EP0433118A1 - Verfahren zur chemischen Konversion von Metallgegenständen, verwendetes Bad dafür und Konzentrat zur Herstellung des Bades - Google Patents

Verfahren zur chemischen Konversion von Metallgegenständen, verwendetes Bad dafür und Konzentrat zur Herstellung des Bades Download PDF

Info

Publication number
EP0433118A1
EP0433118A1 EP90403233A EP90403233A EP0433118A1 EP 0433118 A1 EP0433118 A1 EP 0433118A1 EP 90403233 A EP90403233 A EP 90403233A EP 90403233 A EP90403233 A EP 90403233A EP 0433118 A1 EP0433118 A1 EP 0433118A1
Authority
EP
European Patent Office
Prior art keywords
bath
ions
ion
zinc
bath 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.)
Granted
Application number
EP90403233A
Other languages
English (en)
French (fr)
Other versions
EP0433118B1 (de
Inventor
Joseph Schapira
Patrick Droniou
Patrice Adrien Jules Pelletier
Man Tik Ho
Didier Raimond Charles Pernes
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
Original Assignee
Compagnie Francaise de Produits Industriels 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 filed Critical Compagnie Francaise de Produits Industriels SA
Publication of EP0433118A1 publication Critical patent/EP0433118A1/de
Application granted granted Critical
Publication of EP0433118B1 publication Critical patent/EP0433118B1/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
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations 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
    • C23C22/05—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
    • C23C22/17—Orthophosphates containing zinc cations containing also organic acids
    • 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
    • C23C22/46—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 oxalates
    • C23C22/47—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 oxalates containing also phosphates

Definitions

  • the subject of the invention is a process for the chemical conversion of metallic substrates, in particular based on iron or zinc-plated steel, with a view to increasing their resistance to corrosion, their ability to deformation or simultaneously both.
  • the known crystalline phosphating treatments generally use acid baths which contain at least the following constituents: - orthophosphoric acid H3PO4 - a primary phosphate ion H2PO4 ⁇ one or more metals chosen from zinc or iron, manganese, nickel, copper, cobalt, calcium, - At least one accelerator consisting of an oxidizing agent such as chlorate, nitrate, nitrite or sodium metanitrobenzene sulfonate ions.
  • oxidizing agent such as chlorate, nitrate, nitrite or sodium metanitrobenzene sulfonate ions.
  • These treatments can be carried out on the substrates to be treated by spraying or by immersion.
  • the substrates thus treated can be used as such or else receive a subsequent application of lubricant, protective oil or paint.
  • the nature and composition of the layer of insoluble phosphates obtained essentially depend on: - the nature of the substrate, - the composition of the phosphating bath, - the method of application of the product (sprinkling or immersion), - pre-treatment stages.
  • the layer weight can be increased by adding an organic polyacid in an accelerated chlorate phosphating bath and practically free of ferrous ions.
  • This patent in fact relates to phosphating treatments for metals to be cold deformed; however, the phosphating treatments in question lead to coatings whose layer weight is between 16.1 and 32.2 g / m2 and which it is known that they provide only a low resistance to salt spray when tested as is.
  • the object of the invention is, above all, to remedy this drawback and to provide a chemical conversion bath which, while providing performance equivalent to that of the process described in patent FR-A-2,531,457, can be regenerated by continued.
  • the chemical conversion process according to the invention is characterized in that it comprises the implementation, at the time of the phosphating step proper, of a zinc conversion bath containing phosphate ions. and nitrate as well as ferrous or ferric ions and from about 21 to about 100 g / l of at least one organic chelating agent.
  • the chelating agent is chosen from the group comprising: - polycarboxylic acids, including citric acid, oxalic acid, malic acid, glutamic acid, tartaric acid, aspartic acid, malonic acid and their salts, citric acid being preferred , and - polyhydroxycarboxylic acids, including gluconic acid, glucoheptonic acid, mucic acid and their salts, gluconic acid being preferred.
  • the salts of the above polycarboxylic and polyhydroxycarboxylic acids are chosen from those of the alkali, alkaline earth, ammonium, iron, zinc, manganese, molybdenum, cobalt and nickel metals.
  • the zinc ion present in an amount of 0.5 to 25 g / l, can be introduced in any suitable way, and in particular in the form of its salts with nitric, phosphoric, carbonic, gluconic, citric acids. , or in the form of its oxide. It can be combined with all the metals commonly used in a phosphating bath such as, for example, manganese, nickel, cobalt, calcium, magnesium.
  • the iron ions present in a proportion of 0.1 to 15 g / l, can be introduced either by dissolving iron in the solid state, such as for example iron wool, iron powder, massive parts or scrap of steel parts, either thanks to iron salts with sulfuric, hydrochloric, hydrofluoric, phosphoric or nitric acids; it can be the ferrous ion, the ferric ion or a mixture of the two.
  • the phosphate ions on the one hand and the nitrate ions on the other hand are each present in the bath in a proportion of up to 40 g / l.
  • the bath according to the invention can also contain hydrofluoric, fluosilicic or fluoboric acids or more of them to regulate the balance between the pickling of the support by the acid solution and the growth of the crystalline layer.
  • the bath according to the invention is prepared by dilution from a concentrate characterized in that it contains - up to 500 g / l of organic chelating agent, in particular of citrate or gluconate ion - up to 200 g / l of phosphate ions - up to 125 g / l of zinc ions - up to 200 g / l of nitrate ion.
  • organic chelating agent in particular of citrate or gluconate ion - up to 200 g / l of phosphate ions - up to 125 g / l of zinc ions - up to 200 g / l of nitrate ion.
  • the coatings produced by implementing the process according to the invention provide, in the sense of the test according to standard ASTM B-117, a resistance to salt spray comparable to that obtained according to patent 2,531,457 while allowing continuous regeneration.
  • the substrates treated by implementing the process according to the invention can be stored or used without further protection, but it is also possible to paint these substrates in order to further increase their resistance to corrosion; they can possibly be deformed cold after a possible operation of applying a lubricant.
  • a preferred conversion bath contains: - from 5 to 40 g / l of phosphate ions - from 21 to 100 g / l of citric and / or gluconic ion - from 2 to 40 g / l of nitrate ion - from 0.5 to 25 g / l of zinc ion - from 0.1 to 15 g / l of iron.
  • it contains from 0.02 to 3 g / l of nickel, cobalt or copper.
  • a particularly preferred bath contains: - from 5 to 20 g / l of phosphate ions - from 21 to 60 g / l of citric ion - from 2 to 40 g / l of nitrate ion - from 2 to 10 g / l of zinc ion - from 0.1 to 15 g / l of iron.
  • Another particularly preferred bath contains: - from 5 to 20 g / l of phosphate ions - from 30 to 80 g / l of gluconic ion - from 2 to 40 g / l of nitrate ion - from 2 to 10 g / l of zinc ion - from 0.1 to 15 g / l of iron.
  • the chemical conversion bath according to the invention is implemented by spraying onto the metal substrate to be treated or by immersion of the substrate in the bath, immersion being preferred.
  • the chemical conversion process according to the invention comprises a set of treatment steps, namely: - one or more degreasing steps, - one or more rinsing steps, - optionally, one or more stages of activation or pickling, - a rinsing step, the chemical conversion stage proper by using the bath according to the invention, - a rinsing step, - a drying step.
  • the process is simplified by the elimination of the chromic passivation and protection steps, subsequent to the chemical conversion of phosphating and necessary in the methods of the prior art.
  • the temperature of the bath according to the invention is between around 40 and 100 ° C, and more particularly between 70 and 99 ° C.
  • a conversion bath is constituted according to the prior art containing, in addition to water, the following ions: Zn++: 6 g / l NO3 ⁇ : 10 g / l Ni++: 0.2 g / l Total PO4: 16.7 g / l Total Fe: 1 g / l
  • the plates thus prepared are subjected to 5% salt spray test (according to ASTM B-117).
  • a conversion bath is prepared in accordance with the invention by adding 30 g / l of citric acid to the bath according to example 1.
  • the free acidity of the new bath is brought to 18/19 points.
  • Similar cold-rolled steel plates are treated in the same way as in Example 1 and a 10% rusting is obtained locally after 150 hours of exposure.
  • Citric acid content of the bath (g / l) Salt spray test Beginning of rust Rust at 50% 1 0 immediate less than 1 hour 2 10 5 a.m. 8 a.m. 3 30 sailing after 100 h some rust spots after 150 h
  • Trittening of parts is carried out in case hardened steel HRC 55 (with 0.55% carbon at heart) and in mild steel XC 10 (with 0.1% carbon).
  • composition A Composition A
  • the treatment sequence is the same as that described in Example 1, with the exception of step 3, the nitric pickling being replaced by an aqueous phosphoric pickling carried out in an aqueous solution containing 7.75% v / v d '75% phosphoric acid, for 2 minutes at a temperature of 60 ° C.
  • the baths used at the time of the conversion stage proper are constituted as follows: .
  • Bath 1 - 800 ml of water - 100 ml of composition A - 100 ml of composition C .
  • Bath 2 - 800 ml of water - 100 ml of composition B - 100 ml of composition C.
  • An aqueous bath is prepared containing (by weight / volume): - 25 g / l citric acid - 10 g / l of N03 ion - 16.7 g / l of PO4 ion - 1 g / l of Fe++ ion - 6 g / l of Zn++ ion - 1 g / l of Mn++ ion.
  • the bath is heated to 95 ° C. and the free acidity is brought to a value of 20 points with sodium hydroxide.
  • Cold-rolled steel sheets of the ZES type are treated in a sequence identical to that described in Example 1 (the conversion step using the above-mentioned bath), with the exception of steps 3 and 4 which are omitted .
  • the sheets are tested in a salt spray test (according to ASTM B-117) and, after an exposure of 400 h, no development of rust is observed.
  • the conversion bath mentioned in step 7 has the following composition: - 51 g / l of gluconate ion - 3.6 g / l of zinc ion - 8.2 g / l of phosphate ions - 16.9 g / l of nitrate ion - 0.5 g / l of iron ions. Its pH is 2.7.

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)
  • Manufacture And Refinement Of Metals (AREA)
  • Chemically Coating (AREA)
  • Catalysts (AREA)
EP90403233A 1989-11-16 1990-11-15 Verfahren zur chemischen Konversion von Metallgegenständen, verwendetes Bad dafür und Konzentrat zur Herstellung des Bades Expired - Lifetime EP0433118B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8915042A FR2654440B1 (fr) 1989-11-16 1989-11-16 Procede de conversion chimique de substrats metalliques, bain mis en óoeuvre dans ce procede et concentre pour la preparation du bain.
FR8915042 1989-11-16

Publications (2)

Publication Number Publication Date
EP0433118A1 true EP0433118A1 (de) 1991-06-19
EP0433118B1 EP0433118B1 (de) 1996-01-10

Family

ID=9387459

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90403233A Expired - Lifetime EP0433118B1 (de) 1989-11-16 1990-11-15 Verfahren zur chemischen Konversion von Metallgegenständen, verwendetes Bad dafür und Konzentrat zur Herstellung des Bades

Country Status (7)

Country Link
EP (1) EP0433118B1 (de)
JP (1) JPH0730454B2 (de)
AT (1) ATE132917T1 (de)
CA (1) CA2030126C (de)
DE (1) DE69024774T2 (de)
ES (1) ES2084680T3 (de)
FR (1) FR2654440B1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6346295B1 (en) * 1997-08-06 2002-02-12 Henkel Kommanditgesellschaft Auf Aktien Alkaline strip passivation
EP1875003A2 (de) * 2005-04-06 2008-01-09 REM Technologies, Inc. Feinstbearbeitung von hochdichten carbiden

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2968127B2 (ja) * 1992-04-24 1999-10-25 日本パーカライジング株式会社 亜鉛または亜鉛系めっき鋼板の酸性置換めっき液
JP2968147B2 (ja) * 1993-04-07 1999-10-25 日本パーカライジング株式会社 亜鉛含有金属めっき鋼板用酸性置換めっき液組成物
JP4845050B2 (ja) * 2007-10-04 2011-12-28 ユケン工業株式会社 安定性を高めた６価クロムフリー表面化成処理用濃縮液組成物
WO2011071171A1 (ja) * 2009-12-07 2011-06-16 新日本製鐵株式会社 端面赤錆耐食性に優れたクロメートフリー型プレコート鋼板
EP2892850B1 (de) * 2012-09-05 2017-11-15 Compass Minerals America Inc. Verfahren und zusammensetzung zur verhütung des zusammenbackens von natriumchlorid und zur verhinderung von übergangsmetallflecken

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE975008C (de) * 1952-08-06 1961-08-03 American Chem Paint Co Verfahren zur Herstellung von Phosphatueberzuegen auf Zink und dessen Legierungen
US3116178A (en) * 1961-05-29 1963-12-31 Lubrizol Corp Phosphating solutions
FR1362202A (fr) * 1962-11-13 1964-05-29 Parker Ste Continentale Procédé perfectionné de formation de revêtements phosphatés sur des surfaces métalliques
FR1585660A (de) * 1967-10-18 1970-01-30
US3767476A (en) * 1971-08-31 1973-10-23 Us Army Method and composition for phosphatizing steel under pressure

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB866377A (en) * 1958-11-28 1961-04-26 Pyrene Co Ltd Improvements relating to the production of phosphate coatings on metals
SU1090761A1 (ru) * 1982-07-19 1984-05-07 Московский Ордена Трудового Красного Знамени Вечерний Металлургический Институт Раствор дл катодного нанесени защитных пленок на титановые сплавы
DE3927613A1 (de) * 1989-08-22 1991-02-28 Metallgesellschaft Ag Verfahren zur erzeugung von phosphatueberzuegen auf metalloberflaechen

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE975008C (de) * 1952-08-06 1961-08-03 American Chem Paint Co Verfahren zur Herstellung von Phosphatueberzuegen auf Zink und dessen Legierungen
US3116178A (en) * 1961-05-29 1963-12-31 Lubrizol Corp Phosphating solutions
FR1362202A (fr) * 1962-11-13 1964-05-29 Parker Ste Continentale Procédé perfectionné de formation de revêtements phosphatés sur des surfaces métalliques
FR1585660A (de) * 1967-10-18 1970-01-30
US3767476A (en) * 1971-08-31 1973-10-23 Us Army Method and composition for phosphatizing steel under pressure

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
METAL FINISHING ABSTRACTS, vol. 26, no. 6, novembre/décembre 1984, page 390, Teddington, Middlesex, GB; & SU-A-1090 761 (F.F. AZHOGIN) 19-07-1982 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6346295B1 (en) * 1997-08-06 2002-02-12 Henkel Kommanditgesellschaft Auf Aktien Alkaline strip passivation
EP1875003A2 (de) * 2005-04-06 2008-01-09 REM Technologies, Inc. Feinstbearbeitung von hochdichten carbiden
EP1875003A4 (de) * 2005-04-06 2011-06-08 Rem Technologies Feinstbearbeitung von hochdichten carbiden

Also Published As

Publication number Publication date
JPH0730454B2 (ja) 1995-04-05
DE69024774T2 (de) 1996-07-04
CA2030126C (en) 1999-05-11
JPH03173778A (ja) 1991-07-29
DE69024774D1 (de) 1996-02-22
ES2084680T3 (es) 1996-05-16
ATE132917T1 (de) 1996-01-15
FR2654440A1 (fr) 1991-05-17
CA2030126A1 (en) 1991-05-17
EP0433118B1 (de) 1996-01-10
FR2654440B1 (fr) 1993-07-30

Similar Documents

Publication Publication Date Title
EP0175606B1 (de) Verfahren zur chemischen Konversionsbehandlung von Zink oder seinen Legierungen, Konzentrat und Lösung zum Ausführen dieses Verfahrens
US5089349A (en) Compositions and method for applying coatings to metallic surfaces
CZ281471B6 (cs) Způsob fosfatování kovových povrchů
FR2512840A1 (fr) 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
DE102005047424A1 (de) Phosphatierlösung mit Wasserstoffperoxid und chelatbildenden Carbonsäuren
EP0433118B1 (de) Verfahren zur chemischen Konversion von Metallgegenständen, verwendetes Bad dafür und Konzentrat zur Herstellung des Bades
JP2000516999A (ja) 金属面を燐酸処理するための水溶液及び方法
EP0102284B1 (de) Lösung und Verfahren zur chemischen Konversion metallischer Oberflächen
US5045130A (en) Solution and process for combined phosphatization
US7156905B2 (en) Composition and method for treating magnesium alloys
GB2074611A (en) Phosphating Compositions
FR2502645A1 (fr) Procede et composition pour le traitement de surfaces metalliques phosphatees
JPS63286585A (ja) チタンまたはその合金の化成処理液ならびに該化成処理液でのチタンまたはその合金の表面処理方法
EP0085626B1 (de) Zusammensetzung und Verfahren zur Behandlung von phosphatierten Metalloberflächen
US9309602B2 (en) Electrolytic iron metallizing of zinc surfaces
US6168674B1 (en) Process of phosphatizing metal surfaces
US5932292A (en) Zinc phosphate conversion coating composition and process
WO2002079539A2 (en) Treatment of zinc and zinc alloy surfaces
EP0187597B1 (de) Zusammensetzung und Verfahren zum Beschichten von Metalloberflächen mit einer Konversionsschicht auf der Basis von Zinkphosphat
BE894432A (fr) Solutions d'enduction aqueuses, acides, de phosphate de zinc, concentrats pour les constituer, solutions d'activation et procedes pour leur mise en oeuvre
JPS6123769A (ja) 化成処理されたアルミニウム含有亜鉛めつき合金鋼板
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
BE704812A (de)
BE544861A (de)
JPH03173794A (ja) 上層鉄系電気めっきのカバリングに優れた２層めっき鋼板の製造方法

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 GB IT NL SE

17P Request for examination filed

Effective date: 19910606

17Q First examination report despatched

Effective date: 19920408

ITF It: translation for a ep patent filed

Owner name: UFFICIO TECNICO ING. A. MANNUCCI

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 GB IT NL SE

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19960110

Ref country code: AT

Effective date: 19960110

REF Corresponds to:

Ref document number: 132917

Country of ref document: AT

Date of ref document: 19960115

Kind code of ref document: T

REF Corresponds to:

Ref document number: 69024774

Country of ref document: DE

Date of ref document: 19960222

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

Effective date: 19960305

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

Ref country code: SE

Effective date: 19960410

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2084680

Country of ref document: ES

Kind code of ref document: T3

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
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
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19970128

Year of fee payment: 7

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

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: DE

Payment date: 19971029

Year of fee payment: 8

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: 19971130

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

Ref country code: GB

Payment date: 19980127

Year of fee payment: 8

BERE Be: lapsed

Owner name: CIE FRANCAISE DE PRODUITS INDUSTRIELS

Effective date: 19971130

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: 19981115

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

Ref country code: ES

Payment date: 19981207

Year of fee payment: 9

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

Effective date: 19981115

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 NON-PAYMENT OF DUE FEES

Effective date: 19990901

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: 19991116

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20001214

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: 20051115