EP0036689B1 - Method of applying phosphate coatings - Google Patents

Method of applying phosphate coatings Download PDF

Info

Publication number
EP0036689B1
EP0036689B1 EP81200285A EP81200285A EP0036689B1 EP 0036689 B1 EP0036689 B1 EP 0036689B1 EP 81200285 A EP81200285 A EP 81200285A EP 81200285 A EP81200285 A EP 81200285A EP 0036689 B1 EP0036689 B1 EP 0036689B1
Authority
EP
European Patent Office
Prior art keywords
phosphating solution
brought
contact
metal surfaces
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP81200285A
Other languages
German (de)
French (fr)
Other versions
EP0036689A1 (en
Inventor
Michael Ernest Brooks
Richard Andrew Beck
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GEA Group AG
Continentale Parker Ste
Continentale Parker SA
Original Assignee
Metallgesellschaft AG
Continentale Parker Ste
Continentale Parker SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Metallgesellschaft AG, Continentale Parker Ste, Continentale Parker SA filed Critical Metallgesellschaft AG
Priority to AT81200285T priority Critical patent/ATE8277T1/en
Publication of EP0036689A1 publication Critical patent/EP0036689A1/en
Application granted granted Critical
Publication of EP0036689B1 publication Critical patent/EP0036689B1/en
Expired legal-status Critical Current

Links

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
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations

Definitions

  • the invention relates to a method for applying phosphate coatings on iron, zinc and / or aluminum by means of a phosphating solution containing zinc, manganese, phosphate and accelerator.
  • GB-PS 983 924 a method for applying phosphate coatings on iron or zinc surfaces by spray treatment with a solution of a temperature of 38 ° C or less is known, which contains zinc and manganese phosphate and an oxidizing accelerator.
  • the manganese content of the solution is between 5 and 50% by weight of the zinc content.
  • DE-OS 28 18 426 shows that the introduction of boron fluoride has advantages and in particular leads to the formation of satisfactory phosphate layers on aluminum or greatly improves the quality of the phosphate layers on iron surfaces.
  • oxidizing accelerators for zinc and phosphate-containing phosphating solutions have been proposed in recent years. These include chlorates, nitrates, organic nitro compounds such as sodium metanitrobenzenesulfonate and dinitrobenzenesulfonate, hydrogen peroxide, nitrites, bromates and iodates.
  • GB-PS 15 42 222 describes the use of chlorate and nitrobenzenesulfonate as accelerators in a phosphating process working with zinc and phosphate.
  • the preferred accelerators in the processes according to GB-PS 983 924 or DE-OS 28 18 426 are nitrate, optionally with nitrite. Chlorate is also referred to as a possible additive.
  • the object of the invention is to provide a phosphating process which leads to flawless phosphate layers on iron, zinc and / or aluminum which are firmly adhered to the substrate and which - particularly at low temperatures - runs at a high layer formation rate.
  • 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 whose manganese content is 5 to 33% by weight of the zinc content and which contains chlorate and nitrobenzenesulfonate as accelerators .
  • a preferred embodiment within the method according to the invention is to use a phosphating solution which contains.
  • the manganese content should in particular make up 5 to 20% by weight, preferably 9 to 13% by weight, of the zinc content.
  • a phosphating solution which additionally contains up to 0.5% by weight, preferably 0.01 to 0.03% by weight of Ni ions, and / or additionally aliphatic a- Hydroxy acids or their water-soluble salts, such as tartaric acid or tartrate, in amounts of up to 0.8% by weight, preferably 0.02 to 0.2% by weight (calculated as tartrate), and / or additionally simple, but in particular complex Contains fluoride in amounts of up to 0.4% by weight, preferably 0.05 to 0.1% by weight (calculated as F).
  • accelerators in addition to the accelerator pair chlorate and nitrobenzenesulfonate required to achieve a high layer formation rate, other accelerators, in particular nitrate, can also be used. If nitrate is used, its amount should be less than 2.25% by weight. The preferred range is between 0.4 and 1.0% by weight. Nitrite should result from the inevitable formation nitrous gases should not be added if possible. Otherwise, other additives described in connection with the method according to GB-PS 983 924 and DE-OS 28 18 426 can be made.
  • the pH of the phosphating solution should be 3.4 to 4.4 so that the process according to the invention leads to the desired phosphate layer formation in a sufficiently short time, in particular at the temperatures of 25 to 50 ° C. or particularly advantageously from 25 to 35 ° C. .
  • the total acid 20 and the free acid are preferably 0.8 to 1.0 points.
  • the phosphating solution used in the method according to the invention can be prepared by dissolving the components in water. It is preferably obtained by diluting concentrates which contain the active components in the same ratio as in the working phosphating solution.
  • the contact between the metal surface and the phosphating solution is usually effected by spraying and is about 50 to 120, preferably 80 seconds. Before this, the metal surfaces should be cleaned and rinsed in a conventional manner. After the phosphating layer formation z. B. rinsed with a dilute aqueous solution of chromium compounds and then dried.
  • a phosphating solution was prepared that contained.
  • the phosphate layers produced were smooth, completely opaque and adherent.
  • the sheets were then cathodically electrocoated with a varnish (ED 3002 from International Paints) and dried in the oven at 182 ° C. for 20 minutes.
  • the dry film thickness of the paint was 18 1 1m.
  • the sheets were then cross cut and subjected to the salt spray test according to ASTM B 117-64 for a period of 500 hours. After the test was completed, adhesive tape was stuck over the cross interfaces and removed again to determine the amount of dissolved paint. No paint removal was observed.
  • the example illustrates that the process according to the invention allows good phosphate layers to form within a short treatment time and at low treatment temperatures.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Fertilizers (AREA)
  • Materials For Medical Uses (AREA)
  • Laminated Bodies (AREA)
  • Catalysts (AREA)

Abstract

Phosphate coatings can be formed on iron, aluminium or zinc surfaces by spraying at low temperature with a phosphating solution containing zinc, phosphate, manganese and an oxidising accelerator comprising sodium nitrobenzene sulphonate and chlorate. The solution may also contain nickel, a borofluoride and an alpha-hydroxy aliphatic acid e.g. tartaric acid, or a salt thereof. Nitrate may also be included as an additional oxidising accelerator. The pH of the solution is preferably in the range 3-5.

Description

Die Erfindung betrifft ein Verfahren zum Aufbringen von Phosphatüberzügen auf Eisen, Zink und/oder Aluminium mittels einer Zink, Mangan, Phosphat und Beschleuniger enthaltenden Phosphatierungslösung.The invention relates to a method for applying phosphate coatings on iron, zinc and / or aluminum by means of a phosphating solution containing zinc, manganese, phosphate and accelerator.

Aus der GB-PS 983 924 ist ein Verfahren zum Aufbringen von Phosphatüberzügen auf Eisen- oder Zinkoberflächen durch Spritzbehandlung mit einer Lösung einer Temperatur von 38 °C oder weniger bekannt, die Zink- und Manganphosphat sowie einen oxidierenden Beschleuniger enthält. Der Mangangehalt der Lösung liegt dabei zwischen 5 und 50 Gew.-% des Zinkgehaltes.From GB-PS 983 924 a method for applying phosphate coatings on iron or zinc surfaces by spray treatment with a solution of a temperature of 38 ° C or less is known, which contains zinc and manganese phosphate and an oxidizing accelerator. The manganese content of the solution is between 5 and 50% by weight of the zinc content.

Weiterhin geht aus der DE-OS 28 18 426 hervor, daß der Eintrag von Borfluorid Vorzüge mit sich bringt und insbesondere zur Bildung von befriedigenden phosphatschichten auf Aluminium führt bzw. die Qualität der Phosphatschichten auf Eisenoberflächen stark verbessert.Furthermore, DE-OS 28 18 426 shows that the introduction of boron fluoride has advantages and in particular leads to the formation of satisfactory phosphate layers on aluminum or greatly improves the quality of the phosphate layers on iron surfaces.

In den vergangenen Jahren ist eine große Zahl von oxidierenden Beschleunigern für Zink und Phosphat enthaltende Phosphatierungslösungen vorgeschlagen worden. Hierzu zählen Chlorate, Nitrate, organische Nitroverbindungen, wie Natriummetanitrobenzolsulfonat und -dinitrobenzolsulfonat, Wasserstoffperoxid, Nitrite, Bromate und Jodate.A large number of oxidizing accelerators for zinc and phosphate-containing phosphating solutions have been proposed in recent years. These include chlorates, nitrates, organic nitro compounds such as sodium metanitrobenzenesulfonate and dinitrobenzenesulfonate, hydrogen peroxide, nitrites, bromates and iodates.

Die GB-PS 15 42 222 beschreibt die Verwendung von Chlorat und Nitrobenzolsulfonat als Beschleuniger bei einem mit zink und Phosphat arbeitenden Phosphatierungsverfahren.GB-PS 15 42 222 describes the use of chlorate and nitrobenzenesulfonate as accelerators in a phosphating process working with zinc and phosphate.

Trotz der zahlreichen Erwähnung unterschiedlicher oxidierender Beschleuniger sind die bevorzugten Beschleuniger bei den Verfahren gemäß GB-PS 983 924 bzw. gemäß DE-OS 28 18 426 Nitrat, gegebenenfalls mit Nitrit. Auch Chlorat ist als eventueller Zusatz bezeichnet.Despite the numerous mention of different oxidizing accelerators, the preferred accelerators in the processes according to GB-PS 983 924 or DE-OS 28 18 426 are nitrate, optionally with nitrite. Chlorate is also referred to as a possible additive.

Bei Mischungen, die sowohl Mangan als auch Chlorat enthalten, war zu befürchten, daß sie eine unbefriedigende Lagerstabilität aufweisen würden, die deren Herstellung am Ort und zur Zeit des Verbrauches erforderlich macht. Dies würde Mischungen mit Chlorat weit weniger attraktiv machen als solche, die frei von Chlorat sind.Mixtures containing both manganese and chlorate had to be feared that they would have an unsatisfactory storage stability, which would require their preparation on site and at the time of consumption. This would make blends with chlorate far less attractive than blends free of chlorate.

Aufgabe der Erfindung ist es, ein Phosphatierverfahren bereitzustellen, das zu einwandfreien, mit dem Untergrund fest verwachsenen Phosphatschichten auf Eisen, Zink und/oder Aluminium führt und das - insbesondere auch bei niedrigen Temperaturen - mit hoher Schichtbildungsgeschwindigkeit abläuft.The object of the invention is to provide a phosphating process which leads to flawless phosphate layers on iron, zinc and / or aluminum which are firmly adhered to the substrate and which - particularly at low temperatures - runs at a high layer formation rate.

Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man die Metalloberflächen mit einer Phosphatierungslösung in Berührung bringt, deren Mangangehalt 5 bis 33 Gew.-% des Zinkgehaltes beträgt und die als Beschleuniger Chlorat und Nitrobenzolsulfonat enthält.The object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the metal surfaces are brought into contact with a phosphating solution whose manganese content is 5 to 33% by weight of the zinc content and which contains chlorate and nitrobenzenesulfonate as accelerators .

Eine bevorzugte Ausgestaltung innerhalb des erfindungsgemäßen Verfahrens besteht darin, eine Phosphatierungslösung einzusetzen, die

Figure imgb0001
enthält.A preferred embodiment within the method according to the invention is to use a phosphating solution which
Figure imgb0001
 contains.

Besonders vorteilhaft ist der Einsatz einer Phosphatierungslösung mit einem Gehalt von

Figure imgb0002
The use of a phosphating solution with a content of
Figure imgb0002

Der Mangangehalt sollte insbesondere 5 bis 20 Gew.-%, vorzugsweise 9 bis 13 Gew.-%, des Zinkgehaltes ausmachen.The manganese content should in particular make up 5 to 20% by weight, preferably 9 to 13% by weight, of the zinc content.

Weitere vorteilhafte Ausgestaltungen bestehen darin, die Metalloberflächen mit einer Phosphatierungslösung in Berührung zu bringen, die zusätzlich bis 0,5 Gew.-%, vorzugsweise 0,01 bis 0,03 Gew.-% Ni-lonen, und/oder zusätzlich aliphatische a-Hydroxysäuren bzw. deren wasserlösliche Salze, wie Weinsäure oder Tartrat, in Mengen bis 0,8 Gew.-%, vorzugsweise 0,02 bis 0,2 Gew.-% (berechnet als Tartrat), und/oder zusätzlich einfaches, insbesondere aber komplexes Fluorid in Mengen bis 0,4 Gew.-%, vorzugsweise 0,05 bis 0,1 Gew.-% (berechnet als F) enthält.Further advantageous refinements consist in bringing the metal surfaces into contact with a phosphating solution which additionally contains up to 0.5% by weight, preferably 0.01 to 0.03% by weight of Ni ions, and / or additionally aliphatic a- Hydroxy acids or their water-soluble salts, such as tartaric acid or tartrate, in amounts of up to 0.8% by weight, preferably 0.02 to 0.2% by weight (calculated as tartrate), and / or additionally simple, but in particular complex Contains fluoride in amounts of up to 0.4% by weight, preferably 0.05 to 0.1% by weight (calculated as F).

Für den Fall eines Fluoridzusatzes ist die Verwendung von Borfluorid - zweckmäßig als freie Säure eingebracht - besonders bevorzugt.In the case of a fluoride addition, the use of boron fluoride - appropriately introduced as the free acid - is particularly preferred.

Neben dem zur Erzielung einer hohen Schichtbildungsgeschwindigkeit erforderlichen Beschleunigerpaar Chlorat und Nitrobenzolsulfonat können auch noch weitere Beschleuniger, insbesondere Nitrat, Verwendung finden. Falls Nitrat eingesetzt wird, sollte dessen Menge unter 2,25 Gew.-% sein. Der bevorzugte Bereich liegt zwischen 0,4 und 1,0 Gew.-%. Nitrit sollte infolge der unvermeidlichen Bildung nitroser Gase möglichst nicht zugesetzt werden. Ansonsten können weitere, im Zusammenhang mit den Verfahren gemäß GB-PS 983 924 und DE-OS 28 18 426 beschriebene Zusätze vorgenommen werden.In addition to the accelerator pair chlorate and nitrobenzenesulfonate required to achieve a high layer formation rate, other accelerators, in particular nitrate, can also be used. If nitrate is used, its amount should be less than 2.25% by weight. The preferred range is between 0.4 and 1.0% by weight. Nitrite should result from the inevitable formation nitrous gases should not be added if possible. Otherwise, other additives described in connection with the method according to GB-PS 983 924 and DE-OS 28 18 426 can be made.

Damit das erfindungsgemäße Verfahren insbesondere bei den bevorzugt anzuwendenden Temperaturen von 25 bis 50°C bzw. besonders vorteilhaft von 25 bis 35°C in hinreichend kurzer Zeit zur erwünschten Phosphatschichtausbildung führt, sollte der pH-Wert der Phosphatierungslösung 3,4 bis 4,4 betragen.The pH of the phosphating solution should be 3.4 to 4.4 so that the process according to the invention leads to the desired phosphate layer formation in a sufficiently short time, in particular at the temperatures of 25 to 50 ° C. or particularly advantageously from 25 to 35 ° C. .

Weiterhin betragen vorzugsweise die Gesamtsäure 20 und die freie Säure 0,8 bis 1,0 Punkte.Furthermore, the total acid 20 and the free acid are preferably 0.8 to 1.0 points.

Die beim erfindungsgemäßen Verfahren zur Anwendung kommende Phosphatierungslösung kann durch Auflösen der Komponenten in Wasser hergestellt werden. Vorzugsweise wird sie durch Verdünnen von Konzentraten, die die wirksamen Komponenten im gleichen Verhältnis wie in der arbeitenden Phosphatierungslösung enthalten, gewonnen.The phosphating solution used in the method according to the invention can be prepared by dissolving the components in water. It is preferably obtained by diluting concentrates which contain the active components in the same ratio as in the working phosphating solution.

Der Kontakt zwischen Metalloberfläche und Phosphatierungslösung erfolgt üblicherweise durch Spritzen und beträgt dabei etwa 50 bis 120, vorzugsweise 80 Sekunden. Zuvor sollten die Metalloberflächen in konventioneller Weise gereinigt und gespült werden. Nach der Phosphatierungsschichtausbildung kann z. B. mit einer verdünnten wäßrigen Lösung von Chromverbindungen gespült und dann getrocknet werden.The contact between the metal surface and the phosphating solution is usually effected by spraying and is about 50 to 120, preferably 80 seconds. Before this, the metal surfaces should be cleaned and rinsed in a conventional manner. After the phosphating layer formation z. B. rinsed with a dilute aqueous solution of chromium compounds and then dried.

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

Beispielexample

Es wurde eine Phosphatierungslösung hergestellt, die

Figure imgb0003
enthielt.A phosphating solution was prepared that
Figure imgb0003
 contained.

Stahlbleche, die zuvor mit einer alkalischen Reinigungslösung einer Gesamtalkalinität von 26 Punkten bei 35 °C während 90 Sekunden durch Spritzbehandlung gereinigt und dann mit Wasser gespült worden waren, wurden mit der vorgenannten Phosphatierungslösung 80 Sekunden bei 30 °C im Spritzen behandelt. Anschließend wurde mit Wasser und mit destilliertem Wasser gespült und durch Preßluft getrocknet.Steel sheets that had previously been spray-cleaned with an alkaline cleaning solution with a total alkalinity of 26 points at 35 ° C. for 90 seconds and then rinsed with water were sprayed with the aforementioned phosphating solution for 80 seconds at 30 ° C. It was then rinsed with water and with distilled water and dried by compressed air.

Die erzeugten Phosphatschichten waren'glatt, vollständig deckend und festhaftend.The phosphate layers produced were smooth, completely opaque and adherent.

Die Bleche wurden dann mit einem Lack (ED 3002 der Firma International Paints) kathodisch elektrotauchlackiert und bei 182 °C während 20 Minuten im Ofen getrocknet. Die Trockenfilmdicke des Lackes war 18 11m.The sheets were then cathodically electrocoated with a varnish (ED 3002 from International Paints) and dried in the oven at 182 ° C. for 20 minutes. The dry film thickness of the paint was 18 1 1m.

Danach wurden die Bleche mit einem Kreuzschnitt versehen und dem Salzsprühtest gemäß ASTM B 117-64 während einer Zeitdauer von 500 Stunden unterworfen. Nach Abschluß des Testes wurde zur Ermittlung der Menge gelösten Lackes Klebeband über die Kreuzschnittstellen geklebt und wieder abgezogen. Es wurde keine Lackentfernung beobachtet.The sheets were then cross cut and subjected to the salt spray test according to ASTM B 117-64 for a period of 500 hours. After the test was completed, adhesive tape was stuck over the cross interfaces and removed again to determine the amount of dissolved paint. No paint removal was observed.

Das Beispiel veranschaulicht, daß das erfindungsgemäße Verfahren innerhalb kurzer Behandlungsdauer und bei tiefen Behandlungstemperaturen gute Phosphatschichten entstehen läßt.The example illustrates that the process according to the invention allows good phosphate layers to form within a short treatment time and at low treatment temperatures.

Claims (13)

1. Process for forming phosphate coatings on iron, zinc and/or aluminum by means of a zinc, manganese, phosphate and accelerator containing phosphating solution, characterized in that the metal surfaces are brought in contact with a phosphating solution containing manganese in an amount of 5 to 33 weight % of the zinc content and as accelerators chlorate and nitrobenzene sulphonate.
2. Process according to claim 1, characterized in that the metal surfaces are brought in contact with a phosphating solution containing
Figure imgb0006
3. Process according to claim 1, characterized in that the metal surfaces are brought in contact with a phosphating solution containing
Figure imgb0007
4. Process according to claim 1, 2 or 3, characterized in that the metal surfaces are brought in contact with a phosphating solution containing additionally up to 0.5 weight % Ni-ions.
5. Process according to claim 4, characterized in that the metal surfaces are brought in contact with a phosphating solution containing 0.01 to 0.03 weight % Ni-ions.
6. Process according to one or more of the claims 1 to 5, characterized in that the metal surfaces are brought in contact with a phosphating solution containing additionally aliphatic «-hydroxyacids or a water soluble salt thereof in an amount up to 0.8 weight % (calculated as tartrate).
7. Process according to claim 6, characterized in that the metal surfaces are brought in contact with a phosphating solution containing tartaric acid or tartrate.
8. Process according to one or more of the claims 1 to 7, characterized in that the metal surfaces are brought in contact with a phosphating solution containing additionally fluoride.
9. Process according to claim 8, characterized in that the metal surfaces are brought in contact with a phosphating solution containing complex fluoride in an amount up to 0.4 weight % (calculated as F).
10. Process according to claim 9, characterized in that the metal surfaces are brought in contact with a phosphating solution containing complex fluoride in an amount from 0.05 to 0.1 weight % (calculated as F).
11. Process according to one or more of the claims 1 to 10, characterized in that the metal surfaces are brought in contact with a phosphating solution having a pH-value of 3.4 to 4.4.
12. Process according to one or more of the claims 1 to 11, characterized in that the metal surfaces are brought in contact with a phosphating solution having a temperature of 25 to 50 °C.
13. Process according to claim 12, characterized in that the metal surfaces are brought in contact with a phosphating solution having a temperature of 25 to 35 °C.
EP81200285A 1980-03-21 1981-03-13 Method of applying phosphate coatings Expired EP0036689B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81200285T ATE8277T1 (en) 1980-03-21 1981-03-13 PROCESS FOR APPLYING PHOSPHATE COATINGS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8009621 1980-03-21
GB8009621 1980-03-21

Publications (2)

Publication Number Publication Date
EP0036689A1 EP0036689A1 (en) 1981-09-30
EP0036689B1 true EP0036689B1 (en) 1984-07-04

Family

ID=10512280

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81200285A Expired EP0036689B1 (en) 1980-03-21 1981-03-13 Method of applying phosphate coatings

Country Status (9)

Country Link
EP (1) EP0036689B1 (en)
JP (1) JPS56142872A (en)
AT (1) ATE8277T1 (en)
BR (1) BR8101682A (en)
DE (1) DE3164514D1 (en)
ES (1) ES501134A0 (en)
GB (1) GB2072225B (en)
PH (1) PH17558A (en)
PT (1) PT72709B (en)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57152472A (en) * 1981-03-16 1982-09-20 Nippon Paint Co Ltd Phosphating method for metallic surface for cation type electrodeposition painting
US4673444A (en) * 1981-03-16 1987-06-16 Koichi Saito Process for phosphating metal surfaces
US6342107B1 (en) * 1982-08-24 2002-01-29 Henkel Corporation Phosphate coatings for metal surfaces
JPS5935681A (en) * 1982-08-24 1984-02-27 Nippon Paint Co Ltd Method for phosphating metallic surface for coating by cationic electrodeposition
DE3244715A1 (en) * 1982-12-03 1984-06-07 Gerhard Collardin GmbH, 5000 Köln METHOD FOR PHOSPHATING METAL SURFACES, AND BATH SOLUTIONS SUITABLE FOR THIS
ATE24206T1 (en) * 1983-03-15 1986-12-15 Metallgesellschaft Ag PREPARING IRON OR STEEL SURFACES FOR PAINTING.
DE3378641D1 (en) * 1983-08-22 1989-01-12 Nippon Paint Co Ltd Phosphating metal surfaces
AU605301B2 (en) * 1983-08-23 1991-01-10 Nippon Paint Co., Ltd. Process for phosphating metal surfaces
GB8329250D0 (en) * 1983-11-02 1983-12-07 Pyrene Chemical Services Ltd Phosphating processes
DE3408577A1 (en) * 1984-03-09 1985-09-12 Metallgesellschaft Ag, 6000 Frankfurt METHOD FOR PHOSPHATING METALS
DE3537108A1 (en) * 1985-10-18 1987-04-23 Collardin Gmbh Gerhard METHOD FOR PHOSPHATING ELECTROLYTICALLY GALVANIZED METALWARE
DE3630246A1 (en) * 1986-09-05 1988-03-10 Metallgesellschaft Ag METHOD FOR PRODUCING PHOSPHATE COVER AND ITS APPLICATION
DE3636390A1 (en) * 1986-10-25 1988-04-28 Metallgesellschaft Ag METHOD FOR PRODUCING PHOSPHATE COATINGS ON METALS
US5200000A (en) * 1989-01-31 1993-04-06 Nihon Parkerizing Co., Ltd. Phosphate treatment solution for composite structures and method for treatment
CN1041001C (en) * 1993-09-06 1998-12-02 汉克尔股份两合公司 Nickel-free phosphatization process
DE19606018A1 (en) * 1996-02-19 1997-08-21 Henkel Kgaa Zinc phosphating with low levels of nickel and / or cobalt
DE19639597C2 (en) * 1996-09-26 2000-01-20 Henkel Kgaa Process for the phosphating of running strips made of cold or hot rolled steel in high-speed conveyor systems

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT325372B (en) * 1972-01-10 1975-10-27 Metallgesellschaft Ag METHOD OF PHOSPHATING STEEL
JPS5241735B2 (en) * 1972-04-27 1977-10-20
JPS52119435A (en) * 1976-04-01 1977-10-06 Nippon Packaging Kk Phosphating process
JPS53138937A (en) * 1977-05-11 1978-12-04 Nippon Paint Co Ltd Chemical treating method for iron phosphate film
BE864899A (en) * 1978-03-14 1978-09-14 Centre Rech Metallurgique PROCESS FOR THE SURFACE TREATMENT OF A METAL STRIP

Also Published As

Publication number Publication date
PT72709A (en) 1981-04-01
EP0036689A1 (en) 1981-09-30
ATE8277T1 (en) 1984-07-15
JPS56142872A (en) 1981-11-07
DE3164514D1 (en) 1984-08-09
GB2072225A (en) 1981-09-30
GB2072225B (en) 1983-11-02
PH17558A (en) 1984-09-27
ES8205878A1 (en) 1982-08-16
BR8101682A (en) 1981-09-22
PT72709B (en) 1982-03-24
ES501134A0 (en) 1982-08-16

Similar Documents

Publication Publication Date Title
EP0036689B1 (en) Method of applying phosphate coatings
EP0633950B1 (en) Nickel-free phosphatization process
EP0056881B1 (en) Method of phosphating metals
DE1933013B2 (en) PROCESS FOR THE PRODUCTION OF PROTECTIVE COATINGS ON ALUMINUM, IRON AND ZINC USING COMPLEX SOLUTIONS CONTAINING FLUORIDES
DE3234558C2 (en)
DE3629382A1 (en) METHOD FOR PRODUCING CONVERSION LAYERS ON ZINC AND / OR ZINC ALLOYS
DE2428065A1 (en) SEALING FLUSH FOR PHOSPHATE COATINGS ON METALS
EP0478648B1 (en) Process for producing zinc phosphate coatings containing manganese and magnesium
DE2155670B2 (en) ZINC PHOSPHATING SOLUTION FOR ALUMINUM, ZINC OR IRON
EP0796356A1 (en) Method of applying phosphate coatings to metal surfaces
DE69003403T2 (en) Phosphating solution for complex structures and processes for their use.
EP0359296B1 (en) Phosphating process
DE69119138T2 (en) Process for phosphating metal surfaces
DE2315180C2 (en) Phosphating solution
EP0361375A1 (en) Phosphate-coating process
EP0155547A1 (en) Process for the zinc-calcium phosphatizing of metal surfaces at a low treating temperature
DE3924984A1 (en) METHOD FOR PASSIVATING RINSING OF PHOSPHATE LAYERS
EP0039093B1 (en) Method of phosphating the surfaces of metals, and its use
EP0264811B1 (en) Process for producing phosphate coatings
DE2715291A1 (en) PROCESS FOR PRODUCING AMORPHERIC, LIGHTWEIGHT, ADHESIVE PHOSPHATE COATINGS ON IRON METAL SURFACES
DE1248427B (en) Method and solution for applying coatings to aluminum and its alloys
EP1019564A1 (en) Method for phosphatizing a steel strip
WO1986004931A1 (en) Process for the phosphating of metal surfaces
DE974503C (en) Process for the production of coatings on metals
DE2506349A1 (en) Soln for producing phosphate coatings - contains boric acid apart from phosphates and surface active agents

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE CH DE FR NL SE

17P Request for examination filed

Effective date: 19820210

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): AT BE CH DE FR LI NL SE

REF Corresponds to:

Ref document number: 8277

Country of ref document: AT

Date of ref document: 19840715

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3164514

Country of ref document: DE

Date of ref document: 19840809

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19890331

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19901001

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

EAL Se: european patent in force in sweden

Ref document number: 81200285.5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19951221

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19951228

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19960221

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19960321

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19960327

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19960418

Year of fee payment: 16

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19960530

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Effective date: 19970313

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19970314

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19970331

Ref country code: CH

Effective date: 19970331

Ref country code: LI

Effective date: 19970331

BERE Be: lapsed

Owner name: SOC. CONTINENTALE PARKER

Effective date: 19970331

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19971128

EUG Se: european patent has lapsed

Ref document number: 81200285.5

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST