,12) : 1 und von Ni zu Zn auf einen Wert von (0 bis 1,5) : 1 eingestellt ist, wird zwecks Erhalt einwandfreier Phosphatierergebnisse über lange Zeit mit einem Konzentrat, in dem Zn, Ni und P2O5 in einem Gewichtsverhältnis von (0,18 bis 0,33) : (0 bis 0,06) : 1 vorliegen, ergänzt. Vorzugsweise werden die Zinkphosphatierungslösungen, die zusätzlich noch einfache oder komplexe Fluoride und Schichtgewicht reduzierende Verbindungen enthalten können, bei einer Temperatur im Bereich von 30 bis 65°C angewendet.In the phosphating of metals, in particular iron, steel and zinc, with acidic aqueous oxidizing agent-containing zinc phosphate solutions which contain 0.4 to 1.5 g / l Zn 0 to 1.3 g / l Ni 10 to 26 g / l P2O5 and in for which the weight ratio of Zn to P2O5 is set to a value of (0.012 to 0.12): 1 and that of Ni to Zn to a value of (0 to 1.5): 1 is used for the purpose of obtaining perfect phosphating results for a long time a concentrate in which Zn, Ni and P2O5 are present in a weight ratio of (0.18 to 0.33): (0 to 0.06): 1. The zinc phosphating solutions, which may additionally contain simple or complex fluorides and layer-weight-reducing compounds, are preferably used at a temperature in the range from 30 to 65.degree.
Description
Die Erfindung betrifft ein Verfahren zur Phosphatierung von . Metallen, insbesondere Eisen, Stahl und Zink,mit sauren, wäßrigen oxidationsmittelhaltigen Zinkphosphatlösungen sowie dessen Anwendung zur Vorbehandlung der Metalloberflächen für die Elektrotauchlackierung.The invention relates to a method for phosphating. Metals, especially iron, steel and zinc, with acidic, aqueous oxidizing agent-containing zinc phosphate solutions and its use for pretreating the metal surfaces for electrocoating.
In der DE-OS 22 32 067 werden wäßrige saure Phosphatierlösungen mit einem Gewichtsverhältnis von Zn : POd = 1 : (12 bis 110), bzw. umgerechnet Zn : P205 = (0,11 bis 0,012) : 1, zur Oberflächenbehandlung von Metallen, insbesondere Eisen und Stahl, beschrieben. Der gegenüber den üblichen Phosphatierbädern verringerte Zinkgehalt führt zu verbesserten dünnen und gleichmäßigen Phosphatüberzügen, die sehr haftfest und beständig und als Grundlage für die anschließende Elektrotauchlackierung besonders geeignet sind.In DE-OS 22 32 067 aqueous acid phosphating solutions with a weight ratio of Zn: PO d = 1: (12 to 110), or converted Zn: P 2 0 5 = (0.11 to 0.012): 1, for Surface treatment of metals, especially iron and steel. The reduced zinc content compared to the usual phosphating baths leads to improved thin and uniform phosphate coatings, which are very adhesive and durable and are particularly suitable as a basis for the subsequent electrocoating.
Aus der DE-OS 30 04 927 ist ein Verfahren zur Phosphatierung von Metallen bekannt, die anschließend elektroplattiert werden. Es werden wäßrige saure Lösungen mit 0,5 bis 1,5 g/1 Zn, 5 bis 30 g/1 Phosphat und Nitrit und/oder eine aromatische Nitroverbindung verwendet und die Werkstücke zunächst getaucht und anschließend gespritzt.From DE-OS 30 04 927 a method for phosphating metals is known, which are then electroplated. Aqueous acidic solutions containing 0.5 to 1.5 g / 1 Zn, 5 to 30 g / 1 phosphate and nitrite and / or an aromatic nitro compound are used and the workpieces are first immersed and then sprayed.
DE-OS 25 38 347 beschreibt saure wäßrige Phosphatierlösungen, die wenigstens 0,5 % Phosphationen und wenigstens 0,03 % Zn enthalten und in denen das molare Gewichtsverhältnis von Phosphationen zu Nitrationen etwa 1:(0,7 bis 1,3) und das molare Gewichtsverhältnis von Zinkionen zu Phosphationen weniger als 0,116:1 (umgerechnet auf Gewichtsverhältnis Zn:P2O5<0,107:1) beträgt.DE-OS 25 38 347 describes acidic aqueous phosphating solutions which contain at least 0.5% phosphate ions and at least 0.03% Zn and in which the molar weight ratio of phosphate ions to nitrate ions is about 1: (0.7 to 1.3) and the molar weight ratio of zinc ions to phosphate ions is less than 0.116: 1 (converted to weight ratio Zn: P 2 O 5 <0.107: 1).
Bei der praktischen Anwendung der vorgenannten Verfahren wurde festgestellt, daß während des ersten Materialdurchsatzes nach dem Badansatz qualitativ hochwertige Phosphatschichten ausgebildet werden. Mit steigendem Durchsatz werden die Phosphatierergebnisse jedoch vielfach unregelmäßig und schwankend. So können die Schichten z.B. ihr gleichmäßiges Aussehen beibehalten, aber im Korrosionsschutz in Verbindung mit einer organischen Beschichtung erheblich an Qualität einbüßen. In anderen Fällen wurde jedoch auch eine Verschlechterung des Schichtaussehens beobachtet. Anstelle gleichmäßig grauer Schichten entstanden irisierende Passivierungsschichten, teils auch schlammige Beläge.In the practical application of the aforementioned methods, it was found that high-quality phosphate layers are formed during the first material throughput after the bath batch. However, the phosphating results often become irregular and fluctuating with increasing throughput. The layers can e.g. Maintain their uniform appearance, but lose a lot of quality in corrosion protection combined with an organic coating. In other cases, however, a deterioration in the layer appearance was also observed. Instead of uniformly gray layers, there were iridescent passivation layers, sometimes also muddy deposits.
Aufgabe der Erfindung ist es, ein Verfahren bereitzustellen, das die Nachteile der bekannten Verfahren nicht aufweist und auch über große Durchsätze hin gleichmäßige, sehr korrosionsbeständige Phosphatschichten liefert.The object of the invention is to provide a method which does not have the disadvantages of the known methods and which also provides uniform, very corrosion-resistant phosphate layers over large throughputs.
Die Aufgabe wird gelöst, indem man das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet, daß die Metalloberflächen mit Zinkphosphatlösungen in Berührung gebracht werden, die
Das Überraschende an der Erfindung ist, daß die Mengenverhältnisse für Zn:Ni:P205 im arbeitenden Bad und in der Ergänzung erheblich voneinander abweichen müssen, um auf die Dauer befriedigende Phosphatierergebnisse zu liefern.The surprising thing about the invention is that the quantitative ratios for Zn: Ni: P 2 0 5 in the working bath and in the addition must differ considerably from one another in order to provide satisfactory phosphating results in the long run.
Das erfindungsgemäße Verfahren ist insbesondere für die Behandlung von Eisen, Stahl und Zink gedacht. Es eignet sich jedoch auch 'für die Phosphatierung von Aluminium.The method according to the invention is intended in particular for the treatment of iron, steel and zinc. However, it is also suitable for the phosphating of aluminum.
Die Behandlung der Metalloberflächen kann im Spritzverfahren, im Flutverfahren und auch im Tauchverfahren erfolgen. Es ist jedoch auch bei kombinierten Arbeitsweisen, z.B. Spritzen - Tauchen - Spritzen, Spritzen - Tauchen, Tauch-Spritzen und dergleichen anwendbar.The metal surfaces can be treated by spraying, flooding and also immersion. However, it is also possible with combined working methods, e.g. Syringes - Diving - Syringes, Syringes - Diving, Dip-Spraying and the like are applicable.
Die Kontaktzeiten für die Phosphatierlösung mit der Metalloberfläche liegen im üblichen Rahmen und können z.B. für das Spritzen 75 sec bis 3 min, für das Tauchen 2 bis 5 min und für das Spritzen - Tauchen 20 sec Spritzen, 3 min Tauchen betragen.The contact times for the phosphating solution with the metal surface are in the usual range and can e.g. for spraying 75 seconds to 3 minutes, for diving 2 to 5 minutes and for spraying - diving 20 seconds spraying, 3 minutes diving.
Die Badtemperaturen liegen üblicherweise zwischen 30 und 65°C.The bath temperatures are usually between 30 and 65 ° C.
Die Zugabe von Nickel wirkt sich insbesondere günstig bei der Behandlung von Zinkoberflächen aus. Aber auch bei Stahl führt es vielfach zu einer Verbesserung der Schichtqualität.The addition of nickel is particularly beneficial in the treatment of zinc surfaces. But also with steel it often leads to an improvement in the layer quality.
Die Lösungen können noch weitere Kationen enthalten, z.B. Calcium, Kupfer, Mangan, Kobalt, Magnesium. Üblicherweise liegt ihr Gehalt jedoch nicht über 0,5 g/l. Die Konzentration an zweiwertigem Eisen im Bad wird durch die Mitverwendung von Oxidationsmitteln, die Eisen(II) zu Eisen(III) oxidieren, niedrig gehalten und beträgt in der Regel nicht mehr als 50 bis 100 mg/l. Häufig ist zweiwertiges Eisen überhaupt nicht vorhanden. Eisen(III) ist normalerweise in der durch die geringe Löslichkeit von Eisen(III)-phosphat gegebenen Konzen-tration anwesend, die je nach spezieller Badzusammensetzung zwischen 3 und 40 mg/1 Fe(III) liegen kann. Außer den genannten Kationen sind jedoch immer noch Kationen aus der Alkalimetall- und/oder Ammoniumgruppe anwesend.The solutions can also contain other cations, for example calcium, copper, manganese, cobalt, magnesium. Usually, however, their content does not exceed 0.5 g / l. The concentration of divalent iron in the bath is kept low by the use of oxidizing agents that oxidize iron (II) to iron (III) and is usually not more than 50 to 100 mg / l. Divalent iron is often not present at all. Iron (III) is normally in the concentration given by the low solubility of iron (III) phosphate. tration present, which can be between 3 and 40 mg / 1 Fe (III) depending on the particular bath composition. In addition to the cations mentioned, cations from the alkali metal and / or ammonium group are still present.
Die nach dem erfindungsgemäßen Verfahren zur Anwendung kommenden Bäder enthalten ein oder mehrere Oxidationsmittel, die in der Lage sind, zwei- in dreiwertiges Eisen zu oxidieren. Günstige Ergebnisse werden z.B. mit folgenden Zusätzen erzielt: 2 bis 25 g/l NO3; 1 bis 6 g/l C103; 0,1 bis 2 g/1 organische Nitroverbindungen, z.B. Na-m-nitrobenzolsulfonat; 0,05 bis 0,5 g/1 Alkalinitrit; 0,02 bis 0,1 g/1 H202.The baths used in the process according to the invention contain one or more oxidizing agents which are capable of oxidizing divalent to trivalent iron. Favorable results are achieved, for example, with the following additives: 2 to 25 g / l NO 3 ; 1 to 6 g / l C10 3 ; 0.1 to 2 g / 1 organic nitro compounds, for example Na-m-nitrobenzenesulfonate; 0.05 to 0.5 g / l alkali nitrite; 0.02 to 0.1 g / 1 H 2 0 2 .
Insbesondere bei der Mitbehandlung von Zink-und/oder Aluminiumflächen, aber auch bei der alleinigen Behandlung von Eisen und Stahl kann die Schichtbildung durch Zusätze von einfachen und/oder komplexen Fluoriden verbessert werden.In particular when treating zinc and / or aluminum surfaces, but also when treating iron and steel alone, the layer formation can be improved by adding simple and / or complex fluorides.
Ferner können die Lösungen zur Reduzierung des Phosphatschichtgewichtes hierfür an sich bekannte Verbindungen, wie Hydroxycarbonsäuren (z.B. Weinsäure, Zitronensäure) Polyphosphate (z.B. Tripolyphosphat, Hexametaphosphat), enthalten.Furthermore, the solutions for reducing the phosphate layer weight may contain compounds known per se, such as hydroxycarboxylic acids (e.g. tartaric acid, citric acid), polyphosphates (e.g. tripolyphosphate, hexametaphosphate).
Die Kationen und Anionen im Phosphatierungsbad müssen in einem solchen Mengenverhältnis vorliegen, daß die Acidität des Bades im oder in der Nähe des Phosphatierungsgleichgewichtes liegt.The cations and anions in the phosphating bath must be present in such a proportion that the acidity of the bath is in or near the phosphating equilibrium.
Das Flächengewicht der nach dem erfindungsgemäßen Verfahren erzeugten Phosphatschichten liegt i.a. im Bereich zwischen 0,8 und 5 g/m2. Um besonders dünne, feinkristalline Schichten zu erzeugen, empfiehlt sich die Anwendung von Aktivierungsmitteln, z.B. auf Titanphosphatbasis, im Vorspülbad oder in der letzten Reinigerstufe.The weight per unit area of the phosphate layers produced by the process according to the invention is generally in the range between 0.8 and 5 g / m 2 . In order to produce particularly thin, finely crystalline layers, the use of activating agents, eg based on titanium phosphate, in the pre-rinse bath or in the last cleaning stage is recommended.
Die mit dem erfindungsgemäßen Verfahren erzeugten Phosphatschichten eignen sich im Prinzip für alle Anwendungsarten der bis heute bekannten Phosphatschichten. In Verbindung mit einer Lackierung bewirken die Schichten eine ungewöhnlich starke Verbesserung der Beständigkeit des Lackfilmes gegen Unterwanderung bei korrosiver Beanspruchung sowie eine erhebliche Erhöhung der Lackhaftung zum metallischen Untergrund. Diese Vorteile werden besonders bei der Elektrotauchlackierung, insbesondere bei der kathodischen Elektrotauchlackierung deutlich, weshalb das Verfahren vorzugsweise als Vorbereitung für diese Lackierart dient. Praktische Anwendung findet das erfindungsgemäße Verfahren z.B. für die Phosphatierung von Autokarosserien.The phosphate layers produced with the method according to the invention are suitable in principle for all types of application phosphate layers known until today. In conjunction with a coating, the layers result in an unusually strong improvement in the resistance of the coating film against infiltration under corrosive stress as well as a significant increase in the paint adhesion to the metallic substrate. These advantages are particularly evident in electrocoating, in particular in cathodic electrocoating, which is why the method preferably serves as preparation for this type of painting. The method according to the invention is used in practice, for example, for phosphating car bodies.
Das erfindungsgemäße Verfahren wird anhand der folgenden Beispiele beispielsweise und näher erläutert:
- Mit mildalkalischem, aktivierendem Reiniger entfettete Bleche aus Stahl, verzinktem Stahl und Aluminium wurden mit den in der folgenden Tabelle aufgeführten Lösungen behandelt und ergänzt. Hierbei veranschaulichen die Beispiele 1 bis 4 die erfindungsgemäße Arbeitsweise. Beispiel 5 stellt einen Vergleichsversuch dar, bei dem die Ergänzung mit einem Konzentrat erfolgt, in dem das Verhältnis Zn : Ni : P2O5, etwa gleich
- . dem Verhältnis des arbeitenden Bades, ist.
- Steel, galvanized steel and aluminum sheets degreased with mildly alkaline, activating cleaner were treated and supplemented with the solutions listed in the following table. Examples 1 to 4 illustrate the procedure according to the invention. Example 5 represents a comparative experiment in which the addition is carried out with a concentrate in which the ratio Zn: Ni: P 2 O 5 is approximately the same
- . the ratio of the working bath.
Bei Ergänzung mit den angegebenen Konzentraten gemäß Beispielen 1 bis 4 konnten die Bäder praktisch unbegrenzt im optimalen Bereich gehalten werden. Die Schichtausbildung war in allen Fällen einwandfrei. In den nitrithaltigen Bädern mußte lediglich noch der Nitritbeschleuniger in an sich bekannter Weise ergänzt werden. Zum Bad 4 mußte von Zeit zu Zeit etwas Natronlauge zugegeben werden, um die Freie Säure auf dem Sollwert zu halten.When supplemented with the specified concentrates according to Examples 1 to 4, the baths could be kept in the optimal range practically indefinitely. The layer formation was flawless in all cases. In the nitrite-containing baths, it was only necessary to add the nitrite accelerator in a manner known per se. From time to time, a little sodium hydroxide solution had to be added to bath 4 in order to keep the free acid at the desired value.
Bei einer Ergänzung mit dem Konzentrat gemäß Beispiel 5 auf konstante Gesamtsäure war nach einem Durchsatz von weniger als 0,5 m2/l Badlösung das Phosphatierbad nicht mehr in der Lage, einwandfreie Schichten auszubilden. Statt dessen entstanden irisierende Passivierungsschichten mit teils schlammigen Belägen.For an addition with the concentrate according to Example 5 at a constant total acid was after a throughput of less than 0, 5 not m 2 / l of bath solution in the phosphating more capable of forming proper layers. Instead, iridescent passivation layers with partly muddy deposits were created.
Claims (6)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3118375 | 1981-05-09 | ||
| DE19813118375 DE3118375A1 (en) | 1981-05-09 | 1981-05-09 | METHOD FOR PHOSPHATING METALS AND ITS APPLICATION FOR PRE-TREATMENT FOR ELECTRO DIP PAINTING |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0064790A1 true EP0064790A1 (en) | 1982-11-17 |
Family
ID=6131837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP82200514A Ceased EP0064790A1 (en) | 1981-05-09 | 1982-05-01 | Method of phosphating metals, as well as its use in the electrodip painting pretreatment |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US4419199A (en) |
| EP (1) | EP0064790A1 (en) |
| JP (1) | JPS6056429B2 (en) |
| AU (1) | AU527375B2 (en) |
| BR (1) | BR8202637A (en) |
| CA (1) | CA1200470A (en) |
| DE (1) | DE3118375A1 (en) |
| ES (1) | ES511885A0 (en) |
| GB (1) | GB2098242B (en) |
| MX (1) | MX159701A (en) |
| PT (1) | PT74827B (en) |
| ZA (1) | ZA822715B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2512840A1 (en) * | 1981-09-17 | 1983-03-18 | Amchem Prod | AQUEOUS ACID SOLUTIONS FOR ZINC PHOSPHATE COATINGS AND CONCENTRATES, METHODS OF COATING THEM USING THEM AND METAL ACTIVATION SOLUTIONS USED IN SUCH PROCESSES |
| EP0141341A1 (en) * | 1983-10-26 | 1985-05-15 | Metallgesellschaft Ag | Process for applying phosphate coatings |
| EP0261597A2 (en) * | 1986-09-26 | 1988-03-30 | Ppg Industries, Inc. | Method of applying a zinc-nickel phosphate coating |
| GB2196024A (en) * | 1986-09-05 | 1988-04-20 | Pyrene Chemical Services Ltd | Process for producing phosphate coatings |
| GB2199047A (en) * | 1986-10-16 | 1988-06-29 | Nihon Parkerizing | Forming phosphate coatings |
| EP0315059A1 (en) * | 1987-10-30 | 1989-05-10 | HENKEL CORPORATION (a Delaware corp.) | Process and composition for zinc phosphate coating |
| US5904786A (en) * | 1994-12-09 | 1999-05-18 | Metallgesellschaft Aktiengesellschaft | Method of applying phosphate coatings to metal surfaces |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0091441A1 (en) * | 1981-10-22 | 1983-10-19 | Data Peripherals | Method and apparatus for positioning a transducer using embedded servo track encoding and microprocessor control |
| DE3245411A1 (en) * | 1982-12-08 | 1984-07-05 | Gerhard Collardin GmbH, 5000 Köln | METHOD FOR PHOSPHATING ELECTROLYTICALLY GALVANIZED METAL GOODS |
| DE3325974A1 (en) * | 1983-07-19 | 1985-01-31 | Gerhard Collardin GmbH, 5000 Köln | METHODS AND UNIVERSALLY APPLICABLE MEANS FOR THE ACCELERATED APPLICATION OF PHOSPHATE COATINGS ON METAL SURFACES |
| AU605301B2 (en) * | 1983-08-23 | 1991-01-10 | Nippon Paint Co., Ltd. | Process for phosphating metal surfaces |
| DE3407513A1 (en) * | 1984-03-01 | 1985-09-05 | Gerhard Collardin GmbH, 5000 Köln | METHOD FOR ZINC-CALCIUM PHOSPHATION OF METAL SURFACES AT LOW TREATMENT TEMPERATURE |
| DE3408577A1 (en) * | 1984-03-09 | 1985-09-12 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR PHOSPHATING METALS |
| ES8606528A1 (en) * | 1985-02-22 | 1986-04-01 | Henkel Iberica | Process for the phosphating of metal surfaces. |
| JPS6267181A (en) * | 1985-09-19 | 1987-03-26 | Nippon Parkerizing Co Ltd | Aqueous solution for chemical conversion of titanium or alloy thereof |
| JPS6283477A (en) * | 1985-10-08 | 1987-04-16 | Nippon Parkerizing Co Ltd | Surface treatment of iron and steel products |
| US4663007A (en) * | 1985-10-25 | 1987-05-05 | Chrysler Motors Corporation | Method to evaluate sheet metal lubricants cratering potential on metal primer |
| GB8527833D0 (en) * | 1985-11-12 | 1985-12-18 | Pyrene Chemicals Services Ltd | Phosphate coating of metals |
| US5024697A (en) * | 1986-01-13 | 1991-06-18 | Ashland Oil, Inc. | Coating composition and method for forming a self-heating corrosion preventative film |
| US5153032A (en) * | 1986-01-13 | 1992-10-06 | Ashland Oil, Inc. | Coating compositions and method for forming a self-healing corrosion preventative film |
| US4981757A (en) * | 1986-01-13 | 1991-01-01 | Ashland Oil, Inc. | Coating compositions and method for forming a self-healing corrosion preventative film |
| DE3631759A1 (en) * | 1986-09-18 | 1988-03-31 | Metallgesellschaft Ag | METHOD FOR PRODUCING PHOSPHATE COATINGS ON METAL SURFACES |
| US5238506A (en) * | 1986-09-26 | 1993-08-24 | Chemfil Corporation | Phosphate coating composition and method of applying a zinc-nickel-manganese phosphate coating |
| EP0327153B1 (en) * | 1988-02-03 | 1993-08-04 | Metallgesellschaft Ag | Process for applying phosphate coatings to metals |
| DE3913089A1 (en) * | 1989-04-21 | 1990-10-25 | Henkel Kgaa | CHLORATE- AND NITRITE-FREE METHOD FOR THE PRODUCTION OF NICKEL- AND MANGANE-CONTAINING ZINC PHOSPHATE LAYERS |
| US5797987A (en) * | 1995-12-14 | 1998-08-25 | Ppg Industries, Inc. | Zinc phosphate conversion coating compositions and process |
| JP3219371B2 (en) * | 1996-03-21 | 2001-10-15 | 日本ペイント株式会社 | How to paint metal moldings |
| EP1198618B1 (en) * | 1999-05-28 | 2003-11-26 | Henkel Kommanditgesellschaft auf Aktien | Post-passivation of a phosphatized metal surface |
| JP2001170557A (en) * | 1999-12-21 | 2001-06-26 | Nisshin Steel Co Ltd | Surface treatment liquid for plated steel plate and treating method therefor |
| WO2001076811A1 (en) * | 2000-04-07 | 2001-10-18 | Whyco Technologies, Inc. | Method of masking coatings and resultant object |
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| DE2049350A1 (en) * | 1969-10-08 | 1971-04-15 | Lubrizol Corp | Phosphating solutions and their use for the corrosion protection of ferrous metal and zinc surfaces |
| DE2232067A1 (en) * | 1971-07-06 | 1973-01-18 | Metallgesellschaft Ag | PHOSPHATING SOLUTIONS |
| DE2342558A1 (en) * | 1973-08-23 | 1975-03-20 | Metallgesellschaft Ag | METAL PHOSPHATING METHOD |
| DE2538347A1 (en) * | 1974-08-30 | 1976-03-11 | Nippon Paint Co Ltd | ZINC PHOSPHATE SOLUTIONS FOR THE FORMATION OF ZINC PHOSPHATE COATINGS ON METALS |
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| JPS506418A (en) * | 1973-05-21 | 1975-01-23 | ||
| GB2009253B (en) * | 1977-11-29 | 1982-06-23 | Ici Ltd | Coating process |
| JPS555589A (en) * | 1978-06-29 | 1980-01-16 | Mitsubishi Electric Corp | Audio amplifying circuit |
| JPS5554576A (en) * | 1978-10-13 | 1980-04-21 | Nippon Parkerizing Co Ltd | Forming method for phosphate film of steel |
| JPS5811515B2 (en) * | 1979-05-11 | 1983-03-03 | 日本ペイント株式会社 | Composition for forming a zinc phosphate film on metal surfaces |
-
1981
- 1981-05-09 DE DE19813118375 patent/DE3118375A1/en active Granted
-
1982
- 1982-04-08 CA CA000400721A patent/CA1200470A/en not_active Expired
- 1982-04-13 AU AU82564/82A patent/AU527375B2/en not_active Ceased
- 1982-04-21 ZA ZA822715A patent/ZA822715B/en unknown
- 1982-04-30 PT PT74827A patent/PT74827B/en unknown
- 1982-04-30 US US06/373,475 patent/US4419199A/en not_active Expired - Lifetime
- 1982-05-01 EP EP82200514A patent/EP0064790A1/en not_active Ceased
- 1982-05-03 ES ES82511885A patent/ES511885A0/en active Granted
- 1982-05-06 GB GB8213119A patent/GB2098242B/en not_active Expired
- 1982-05-07 MX MX192583A patent/MX159701A/en unknown
- 1982-05-07 JP JP57076448A patent/JPS6056429B2/en not_active Expired
- 1982-05-07 BR BR8202637A patent/BR8202637A/en not_active IP Right Cessation
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|---|---|---|---|---|
| DE2049350A1 (en) * | 1969-10-08 | 1971-04-15 | Lubrizol Corp | Phosphating solutions and their use for the corrosion protection of ferrous metal and zinc surfaces |
| DE2232067A1 (en) * | 1971-07-06 | 1973-01-18 | Metallgesellschaft Ag | PHOSPHATING SOLUTIONS |
| DE2342558A1 (en) * | 1973-08-23 | 1975-03-20 | Metallgesellschaft Ag | METAL PHOSPHATING METHOD |
| DE2538347A1 (en) * | 1974-08-30 | 1976-03-11 | Nippon Paint Co Ltd | ZINC PHOSPHATE SOLUTIONS FOR THE FORMATION OF ZINC PHOSPHATE COATINGS ON METALS |
| DE3004927A1 (en) * | 1979-02-13 | 1980-08-21 | Nippon Paint Co Ltd | METHOD FOR PHOSPHATING METALS |
| DE2907094A1 (en) * | 1979-02-23 | 1980-09-04 | Metallgesellschaft Ag | PHOSPHATION SOLUTIONS |
| EP0018841A1 (en) * | 1979-05-02 | 1980-11-12 | Amchem Products, Inc. a Corporation organised under the Laws of the State of Delaware United States of America | Composition and process for zinc-phosphate coating a metal surface, coated metal surface and a process for painting the coated surface |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2512840A1 (en) * | 1981-09-17 | 1983-03-18 | Amchem Prod | AQUEOUS ACID SOLUTIONS FOR ZINC PHOSPHATE COATINGS AND CONCENTRATES, METHODS OF COATING THEM USING THEM AND METAL ACTIVATION SOLUTIONS USED IN SUCH PROCESSES |
| EP0141341A1 (en) * | 1983-10-26 | 1985-05-15 | Metallgesellschaft Ag | Process for applying phosphate coatings |
| GB2196024A (en) * | 1986-09-05 | 1988-04-20 | Pyrene Chemical Services Ltd | Process for producing phosphate coatings |
| EP0261597A2 (en) * | 1986-09-26 | 1988-03-30 | Ppg Industries, Inc. | Method of applying a zinc-nickel phosphate coating |
| EP0261597A3 (en) * | 1986-09-26 | 1988-07-13 | Chemfil Corporation | Phosphate coating composition and method of applying a zinc-nickel phosphate coating |
| GB2199047A (en) * | 1986-10-16 | 1988-06-29 | Nihon Parkerizing | Forming phosphate coatings |
| GB2199047B (en) * | 1986-10-16 | 1990-12-12 | Nihon Parkerizing | Processes for forming phosphate coatings |
| EP0315059A1 (en) * | 1987-10-30 | 1989-05-10 | HENKEL CORPORATION (a Delaware corp.) | Process and composition for zinc phosphate coating |
| US4865653A (en) * | 1987-10-30 | 1989-09-12 | Henkel Corporation | Zinc phosphate coating process |
| US5904786A (en) * | 1994-12-09 | 1999-05-18 | Metallgesellschaft Aktiengesellschaft | Method of applying phosphate coatings to metal surfaces |
Also Published As
| Publication number | Publication date |
|---|---|
| MX159701A (en) | 1989-08-08 |
| JPS6056429B2 (en) | 1985-12-10 |
| CA1200470A (en) | 1986-02-11 |
| PT74827A (en) | 1982-05-01 |
| AU8256482A (en) | 1982-11-18 |
| ZA822715B (en) | 1983-06-29 |
| ES8302794A1 (en) | 1983-02-16 |
| ES511885A0 (en) | 1983-02-16 |
| JPS57194258A (en) | 1982-11-29 |
| GB2098242A (en) | 1982-11-17 |
| DE3118375A1 (en) | 1982-11-25 |
| AU527375B2 (en) | 1983-03-03 |
| DE3118375C2 (en) | 1989-06-15 |
| GB2098242B (en) | 1984-05-02 |
| US4419199A (en) | 1983-12-06 |
| PT74827B (en) | 1983-11-14 |
| BR8202637A (en) | 1983-04-19 |
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