EP0258922A1 - Procédé pour produire des revêtements de phosphate et leur utilisation - Google Patents

Procédé pour produire des revêtements de phosphate et leur utilisation Download PDF

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Publication number
EP0258922A1
EP0258922A1 EP87201522A EP87201522A EP0258922A1 EP 0258922 A1 EP0258922 A1 EP 0258922A1 EP 87201522 A EP87201522 A EP 87201522A EP 87201522 A EP87201522 A EP 87201522A EP 0258922 A1 EP0258922 A1 EP 0258922A1
Authority
EP
European Patent Office
Prior art keywords
zinc
phosphating
chlorate
accelerator
phosphate
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.)
Withdrawn
Application number
EP87201522A
Other languages
German (de)
English (en)
Inventor
Dieter Hauffe
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
Original Assignee
Metallgesellschaft AG
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 filed Critical Metallgesellschaft AG
Publication of EP0258922A1 publication Critical patent/EP0258922A1/fr
Withdrawn legal-status Critical Current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
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/14—Orthophosphates containing zinc cations containing also chlorate 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
    • C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions

Definitions

  • the invention relates to a process for the production of phosphate layers on surfaces which consist partially or entirely of zinc or zinc alloys by means of zinc, phosphate, accelerator and nickel-containing phosphating solutions in dipping or flooding, and its application to the preparation of the surfaces for painting, in particular the Electro dip painting.
  • Phosphating solutions for the phosphating of surfaces consisting at least partially of zinc or zinc alloys contain, in particular, zinc and phosphate as components determining the layer formation.
  • other cations such as nickel, copper, calcium, manganese and alkali metal can be present to modify the layer formation.
  • oxidizing agents e.g. from the group nitrate, chlorate, nitrite, peroxide, organic nitro compounds.
  • Other possible additives include Fluoride, complex fluoride, chloride, organic polyhydroxycarboxylic acid, complex phosphates and surfactants.
  • the baths are used in the immersion, spraying / immersion and spraying process at temperatures of typically 30 to 70 ° C. and treatment times of, for example, 0.5 to 5 minutes (EP - A - 69 950).
  • EP-A-137 540 provides for the electrolytic production of zinc coatings on steel with a sulfuric acid electrolyte solution which contains one or more oxygen acids of the sulfur with an oxidation number of the sulfur of +5 to + 1 contains to work.
  • Suitable acids of this type are e.g. sulfuric acid, sulfoxylic acid, dithionic acid and thiosulfuric acid.
  • the object of the invention is therefore to design the phosphating process itself in such a way that the formation of specks on any zinc or zinc alloy surfaces is avoided.
  • 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 surface is brought into contact with a phosphating solution which, when using chlorate as an accelerator, is practically free of nitrate and nitrite and when using nitrate and / or nitrite as an accelerator is kept practically free of chlorate and chloride.
  • the method according to EP-A-69 950 provides, inter alia, for the phosphating of galvanized steel with phosphating solutions which must contain chlorate but expediently also contain nitrate (cf. Examples 1 and 3).
  • a further content of nitrate is prescribed in addition to a content of chlorate.
  • galvanized steel only provides for a content of nitrite or nitrobenzenesulfonate, but it is pointed out that the use of further oxidation accelerators, for example chlorate, is possible and can be advantageous.
  • EP - A - l2l 274 also designated as suitable for the treatment of zinc and zinc alloys works with nitrite accelerated phosphating solutions.
  • chlorate is also said to be necessary or desirable.
  • any phosphating solutions based on zinc phosphate can be used to carry out the phosphating. They can belong to the so-called low zinc as well as the normal zinc technology. That is, the surfaces can with a phosphating solution in which the weight ratio of Zn to P2O5 is set to l: (8 to 85), or with a phosphating solution in which the weight ratio of Zn to P2O5 is set to l: (0.3 to ⁇ 8).
  • phosphating processes result, which are characterized by a higher phosphating speed in comparison to the low zinc processes.
  • the phosphate layers they produce have good properties for a wide range of applications in the areas of corrosion protection and non-cutting cold forming.
  • aqueous acidic solutions based on zinc phosphate to be used in the context of the invention contain primary zinc phosphate, optionally alkali metal phosphate, and a certain amount of free acid which is matched to the respective bath 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 phosphating solutions can also contain other cations known in phosphating technology, for example Co, Cu, Mn, Ca, Mg, Fe, Na, K, Li, NH4 and others.
  • concentrations of the most important of these ions should be: at Mn and Ca up to 5 g / l, preferably up to 2.1 g / l, at Fe (II) up to 8 g / l, preferably up to 5 g / l.
  • the use of other anions different from phosphate for example SO4, F, BF4, SiF6, citrate, tartrate, etc., may be necessary or desirable.
  • the contact time for the phosphating solution used in the immersion treatment is usually between 1 and 10 minutes. When treating zinc or zinc alloys alone, shorter treatment times, e.g. from 2 to 30 sec., sufficient.
  • the temperature of the phosphating solution is approximately 30 to 60 ° C. The lower the temperature, the longer the contact time.
  • the measures customary in connection with phosphating processes can also be used in the present process. These are in particular degreasing and rust removal, pre-rinsing to activate the formation of the phosphate layer and after-treatment with rinsing solutions based on Cr (VI) and / or Cr (III) etc. or with impregnating agents such as rust protection oils, waxes and synthetic resins.
  • the stock solution mentioned under 5. was modified by adding NO3, ClO3, Cl, nickel and nitrobenzenesulfonate (NBS) according to the table below.

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)
EP87201522A 1986-09-05 1987-08-11 Procédé pour produire des revêtements de phosphate et leur utilisation Withdrawn EP0258922A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863630246 DE3630246A1 (de) 1986-09-05 1986-09-05 Verfahren zur erzeugung von phosphatueberzuegen sowie dessen anwendung
DE3630246 1986-09-05

Publications (1)

Publication Number Publication Date
EP0258922A1 true EP0258922A1 (fr) 1988-03-09

Family

ID=6308977

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87201522A Withdrawn EP0258922A1 (fr) 1986-09-05 1987-08-11 Procédé pour produire des revêtements de phosphate et leur utilisation

Country Status (5)

Country Link
EP (1) EP0258922A1 (fr)
JP (1) JPS63145784A (fr)
DE (1) DE3630246A1 (fr)
GB (1) GB2196024A (fr)
ZA (1) ZA876589B (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0304108A1 (fr) * 1987-08-19 1989-02-22 Metallgesellschaft Ag Procédé de phosphatation de métaux
WO1990012901A1 (fr) * 1989-04-21 1990-11-01 Henkel Kommanditgesellschaft Auf Aktien Procede sans chlorate ni nitrite pour produire des couches de phosphate de zinc contenant du nickel et du manganese
WO1997016581A2 (fr) * 1995-10-27 1997-05-09 Henkel Kommanditgesellschaft Auf Aktien Phosphatation au zinc, a l'aide d'une solution sans manganese et a faible teneur en nitrate
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

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0730455B2 (ja) * 1988-09-27 1995-04-05 日本パーカライジング株式会社 リン酸塩化成処理液
DE4228470A1 (de) * 1992-08-27 1994-03-03 Henkel Kgaa Verfahren zur Phospatierung von einseitig verzinktem Stahlband
DE4241134A1 (de) * 1992-12-07 1994-06-09 Henkel Kgaa Verfahren zur Phosphatierung von Metalloberflächen
AU1581700A (en) * 1998-07-21 2000-02-28 Brent International Plc Nickel-zinc phosphate conversion coatings

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2033717A5 (fr) * 1969-03-07 1970-12-04 Parker Ste Continentale
EP0056881A1 (fr) * 1981-01-22 1982-08-04 Metallgesellschaft Ag Procédé pour la phosphatation de métaux
EP0111246A2 (fr) * 1982-12-08 1984-06-20 Gerhard Collardin GmbH Procédé pour phosphater des objets métalliques zingués électrolytiquement
EP0121274A1 (fr) * 1983-03-31 1984-10-10 Metallgesellschaft Ag Procédé de phosphatation de surfaces métalliques
GB2148951A (en) * 1983-11-02 1985-06-05 Pyrene Chemical Services Ltd Phosphating processes and compositions
US4595424A (en) * 1985-08-26 1986-06-17 Parker Chemical Company Method of forming phosphate coating on zinc
EP0228151A1 (fr) * 1985-08-27 1987-07-08 HENKEL CORPORATION (a Delaware Corp.) Solutions aqueuses acides de phosphatation pour leur utilisation dans un procédé de phosphatation de surfaces métalliques

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1040806A (en) * 1964-04-30 1966-09-01 Pyrene Co Ltd Improvements in painting metal surfaces
US3620949A (en) * 1969-04-11 1971-11-16 Balm Paints Ltd Metal pretreatment and coating process
GB1542222A (en) * 1977-01-06 1979-03-14 Pyrene Chemical Services Ltd Phosphate coating compositions
JPS5811514B2 (ja) * 1979-05-02 1983-03-03 日本ペイント株式会社 金属表面の保護方法
JPS5811515B2 (ja) * 1979-05-11 1983-03-03 日本ペイント株式会社 金属表面にリン酸亜鉛皮膜を形成するための組成物
GB2072225B (en) * 1980-03-21 1983-11-02 Pyrene Chemical Services Ltd Process and composition for coating metal surfaces
DE3118375A1 (de) * 1981-05-09 1982-11-25 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metallen sowie dessen anwendung zur vorbehandlung fuer die elektrotauchlackierung
US4498935A (en) * 1981-07-13 1985-02-12 Parker Chemical Company Zinc phosphate conversion coating composition
DE3408577A1 (de) * 1984-03-09 1985-09-12 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metallen

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2033717A5 (fr) * 1969-03-07 1970-12-04 Parker Ste Continentale
EP0056881A1 (fr) * 1981-01-22 1982-08-04 Metallgesellschaft Ag Procédé pour la phosphatation de métaux
EP0111246A2 (fr) * 1982-12-08 1984-06-20 Gerhard Collardin GmbH Procédé pour phosphater des objets métalliques zingués électrolytiquement
EP0121274A1 (fr) * 1983-03-31 1984-10-10 Metallgesellschaft Ag Procédé de phosphatation de surfaces métalliques
GB2148951A (en) * 1983-11-02 1985-06-05 Pyrene Chemical Services Ltd Phosphating processes and compositions
US4595424A (en) * 1985-08-26 1986-06-17 Parker Chemical Company Method of forming phosphate coating on zinc
EP0228151A1 (fr) * 1985-08-27 1987-07-08 HENKEL CORPORATION (a Delaware Corp.) Solutions aqueuses acides de phosphatation pour leur utilisation dans un procédé de phosphatation de surfaces métalliques

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0304108A1 (fr) * 1987-08-19 1989-02-22 Metallgesellschaft Ag Procédé de phosphatation de métaux
WO1990012901A1 (fr) * 1989-04-21 1990-11-01 Henkel Kommanditgesellschaft Auf Aktien Procede sans chlorate ni nitrite pour produire des couches de phosphate de zinc contenant du nickel et du manganese
WO1997016581A2 (fr) * 1995-10-27 1997-05-09 Henkel Kommanditgesellschaft Auf Aktien Phosphatation au zinc, a l'aide d'une solution sans manganese et a faible teneur en nitrate
WO1997016581A3 (fr) * 1995-10-27 1997-06-19 Henkel Kgaa Phosphatation au zinc, a l'aide d'une solution sans manganese et a faible teneur en nitrate
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

Also Published As

Publication number Publication date
ZA876589B (en) 1989-05-30
DE3630246A1 (de) 1988-03-10
GB8720788D0 (en) 1987-10-14
JPS63145784A (ja) 1988-06-17
GB2196024A (en) 1988-04-20

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