EP0187597B1 - Zusammensetzung und Verfahren zum Beschichten von Metalloberflächen mit einer Konversionsschicht auf der Basis von Zinkphosphat - Google Patents

Zusammensetzung und Verfahren zum Beschichten von Metalloberflächen mit einer Konversionsschicht auf der Basis von Zinkphosphat Download PDF

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Publication number
EP0187597B1
EP0187597B1 EP85402589A EP85402589A EP0187597B1 EP 0187597 B1 EP0187597 B1 EP 0187597B1 EP 85402589 A EP85402589 A EP 85402589A EP 85402589 A EP85402589 A EP 85402589A EP 0187597 B1 EP0187597 B1 EP 0187597B1
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EP
European Patent Office
Prior art keywords
ion
zinc
bath
fact
phosphatization
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.)
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EP85402589A
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English (en)
French (fr)
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EP0187597A1 (de
Inventor
Joseph Schapira
Victor Ken
Christian Hoessler
Louis Cot
Jean-Henri Durand
Patrice Pelletier
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.)
Compagnie Francaise de Produits Industriels SA
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Compagnie Francaise de Produits Industriels SA
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Priority to AT85402589T priority Critical patent/ATE46544T1/de
Publication of EP0187597A1 publication Critical patent/EP0187597A1/de
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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
    • C23C22/34—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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/362—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also zinc cations

Definitions

  • the subject of the invention is a bath and a process for the chemical conversion to zinc of metallic substrates, in particular those based on iron, zinc, aluminum and alloys of these metals.
  • These treatments can be carried out by spraying the above-mentioned solutions onto the objects to be treated or by immersing them in baths formed by these solutions, generally at temperatures above 30 ° C.
  • the Applicant Company has worked to improve the existing chemical conversion baths and had the merit of finding, after extensive research, that the implementation in a zinc phosphating bath of an effective amount of at least one compound comprising at least one fluorine atom chemically bonded to an atom phosphorus, preferably an effective amount of fluorophosphate ion, allowed to achieve the desired goal.
  • the fluorophosphate ion can be introduced into the bath using the corresponding acid or one of its alkaline, alkaline-earth or ammonium salts or its zinc salt.
  • the above-mentioned bath preferably comprises from 2 to 7 gA of zinc ion and from 2 to 7 g / I of fluorophosphate ion.
  • the invention also relates to a kit, as defined in claim II, for the preparation of the bath of the invention.
  • the invention also relates to a certain number of other arrangements which will be discussed below.
  • a conventional chemical conversion bath to zinc is made to contain an amount of 1 to 10 g / l, preferably 2 to 7 g / l , of zinc ion and from 1 to 10 g / l, preferably from 2 to 7 g / I, of fluorophosphate ion.
  • the zinc ion can be brought in any suitable way and in particular in the form of its salts such as nitrate or phosphate or of its oxide.
  • the phosphate ion is present in an amount between 3 and 20 g / l, preferably between 3 and 15 g / l, and the nickel ion in an amount between 0.5 and 2 g / l, preferably 0 , 5 to 1 g / I.
  • the accelerator can be present in an amount between 40 and 150 mg / l.
  • Conventional ions such as Fe, Ca, Mn can be present in an amount between 0 and 5 g / I.
  • test pieces are treated either in a chemical dip bath conventionally used in industry, or in various baths according to the invention.
  • test pieces are immersed for 150 seconds in one of the above-mentioned chemical conversion baths.
  • Bath A This is a comparative example using a conventional bath, hereinafter designated by Bath A and the composition of which is as follows:
  • Bain B a bath in accordance with the invention, hereinafter called Bain B and the composition of which is as follows:
  • Bain D a bath according to the invention, hereinafter called Bain D and the composition of which is as follows:
  • Bath E This is an example using a bath in accordance with the invention, hereinafter called Bath E and the composition of which is as follows:

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Chemically Coating (AREA)

Claims (11)

1. Chromionenfreies Zinkphosphatierungsbad, dadurch gekennzeichnet, daß es
- 1 bis 10 g/l Fluorphosphation der Formel :
Figure imgb0018
- 1 bis 10 g/l Zinkion,
- 3 bis 20 g/I Phosphation und
- 0,5 bis 2 g/I Nickelion enthält.
2. Zinkphosphatierungsbad nach Anspruch 1, dadurch gekennzeichnet, daß es 2 bis 7 g/I Fluorphosphation enthält.
3. Zinkphosphatierungsbad, nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, daß es 2 bis 7 g/I Zinkion enthält.
4. Zinkphosphatierungsbad nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß es 3 bis 15 g/I Phosphation enthält.
5. Zinkphosphatierungsbad nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß es 0,5 bis 1 g/l Nickelion enthält.
6. Chromionenfreies Zinkphosphatierungsbad nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es
- 2 bis 7 g/l Fluorphosphation der Formel :
Figure imgb0019
―2 bis 7 g/) Zinkion,
- 3 bis 15 g/I Phosphation und
- 0,5 bis 1 g/I Nickelion enthält.
7. Bad nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß es die folgende Zusammensetzung aufweist :
Figure imgb0020
8. Verfahren zum Zinkphosphatieren von Metallsubstraten, insbesondere auf der Basis von Eisen, Zink, Aluminium und den Legierungen dieser Metalle, umfassend :
- eine oder mehrere Entfettungsstufen,
- eine oder mehrere Spülstufen,
- bevorzugt eine Stufe zur Konditionierung der Oberfläche des zu behandelnden Substrats,
- die eigentliche Zinkphosphatierungsstufe,
- eine Spülstufe,
- vorzugsweise eine Passivierungsstufe in einem Chrommilieu,
- eine Spülstufe,
- eine Trocknungsstufe oder Ofentrocknungsstufe,
dadurch gekennzeichnet, daß es die Anwendung eines Phosphatierungsbades nach einem der Ansprüche 1 bis 7 auf dem zu behandelnden Substrat durch Aufsprühen oder durch Eintauchen des Substrates umfaßt, wobei die Badtemperatur 30 bis 70 °C beträgt und der Kontakt zwischen Bad und Substrat 5 bis 200 Sekunden lang aufrechterhalten wird.
9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß die Temperatur des Phosphatierungsbades 50 bis 55 °C beträgt.
10. Zur Herstellung eines Phosphatierungsbades nach einem der Ansprüche 1 bis 7 geeignetes Konzentrat, welches Bad durch Verdünnen mit einer entsprechenden Wassermenge erhalten wird, dadurch gekennzeichnet, daß das Konzentrat die folgende Zentesimalzusammensetzung aufweist :
- Zinkion von 2 bis 20 g, vorzugsweise 2 bis 14 g, je 100 g Konzentrat,
- Monofluorphosphation von 2 bis 20 g, vorzugsweise 1 bis 14 g, je 100 g Konzentrat,
- Phosphation von 6 bis 40 g, vorzugsweise 6 bis 30 g, je 100 g Konzentrat,
- Nickelion von 1 bis 4 g, vorzugsweise 1 bis 2 g je 100 g Konzentrat.
11. Kit oder Satz zur Bereitung des Bades nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß er in zwei getrennter Behältern enthält :
- ein Konzentrat nach Anspruch 10, das sich zur Verdünnung mit 95 % Wasser eignet und die folgende Zusammensetzung auf je 100 g aufweist :
Figure imgb0021
- eine Lösung von 3,8 g K2PO3F in 96,2 g Industriewasser, die sich zur Einstellung des K2PO3F-Gehaltes eignet
EP85402589A 1984-12-21 1985-12-20 Zusammensetzung und Verfahren zum Beschichten von Metalloberflächen mit einer Konversionsschicht auf der Basis von Zinkphosphat Expired EP0187597B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85402589T ATE46544T1 (de) 1984-12-21 1985-12-20 Zusammensetzung und verfahren zum beschichten von metalloberflaechen mit einer konversionsschicht auf der basis von zinkphosphat.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8419709 1984-12-21
FR8419709A FR2575188B1 (fr) 1984-12-21 1984-12-21 Bain et procede de conversion chimique de substrats metalliques

Publications (2)

Publication Number Publication Date
EP0187597A1 EP0187597A1 (de) 1986-07-16
EP0187597B1 true EP0187597B1 (de) 1989-09-20

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP85402589A Expired EP0187597B1 (de) 1984-12-21 1985-12-20 Zusammensetzung und Verfahren zum Beschichten von Metalloberflächen mit einer Konversionsschicht auf der Basis von Zinkphosphat

Country Status (7)

Country Link
US (1) US4668307A (de)
EP (1) EP0187597B1 (de)
JP (1) JPS61183477A (de)
AT (1) ATE46544T1 (de)
CA (1) CA1270730A (de)
DE (1) DE3573140D1 (de)
FR (1) FR2575188B1 (de)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1177292A (fr) * 1957-06-14 1959-04-22 Parker Ste Continentale Procédé de revêtement du titane et de ses alliages
FR1477179A (fr) * 1965-04-26 1967-04-14 Pennsalt Chemicals Corp Enduits de métaux pour en augmenter la résistance à la corrosion et l'adhérence de la peinture
FR1538275A (fr) * 1967-10-02 1968-08-30 Parker Ste Continentale Procédé de revêtement de surfaces métalliques et composition pour sa mise en oeuvre
FR2352895A1 (fr) * 1976-04-21 1977-12-23 Diversey France Nouveau procede de traitement de surfaces metalliques au moyen de composes oxyfluores du phosphore 5
US4153478A (en) * 1976-04-21 1979-05-08 The Diversey Corporation Process for treatment of metallic surfaces by means of fluorophosphate salts
US4391652A (en) * 1982-01-29 1983-07-05 Chemical Systems, Inc. Surface treatment for aluminum and aluminum alloys

Also Published As

Publication number Publication date
CA1270730A (en) 1990-06-26
JPS61183477A (ja) 1986-08-16
FR2575188A1 (fr) 1986-06-27
JPH0129871B2 (de) 1989-06-14
DE3573140D1 (en) 1989-10-26
FR2575188B1 (fr) 1993-02-12
US4668307A (en) 1987-05-26
ATE46544T1 (de) 1989-10-15
EP0187597A1 (de) 1986-07-16

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