EP0298827B1 - Lösung und Verfahren zur gemischten Phosphatisierung - Google Patents

Lösung und Verfahren zur gemischten Phosphatisierung Download PDF

Info

Publication number
EP0298827B1
EP0298827B1 EP88401614A EP88401614A EP0298827B1 EP 0298827 B1 EP0298827 B1 EP 0298827B1 EP 88401614 A EP88401614 A EP 88401614A EP 88401614 A EP88401614 A EP 88401614A EP 0298827 B1 EP0298827 B1 EP 0298827B1
Authority
EP
European Patent Office
Prior art keywords
ion
acid
zinc
fact
solution according
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
EP88401614A
Other languages
English (en)
French (fr)
Other versions
EP0298827A1 (de
Inventor
Serge Gosset
Jean-Claude Malras
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
Roquette Freres SA
Original Assignee
Compagnie Francaise de Produits Industriels SA
Roquette Freres 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 Compagnie Francaise de Produits Industriels SA, Roquette Freres SA filed Critical Compagnie Francaise de Produits Industriels SA
Priority to AT88401614T priority Critical patent/ATE92979T1/de
Publication of EP0298827A1 publication Critical patent/EP0298827A1/de
Application granted granted Critical
Publication of EP0298827B1 publication Critical patent/EP0298827B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C23C22/23—Condensed phosphates

Definitions

  • the subject of the invention is an acidic aqueous solution for mixed phosphating, this expression designating any phosphating capable of leading on a metal substrate to the concomitant deposition of at least two metal ions, at least one of which is generally chosen from the group including zinc, manganese and iron.
  • the metallic substrates suitable for being treated by implementing the above-mentioned solution and method are in particular those based on iron and alloys of this metal.
  • the nickel ion will be introduced into the acid solution of mixed phosphating, in addition to or completely replacing manganese.
  • the invention also relates to a certain number of other arrangements implemented in isolation or in combination and which will be discussed.
  • the upper limits of the quantities of polyphosphate, of organic chelating agent, of Zn ions, of Mn ions and of Ni ions brought in the form of salts, possibly those of the chelating agent, entering into the composition of the solution according to the invention are imposed, in theory, only by the solubility limits; in practice, care will be taken to choose an amount of polyphosphate compatible with a good yield from the process which is the subject of the invention, while preventing the sludge formed from being too large.
  • the above solution is also characterized in that it comprises at least one of the following combinations of metal ions from the group comprising zinc, manganese and nickel: 0.5 g / l n Zn ion ⁇ 10 g / l 2 g / l M ion Mn ⁇ 6 g / l and 0.5 g / l n Zn ion ⁇ 10 g / l 0.5 g / l Ni Ni ion ⁇ 6 g / l.
  • the polyphosphate is chosen from the group consisting of sodium trimeta-, tetrameta- and hexametaphosphate, sodium hexametaphosphate or HMPP being preferred.
  • the solution according to the invention comprises a mineral acid chosen from the group consisting of sulfuric, hydrochloric and nitric acids, nitric acid being preferred, in an amount sufficient to bring the pH to a initial value less than 2, preferably between 0.5 and 1.7.
  • nitric acid is preferred is linked to its oxidizing nature.
  • the zinc ion and the manganese ion are introduced in the form of salts in particular chosen from the group consisting of oxides, sulfates, nitrates, carbonates and phosphates.
  • the zinc ion and / or the manganese ion are introduced in combined form with the chelating agent, preferably in the form of citrate, tartrate, glucoheptonate and especially in the form of gluconate.
  • the phosphating solution in accordance with the invention comprises from 8 g / l to 350 g / l, preferably from 14 to 300 g / l and, more preferably still, from 30 to 230 g / l of a composition consisting of polyphosphate, of the chelating agent and zinc and manganese ions in the form of their salts which may be those of the chelating agent.
  • the mixture constituted by the zinc ion and the manganese ion is used in an amount between 2.5 and 30 g / l and the amount of hexametaphosphate used is 2 to 30 g / l.
  • the objects treated by implementing the method according to the invention can be stored in the open air without any prior protective treatment, without the appearance of degradation of the layer phenomena.
  • the pH of the phosphating solution is changed from the initial value between 0.5 and 1.7 to a value between 2.3 and 2.9 by adding a sufficient quantity of iron filings, between 0.3 and 5 g / l of solution and more preferably between 1 and 4 g / l.
  • the phosphating solution After placement and curing, the phosphating solution is ready to use.
  • Iron plays a role of catalyst (or reducer) of conversion. In fact, in the absence of iron or in the presence of too small an amount of iron, less than 0.3 g / l, it can be seen that no phosphate deposit forms on the metal substrate. It is only when, due to the attack of the substrate by the solution, the concentration of the latter in iron has reached the minimum value necessary, that the conversion phenomenon takes place.
  • the nickel content in the bath may be between 0.5 and 6 g / l and preferably between 0.5 and 3 g / l.
  • nitric acid is particularly preferred as an accelerating agent, and makes it possible to considerably improve the speed of formation of the deposit.
  • the preferred concentration of nitric acid is between 0.4 g / l and 60 g / l, more preferably between 2 and 50 g / l and, more preferably still, between 5 and 30 g / l.
  • the solution according to the invention leads to conversion layers having particularly advantageous characteristics.
  • the analysis of deposits taken from the surface of the treated objects revealed that, surprisingly, the composition of these deposits was characterized by a manganese content significantly higher than that obtained with the phosphating solutions used in the prior art, this content may exceed 10%.
  • the surface condition makes it possible to reduce the frictional forces, to increase the forming rates and to reduce the wear of the material.
  • the thickness of the layers obtained is sufficient to ensure that the mechanical stresses are absorbed.
  • the deposits obtained thanks to the solution according to the invention have remarkable resistance to corrosion and constitute an excellent bonding base. for most organic coatings.
  • the bath temperature is maintained at 97 ° C.
  • the plates are rinsed with demineralized water and dried.
  • the crystalline deposit formed is collected by scraping.
  • the duration of the treatment is 15 minutes, the temperature of the solution being adjusted to 97 ° C.
  • this deposit has the disadvantage of a small, irregular thickness, comprising gaps in certain places on the treated plate; the irregularity of the deposit is incompatible with good protection against corrosion and effective lubrication of the metal part, in the event that it must undergo a cold deformation operation.
  • the addition of zinc and manganese in the form of gluconate makes it possible to substantially increase the manganese content in the deposit.
  • the gluconic ion by its intervention on the chemical reaction equilibria favors the precipitation of manganese phosphate at the level of the steel plate and influences the size of the crystals: the crystalline deposit is finer and more homogeneous than that obtained with the solution conversion example 1.
  • the thickness of the coating is very irregular and all of the plates treated reveal phosphating defects.
  • This solution leads to the production of a deposit rich in manganese particularly suitable for use as a coating before cold deformation.
  • this fine, dense and regular crystalline deposit ensures good protection against corrosion.
  • This solution leads to a deposit, the manganese content of which is particularly high; this deposit is perfectly suited to cold deformation and also has a crystalline, fine, regular appearance, thus offering good protection against corrosion.
  • This solution leads to the formation of an exceptionally rich manganese deposit. It is stable and regular in operation, and enables a fine, dense crystalline deposit of suitable thickness to be obtained, ensuring good protection against corrosion.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Saccharide Compounds (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Catalysts (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Claims (18)

  1. Saure Phosphatierungslösung auf Polyphosphatbasis, die sich zur Abscheidung gemischter Phosphate auf der Basis von Zink und wenigstens eines anderen, unter Mangan und Nickel ausgewählten Metalles auf einem Metallsubstrat eignet, welche Lösung
    - wenigstens etwa 2 g/l eines Polyphosphats der Formel (XPO₃)n, worin n ≧ 3 bedeutet und X ein Alkalimetall, Erdalkalimetall oder Ammonium darstellt,
    - wenigstens etwa 0,5 g/l eines Chelatbildners,
    - wenigstens 0,3 g/l Eisen und
    - wenigstens eine der beiden nachstehenden Kombinationen von Ionen eines Metalles, ausgewählt aus der Zink, Mangan und Nickel umfassenden Gruppe:
    . Zinkion in einem Anteil von wenigstens 0,5 g/l und Manganion in einem Anteil von wenigstens 2 g/l, und
    . Zinkion in einem Anteil von wenigstens 0,5 g/l und Nickelion in einem Anteil von wenigstens 0,5 g/l
    enthält.
  2. Saure Lösung für gemischte Phosphatierung mit Zink nach Anspruch 1, dadurch gekennzeichnet, daß sie wenigstens eine der nachstehenden Kombinationen von Metallionen der Zink, Mangan und Nickel umfassenden Gruppe enthält:
       0,5 g/l ≦ Zn-Ion ≦ 10 g/l
       2 g/l ≦ Mn-Ion ≦ 6 g/l
    und
       0,5 g/l ≦ Zn-Ion ≦ 10 g/l
       0,5 g/l ≦ Ni-Ion ≦ 6 g/l.
  3. Saure Lösung für gemischte Phosphatierung nach Anspurch 1, dadurch gekennzeichnet, daß sie die folgende Kombination von Metallionen enthält:
       0,5 g/l ≦ Zn-Ion ≦ 6 g/l
       2 g/l ≦ Mn-Ion ≦ 4 g/l.
  4. Saure Lösung für gemischte Phosphatierung nach Anspruch 1, dadurch gekennzeichnet, daß sie die folgende Kombination von Metallionen enthält:
       0,5 g/l ≦ Zn-Ion ≦ 6 g/l
       0,5 g/l ≦ Ni-Ion ≦ 3 g/l
  5. Saure Lösung für gemischte Phosphatierung nach Anspruch 1, dadurch gekennzeichnet,daß sie die folgende Kombination von Metallionen enthält:
       0,5 g/l ≦ Zn-Ion ≦ 6 g/l
       2 g/l ≦ Mn-Ion ≦ 4 g/l
       0,5 g/l ≦ Ni-Ion ≦ 3 g/l.
  6. Saure Lösung für gemischte Phosphatierung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das Polyphosphat aus der aus den Trimeta-, Tetrameta- und Hexametaphosphaten von Natrium bestehenden Gruppe ausgewählt ist.
  7. Saure Lösung für gemischte Phosphatierung nach Anspruch 6, dadurch gekennzeichnet, daß das Polyphosphat das Natriumhexametaphosphat ist.
  8. Saure Lösung für gemischte Phosphatierung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß der Chelatbildner aus der aus Ethylendiamintetraessigsäure (EDTA), Nitrilotriessigsäure (NTA), Diethylentriaminpentaessigsäure (DTPA), den Polycarbonsäuren und den Polyhydroxycarbonsäuren bestehenden Gruppe ausgewählt ist.
  9. Saure Lösung für gemischte Phosphatierung nach Anspurch 8, dadurch gekennzeichnet, daß die Polycarbonsäuren unter Zitronensäure, Oxalsäure, Äpfelsäure, Glutaminsäure, Weinsäure, Asparaginsäure, Malonsäure und ihren Salzen ausgewählt sind.
  10. Saure Lösung für gemischte Phosphatierung nach Anspruch 8, dadurch gekennzeichnet, daß die Polyhydroxycarbonsäuren unter der Glukonsäure und Glucoheptonsäure sowie ihren Salzen ausgewählt sind.
  11. Saure Lösung für gemischte Phosphatierung nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß sie eine aus der aus der Schwefelsäure, Chlorwasserstoffsäure und Salpetersäure bestehenden Gruppe ausgewählte Mineralsäure in einer Menge enthält, die ausreicht, um den pH auf einen Anfangswert von unter 2 zu bringen.
  12. Saure Lösung für gemischte Phosphatierung nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß sie eine aus der aus Schwefelsäure, Chlorwasserstoffsäure und Salpetersäure bestehenden Gruppe ausgewählte Mineralsäure in einer Menge enthält, die ausreicht, um den pH-Wert auf einen Wert zwischen 0,5 und 1,7 zu bringen.
  13. Saure Lösung für gemischte Phosphatierung nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß sie
    - Natriumhexametaphosphat,
    - Gluconsäure in Form eines ihrer Salze oder ihres inneren Lactons,
    - Zinkion,
    - Manganion,
    - Salpetersäure
    enthält.
  14. Saure Lösung für gemischte Phosphatierung nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, daß das Zinkion und das Manganion in Form von Salzen, ausgewählt aus der aus den Oxiden, Sulfaten, Nitraten, Carbonaten und Phosphaten gebildeten Gruppe, eingesetzt werden.
  15. Saure Lösung für gemischte Phosphatierung nach einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, daß das Zinkion und/oder Manganion in Form des Zitrats, des Tartrats, des Glucoheptonats und des Gluconats eingebracht werden.
  16. Saure Lösung für gemischte Phosphatierung nach einem der Ansprüche 1 bis 15, dadurch gekennzeichnet, daß sie
    - Natriumhexametaphosphat,
    - Zinkgluconat,
    - in Form des Salzes oder in Form des Gluconats zugeführtes Manganion und
    - Salpetersäure
    enthält.
  17. Saure Lösung für gemischte Phosphatierung nach einem der Ansprüche 10 bis 16, dadurch gekennzeichnet, daß die Konzentration an Salpetersäure von 0,4 g/l bis 60 g/l beträgt.
  18. Verfahren zum gemischten Phosphatieren, umfassend aufeinanderfolgend eine Entfettungsstufe, eine Spülstufe, eine saure Reaktivierungsstufe, eine fakultative Spülstufe, insbesondere dann, wenn das Reaktivierungsbad aus einer Salpetersäurelösung besteht, die eigentliche Phosphatierungsstufe, eine Spülstufe, anschließend eine fakultative Trocknungsstufe, in Abhängigkeit von den in einer späteren Phase vorgesehenen Behandlungen,
    dadurch gekennzeichnet, daß für die eigentliche Phosphatierungsstufe die Lösung für gemischte Phosphatierung mit Zink nach einem der Ansprüche 1 bis 16 eingesetzt wird, wobei diese Lösung durch Tauchen oder Sprühen aufgebracht wird, wobei
    - einerseits die Temperatur der Lösung zwischen etwa 40°C und 100°C gehalten wird,
    - anderseits der Kontakt zwischen der Phosphatierungslösung und dem Metallsubstat während einer in der Praxis von 2 Sekunden bis 30 Minuten, vorzugsweise von 5 bis 20 Minuten variierenden Zeit gehalten wird.
EP88401614A 1987-06-25 1988-06-24 Lösung und Verfahren zur gemischten Phosphatisierung Expired - Lifetime EP0298827B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88401614T ATE92979T1 (de) 1987-06-25 1988-06-24 Loesung und verfahren zur gemischten phosphatisierung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8708989A FR2618164B1 (fr) 1987-06-25 1987-06-25 Solution et procede de phosphatation mixte.
FR8708989 1987-06-25

Publications (2)

Publication Number Publication Date
EP0298827A1 EP0298827A1 (de) 1989-01-11
EP0298827B1 true EP0298827B1 (de) 1993-08-11

Family

ID=9352522

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88401614A Expired - Lifetime EP0298827B1 (de) 1987-06-25 1988-06-24 Lösung und Verfahren zur gemischten Phosphatisierung

Country Status (7)

Country Link
US (1) US5045130A (de)
EP (1) EP0298827B1 (de)
JP (1) JPS6436772A (de)
AT (1) ATE92979T1 (de)
DE (1) DE3883100T2 (de)
ES (1) ES2042783T3 (de)
FR (1) FR2618164B1 (de)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5595611A (en) * 1996-02-14 1997-01-21 Henkel Corporation Moderate temperature manganese phosphate conversion coating composition and process
US5728235A (en) * 1996-02-14 1998-03-17 Henkel Corporation Moderate temperature manganese phosphate conversion coating composition and process
BR9713452A (pt) * 1996-11-27 2000-03-28 Henkel Corp Composição lìquida aquosa para tratamento de superfìcies matálicas férricas, e, processo de formação sobre um substrato metálico ferrìfero de uma composição que atua diretamente para reduzir a tensão mecânica sobre o substrato.
US6162508A (en) * 1998-11-02 2000-12-19 Nortel Networks Limited Molybdenum phosphate based corrosion resistant conversion coatings
US8092617B2 (en) * 2006-02-14 2012-01-10 Henkel Ag & Co. Kgaa Composition and processes of a dry-in-place trivalent chromium corrosion-resistant coating for use on metal surfaces
WO2007134152A1 (en) * 2006-05-10 2007-11-22 Henkel Ag & Co. Kgaa. Improved trivalent chromium-containing composition for use in corrosion resistant coating on metal surfaces
US10156016B2 (en) 2013-03-15 2018-12-18 Henkel Ag & Co. Kgaa Trivalent chromium-containing composition for aluminum and aluminum alloys

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE973195C (de) * 1951-01-18 1959-12-17 Metallgesellschaft Ag Verfahren zum UEberziehen von Metalloberflaechen mit einer Phosphatschicht
US2826517A (en) * 1954-01-11 1958-03-11 Kelite Products Inc Process and composition for phosphatizing steel
US2955967A (en) * 1958-09-25 1960-10-11 Amchem Prod Method and solution for phosphatizing metals
US3338755A (en) * 1963-09-03 1967-08-29 Hooker Chemical Corp Production of phosphate coatings on metals
DE2160784C3 (de) * 1971-12-08 1979-04-12 Joachim Dipl.-Chem. Dr. 4330 Muelheim Marx Verfahren zur Herstellung von Schutzschichten auf Gegenständen aus Metallen durch Aufbringen von PoIyphosphaten
DE2247165A1 (de) * 1972-09-26 1974-03-28 Kluthe Kg Chem Werke Mischphosphatierungsmittel
US4231812A (en) * 1978-03-14 1980-11-04 Centre De Recherches Metallurgiques-Centrum Voor Research In De Metallurgie Surface treatment of metal strip
IT1120362B (it) * 1979-05-29 1986-03-19 Fosfa Col S A S Di A Dal Pane Soluzione per la fosfatazione a freddo di superfici metalliche
DE3023479A1 (de) * 1980-06-24 1982-01-14 Metallgesellschaft Ag, 6000 Frankfurt Phosphatierverfahren
FR2492413A1 (fr) * 1980-10-22 1982-04-23 Chaffoteaux Et Maury Procede et compositions pour la protection des surfaces de zinc au moyen de depots de pyrophosphates de zinc
FR2531457A1 (fr) * 1982-08-03 1984-02-10 Roquette Freres Solution et procede pour la conversion chimique de substrats metalliques
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
JPH0788585B2 (ja) * 1986-11-21 1995-09-27 日本ペイント株式会社 リン酸塩皮膜処理剤
JPH0672311B2 (ja) * 1987-04-08 1994-09-14 トヨタ自動車株式会社 リン酸亜鉛化成処理方法

Also Published As

Publication number Publication date
DE3883100D1 (de) 1993-09-16
ES2042783T3 (es) 1993-12-16
DE3883100T2 (de) 1994-03-10
US5045130A (en) 1991-09-03
FR2618164A1 (fr) 1989-01-20
FR2618164B1 (fr) 1994-02-04
JPS6436772A (en) 1989-02-07
ATE92979T1 (de) 1993-08-15
EP0298827A1 (de) 1989-01-11

Similar Documents

Publication Publication Date Title
EP2812462B1 (de) Verfahren zur oberflächenbehandlung von teilen aus aluminium oder magnesiumlegierung
FR2475565A1 (fr) Peinture anticorrosion a pigments metalliques
EP0524037B1 (de) Behandlungsverfahren für Werkstoffe aus Eisen zur gleichzeitigen Verbesserung ihrer Korrosionsfestigkeit und ihrer Verschleisseigenschaften
EP0298827B1 (de) Lösung und Verfahren zur gemischten Phosphatisierung
WO1987005337A1 (fr) Composition de flux sans fluorures pour la galvanisation a chaud dans des bains de zinc aluminies
EP0497663B1 (de) Verfahren zum Herstellen von korrosions-beständigen Eisenmetallwerkstücken mit Beibehaltung ihrer Reibungseigenschaften durch Nitrieren und anschliessendem Oxidieren
CA2442502C (fr) Procede de traitement par carboxylatation de surfaces metalliques
EP0102284B1 (de) Lösung und Verfahren zur chemischen Konversion metallischer Oberflächen
EP1963545B1 (de) Behandlungsverfahren der metallischen oberflächen durch carboxilierung, benutzung dieses verfahrens für den zeitweiligen korrosionsschutz und verfahren zur herstellung eines geformten carboxylierten bleches
EP0433118B1 (de) Verfahren zur chemischen Konversion von Metallgegenständen, verwendetes Bad dafür und Konzentrat zur Herstellung des Bades
FR2502645A1 (fr) Procede et composition pour le traitement de surfaces metalliques phosphatees
EP0638661B1 (de) Verfahren zur Verbesserung des Verschleissfestigkeit und Korrosionswiderstand von Eisenmetalgegenständen
FR2551466A1 (fr) Procede de preparation de toles d'acier revetues galvaniquement d'alliage zn-ni ameliorees
EP0085626B1 (de) Zusammensetzung und Verfahren zur Behandlung von phosphatierten Metalloberflächen
EP0285535A1 (de) Verfahren zur chemischen Oberflächenbehandlung von Aluminiumgegenständen vor der Phosphatierung
FR3140382A1 (fr) Procede de colmatage post-anodisation de l’aluminium et des alliages d’aluminium sans utiliser de chrome
FR3073529A1 (fr) Procede de traitement de surface d’une piece revetue d’un revetement de cadmium et composition pour la mise en œuvre d’un tel procede
BE507619A (de)
BE509571A (de)
BE704812A (de)
BE456766A (de)
BE564026A (de)
BE636654A (de)
BE545027A (de)

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: 19890710

17Q First examination report despatched

Effective date: 19910208

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: 92979

Country of ref document: AT

Date of ref document: 19930815

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3883100

Country of ref document: DE

Date of ref document: 19930916

ITF It: translation for a ep patent filed

Owner name: SOCIETA' ITALIANA BREVETTI S.P.A.

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2042783

Country of ref document: ES

Kind code of ref document: T3

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

Effective date: 19931118

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

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

Ref country code: GB

Payment date: 19940621

Year of fee payment: 7

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

Ref country code: SE

Payment date: 19940622

Year of fee payment: 7

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

Ref country code: BE

Payment date: 19940628

Year of fee payment: 7

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

Ref country code: AT

Payment date: 19940630

Year of fee payment: 7

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19950101

EAL Se: european patent in force in sweden

Ref document number: 88401614.8

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19950624

Ref country code: AT

Effective date: 19950624

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

Ref country code: SE

Effective date: 19950625

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

Ref country code: DE

Payment date: 19950629

Year of fee payment: 8

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

Ref country code: BE

Effective date: 19950630

BERE Be: lapsed

Owner name: CIE FRANCAISE DE PRODUITS INDUSTRIELS

Effective date: 19950630

Owner name: ROQUETTE FRERES

Effective date: 19950630

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19950624

EUG Se: european patent has lapsed

Ref document number: 88401614.8

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

Ref country code: DE

Effective date: 19970301

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

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

Ref country code: FR

Payment date: 19990621

Year of fee payment: 12

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

Ref country code: ES

Payment date: 19990622

Year of fee payment: 12

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

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 20000626

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

Ref country code: FR

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

Effective date: 20010228

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20020204

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;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050624