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EP0370535A1 - Procédé pour appliquer des revêtements de phosphate - Google Patents

Procédé pour appliquer des revêtements de phosphate Download PDF

Info

Publication number
EP0370535A1
EP0370535A1 EP89201936A EP89201936A EP0370535A1 EP 0370535 A1 EP0370535 A1 EP 0370535A1 EP 89201936 A EP89201936 A EP 89201936A EP 89201936 A EP89201936 A EP 89201936A EP 0370535 A1 EP0370535 A1 EP 0370535A1
Authority
EP
European Patent Office
Prior art keywords
phosphating solution
zinc
iron
ions
phosphating
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
EP89201936A
Other languages
German (de)
English (en)
Other versions
EP0370535B1 (fr
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/fr
Application granted granted Critical
Publication of EP0370535B1 publication Critical patent/EP0370535B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/34Chemical 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
    • C23C22/36Chemical 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
    • C23C22/364Chemical 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
    • C23C22/365Chemical 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/07Chemical 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
    • C23C22/08Orthophosphates
    • C23C22/12Orthophosphates containing zinc cations
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/07Chemical 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
    • C23C22/08Orthophosphates
    • C23C22/18Orthophosphates containing manganese cations
    • C23C22/182Orthophosphates containing manganese cations containing also zinc cations
    • C23C22/184Orthophosphates 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 their alloys with the aid of phosphating solutions working according to the low zinc technology.
  • 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.
  • the 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.
  • phosphating solutions can also contain layer-refining additives such as hydroxycarboxylic acids, aminocarboxylic 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 hydroxycarboxylic 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.
  • the method according to the invention can be used for all known phosphating solutions working according to the low zinc technology.
  • such solutions are used that 0.4 to 1.5 g / l Zn 10 to 26 g / l P2O5 as well 0 to 1.3 g / l Ni 0 to 1.3 g / l Mn 0 to 1.3 g / l Mg contain.
  • the weight ratio of Zn to P2O5 should be set to a value in the range of (0.075 to 0.015): 1 and - if available - the weight ratio of Ni, Mn and or Mg to Zn to a value of up to 1.5: 1 .
  • phosphating solutions which act as accelerators 2 nos 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 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.

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 Procédé pour appliquer des revêtements de phosphate Expired - Lifetime EP0370535B1 (fr)

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 true EP0370535A1 (fr) 1990-05-30
EP0370535B1 EP0370535B1 (fr) 1992-11-11

Family

ID=6367867

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89201936A Expired - Lifetime EP0370535B1 (fr) 1988-11-25 1989-07-22 Procédé pour appliquer des revêtements de phosphate

Country Status (7)

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

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0401616A1 (fr) * 1989-06-03 1990-12-12 Henkel Kommanditgesellschaft auf Aktien Procédé pour appliquer des couches de phosphate contenant du manganèse sur des surfaces métalliques
EP0439377A1 (fr) * 1990-01-26 1991-07-31 Ppg Industries, Inc. MÀ©thode d'application d'un revêtement de phosphatation au zinc-nickel-manganèse
WO1993003198A1 (fr) * 1991-07-29 1993-02-18 Henkel Corporation Revetement a base de phosphate de zinc et procede correspondant
WO1994005826A1 (fr) * 1992-08-27 1994-03-17 Henkel Kommanditgesellschaft Auf Aktien Procede de phosphatation d'acier zingue d'un seul cote
EP0603921A1 (fr) * 1992-12-19 1994-06-29 Metallgesellschaft Ag Procédé pour former des revêtements de phosphate
EP1012355A4 (fr) * 1996-12-04 2000-06-28 Henkel Corp Procede et composition de reduction de boue et de phosphatation au zinc
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
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)
WO2017174222A1 (fr) * 2015-04-07 2017-10-12 Chemetall Gmbh Procédé amélioré de phosphatation sans nickel de surfaces métalliques
US11124880B2 (en) 2016-04-07 2021-09-21 Chemetall Gmbh Method for nickel-free phosphating metal surfaces

Families Citing this family (7)

* 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
JPH05306497A (ja) 1992-04-30 1993-11-19 Nippondenso Co Ltd リン酸塩化成処理方法
US5645706A (en) * 1992-04-30 1997-07-08 Nippondenso Co., Ltd. Phosphate chemical treatment method
US5797987A (en) * 1995-12-14 1998-08-25 Ppg Industries, Inc. Zinc phosphate conversion coating compositions and process
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

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2401236A1 (fr) * 1977-08-25 1979-03-23 Parker Ste Continentale Procede de phosphatation au zinc avec preneutralisation
FR2401234A1 (fr) * 1977-08-25 1979-03-23 Parker Ste Continentale Procede de phosphatation au zinc avec addition de fer
FR2512840A1 (fr) * 1981-09-17 1983-03-18 Amchem Prod Solutions aqueuses acides pour revetements de phosphate de zinc et leurs concentres, procedes de revetement les mettant en oeuvre et solutions d'activation du metal utilisables dans ces procedes
EP0111246A2 (fr) * 1982-12-08 1984-06-20 Gerhard Collardin GmbH Procédé pour phosphater des objets métalliques zingués électrolytiquement
EP0175606A1 (fr) * 1984-08-16 1986-03-26 Compagnie Francaise De Produits Industriels Procédé de traitement par conversion chimique de substrats en zinc ou en l'un de ses alliages, concentré et bain utilisés pour la mise en oeuvre de ce procédé
EP0264811A1 (fr) * 1986-10-16 1988-04-27 Nihon Parkerizing Co., Ltd. Procédé d'obtention de revêtements de phosphate

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2738282A1 (de) * 1977-08-25 1979-03-01 Metallgesellschaft Ag Verfahren zum aufbringen von phosphatueberzuegen
US4278477A (en) * 1980-03-19 1981-07-14 Amchem Products, Inc. Metal treatment

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2401236A1 (fr) * 1977-08-25 1979-03-23 Parker Ste Continentale Procede de phosphatation au zinc avec preneutralisation
FR2401234A1 (fr) * 1977-08-25 1979-03-23 Parker Ste Continentale Procede de phosphatation au zinc avec addition de fer
FR2512840A1 (fr) * 1981-09-17 1983-03-18 Amchem Prod Solutions aqueuses acides pour revetements de phosphate de zinc et leurs concentres, procedes de revetement les mettant en oeuvre et solutions d'activation du metal utilisables dans ces procedes
EP0111246A2 (fr) * 1982-12-08 1984-06-20 Gerhard Collardin GmbH Procédé pour phosphater des objets métalliques zingués électrolytiquement
EP0175606A1 (fr) * 1984-08-16 1986-03-26 Compagnie Francaise De Produits Industriels Procédé de traitement par conversion chimique de substrats en zinc ou en l'un de ses alliages, concentré et bain utilisés pour la mise en oeuvre de ce procédé
EP0264811A1 (fr) * 1986-10-16 1988-04-27 Nihon Parkerizing Co., Ltd. Procédé d'obtention de revêtements de phosphate

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0401616A1 (fr) * 1989-06-03 1990-12-12 Henkel Kommanditgesellschaft auf Aktien Procédé pour appliquer des couches de phosphate contenant du manganèse sur des surfaces métalliques
WO1990015167A1 (fr) * 1989-06-03 1990-12-13 Henkel Kommanditgesellschaft Auf Aktien Procede pour appliquer sur des surfaces metalliques des couches de phosphate insoluble contenant du manganese
EP0439377A1 (fr) * 1990-01-26 1991-07-31 Ppg Industries, Inc. MÀ©thode d'application d'un revêtement de phosphatation au zinc-nickel-manganèse
WO1993003198A1 (fr) * 1991-07-29 1993-02-18 Henkel Corporation Revetement a base de phosphate de zinc et procede correspondant
US5261973A (en) * 1991-07-29 1993-11-16 Henkel Corporation Zinc phosphate conversion coating and process
CN1038949C (zh) * 1991-07-29 1998-07-01 亨凯尔公司 处理金属基质的磷酸盐水涂液及其浓缩液组合物及处理方法
TR28730A (tr) * 1991-07-29 1997-02-20 Henkel Corp Cinko fosfat ile kimyasal kaplama islemi.
US5516372A (en) * 1992-08-27 1996-05-14 Henkel Kommanditgesellschaft Auf Aktien Process for phosphating steel strip galvanized on one side
WO1994005826A1 (fr) * 1992-08-27 1994-03-17 Henkel Kommanditgesellschaft Auf Aktien Procede de phosphatation d'acier zingue d'un seul cote
US5383982A (en) * 1992-12-19 1995-01-24 Metallgesellschaft Aktiengesellschaft Process of producing phosphate coatings
EP0603921A1 (fr) * 1992-12-19 1994-06-29 Metallgesellschaft Ag Procédé pour former des revêtements de phosphate
EP1012355A4 (fr) * 1996-12-04 2000-06-28 Henkel Corp Procede et composition de reduction de boue et de phosphatation au zinc
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
WO2017174222A1 (fr) * 2015-04-07 2017-10-12 Chemetall Gmbh Procédé amélioré de phosphatation sans nickel de surfaces métalliques
CN109312466A (zh) * 2015-04-07 2019-02-05 凯密特尔有限责任公司 无镍磷化金属表面的改进方法
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

Also Published As

Publication number Publication date
DE58902702D1 (de) 1992-12-17
ES2036023T3 (es) 1993-05-01
DD299968A5 (de) 1992-05-14
JPH02190478A (ja) 1990-07-26
EP0370535B1 (fr) 1992-11-11
JP2845246B2 (ja) 1999-01-13
CA1334371C (fr) 1995-02-14
GB2226829A (en) 1990-07-11
GB2226829B (en) 1993-01-20
GB8917936D0 (en) 1989-09-20

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