EP0370535B1 - Verfahren zum Aufbringen von Phosphatüberzügen - Google Patents

Verfahren zum Aufbringen von Phosphatüberzügen Download PDF

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Publication number
EP0370535B1
EP0370535B1 EP89201936A EP89201936A EP0370535B1 EP 0370535 B1 EP0370535 B1 EP 0370535B1 EP 89201936 A EP89201936 A EP 89201936A EP 89201936 A EP89201936 A EP 89201936A EP 0370535 B1 EP0370535 B1 EP 0370535B1
Authority
EP
European Patent Office
Prior art keywords
zinc
phosphating solution
contacted
phosphating
iron
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 - Lifetime
Application number
EP89201936A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0370535A1 (de
Inventor
Horst Dr. Gehmecker
Dieter Hauffe
Gerhard Müller
Werner Dr. Rausch
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 SA
Original Assignee
Metallgesellschaft AG
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 SA filed Critical Metallgesellschaft AG
Publication of EP0370535A1 publication Critical patent/EP0370535A1/de
Application granted granted Critical
Publication of EP0370535B1 publication Critical patent/EP0370535B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C23C22/34—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
    • C23C22/365—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 containing also zinc and 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
    • C23C22/12—Orthophosphates containing 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
    • C23C22/07—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

Definitions

  • the invention relates to a method for applying phosphate coatings on surfaces made of aluminum and / or zinc or its or their alloys with the aid of phosphating solutions which operate according to the low zinc technology 0.4 to 1.5 g / l zinc and 10 to 16 g / l P2O5 contain,
  • phosphating solutions that work according to the low-zinc technology are those that predominantly contain zinc as a layer-forming cation in a concentration of approx. 0.4 to 1.5 g / l and in which the Zn / PO4 ratio is less than approx. Is 0.08.
  • phosphating solutions used for this usually contain zinc, nickel, manganese, magnesium, cadmium, copper, cobalt, alkali and / or ammonium ions, phosphate ions, accelerating additives such as nitrite, chlorate, bromate, peroxide, m -Nitrobenzenesulfonate, nitrophenol or combinations thereof.
  • accelerating additives such as nitrite, chlorate, bromate, peroxide, m -Nitrobenzenesulfonate, nitrophenol or combinations thereof.
  • aluminum, its alloys and galvanized steel they preferably additionally contain simple and / or complex fluorides.
  • the phosphating solutions can also contain layer-refining additives, such as hydroxy carboxylic acids, amino carboxylic acids or condensed phosphates.
  • the metal surfaces consist to a large extent of steel in addition to varying amounts of galvanized steel and a small amount of aluminum materials and are treated by spraying and / or immersion.
  • the object of the invention is to provide a method for applying phosphate coatings on surfaces made of zinc and / or aluminum or its alloys with phosphating solutions working according to the low zinc technology, in which an increase in the free acid or the acid ratio is prevented and consequently, the disadvantages of the known methods are avoided, which is nevertheless easy to use and economical.
  • 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 contains a minimum concentration of iron (III) ions of 1 mg / l and which is treated per m2 Surface 50 to 2000 mg of iron III ions can be added.
  • the iron ions can be introduced into the phosphating solution in the form of Fe-III ions, but also in the form of Fe-II ions together with an oxidizing agent, such as chlorate, nitrite, peroxide, which oxidizes to Fe-III.
  • Suitable compounds are e.g. the nitrates, chlorides and fluorides of divalent or trivalent iron and iron-III complex compounds of hydroxy carboxylic acids, aminocarboxylic acids and the like.
  • a preferred embodiment of the invention consists in bringing the surface into contact with a phosphating solution, to which 50 to 1000 mg of iron III ions are added per m2 of treated surface.
  • the dosage can take place as mentioned above.
  • such solutions are used that up to 1.3 g / l Ni up to 1.3 g / l Mn up to 1.3 g / l Mg contain.
  • the weight ratio of Ni, Mn and or Mg to Zn should be set to a value of up to 1.5: 1.
  • phosphating solutions which act as accelerators 2 to 25 g / l NO3 1 to 6 g / l ClO3 0.1 to 2 g / l organic nitro compound 0.05 to 0.5 g / l NO2 0.02 to 0.1 g / l peroxide (calculated as H2O2) or mixtures thereof.
  • the phosphating solutions can be applied in a conventional manner. Particularly suitable forms of application are spraying and / or dipping, a temperature in the range from 30 to 70 ° C. being preferred.
  • the method according to the invention is particularly suitable for the treatment of pure aluminum and alloys, e.g. of the qualities AlMgSi, AlMg and AlMgMn.
  • Suitable materials are also solid zinc alloys or steel alloys with e.g. Ni, Fe or Al.
  • iron III citrate By adding iron III citrate, the iron III concentration had been adjusted to 2 mg / l when the phosphating solution was started up.
  • iron III citrate (calc. As Fe) was added to the phosphating solution of 10 l of 250 mg / m 2 surface.
  • the number of free acid points was practically constant.
  • the phosphate coating obtained was consistently uniform and closed.

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)
EP89201936A 1988-11-25 1989-07-22 Verfahren zum Aufbringen von Phosphatüberzügen Expired - Lifetime EP0370535B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3839802 1988-11-25
DE3839802 1988-11-25

Publications (2)

Publication Number Publication Date
EP0370535A1 EP0370535A1 (de) 1990-05-30
EP0370535B1 true EP0370535B1 (de) 1992-11-11

Family

ID=6367867

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89201936A Expired - Lifetime EP0370535B1 (de) 1988-11-25 1989-07-22 Verfahren zum Aufbringen von Phosphatüberzügen

Country Status (7)

Country Link
EP (1) EP0370535B1 (ja)
JP (1) JP2845246B2 (ja)
CA (1) CA1334371C (ja)
DD (1) DD299968A5 (ja)
DE (1) DE58902702D1 (ja)
ES (1) ES2036023T3 (ja)
GB (1) GB2226829B (ja)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5238506A (en) * 1986-09-26 1993-08-24 Chemfil Corporation Phosphate coating composition and method of applying a zinc-nickel-manganese phosphate coating
DE3828676A1 (de) * 1988-08-24 1990-03-01 Metallgesellschaft Ag Phosphatierverfahren
DE3918136A1 (de) * 1989-06-03 1990-12-06 Henkel Kgaa Verfahren zur erzeugung von manganhaltigen phosphatueberzuegen auf metalloberflaechen
EP0439377A1 (en) * 1990-01-26 1991-07-31 Ppg Industries, Inc. Method of applying a zinc-nickel-manganese phosphate coating.
US5261973A (en) * 1991-07-29 1993-11-16 Henkel Corporation Zinc phosphate conversion coating and process
US5645706A (en) * 1992-04-30 1997-07-08 Nippondenso Co., Ltd. Phosphate chemical treatment method
JPH05306497A (ja) 1992-04-30 1993-11-19 Nippondenso Co Ltd リン酸塩化成処理方法
DE4228470A1 (de) * 1992-08-27 1994-03-03 Henkel Kgaa Verfahren zur Phospatierung von einseitig verzinktem Stahlband
DE4243214A1 (de) * 1992-12-19 1994-06-23 Metallgesellschaft Ag Verfahren zur Erzeugung von Phosphatüberzügen
US5797987A (en) * 1995-12-14 1998-08-25 Ppg Industries, Inc. Zinc phosphate conversion coating compositions and process
US5900073A (en) * 1996-12-04 1999-05-04 Henkel Corporation Sludge reducing zinc phosphating process and composition
JP3366826B2 (ja) * 1997-04-30 2003-01-14 本田技研工業株式会社 アルミニウム合金用リン酸亜鉛処理剤
JP4019723B2 (ja) * 2001-02-23 2007-12-12 株式会社デンソー 電解リン酸塩化成処理方法
RU2560891C1 (ru) * 2014-05-05 2015-08-20 Федеральное государственное унитарное предприятие федеральный научно-производственный центр "Производственное объединение "Старт" им. М.В. Проценко" (ФГУП ФНПЦ "ПО "Старт" им. М.В. Проценко") Способ фосфатирования железокобальтового сплава
BR112017021409B1 (pt) * 2015-04-07 2023-02-28 Chemetall Gmbh Método para fosfatação de uma superfície metálica, e, superfície metálica revestida com fosfato
RU2624566C1 (ru) * 2016-02-15 2017-07-04 Федеральное государственное унитарное предприятие федеральный научно-производственный центр "Производственное объединение "Старт" им. М.В. Проценко" (ФГУП ФНПЦ "ПО "Старт" им. М.В. Проценко") Способ фосфатирования магнитомягких сплавов типа пермаллой (варианты)
US11124880B2 (en) 2016-04-07 2021-09-21 Chemetall Gmbh Method for nickel-free phosphating metal surfaces

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2738281A1 (de) * 1977-08-25 1979-03-01 Metallgesellschaft Ag Verfahren zur phosphatierung von metallen
DE2738282A1 (de) * 1977-08-25 1979-03-01 Metallgesellschaft Ag Verfahren zum aufbringen von phosphatueberzuegen
DE2738283A1 (de) * 1977-08-25 1979-03-01 Metallgesellschaft Ag Verfahren zur phosphatierung von metallen
US4278477A (en) * 1980-03-19 1981-07-14 Amchem Products, Inc. Metal treatment
US4486241A (en) * 1981-09-17 1984-12-04 Amchem Products, Inc. Composition and process for treating steel
DE3245411A1 (de) * 1982-12-08 1984-07-05 Gerhard Collardin GmbH, 5000 Köln Verfahren zur phosphatierung elektrolytisch verzinkter metallwaren
FR2569203B1 (fr) * 1984-08-16 1989-12-22 Produits Ind Cie Fse Procede de traitement par conversion chimique de substrats en zinc ou en l'un de ses alliages, concentre et bain utilises pour la mise en oeuvre de ce procede
JPS63100185A (ja) * 1986-10-16 1988-05-02 Nippon Parkerizing Co Ltd 冷延鋼板または亜鉛めっき鋼板のりん酸塩化成処理方法

Also Published As

Publication number Publication date
GB8917936D0 (en) 1989-09-20
EP0370535A1 (de) 1990-05-30
DE58902702D1 (de) 1992-12-17
JPH02190478A (ja) 1990-07-26
CA1334371C (en) 1995-02-14
DD299968A5 (de) 1992-05-14
GB2226829A (en) 1990-07-11
JP2845246B2 (ja) 1999-01-13
ES2036023T3 (es) 1993-05-01
GB2226829B (en) 1993-01-20

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