EP0036689A1 - Procédé pour l'application de revêtements phosphatés - Google Patents

Procédé pour l'application de revêtements phosphatés Download PDF

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Publication number
EP0036689A1
EP0036689A1 EP81200285A EP81200285A EP0036689A1 EP 0036689 A1 EP0036689 A1 EP 0036689A1 EP 81200285 A EP81200285 A EP 81200285A EP 81200285 A EP81200285 A EP 81200285A EP 0036689 A1 EP0036689 A1 EP 0036689A1
Authority
EP
European Patent Office
Prior art keywords
phosphating solution
weight
contact
brought
metal surfaces
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.)
Granted
Application number
EP81200285A
Other languages
German (de)
English (en)
Other versions
EP0036689B1 (fr
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/de
Publication of EP0036689A1 publication Critical patent/EP0036689A1/fr
Application granted granted Critical
Publication of EP0036689B1 publication Critical patent/EP0036689B1/fr
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—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 0 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 using 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.
  • phosphating solution which additionally up to 0.5% by weight, preferably 0.01 to 0.03% by weight of Ni ions, and / or additionally aliphatic e-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 fluoride in amounts of up to 0.4% by weight, preferably 0.05 to 0.1% by weight (calculated as F) contains.
  • a phosphating solution which additionally up to 0.5% by weight, preferably 0.01 to 0.03% by weight of Ni ions, and / or additionally aliphatic e-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 fluoride in amounts of up to 0.4% by weight, preferably 0.05 to 0.1% by weight (
  • accelerators in particular nitrate
  • the amount should be less than 2.25 wt .-%. The preferred range is between 0.4 and 1.0% by weight.
  • Nitrite should not be added if possible due to the inevitable formation of nitrous gases. 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, e.g. 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 an oven at 182 ° C. for 20 minutes.
  • the dry film thickness of the lacquer was 18 ⁇ m.
  • 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, the amount of dissolved paint was determined Adhesive tape stuck over the cross interfaces and removed again. 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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (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)
EP81200285A 1980-03-21 1981-03-13 Procédé pour l'application de revêtements phosphatés Expired EP0036689B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81200285T ATE8277T1 (de) 1980-03-21 1981-03-13 Verfahren zum aufbringen von phosphatueberzuegen.

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 true EP0036689A1 (fr) 1981-09-30
EP0036689B1 EP0036689B1 (fr) 1984-07-04

Family

ID=10512280

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81200285A Expired EP0036689B1 (fr) 1980-03-21 1981-03-13 Procédé pour l'application de revêtements phosphatés

Country Status (9)

Country Link
EP (1) EP0036689B1 (fr)
JP (1) JPS56142872A (fr)
AT (1) ATE8277T1 (fr)
BR (1) BR8101682A (fr)
DE (1) DE3164514D1 (fr)
ES (1) ES8205878A1 (fr)
GB (1) GB2072225B (fr)
PH (1) PH17558A (fr)
PT (1) PT72709B (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0060716A1 (fr) * 1981-03-16 1982-09-22 Nippon Paint Co., Ltd. Phosphatation de surfaces métalliques
EP0106459A1 (fr) * 1982-08-24 1984-04-25 HENKEL CORPORATION (a Delaware Corp.) Phosphatation de surfaces métalliques
EP0111223A1 (fr) * 1982-12-03 1984-06-20 Gerhard Collardin GmbH Procédé de phosphatation de surfaces métalliques et compositions appropriées à ce procédé
EP0135622A1 (fr) * 1983-08-22 1985-04-03 Nippon Paint Co., Ltd. Phosphatation de surfaces métalliques
EP0269138A1 (fr) * 1986-10-25 1988-06-01 Metallgesellschaft Ag Procédé pour produire des revêtements de phosphate sur des métaux
WO1997030189A1 (fr) * 1996-02-19 1997-08-21 Henkel Kommanditgesellschaft Auf Aktien Procede de phosphatisation au zinc a l'aide de faibles teneurs en nickel et/ou en cobalt
WO1998013535A1 (fr) * 1996-09-26 1998-04-02 Henkel Kommanditgesellschaft Auf Aktien Procede de phosphatation pour installations a defilement rapide des feuillards
US5792283A (en) * 1993-09-06 1998-08-11 Henkel Kommanditgesellschaft Auf Aktien Nickel-free phosphating process

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
DE3461653D1 (en) * 1983-03-15 1987-01-22 Metallgesellschaft Ag Preparation of iron or steel surfaces for painting
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 (de) * 1984-03-09 1985-09-12 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metallen
DE3537108A1 (de) * 1985-10-18 1987-04-23 Collardin Gmbh Gerhard Verfahren zur phosphatierung elektrolytisch verzinkter metallwaren
DE3630246A1 (de) * 1986-09-05 1988-03-10 Metallgesellschaft Ag Verfahren zur erzeugung von phosphatueberzuegen sowie dessen anwendung
US5200000A (en) * 1989-01-31 1993-04-06 Nihon Parkerizing Co., Ltd. Phosphate treatment solution for composite structures and method for treatment

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT321663B (de) * 1972-04-27 1975-04-10 Metallgesellschaft Ag Phosphatierungslösung
AT325372B (de) * 1972-01-10 1975-10-27 Metallgesellschaft Ag Verfahren zur phosphatierung von stahl
DE2819912A1 (de) * 1977-05-11 1978-11-23 Nippon Paint Co Ltd Verfahren zur phosphatierung von eisen
DE2909698A1 (de) * 1978-03-14 1979-09-27 Centre Rech Metallurgique Verfahren zur oberflaechenbehandlung von metallband

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52119435A (en) * 1976-04-01 1977-10-06 Nippon Packaging Kk Phosphating process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT325372B (de) * 1972-01-10 1975-10-27 Metallgesellschaft Ag Verfahren zur phosphatierung von stahl
AT321663B (de) * 1972-04-27 1975-04-10 Metallgesellschaft Ag Phosphatierungslösung
DE2819912A1 (de) * 1977-05-11 1978-11-23 Nippon Paint Co Ltd Verfahren zur phosphatierung von eisen
DE2909698A1 (de) * 1978-03-14 1979-09-27 Centre Rech Metallurgique Verfahren zur oberflaechenbehandlung von metallband

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0060716A1 (fr) * 1981-03-16 1982-09-22 Nippon Paint Co., Ltd. Phosphatation de surfaces métalliques
EP0106459A1 (fr) * 1982-08-24 1984-04-25 HENKEL CORPORATION (a Delaware Corp.) Phosphatation de surfaces métalliques
EP0111223A1 (fr) * 1982-12-03 1984-06-20 Gerhard Collardin GmbH Procédé de phosphatation de surfaces métalliques et compositions appropriées à ce procédé
EP0135622A1 (fr) * 1983-08-22 1985-04-03 Nippon Paint Co., Ltd. Phosphatation de surfaces métalliques
EP0269138A1 (fr) * 1986-10-25 1988-06-01 Metallgesellschaft Ag Procédé pour produire des revêtements de phosphate sur des métaux
GB2203453A (en) * 1986-10-25 1988-10-19 Pyrene Chemical Services Ltd Phosphate coating solutions and processes
GB2203453B (en) * 1986-10-25 1990-12-05 Pyrene Chemical Services Ltd Phosphate coating solutions and processes
US5792283A (en) * 1993-09-06 1998-08-11 Henkel Kommanditgesellschaft Auf Aktien Nickel-free phosphating process
WO1997030189A1 (fr) * 1996-02-19 1997-08-21 Henkel Kommanditgesellschaft Auf Aktien Procede de phosphatisation au zinc a l'aide de faibles teneurs en nickel et/ou en cobalt
WO1998013535A1 (fr) * 1996-09-26 1998-04-02 Henkel Kommanditgesellschaft Auf Aktien Procede de phosphatation pour installations a defilement rapide des feuillards

Also Published As

Publication number Publication date
ES501134A0 (es) 1982-08-16
GB2072225B (en) 1983-11-02
JPS56142872A (en) 1981-11-07
PH17558A (en) 1984-09-27
ATE8277T1 (de) 1984-07-15
PT72709B (en) 1982-03-24
PT72709A (en) 1981-04-01
DE3164514D1 (en) 1984-08-09
ES8205878A1 (es) 1982-08-16
BR8101682A (pt) 1981-09-22
GB2072225A (en) 1981-09-30
EP0036689B1 (fr) 1984-07-04

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