EP0414296B1 - Verfahren zur Erzeugung von Phosphatüberzügen auf Metallen - Google Patents

Verfahren zur Erzeugung von Phosphatüberzügen auf Metallen Download PDF

Info

Publication number
EP0414296B1
EP0414296B1 EP90202104A EP90202104A EP0414296B1 EP 0414296 B1 EP0414296 B1 EP 0414296B1 EP 90202104 A EP90202104 A EP 90202104A EP 90202104 A EP90202104 A EP 90202104A EP 0414296 B1 EP0414296 B1 EP 0414296B1
Authority
EP
European Patent Office
Prior art keywords
phosphating solution
phosphating
brought
contact
quantities
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
EP90202104A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0414296A1 (de
Inventor
Horst Dr. Gehmecker
Dieter Hauffe
Dirk Meyer
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.)
Chemetall GmbH
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
Priority to AT90202104T priority Critical patent/ATE91159T1/de
Publication of EP0414296A1 publication Critical patent/EP0414296A1/de
Application granted granted Critical
Publication of EP0414296B1 publication Critical patent/EP0414296B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/16—Orthophosphates containing zinc cations containing also peroxy-compounds
    • 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
    • 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
    • C23C22/73—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 characterised by the process
    • C23C22/77—Controlling or regulating of the coating process

Definitions

  • the invention relates to a method for phosphating iron and steel surfaces according to the low-zinc technology with nitrite-free, zinc, phosphate and nitrate-containing phosphating solutions and its application to the preparation of iron and steel surfaces for painting.
  • the zinc phosphating process is widely used in the metalworking industry.
  • the phosphate layers produced on the treated metal surfaces with this process are used in particular to facilitate sliding and non-cutting cold forming, as well as for corrosion protection and as a paint primer.
  • a phosphating process which belongs to the genus of normal zinc processes and works on the iron side with iron II concentrations of 0.1 to 7 g / l is dealt with in EP-A-287133.
  • phosphating processes that make use of low-zinc technology bring special advantages.
  • the bath solutions used here contain zinc in concentrations of only about 0.4 to 1.7 g / l and produce phosphate layers on steel with a high proportion of phosphophyllite, which offers better paint adhesion and greater resistance to paint infiltration when exposed to corrosion than Hopeit from phosphating baths with a higher zinc content.
  • nitrite and chlorate and organic nitro compound have proven themselves as accelerators in low-zinc phosphating baths.
  • One containing nitrite and possibly also nitrate and / or chlorate Phosphating bath is described in FR-A-2449135. These baths deliver high-quality, uniformly covering phosphate layers in a short time.
  • peroxides as accelerators in low-zinc phosphating baths. These would be preferable to the use of the aforementioned accelerators for reasons of workplace hygiene and environmental protection, but their acceleration effect is sufficient among those previously used Treatment conditions did not rule out.
  • Another disadvantage of the per compounds is that comparatively thin phosphate layers with only moderate corrosion protection can be achieved even with a long treatment time.
  • the object of the invention is to provide a method according to the preamble of claim 1, which does not have the known, in particular the aforementioned disadvantages.
  • the object is achieved by the method of the type mentioned according to the invention is designed such that the weight ratio of free P2O5 to total P2O5 is set to a value in the range of 0.04 to 0.20 in the acidic phosphate solution, and that the acidic phosphating solution H2O2 or alkali perborate is added in such an amount that - in the incorporated state - its maximum peroxide concentration 17 mg / l (calc. as H2O2) or its maximum Fe (II) concentration 60 mg / l (calc. as Fe).
  • the method according to the invention is intended for the surface treatment of iron and steel.
  • low-alloy steel, galvanized steel, alloy-galvanized steel, ie with ZnAl, ZnFe and ZnNi coated steel, aluminized steel, aluminum and its alloys are treated.
  • the phosphating is carried out in the temperature range from 30 to 65 ° C. Below 30 ° C the phosphating speed is no longer sufficient for modern series production, while at temperatures higher than 65 ° C disadvantages, e.g. due to increased system incrustation.
  • the weight ratio of Zn to P2O5 in the phosphating solution is preferably (0.075 to 0.015): 1.
  • the content of peroxide or Fe (II) present in the phosphating solution is determined in a conventional manner, for example by titration with potassium permanganate.
  • the surfaces are brought into contact with a phosphating solution in which the addition of H2O2 and / or alkali perborate is controlled in accordance with the electrochemical potential determined with a redox electrode.
  • a platinum electrode and a suitable reference electrode e.g. a calomel or silver / silver chloride electrode.
  • the phosphating solution can be monitored continuously and the peroxide added in such a way that both the stationary Fe (II) ion concentration and the stationary concentration of the hydrogen peroxide remain within the aforementioned limit values.
  • the coordination of the type and amount of cations and anions in the phosphating solution used in the process according to the invention is carried out in such a way that the ratio of free P2O5 to total P2O5 is between 0.04 and 0.20.
  • the ratio of free P2O5 to total P2O5 is between 0.04 and 0.20.
  • a preferred embodiment of the method according to the invention provides for the surfaces to be brought into contact with a phosphating solution to which H2O2 and / or alkali perborate has been added in such an amount that their maximum peroxide concentration is 8 mg / l or their maximum Fe (II) concentration Is 30 mg / l.
  • the surfaces are brought into contact with a phosphating solution which additionally contains manganese in an amount of up to 3 g / l, nickel and / or cobalt in an amount of up to 3 g / l, magnesium in an amount of contains up to 3 g / l and / or calcium in amounts up to 3 g / l.
  • a phosphating solution which additionally contains manganese in an amount of up to 3 g / l, nickel and / or cobalt in an amount of up to 3 g / l, magnesium in an amount of contains up to 3 g / l and / or calcium in amounts up to 3 g / l.
  • Nickel and / or cobalt are preferably used to increase the aggressiveness of the phosphating solution on steel and - if zinc surfaces are also treated - to improve the phosphating of zinc surfaces.
  • a possible addition of small amounts of copper increases the accelerating effect of the phosphating solution.
  • Alkali and / or ammonium primarily serve to set the desired acid ratio.
  • Another advantageous embodiment of the invention is to bring the surfaces into contact with a phosphating solution, the fluoborate in amounts up to 3 g / l (calculated as BF4) and / or silicofluoride in amounts up to 3 g / l (calculated as SiF6) and / or fluoride in quantities up to 1.5 g / l (calculated as F).
  • the anions fluoborate, silicofluoride and / or fluoride generally increase the rate of phosphating and are also particularly advantageous when the treatment of aluminum-containing zinc surfaces is intended.
  • the presence of free fluoride (F ⁇ ) is essential for the crystalline phosphating of aluminum and its alloys.
  • Chloride and sulfate can be used to adjust the electroneutrality of the phosphating solution and in special cases to increase the aggressiveness.
  • the weight ratio of Mn: Zn, of (Ni and / or Co): Zn, of Mg: Zn and / or Ca: Zn should be a maximum Be 2: 1.
  • the surfaces are brought into contact with a phosphating solution, the free P2O5 or the ratio of free P2O5 to total P2O5 is set during the work by adding manganese carbonate, zinc carbonate and / or zinc oxide. It is advisable to use the components mentioned in the form of an aqueous dispersion.
  • the process according to the invention can be carried out in spraying, dipping, spray-dipping or flooding.
  • a further advantageous embodiment of the invention provides for the metal surfaces to be brought into contact with a phosphating solution, from which water is removed and compensated for by adding rinsing water to the subsequent rinsing step or rinsing steps.
  • the water removal from the phosphating bath takes place, for example, by evaporation, reverse osmosis and / or electrodialysis.
  • H2O2 as a peroxide component, it is possible to operate the method according to the invention in such a way that no waste water contaminated with phosphate is obtained from the rinsing process after the phosphating.
  • the rinsing stages which are expediently designed as a rinsing bath cascade, work in the last rinsing bath with salt-free or low-salt water, which is supplied to the phosphating bath in the opposite direction from the rinsing stage to rinsing stage.
  • the phosphating bath it complements the above-mentioned dehydration of the phosphating solution.
  • the water extracted from the phosphating bath for example by reverse osmosis or electrodialysis, can be returned to the rinsing stages.
  • a further advantageous embodiment of the method according to the invention provides for the surfaces to be brought into contact with a phosphating solution which, by adding phosphate, has a ratio of free P2O5 to total P2O5 when adding (- 0.50 to + 0.20) : 1 is added.
  • a phosphating solution which, by adding phosphate, has a ratio of free P2O5 to total P2O5 when adding (- 0.50 to + 0.20) : 1 is added.
  • the minus sign means that there is no free P2O5, but rather part of the phosphate is in the secondary phosphate stage.
  • the value minus 0.19 means, for example, that 19% of the total P2O5 are present as secondary phosphate.
  • the phosphate components in the supplement are in a range which is defined by 50% secondary and 50% primary phosphate (calc. As P2O5) on the one hand and limited by 80% primary phosphate and 20% free phosphoric acid (calculated as P2O5) on the other.
  • liquid supplement concentrates in the range from free P2O5 to total P2O5 are not stable, the addition in the method according to the invention is generally carried out with at least two separate concentrates.
  • the method according to the invention is of particular advantage in the preparation of surfaces for painting, in particular for electrocoating. Preparation for cataphoretic electrocoating is particularly important.
  • H2O2 concentration was varied by adding H2O2 between 10 and 70 mg / l H2O2 and, in the absence of H2O2, the iron (II) concentration by incorporating steel sheet between 10 and 90 mg / l Fe (II).
  • Fig.1 shows the phosphate layer weight obtained with a 3 min spraying time.
  • Fig. 2 contains the minimum phosphating times found in these tests, ie the treatment times that were necessary to deposit phosphate layers with uniform coverage on the metal sheets.
  • the temperature of the solution was 55 to 60 ° C.
  • the treatment was carried out by spraying for 3 minutes.
  • the throughput was 3 m2 / l bath volume with a throughput density of 0.1 m2 / h.
  • the bath composition was maintained over the total throughput by adding zinc carbonate and a correspondingly supplemented solution.
  • Hydrogen peroxide was dosed according to the measured electrochemical potential so that both the stationary Fe (II) ion concentration and the H2O2 concentration in the bath was a maximum of 10 mg / l.
  • the phosphate coatings obtained were consistently uniform and closed and had layer weights of 2.0 ⁇ 0.2 g / m2 for steel and 2.5 ⁇ 0.2 g / m2 for electrolytically galvanized steel.

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)
  • Materials For Medical Uses (AREA)
  • Manufacture And Refinement Of Metals (AREA)
EP90202104A 1989-08-22 1990-08-02 Verfahren zur Erzeugung von Phosphatüberzügen auf Metallen Expired - Lifetime EP0414296B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90202104T ATE91159T1 (de) 1989-08-22 1990-08-02 Verfahren zur erzeugung von phosphatueberzuegen auf metallen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3927614A DE3927614A1 (de) 1989-08-22 1989-08-22 Verfahren zur erzeugung von phosphatueberzuegen auf metallen
DE3927614 1989-08-22

Publications (2)

Publication Number Publication Date
EP0414296A1 EP0414296A1 (de) 1991-02-27
EP0414296B1 true EP0414296B1 (de) 1993-06-30

Family

ID=6387566

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90202104A Expired - Lifetime EP0414296B1 (de) 1989-08-22 1990-08-02 Verfahren zur Erzeugung von Phosphatüberzügen auf Metallen

Country Status (11)

Country Link
EP (1) EP0414296B1 (es)
JP (1) JP2992619B2 (es)
AT (1) ATE91159T1 (es)
BR (1) BR9004117A (es)
CA (1) CA2022728C (es)
DD (1) DD299662A5 (es)
DE (2) DE3927614A1 (es)
ES (1) ES2042199T3 (es)
PL (1) PL286572A1 (es)
PT (1) PT95053B (es)
ZA (1) ZA906673B (es)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3219453B2 (ja) * 1992-03-17 2001-10-15 日本パーカライジング株式会社 耐黒変性に優れた亜鉛系めっき鋼板の製造方法
DE4243214A1 (de) * 1992-12-19 1994-06-23 Metallgesellschaft Ag Verfahren zur Erzeugung von Phosphatüberzügen
JPH0790614A (ja) * 1993-09-22 1995-04-04 Elna Co Ltd アルミニウムまたはアルミニウム合金類およびこれらの化成処理方法
AU699822B2 (en) * 1995-03-07 1998-12-17 Henkel Corporation Composition and process for forming an underpaint coating on metals
US5888315A (en) * 1995-03-07 1999-03-30 Henkel Corporation Composition and process for forming an underpaint coating on metals
DE19523919A1 (de) * 1995-06-30 1997-01-02 Metallgesellschaft Ag Verfahren zur Ergänzung von Phosphatierungslösung
DE19544614A1 (de) * 1995-11-30 1997-06-05 Metallgesellschaft Ag Verfahren zur Phospatierung von Metalloberflächen
US5797987A (en) * 1995-12-14 1998-08-25 Ppg Industries, Inc. Zinc phosphate conversion coating compositions and process
DE19808755A1 (de) 1998-03-02 1999-09-09 Henkel Kgaa Schichtgewichtsteuerung bei Bandphosphatierung
WO1999048819A1 (de) * 1998-03-25 1999-09-30 Henkel Kommanditgesellschaft Auf Aktien Abwasseraufbereitung bei der phosphatierung
DE10118552A1 (de) * 2001-04-14 2002-10-17 Henkel Kgaa Bestimmung der Beschleunigerkonzentration in Phosphatierbäder

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1796218B1 (de) * 1968-09-23 1971-10-07 Metallgesellschaft Ag Verfahren zur phosphatierung von metallen
GB1585057A (en) * 1976-06-28 1981-02-25 Ici Ltd Sensing concentration of coating solution
JPS5811513B2 (ja) * 1979-02-13 1983-03-03 日本ペイント株式会社 金属表面の保護方法
JPS6043491A (ja) * 1983-08-19 1985-03-08 Nippon Denso Co Ltd 鉄鋼表面に燐酸塩化成被膜を形成する方法
JPS63270478A (ja) * 1986-12-09 1988-11-08 Nippon Denso Co Ltd リン酸塩化成処理方法
DE3712339A1 (de) * 1987-04-11 1988-10-20 Metallgesellschaft Ag Verfahren zur phosphatierung vor der elektrotauchlackierung

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
W. Rausch "Fortschritte auf dem Gebiet der chemischen Oberflächenbehandlung von Metallen" Interfinish 68, Tagungsberichtsband, Hannover 5.-9. Mai 1968, 162-167. *
W. Rausch et al. "Die Phosphertierung von Metallen", 1974 Eugen Leuze Verlag, Saulgau/Württ, Deutschland *

Also Published As

Publication number Publication date
EP0414296A1 (de) 1991-02-27
ZA906673B (en) 1992-04-29
PT95053B (pt) 1997-04-30
JP2992619B2 (ja) 1999-12-20
ES2042199T3 (es) 1993-12-01
JPH0387374A (ja) 1991-04-12
DE3927614A1 (de) 1991-02-28
CA2022728C (en) 2000-02-01
ATE91159T1 (de) 1993-07-15
PL286572A1 (en) 1992-02-10
PT95053A (pt) 1991-04-18
DE59001884D1 (de) 1993-08-05
DD299662A5 (de) 1992-04-30
CA2022728A1 (en) 1991-02-23
BR9004117A (pt) 1991-09-03

Similar Documents

Publication Publication Date Title
EP0459541B1 (de) Verfahren zur Phosphatierung von Metalloberflächen
DE69633735T2 (de) Zinkphosphat konversionsüberzugszusammensetzung und verfahren
EP0414301B1 (de) Verfahren zur Erzeugung von Phosphatüberzügen auf Metalloberflächen
EP0287133B1 (de) Verfahren zur Phosphatierung vor der Elektrotauchlackierung
EP0478648B1 (de) Verfahren zur herstellung von mangan- und magnesiumhaltigen zinkphosphatüberzügen
EP0370535B1 (de) Verfahren zum Aufbringen von Phosphatüberzügen
EP0414296B1 (de) Verfahren zur Erzeugung von Phosphatüberzügen auf Metallen
EP0069950B1 (de) Verfahren zum Aufbringen von Phosphatüberzügen auf Metalloberflächen
WO1996017977A1 (de) Verfahren zum aufbringen von phosphatüberzügen auf metalloberflächen
EP0359296B1 (de) Phosphatierverfahren
EP0578670B1 (de) Verfahren zum phosphatieren von metalloberflächen
EP0361375A1 (de) Verfahren zum Aufbringen von Phosphatüberzügen
EP0134895B1 (de) Verfahren und Mittel zum beschleunigten und schichtverfeinernden Aufbringen von Phosphatüberzügen auf Metalloberflächen
EP0155547B1 (de) Verfahren zur Zink-Calcium-Phosphatierung von Metalloberflächen bei niedriger Behandlungstemperatur
EP0486576B1 (de) Verfahren zur herstellung von manganhaltigen zinkphosphatschichten auf verzinktem stahl
DE4326388A1 (de) Verfahren zur phosphatierenden Behandlung von einseitig verzinktem Stahlband
DE1285831B (de) Phosphatierungsloesung
DE4228470A1 (de) Verfahren zur Phospatierung von einseitig verzinktem Stahlband
EP1060290B1 (de) Wässrige lösung und verfahren zur phosphatierung metallischer oberflächen
EP0264811B1 (de) Verfahren zum Erzeugen von Phosphatüberzügen
WO1994008074A1 (de) Verfahren zum phosphatieren von verzinkten stahloberflächen
EP0866888B1 (de) Verfahren zur phosphatierung von metalloberflächen
DE19500927A1 (de) Lithiumhaltige Zinkphosphatierlösung
DE3637944A1 (de) Chemischer umwandler-film auf der basis von zinkphosphat und verfahren zu dessen erzeugung

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE DE ES FR GB IT NL SE

17P Request for examination filed

Effective date: 19910803

17Q First examination report despatched

Effective date: 19911014

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE DE ES FR GB IT NL SE

REF Corresponds to:

Ref document number: 91159

Country of ref document: AT

Date of ref document: 19930715

Kind code of ref document: T

REF Corresponds to:

Ref document number: 59001884

Country of ref document: DE

Date of ref document: 19930805

ET Fr: translation filed
ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19931001

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2042199

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
EAL Se: european patent in force in sweden

Ref document number: 90202104.7

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

NLS Nl: assignments of ep-patents

Owner name: CHEMETALL GMBH

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20070830

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20070816

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20070823

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20070815

Year of fee payment: 18

Ref country code: IT

Payment date: 20070824

Year of fee payment: 18

Ref country code: BE

Payment date: 20070905

Year of fee payment: 18

Ref country code: NL

Payment date: 20070814

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20070812

Year of fee payment: 18

EUG Se: european patent has lapsed
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20080802

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080802

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20090301

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090301

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20090430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080802

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080901

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20080804

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080802

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080804

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20091029

Year of fee payment: 20

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080803

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20100802