EP0121274A1 - Process for phosphating metal surfaces - Google Patents

Process for phosphating metal surfaces Download PDF

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Publication number
EP0121274A1
EP0121274A1 EP84200316A EP84200316A EP0121274A1 EP 0121274 A1 EP0121274 A1 EP 0121274A1 EP 84200316 A EP84200316 A EP 84200316A EP 84200316 A EP84200316 A EP 84200316A EP 0121274 A1 EP0121274 A1 EP 0121274A1
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Prior art keywords
metal surfaces
phosphating
nitrobenzenesulfonate
contact
brought
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EP84200316A
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German (de)
French (fr)
Inventor
Gerd Müller
Werner Dr. Rausch
Wolfgang Wuttke
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GEA Group AG
Continentale Parker Ste
Continentale Parker SA
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Metallgesellschaft AG
Continentale Parker Ste
Continentale Parker SA
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    • 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
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/14—Orthophosphates containing zinc cations containing also chlorate anions

Definitions

  • the invention relates to a method for applying P HOS phatüberratn on metal surfaces by means of nitrite accelerated phosphating solutions based on zinc phosphate.
  • aqueous acidic zinc phosphate solution to accelerate the film formation and oxidation of the dissolved iron in the trivalent form of nitrites, in particular A lkalinitrite to add (DE-PSs 845 135 907 966 D E-ASs 10 31 083, 12 77 645, DE-OS 17 71 769).
  • the methods are widely used in practice. They are characterized by a high degree of phosphating, however, provide a layer refinement unless specific substances, such as P olyphos- phosphates (E-AS 10 62 083) are added to phosphate layers having relatively high basis weights.
  • the object of the invention is to provide a method which does not have the disadvantages of the known methods and, with a high acceleration effect, provides extremely fine-grained, flexible phosphate layers with a low basis weight.
  • the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the metal surfaces are brought into contact with a phosphating solution additionally containing nitrobenzenesulfonate, the nitrobenzenesulfonate content of which is such that the resulting layer weight is less than 2 g / m 2.
  • the method according to the invention is intended in particular for the treatment of iron and steel. However, it is also suitable for phosphating zinc and aluminum materials as well as steel with coatings made of zinc, zinc alloys, aluminum and aluminum alloys, which are produced using a wide variety of processes.
  • the metal surfaces can be treated by spraying, flooding and also immersion. However, it is also possible with combined working methods, e.g. Splash-diving, diving-spraying, splash-diving-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. 45 seconds to 3 minutes for spraying, 2 to 10 minutes for diving and 20 seconds of spraying and 3 minutes for diving.
  • the temperatures of the phosphating solutions used in the process according to the invention are usually between 30 and 60 ° C. The lower the temperature, the longer i.a. the contact time.
  • the desired layer weights can be set by suitable dosing below 2 g / m 2 .
  • Layer weights of up to approximately 1 g / m 2 can be set.
  • an advantageous embodiment of the invention provides the metal surface with an P hospha- t istsown be brought into contact, the Nitrobenzolsulfonatgehalt is dimensioned such that the resulting S chichtactis below 1.5 g / m 2.
  • the metal surfaces it is advantageous to bring the metal surfaces into contact with a phosphating solution whose nitrobenzenesulfonate content is at least 300 mg / l.
  • the contents of the individual effective bath components are within the usual limits.
  • the nitrite content is preferably in the range from 10 to 300 mg / l.
  • the upper limit for the content of nitrobenzenesulfonate is about 2 g / 1. Higher levels are practically associated with no additional effect.
  • nitrite and nitrobenzenesulfonate accelerators are usually added to the phosphating bath in the form of the alkali salts.
  • the nitrobenzenesulfonate can also be introduced as the corresponding sulfonic acid.
  • aqueous acidic solutions based on zinc phosphate to be used in the context of the invention contain primary zinc phosphate and a certain amount of free acid which is matched to the respective building concentration, type of application and bath temperature.
  • the pH of the baths is between 2.0 and 3.9, depending on the process conditions.
  • the baths can also contain other cations known in phosphating technology, for example Ni, Co, Cu, Mn, Ca, Mg, Fe, Na, K , Li, NH 4 and others.
  • other anions different from phosphate for example NO 3 , C10 3 , Cl, SO 4 , F, BF 4 , SiF 6 , citrate, tartrate, etc., may be necessary or desirable .
  • the metal surfaces to be brought into contact with a phosphating solution in which the weight ratio of Zn to P 2 O 5 is set to 1: (8 to 85), or the metal surfaces with a Phos to bring phating solution in contact, in which the weight ratio of Zn to P 2 0 5 is set to 1: (0.3 to 7).
  • phosphate layers with a high proportion of phosphophyllite to hopite are formed on steel. Because of their excellent corrosion protection, these coatings are particularly suitable as a preparation for painting, with the best protective properties being achieved in connection with cathodic electrocoating.
  • Steel sheets were degreased in an alkaline, aqueous cleaner, rinsed with water and then treated with various phosphating solutions by spraying at 55 ° C. for 2 minutes.

Abstract

A zinc phosphate coating of below 2 g/m<2> is formed on a metal surface by use of an aqueous acidic zinc phosphate coating solution that is free of chlorate and chloride and that is accelerated by a mixture of nitrite and water-soluble organic nitro compound, such as a nitrobenzene sulphonate.

Description

Die Erfindung betrifft ein Verfahren zum Aufbringen von Phos- phatüberzügen auf Metalloberflächen mittels nitritbeschleunigter Phosphatierungslösungen auf Basis Zinkphosphat.The invention relates to a method for applying P HOS phatüberzügen on metal surfaces by means of nitrite accelerated phosphating solutions based on zinc phosphate.

Es ist bekannt, wäßrigen sauren Zinkphosphatlösungen zur Beschleunigung der Schichtbildung und zur Oxidation des aufgelösten Eisens in die dreiwertige Form Nitrite, insbesondere Alkalinitrite, zuzusetzen (DE-PSs 845 135, 907 966, DE-ASs 10 31 083, 12 77 645, DE-OS 17 71 769). Die Verfahren werden in großem Umfang praktisch angewendet. Sie zeichnen sich durch eine hohe Phosphatiergeschwindigkeit aus, liefern jedoch, sofern nicht spezielle schichtverfeinernde Stoffe, z.B. Polyphos- phate (DE-AS 10 62 083), zugesetzt werden, Phosphatschichten mit relativ hohen Flächengewichten.It is known aqueous acidic zinc phosphate solution to accelerate the film formation and oxidation of the dissolved iron in the trivalent form of nitrites, in particular A lkalinitrite to add (DE-PSs 845 135 907 966 D E-ASs 10 31 083, 12 77 645, DE-OS 17 71 769). The methods are widely used in practice. They are characterized by a high degree of phosphating, however, provide a layer refinement unless specific substances, such as P olyphos- phosphates (E-AS 10 62 083) are added to phosphate layers having relatively high basis weights.

Durch Mitverwendung von Chloraten in nitritbeschleunigten Phosphatierlösungen (DE-AS 15 21 678) kann zwar das Phosphatschichtgewicht etwas vermindert werden. Diese Arbeitsweise hat jedoch den Nachteil, daß größere Reduktionen des Schichtgewichtes nur mit hohen Chloratkonzentrationen möglich sind und damit die Nebenreaktion zwischen Chlorat und Nitrit unter Bildung von Chlorid und Nitrat ein unerwünscht hohes Ausmaß annimmt.By using chlorates in nitrite-accelerated phosphating solutions (DE-AS 15 21 678), the phosphate layer weight can be reduced somewhat. However, this procedure has the disadvantage that major reductions in the layer weight are only possible with high chlorate concentrations, and the side reaction between chlorate and nitrite takes on an undesirably high level with the formation of chloride and nitrate.

Bei einem neueren Phosphatierverfahren wird zur Beschleunigung ein Gemisch aus Chlorat und organischer Nitroverbindung, beispielsweise Nitrobenzolsulfonat, verwendet (EP-OS 36 689). Hiermit werden dünne, feinkristalline Phosphatschichten erzeugt. Ein Nachteil ist jedoch auch hier die Anreicherung von Chlorid in den Behandlungsbädern, das in größeren Mengen die Schichtqualität nachteilig beeinflussen kann.In a newer phosphating process, a mixture of chlorate and organic nitro compound is used for acceleration for example nitrobenzenesulfonate used (EP-OS 36 689). This produces thin, fine crystalline phosphate layers. However, a disadvantage here is the accumulation of chloride in the treatment baths, which in large quantities can adversely affect the layer quality.

Aufgabe der Erfindung ist es, ein Verfahren bereitzustellen, das die Nachteile der bekannten Verfahren nicht aufweist und bei hoher Beschleunigungswirkung äußerst feinkörnige, flexible Phosphatschichten mit niedrigem Flächengewicht liefert.The object of the invention is to provide a method which does not have the disadvantages of the known methods and, with a high acceleration effect, provides extremely fine-grained, flexible phosphate layers with a low basis weight.

Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung dahingehend ausgestaltet wird, daß man die Metalloberflächen mit einer zusätzlich Nitrobenzolsulfonat enthaltenden Phosphatierungslösung in Berührung bringt, deren Nitrobenzolsulfonatgehalt derart bemessen ist, daß das resultierende Schichtgewicht unter 2 g/m2 liegt.The object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the metal surfaces are brought into contact with a phosphating solution additionally containing nitrobenzenesulfonate, the nitrobenzenesulfonate content of which is such that the resulting layer weight is less than 2 g / m 2.

Zwar ist es aus der DE-OS 30 04 927 für ein spezielles, sogenanntes Niedrigzinkverfahren bekannt, eine Phosphatierungslösung einzusetzen, die auch die Beschleunigerkombination Nitrit und aromatische Nitroverbindung, wie Nitrobenzolsulfonat, umfaßt. Jedoch ist offensichtlich weder die Bedeutung gerade dieser speziellen Kombination noch die Möglichkeit, durch gezielte Nitrobenzolsulfonat-Dosierung das Schichtgewicht unter 2 gim2 reduzieren zu können, erkannt worden (vgl. dort insbesondere auch die Ausführungsbeispiele).It is known from DE-OS 30 04 927 for a special, so-called low zinc process to use a phosphating solution which also comprises the accelerator combination nitrite and aromatic nitro compound, such as nitrobenzenesulfonate. However, neither the importance of this particular combination, nor the possibility of being able to reduce the layer weight below 2 gim2 by targeted nitrobenzenesulfonate dosing, has obviously been recognized (cf. there in particular also the exemplary embodiments).

Das erfindungsgemäße verfahren ist insbesondere für die Behandlung von Eisen und Stahl gedacht. Es eignet sich jedoch auch für die Phosphatierung von Zink- und Aluminiumwerkstoffen sowie von Stahl mit nach den verschiedensten Verfahren erzeugten Überzügen aus Zink, Zinklegierungen, Aluminium und Aluminiumlegierungen.The method according to the invention is intended in particular for the treatment of iron and steel. However, it is also suitable for phosphating zinc and aluminum materials as well as steel with coatings made of zinc, zinc alloys, aluminum and aluminum alloys, which are produced using a wide variety of processes.

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, Tauchen-Spritzen, Spritzen-Tauchen-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. Splash-diving, diving-spraying, splash-diving-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 45 sec bis 3 min, für das Tauchen 2 bis 10 min und für das Spritzen-Tauchen 20 sec Spritzen und 3 min Tauchen betragen.The contact times for the phosphating solution with the metal surface are in the usual range and can e.g. 45 seconds to 3 minutes for spraying, 2 to 10 minutes for diving and 20 seconds of spraying and 3 minutes for diving.

Die Temperaturen der nach dem erfindungsgemäßen Verfahren zum Einsatz kommenden Phosphatierungslösungen liegen üblicherweise zwischen 30 und 60 °C. Je niedriger die Temperatur ist, um so länger muß i.a. die Kontaktzeit sein.The temperatures of the phosphating solutions used in the process according to the invention are usually between 30 and 60 ° C. The lower the temperature, the longer i.a. the contact time.

Bei Durchführung der Phosphatierung mit den Beschleunigern Nitrit und Nitrobenzolsulfonat lassen sich durch geeignete Dosierung unterhalb 2 g/m2 die jeweils erwünschten Schichtgewichte einstellen. Es sind Schichtgewichte bis etwa 1 g/m2 einstellbar.When carrying out the phosphating with the accelerators nitrite and nitrobenzenesulfonate, the desired layer weights can be set by suitable dosing below 2 g / m 2 . Layer weights of up to approximately 1 g / m 2 can be set.

Im Hinblick auf eine besonders hohe Flexibilität der erzeugten Phosphatschicht sowie große Glätte, aber auch einen geringen Chemikalienverbrauch, sieht eine vorteilhafte Ausführungsform der Erfindung vor, die Metalloberflächen mit einer Phospha- tierungslösung in Berührung zu bringen, deren Nitrobenzolsulfonatgehalt derart bemessen ist, daß das resultierende Schichtgewicht unter 1,5 g/m2 liegt. Hierfür ist es vorteilhaft, die Metalloberflächen mit einer Phosphatierungslösung in Berührung zu bringen, deren Gehalt an Nitrobenzolsulfonat mindestens 300 mg/1 beträgt.With respect to a particularly high flexibility of the P generated hosphatschicht and great smoothness, as well as a low consumption of chemicals, an advantageous embodiment of the invention provides the metal surface with an P hospha- tierungslösung be brought into contact, the Nitrobenzolsulfonatgehalt is dimensioned such that the resulting S chichtgewicht below 1.5 g / m 2. For this purpose, it is advantageous to bring the metal surfaces into contact with a phosphating solution whose nitrobenzenesulfonate content is at least 300 mg / l.

Die Gehalte der einzelnen wirksamen Badbestandteile bewegen sich innerhalb der üblichen Grenzen. Der Nitritgehalt liegt vorzugsweise im Bereich von 10 bis 300 mg/1. Die obere Grenze für den Gehalt an Nitrobenzolsulfonat beträgt etwa 2 g/1. Höhere Gehalte sind praktisch mit keiner zusätzlichen Wirkung verbunden.The contents of the individual effective bath components are within the usual limits. The nitrite content is preferably in the range from 10 to 300 mg / l. The upper limit for the content of nitrobenzenesulfonate is about 2 g / 1. Higher levels are practically associated with no additional effect.

Üblicherweise werden der Nitrit- und Nitrobenzolsulfonatbeschleuniger dem Phosphatierbad in Form der Alkalisalze zugesetzt. Das Nitrobenzolsulfonat läßt sich jedoch auch als die entsprechende Sulfonsäure einbringen. In Spezialfällen ist es möglich, das Nitrit im Phosphatierbad durch autokatalytische Bildung aus Nitrat zu erzeugen und, falls erforderlich, lediglich nach längeren Arbeitspausen zum Start der Phosphatierbäder Nitrit gesondert zuzusetzen.The nitrite and nitrobenzenesulfonate accelerators are usually added to the phosphating bath in the form of the alkali salts. However, the nitrobenzenesulfonate can also be introduced as the corresponding sulfonic acid. In special cases, it is possible to generate the nitrite in the phosphating bath by autocatalytic formation from nitrate and, if necessary, only add nitrite separately after longer breaks to start the phosphating baths.

Die im Rahmen der Erfindung zu verwendenden wäßrigen sauren Lösungen auf Basis Zinkphosphat enthalten primäres Zinkphosphat und eine gewisse, auf die jeweilige Baakonzentration, Anwendungsart und Badtemperatur abgestimmte Menge an freier Säure. Der pH-Wert der Bäder liegt, abhängig von den Verfahrensbedingungen, etwa zwischen 2,0 und 3,9.The aqueous acidic solutions based on zinc phosphate to be used in the context of the invention contain primary zinc phosphate and a certain amount of free acid which is matched to the respective building concentration, type of application and bath temperature. The pH of the baths is between 2.0 and 3.9, depending on the process conditions.

Die Bäder können ferner in der Phosphatiertechnik bekannte weitere Kationen, z.B. Ni, Co, Cu, Mn, Ca, Mg, Fe, Na, K, Li, NH4 u.a., enthalten. Zur Einstellung des Säureverhältnisses und zur Erzielung spezieller technischer Effekte kann die Mitverwendung weiterer, von Phosphat verschiedener Anionen, z.B. NO3, C103, Cl, SO4, F, BF4, SiF6, Citrat, Tartrat u.a., erforderlich bzw. wünschenswert sein.The baths can also contain other cations known in phosphating technology, for example Ni, Co, Cu, Mn, Ca, Mg, Fe, Na, K , Li, NH 4 and others. To adjust the acid ratio and to achieve special technical effects, the use of other anions different from phosphate, for example NO 3 , C10 3 , Cl, SO 4 , F, BF 4 , SiF 6 , citrate, tartrate, etc., may be necessary or desirable .

Überraschenderweise hat sich gezeigt, daß die Beschleunigerkombination Nitrit/Nitrobenzolsulfonat sowohl in Verbindung mit der sogenannten Niedrigzink- als auch der Normalzink-Technologie in gleicher Weise wirksam ist. Demzufolge sehen vorteilhafte Ausgestaltungen der Erfindung vor, die Metalloberflächen mit einer Phosphatierungslösung in Berührung zu bringen, in der das Gewichtsverhältnis von Zn zu P2O5 auf l:(8 bis 85) eingestellt ist, oder aber die Metalloberflächen mit einer Phosphatierungslösung in Berührung zu bringen, in der das Gewichtsverhältnis von Zn zu P205 auf 1:(0,3 bis 7) eingestellt ist.Surprisingly, it has been shown that the nitrite / nitrobenzenesulfonate accelerator combination is equally effective in combination with the so-called low zinc and normal zinc technology. Accordingly, advantageous refinements of the invention provide for the metal surfaces to be brought into contact with a phosphating solution in which the weight ratio of Zn to P 2 O 5 is set to 1: (8 to 85), or the metal surfaces with a Phos to bring phating solution in contact, in which the weight ratio of Zn to P 2 0 5 is set to 1: (0.3 to 7).

Im ersten Fall entstehen auf Stahl Phosphatschichten mit einem hohen Anteil an Phosphophyllit zu Hopeit. Diese Überzüge eignen sich wegen ihres ausgezeichneten Korrosionsschutzes insbesondere als Vorbereitung für die Lackierung, wobei die besten Schutzeigenschaften in Verbindung mit der kathodischen Elektrotauchlackierung erzielt werden.In the first case, phosphate layers with a high proportion of phosphophyllite to hopite are formed on steel. Because of their excellent corrosion protection, these coatings are particularly suitable as a preparation for painting, with the best protective properties being achieved in connection with cathodic electrocoating.

Im zweiten Fall resultieren Phosphatierverfahren, die sich im Vergleich zu den Niedrigzink-Verfahren durch eine höhere Phos- phatiergeschwindigkeit auszeichnen. Die mit ihnen erzeugten Phosphatschichten besitzen gute Eigenschaften für ein breites Anwendungsspektrum aus den Bereichen des Korrosionsschutzes und der spanlosen Kaltumformung.In the second case phosphating result, the HOS in comparison to the low-zinc processes with a higher P phatiergeschwindigkeit distinguished. The hosphatschichten with them generated P have good properties for a wide A nwendungsspektrum in the areas of corrosion protection and chipless cold forming.

Das erfindungsgemäße Verfahren wird anhand der folgenden Beispiele und der Figur beispielsweise und näher erläutert.The method according to the invention is explained, for example and in more detail, using the following examples and the figure.

Beispiele:Examples:

Stahlbleche wurden in einem alkalischen, wäßrigen Reiniger entfettet, mit Wasser gespült und anschließend mit verschiedenen Phosphatierungslösungen 2 min bei 55 °C im Spritzen behandelt.Steel sheets were degreased in an alkaline, aqueous cleaner, rinsed with water and then treated with various phosphating solutions by spraying at 55 ° C. for 2 minutes.

Badlösung 1:Bath solution 1:

  • 1,4 g/1 Zn1.4 g / 1 Zn
  • 0,4 g/1 Ni0.4 g / 1 Ni
  • 17,8 g/1 P2O5 17.8 g / 1 P 2 O 5
  • 6,0 g/1 N0 3 6.0 g / 1 N 0 3
  • 100 mg/1 N02 als NaN02 100 mg / 1 N0 2 as NaN0 2
  • + NaOH zur Einstellung des Phosphatiergleichgewichtes
    Figure imgb0001
    + N a OH to adjust the phosphating balance
    Figure imgb0001
Badlösung 2:Bath solution 2:

  • 0,8 g/1 Zn0.8 g / 1 Zn
  • 0,5 g/1 Ni0.5 g / 1 Ni
  • 1,5 g/l ClO3 1.5 g / l ClO 3
  • 14 g/l P2O5 14 g / l P 2 O 5
  • 2 g/1 N0 3 2 g / 1 N0 3
  • 100 mg/1 NO2 als NaNO2 100 mg / 1 NO 2 as NaNO 2
  • + NaOH zur Einstellung des Phosphatiergleichgewichts+ NaOH to adjust the phosphating balance
Figure imgb0002
Figure imgb0002
 Badlösung 3: B adlösung 3:

  • 3 g/1 Zn3 g / 1 Zn
  • 0,012 g/l Ni0.012 g / l Ni
  • 1,5 g/1 ClO3 1.5 g / 1 ClO 3
  • 7,2 g/l P2O5 7.2 g / l P 2 O 5
  • 1,3 g/l N031.3 g / l N03
  • 133 mg/1 NO2 als NaNO2 133 mg / 1 NO 2 as NaNO 2
  • + NaOH zurEinstellung des Phosphatiergleichgewichtes+ NaOH to adjust the phosphating balance
Figure imgb0003
Figure imgb0003
 Badlösung 4:Bath solution 4:

  • 3,2 g/1 Zn3.2 g / 1 Zn
  • 6,8 g/l P2O5 6.8 g / l P 2 O 5
  • 2,6 g/1 N0 3 2.6 g / 1 N0 3
  • 150 mg/1 NO2 als NaNO2 150 mg / 1 NO 2 as NaNO 2
  • + NaOH zur Einstellung des Phosphatiergleichgewichts+ NaOH to adjust the phosphating balance
Figure imgb0004
Figure imgb0004

Der für die einzelnen Badlösungen erhaltene Verlauf der Schichtgewichte [g/m2] wurde in der Figur als Funktion der Konzentration an Nitrobenzolsulfonat [mg/l] aufgetragen.The course of the S chichtgewichte [g / m 2] obtained for each bath solutions was plotted in the figure as a function of the concentration of N itrobenzolsulfonat [mg / l].

"Badlösung 1" und "Badlösung 2" entsprechen der Niedrigzinktechnologie, "Badlösung 3" und "Badlösung 4" der Normalzinktechnologie. Anhand des Kurvenverlaufs ergibt sich, daß innerhalb beider Verfahrensarten die Nitrobenzolsulfonat-Dosierung in gleicher Weise wirksam und mit einer beträchtlichen Absenkung des Schichtgewichtes verbunden ist."Bath solution 1" and "Bath solution 2" correspond to the low zinc technology, "Bath solution 3" and "Bath solution 4" to the normal zinc technology. On the basis of the curve shows that within both the V-nitrobenzenesulfonate dosage learn types equally effective and is associated with a considerable reduction of the layer weight.

Claims (6)

1. Verfahren zum Aufbringen von Phosphatüberzügen auf Metalloberflächen mittels nitritbeschleunigter Phosphatierungslösungen auf Basis Zinkphosphat, dadurch gekennzeichnet, daß man die Metalloberflächen mit einer zusätzlich Nitrobenzolsulfonat enthaltenden Phosphatierungslösung in Berührung bringt, deren Nitrobenzolsulfonatgehalt derart bemessen ist, daß das resultierende Schichtgewicht unter 2 g/m2 liegt.1. A process for applying phosphate coatings on metal surfaces by means of nitrite-accelerated phosphating solutions based on zinc phosphate, characterized in that the metal surfaces are brought into contact with a phosphating solution additionally containing nitrobenzenesulfonate, the nitrobenzenesulfonate content of which is such that the resulting layer weight is less than 2 g / m 2 . 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Metalloberflächen mit einer Phosphatierungslösung in Berührung bringt, deren Nitrobenzolsulfonatgehalt derart bemessen ist, daß das resultierende Schichtgewicht unter 1,5 g/m2 liegt. 2nd Process according to Claim 1, characterized in that the metal surfaces are brought into contact with a phosphating solution, the nitrobenzenesulfonate content of which is such that the resulting layer weight is below 1.5 g / m 2 . 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man die Metalloberflächen mit einer Phosphatierungslösung in Berührung bringt, deren Gehalt an Nitrobenzolsulfonat mindestens 300 mg/1 beträgt.3. The method according to claim 1 or 2, characterized in that the metal surfaces are brought into contact with a phosphating solution whose content of nitrobenzenesulfonate is at least 300 mg / 1. 4. Verfahren nach Anspruch 1, 2 oder 3, dadurch gekennzeichnet, daß man die Metalloberflächen mit einer Phosphatierungslösung in Berührung bringt, deren Nitritgehalt 10 bis 300 mg/1 beträgt.4. The method according to claim 1, 2 or 3, characterized in that the metal surfaces are brought into contact with a phosphating solution whose nitrite content is 10 to 300 mg / 1. 5. Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man die Metalloberflächen mit einer Phosphatierungslösung in Berührung bringt, in der das Gewichtsverhältnis von Zn zu P205 auf 1:(8 bis 85) eingestellt ist.Brings 5. The method according to one or more of claims 1 to 4, characterized in that the metal surfaces with a hosphatierungslösung P in contact, in which the weight ratio of Zn to P205 to 1: (8 to 85) is set. 6. Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man die Metalloberflächen mit einer Phosphatierungslösung in Berührung bringt, in der das Gewichtsverhältnis von Zn zu P2O5 auf 1:(0,3 bis 7) eingestellt ist.6. The method according to one or more of claims 1 to 4, characterized in that the metal surfaces with a hosphatierungslösung P brought into contact, in which the weight ratio of Zn to P 2 O 5 to 1: (0.3 to 7) is set is.
EP84200316A 1983-03-31 1984-03-06 Process for phosphating metal surfaces Withdrawn EP0121274A1 (en)

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DE3311738 1983-03-31
DE19833311738 DE3311738A1 (en) 1983-03-31 1983-03-31 METHOD FOR PHOSPHATING METAL SURFACES

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GB (1) GB2137231B (en)
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Cited By (2)

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Publication number Priority date Publication date Assignee Title
EP0258922A1 (en) * 1986-09-05 1988-03-09 Metallgesellschaft Ag Process for producing phosphate coatings and their use
EP0287133A1 (en) * 1987-04-11 1988-10-19 Metallgesellschaft Ag Phosphating treatment before electrophoretic dip painting

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* Cited by examiner, † Cited by third party
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DE3408577A1 (en) * 1984-03-09 1985-09-12 Metallgesellschaft Ag, 6000 Frankfurt METHOD FOR PHOSPHATING METALS
US5234509A (en) * 1984-12-20 1993-08-10 Henkel Corporation Cold deformation process employing improved lubrication coating
CA1257527A (en) * 1984-12-20 1989-07-18 Thomas W. Tull Cold deformation process employing improved lubrication coating
US4595424A (en) * 1985-08-26 1986-06-17 Parker Chemical Company Method of forming phosphate coating on zinc
USRE35958E (en) * 1985-08-26 1998-11-17 Henkel Corporation Method of forming phosphate coating on zinc
GB8523572D0 (en) * 1985-09-24 1985-10-30 Pyrene Chemicals Services Ltd Coating metals
US5236565A (en) * 1987-04-11 1993-08-17 Metallgesellschaft Aktiengesellschaft Process of phosphating before electroimmersion painting
DE3871031D1 (en) * 1987-08-19 1992-06-17 Metallgesellschaft Ag METHOD FOR PHOSPHATING METALS.

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EP0069950A1 (en) * 1981-07-13 1983-01-19 Metallgesellschaft Ag Process for phosphating metal surfaces

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EP0069950A1 (en) * 1981-07-13 1983-01-19 Metallgesellschaft Ag Process for phosphating metal surfaces

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0258922A1 (en) * 1986-09-05 1988-03-09 Metallgesellschaft Ag Process for producing phosphate coatings and their use
EP0287133A1 (en) * 1987-04-11 1988-10-19 Metallgesellschaft Ag Phosphating treatment before electrophoretic dip painting

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AU2629184A (en) 1984-10-04
DE3311738A1 (en) 1984-10-04
GB2137231B (en) 1986-06-18
ES8504270A1 (en) 1985-05-01
ES531002A0 (en) 1985-05-01
GB8408006D0 (en) 1984-05-10
BR8401487A (en) 1984-11-13
PT78335A (en) 1984-04-01
CA1206852A (en) 1986-07-02
GB2137231A (en) 1984-10-03
ZA842173B (en) 1984-10-31
PT78335B (en) 1986-04-30

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