EP0261704B1 - Process for producing phosphate coatings on metal surfaces - Google Patents
Process for producing phosphate coatings on metal surfaces Download PDFInfo
- Publication number
- EP0261704B1 EP0261704B1 EP87201520A EP87201520A EP0261704B1 EP 0261704 B1 EP0261704 B1 EP 0261704B1 EP 87201520 A EP87201520 A EP 87201520A EP 87201520 A EP87201520 A EP 87201520A EP 0261704 B1 EP0261704 B1 EP 0261704B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- process according
- contacted
- phosphating solution
- fluoride
- aqueous 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims description 24
- 229910019142 PO4 Inorganic materials 0.000 title claims description 23
- 239000010452 phosphate Substances 0.000 title claims description 23
- 238000000576 coating method Methods 0.000 title claims description 11
- 229910052751 metal Inorganic materials 0.000 title description 9
- 239000002184 metal Substances 0.000 title description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 18
- 239000011701 zinc Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229910000831 Steel Inorganic materials 0.000 claims description 10
- 239000010959 steel Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 5
- -1 fluoride ions Chemical class 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 150000002828 nitro derivatives Chemical class 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 claims description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 11
- 229910001335 Galvanized steel Inorganic materials 0.000 description 7
- 239000008397 galvanized steel Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- JCYPECIVGRXBMO-FOCLMDBBSA-N methyl yellow Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1 JCYPECIVGRXBMO-FOCLMDBBSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/362—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 producing phosphate coatings on surfaces which are formed from aluminum or its alloys and at least one of the materials steel or galvanized steel, in spraying or spray-dipping by means of phosphating solutions containing zinc, phosphate, fluoride ions and accelerators, and its use as Preparation of the surfaces for electrocoating.
- a normal zinc process is known from FR-A-2159181, in which metal surfaces from the group aluminum, iron, steel and zinc are brought into contact with phosphating solutions which contain zinc, phosphate, nitrate, nitrite and fluoride ions in such solutions
- Quantities and ratios include that the free acid is 0.2 to 5 points and the total acid is at least 4 points.
- the weight ratio of metal to phosphate should be set to at least 1: 1.
- the preferred concentrations are between 0.7 and 6 g / l for zinc, between 1.0 and 20 g / l for phosphate and between 1.5 and 10 g / l for nitrate.
- the object of the invention is to provide a method for producing phosphate coatings on surfaces which are formed from aluminum or its alloys and at least one of the materials steel or galvanized steel, which does not have the aforementioned disadvantages, in particular leads to uniform phosphate coatings and without effort is feasible with regard to the solution components and the procedure.
- the partial surface consisting of aluminum materials to be treated by the method according to the invention comprises the pure metal and its alloys. Pure aluminum, AIMg and AIMgSi kneading materials may be mentioned as examples. A detailed description of the aluminum materials can be found e.g. in the aluminum paperback, 14th edition, aluminum publishing house, Düsseldorf, 1983.
- the other partial area consists of steel and / or galvanized steel.
- steel is understood to mean low-alloy steel, as it is e.g. in the form of sheets for body construction.
- galvanized steel includes e.g. Galvanized and hot-dip galvanized and refers to zinc and zinc alloys, e.g. ZnNi, ZnFe, ZnAI.
- the method according to the invention is used in spraying and splash immersion.
- the spraying time must be at least as long as is necessary for an at least largely closed phosphate layer formation on the aluminum. This usually takes at least 60 seconds.
- the required fluoride concentration corresponds approximately to the proportion of dissociated fluoride (F-) present in the phosphating solution.
- F (el) value 80 to 220 mg / 1 at the usual bath pH values of the low-zinc phosphating baths, about 0.4 to 0.9 g / l NH 4 HF 2 or equivalent amounts of other simple must -Fluoride containing salts are added.
- the bath is preferably supplemented by adding enough simple fluoride-containing salt to the bath until the desired measured value of F (el) is reached. At least part of the fluoride is added as single fluoride.
- the phosphating solutions can also contain complex fluoride, e.g. of boron or silicon, contained in the amounts customary in phosphating technology. Any fluoride released by dissociation, which is also detected by the fluoride-sensitive electrode and is therefore contained in the setpoint to be set.
- complex fluoride e.g. of boron or silicon
- the low value in the brackets applies to low concentrations of P z 0 5 , the higher value for higher concentrations in the phosphating solution.
- the correction element K takes into account the influence of the measured fluoride activity (F (el)) on the optimal free acid content.
- F (el) is used in the dimension (mg / l).
- F (el) is used in the dimension (mg / l).
- 10 ml bath sample are diluted with approx. 100 ml deionized water and titrated with 0.1 N NaOH against the change from dimethyl yellow to a weak yellow color, which corresponds to a pH value of 4.25.
- FS is equal in number to the ml of sodium hydroxide solution used.
- the substances generally used in phosphating technology can be used as accelerators. It is particularly advantageous to bring the surface into contact with an aqueous phosphating solution, the accelerator being chlorate, bromate, nitrate, nitrite, peroxide and / or organic nitro compounds.
- the accelerator being chlorate, bromate, nitrate, nitrite, peroxide and / or organic nitro compounds.
- a particularly suitable organic nitro compound is meta-nitrobenzosulfonate. They are dosed in the usual quantities.
- the phosphating bath temperature is usually chosen between 40 and 60 ° C and the spraying time between 1 and 3 minutes.
- the phosphate layers produced by the process according to the invention have a weight per unit area of approximately 1 to 5 g / m 2 and can be used well in all areas in which phosphate coatings are used.
- a particularly advantageous application is the preparation of the metal surfaces for painting.
- the method can be used with particular advantage as preparation for the electrocoating process.
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)
Description
Die Erfindung betrifft ein Verfahren zum Erzeugen von Phosphatüberzugen auf Oberflächen, die aus Aluminium oder dessen Legierungen sowie mindestens einem der Werkstoffe Stahl oder verzinktem Stahl gebildet werden, im Spritzen oder Spritztauchen mittels Zink-, Phosphat-, Fluoridionen und Beschleuniger enthaltenden Phosphatierungslösungen sowie dessen Anwendung als Vorbereitung der Oberflächen für die Elektrotauchlackierung.The invention relates to a method for producing phosphate coatings on surfaces which are formed from aluminum or its alloys and at least one of the materials steel or galvanized steel, in spraying or spray-dipping by means of phosphating solutions containing zinc, phosphate, fluoride ions and accelerators, and its use as Preparation of the surfaces for electrocoating.
Est ist bekannt, die Spritzphosphatierung von Metalloberflächen, die aus Aluminium und dessen Legierungen sowie Stahl und/oder verzinktem Stahl gebildet sind, Fluorid enthaltende Zinkphosphatlösungen einzusetzen. Diese Arbeitweise hat sich bei den sogenannten Normalzink-Verfahren mit Zinkgehalten in der Phosphatierungslösung von z.B. 2 bis 6 g/I gut bewährt.It is known to use the spray phosphating of metal surfaces, which are formed from aluminum and its alloys as well as steel and / or galvanized steel, with zinc phosphate solutions containing fluoride. This procedure has been used in the so-called normal zinc processes with zinc contents in the phosphating solution of e.g. Well proven 2 to 6 g / l.
Aus der FR-A-2159181 ist ein Normalzink-Verfahren bekannt, bei dem man Metalloberflächen aus der Gruppe Aluminium, Eisen, Stahl und Zink mit Phosphatierungslösungen in Kontakt bringt, die Zink-, Phosphat-, Nitrat-, Nitrit- und Fluoridionen in solchen Mengen und Verhältnissen enthalten, daß die freie Säure 0,2 bis 5 Punkte und die Gesamtsäure mindestens 4 Punkte betragen. Das Gewichtsverhältnis von Metall zu Phosphat soll dabei wenigstens auf 1:1 eingestellt sein. Die bevorzugten Konzentrationen liegen liegen für Zink zwischen 0,7 und 6 g/I, für Phosphat zwischen 1,0 und 20 g/I und für Nitrat zwischen 1,5 und 10 g/i.A normal zinc process is known from FR-A-2159181, in which metal surfaces from the group aluminum, iron, steel and zinc are brought into contact with phosphating solutions which contain zinc, phosphate, nitrate, nitrite and fluoride ions in such solutions Quantities and ratios include that the free acid is 0.2 to 5 points and the total acid is at least 4 points. The weight ratio of metal to phosphate should be set to at least 1: 1. The preferred concentrations are between 0.7 and 6 g / l for zinc, between 1.0 and 20 g / l for phosphate and between 1.5 and 10 g / l for nitrate.
Eine Übertragung dieser Arbeitsweise auf die sogenannte Niedrigzink-Phosphatierung im Spritzen, bei der mit Zinkhalten in der Phosphatierungslösung von unter 1 g/I gearbeitet wird, bereitete erhebliche Schwierigkeiten. Die Gleichmäßigkeit und Deckungsgrad der Phosphatschichten auf dem Aluminium unterliegen erheblichen Schwankungen, so daß eine befriedigende Anwendung dieser Arbeitweise in der Praxis nicht möglich ist.Transferring this procedure to the so-called low-zinc phosphating in spraying, in which zinc contents in the phosphating solution of less than 1 g / l are used, presented considerable difficulties. The uniformity and degree of coverage of the phosphate layers on the aluminum are subject to considerable fluctuations, so that a satisfactory application of this method of operation is not possible in practice.
Aufgabe der Erfindung ist es, ein Verfahren zur Erzeugung von Phosphatüberzügen auf Oberflächen, die aus Aluminium oder dessen Legierungen sowie mindestens einem der Werkstoffe Stahl oder verzinktem Stahl gebildet werden, bereitzustellen, das die vorgenannten Nachteile nicht aufweist, insbesondere zu gleichmäßigen Phosphatüberzügen führt und ohne Aufwand hinsichtlich der Lösungsbestandteile und der Verfahrensführung durchführbar ist.The object of the invention is to provide a method for producing phosphate coatings on surfaces which are formed from aluminum or its alloys and at least one of the materials steel or galvanized steel, which does not have the aforementioned disadvantages, in particular leads to uniform phosphate coatings and without effort is feasible with regard to the solution components and the procedure.
Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man die Oberflächen mit einer wäßrigen Phosphatierungslösung in Berührung bringt, die
- 0,4 bis 0,8 g/I Zn
- 10 bis 20 g/1 P205
- mindestens eine Beschleuniger sowie
- 80 bis 220 mg/I Fluorid ("F(el)", bestimmt durch eine in die Badlösung eingetauchte fluoridintensive Elektrode)
enthält und in der der Gehalt an Freier Säure (FS) auf einen Wert entsprechend
- 0.4 to 0.8 g / l Zn
- 10 to 20 g / 1 P 2 0 5
- at least one accelerator as well
- 80 to 220 mg / l fluoride ("F (el)", determined by a fluoride-intensive electrode immersed in the bath solution)
contains and in which the content of free acid (FS) to a value accordingly
Die nach dem erfindungsgemäßen Verfahren zu behandelnde, aus Aluminium-Werkstoffen bestehende Teilfläche umfaßt das reine Metall und dessen Legierungen. Als Beispiele seien Reinaluminium-, AIMg und AIMgSi-Knetwerkstoffe genannt. Eine ausführliche Darstellung der Aluminiumwerkstoffe findet sich z.B. im Aluminium-Taschenbuch, 14. Auflage, Aluminium-Verlag, Düsseldorf, 1983.The partial surface consisting of aluminum materials to be treated by the method according to the invention comprises the pure metal and its alloys. Pure aluminum, AIMg and AIMgSi kneading materials may be mentioned as examples. A detailed description of the aluminum materials can be found e.g. in the aluminum paperback, 14th edition, aluminum publishing house, Düsseldorf, 1983.
Die weitere Teilfläche besteht aus Stahl und/oder verzinktem Stahl. Unter dem Begriff Stahl wird unbis niedriglegierter Stahl verstanden, wie er z.B. in Form von Blechen für den Karosseriebau Verwendung findet. Der Begriff verzinkter Stahl umfaßt z.B. Verzinkungen auf elektrolytischem und auf dem Schmelztauch-Wege und bezieht sich auf Zink und Zinklegierungen, z.B. ZnNi, ZnFe, ZnAI.The other partial area consists of steel and / or galvanized steel. The term steel is understood to mean low-alloy steel, as it is e.g. in the form of sheets for body construction. The term galvanized steel includes e.g. Galvanized and hot-dip galvanized and refers to zinc and zinc alloys, e.g. ZnNi, ZnFe, ZnAI.
Die Anwendung des erfindungsgemäßen Verfahrens erfolgt im Spritzen und Spritztauchen. Bei der letztgenannten Variante muß die Spritzzeit mindestens so lange sein, wie zu einer mindestens weitgehend geschlossenen Phosphatschichtausbildung auf dem Aluminium erforderlich ist. Überlicherweise sind hierfür mindestens 60 sec notwendig.The method according to the invention is used in spraying and splash immersion. In the latter variant, the spraying time must be at least as long as is necessary for an at least largely closed phosphate layer formation on the aluminum. This usually takes at least 60 seconds.
Die zu behandelnden Metalloberflächen müssen frei sein von störenden Belägen aus Ölen, Schmierstoffen, Oxiden und dergleichen, die eine einwandfreie Schichtbildung beeinträchtigen können. Hierzu werden die Oberflächen in geeigneter Weise gereinigt. Zur Unterstützung der Phosphatschichtbildung wird die Oberfläche vorzugsweise vor der Erzeugung des Phosphatüberzuges mit einem an sich bekannten Aktivierungsmittel, z.B. einer titanphosphathaltigen wäßrigen Suspension, aktiviert. Das Aktivierungsittel kann im Reinigerbad oder als getrennte Verfahrensstufe zum Einsatz kommen.The metal surfaces to be treated must be free from disruptive deposits of oils, lubricants, oxides and the like, which can impair proper layer formation. For this purpose, the surfaces are cleaned in a suitable manner. In order to support the formation of the phosphate layer, the surface is preferably coated before the phosphate coating is produced an activating agent known per se, for example an aqueous suspension containing titanium phosphate. The activating agent can be used in the cleaning bath or as a separate process step.
Die Einhaltung der Konzentrationen an Zink und P205 ist ausschlaggebend für die Erzeugung von qualitativ hochwertigen Phosphatüberzügen. Bei Unterschreitung der Konzentrationen werden die Schichten ungleichmäßig. Insbesondere nimmt ihre Eignung als Vorbereitung für die Lackierung ab. Bei Überschreitung der Grenzwerte vermindert sich ebenfalls die Qualität in Verbindung mit einer Lackierung, während der visuelle Eindruck weiterhin gut bleibt.Compliance with the concentrations of zinc and P 2 0 5 is crucial for the production of high quality phosphate coatings. If the concentrations are undershot, the layers become uneven. In particular, their suitability as preparation for painting decreases. If the limit values are exceeded, the quality in connection with painting is also reduced, while the visual impression remains good.
Die geforderte und mit der fluoridsensitiven Elektrode erfaßte Konzentration an Fluorid entspricht etwa dem in der Phosphatierungslösung vorliegenden Anteil an dissoziiertem Fluorid (F-). Um einen F(el)-Wert von 80 bis 220 mg/1 bei den üblichen Bad-pH-Werten der Niedrigzink-Phosphatierbäder einzustellen, müssen etwa 0,4 bis 0,9 g/I NH4HF2 oder äquivalente Mengen anderer Einfach-Fluorid enthaltender Salze zugegeben werden. Die Badergänzung erfolgt vorzugsweise so, daß man dem Bad so viel Einfach-Fluorid enthaltendes Salz zusetzt, bis der gewünschte Meßwert von F(el) erreicht ist. Mindestens ein Teil des Fluorides wird als Einfach-Fluorid zugesetzt.The required fluoride concentration, measured with the fluoride-sensitive electrode, corresponds approximately to the proportion of dissociated fluoride (F-) present in the phosphating solution. In order to set an F (el) value of 80 to 220 mg / 1 at the usual bath pH values of the low-zinc phosphating baths, about 0.4 to 0.9 g / l NH 4 HF 2 or equivalent amounts of other simple must -Fluoride containing salts are added. The bath is preferably supplemented by adding enough simple fluoride-containing salt to the bath until the desired measured value of F (el) is reached. At least part of the fluoride is added as single fluoride.
Zusätzlich zum Einfach-Fluorid können die Phosphatierungslösungen auch komplexes Fluorid, z.B. von Bor oder Silizium, in den in der Phosphatiertechnik üblichen Mengen enthalten. Durch Dissoziation gegebenenfalls freigesetztes Fluorid worin von der fluoridsensitiven Elektrode ebenfalls erfaßt und ist mithin im einzustellenden Sollwert enthalten.In addition to single fluoride, the phosphating solutions can also contain complex fluoride, e.g. of boron or silicon, contained in the amounts customary in phosphating technology. Any fluoride released by dissociation, which is also detected by the fluoride-sensitive electrode and is therefore contained in the setpoint to be set.
Die Grenzen für den mit der fluoridsensitiven Elektrode erfaßten Fluoridgehalt sind von wesentlicher Bedeutung. Wenn die Grenze für F(el) von 80 mg/I unterschritten wird, reicht der Beizangriff der Phosphatierungslösung nicht aus, um gleichmäßig deckende Phosphatschichten zu erzeugen. Bei Überschreitung der Obergrenze von F(el) = 220 mg/I wird eine ordnungsgemäße Phosphatschichtausbildung durch den parallel ablaufenden zu hohen Beizangriff gestört.The limits for the fluoride content measured with the fluoride-sensitive electrode are of essential importance. If the limit for F (el) falls below 80 mg / I, the pickling attack of the phosphating solution is not sufficient to produce uniformly covering phosphate layers. If the upper limit of F (el) = 220 mg / I is exceeded, proper formation of the phosphate layer is disrupted by the excessive pickling attack which runs in parallel.
Die richtige Einstellung der Freien Säure (FS) in der Phosphatierungslösung ist von wesentlicher Bedeutung fü die Art der Ausbildung des Phosphatüberzuges. Grundsätzlich ist zu sagen, daß in den im erfindungsgemäßen Verfahren zum Einsatz kommenden Phosphatierungslösung die Freie Säure deutlich höher liegt als in den korrespondierenden fluoridfreien Phosphatierungslösung. Versucht man, nach Zugabe von Fluorid, den gewohnten Wert für die Freie Säure vor der Zugabe aufrechtzuerhalten, so findet eine schnelle Abnahme der Zinkkonzentration statt und die Qualität der erzeugten Schichten verschlechtert sich.The correct setting of the free acid (FS) in the phosphating solution is essential for the type of formation of the phosphate coating. Basically, it can be said that in the phosphating solution used in the process according to the invention the free acid is significantly higher than in the corresponding fluoride-free phosphating solution. If one tries to maintain the usual free acid value after the addition of fluoride, the zinc concentration decreases rapidly and the quality of the layers produced deteriorates.
In der Beziehung für den einzustellenden FS-Wert gilt der niedrige Wert in der Klammer für niedrige Konzentrationen an Pz05, der höhere Wert für höhere Konzentrationen in der Phosphatierungslösung. Das Korrekturglied K berücksichtigt den Einfluß der gemessenen Fluoridaktivität (F(el)) auf den optimalen Gehalt an Freier Säure.In the relationship for the FS value to be set, the low value in the brackets applies to low concentrations of P z 0 5 , the higher value for higher concentrations in the phosphating solution. The correction element K takes into account the influence of the measured fluoride activity (F (el)) on the optimal free acid content.
Bei der Ermittlung des Korrekturgliedes Wird F(el) in der Dimension (mg/l) eingesetzt. Zur Bestimmumg der Freien Säure (FS) werden 10 ml Badprobe mit ca. 100 ml vollentsalztem Wasser verdünnt und mit 0,1 n NaOH gegen den Umschlag von Dimethylgelb auf schwache Gelbfärbung, die etwa einem pH-Wert von 4,25 entspricht, titriert. FS ist zahlengleich den verbrauchten ml an Natronlauge.When determining the correction element, F (el) is used in the dimension (mg / l). To determine the free acidity (FS), 10 ml bath sample are diluted with approx. 100 ml deionized water and titrated with 0.1 N NaOH against the change from dimethyl yellow to a weak yellow color, which corresponds to a pH value of 4.25. FS is equal in number to the ml of sodium hydroxide solution used.
Besonders günstige Ergebnisse hinsichtlich der Qualität des erzeugten Phosphatüberzuges werden erhalten, wenn entsprechend eine bevorzugten Ausgestaltung der Erfindung die Metalloberfläche mit einer Phosphatierungslösung in Berührung gebracht wird, in der die Freie Säure (FS) auf einen Wert entsprechend
Als Beschleuniger können die in der Phosphatierungstechnik generell üblichen Substanzen verwendet werden. Von besonderem Vorteil ist es, die Oberfläche mit einer wäßrigen Phosphatierungslösung in Berührung zu bringen, die als Beschleuniger Chlorat, Bromat, Nitrat, Nitrit, Peroxid und/oder organische Nitroverbindungen. Eine besonderes geeignete organische Nitroverbindung ist meta-Nitrobenzosulfonat. Ihre Dosierung erfolgt in den üblichen Mengen.The substances generally used in phosphating technology can be used as accelerators. It is particularly advantageous to bring the surface into contact with an aqueous phosphating solution, the accelerator being chlorate, bromate, nitrate, nitrite, peroxide and / or organic nitro compounds. A particularly suitable organic nitro compound is meta-nitrobenzosulfonate. They are dosed in the usual quantities.
Eine weitere zweckmäßige Ausfuhrungsform der Erfindung sieht vor, die Phosphatüberzüge zu erzeugen, indem man die Oberflächen mit einer wäßrigen Phosphatierungslösung in Berührung bringt, die zusätzlich ein oder mehrere Kationen aus der Gruppe Ni, Mn, Mg, Ca aufweisen. Die Phosphatierungslösungen sollten die vorgenannten Kationen in Mengen von 0,1 bis 1,5 g/I enthalten. Diese Kationen werden zum Teil mit in die Phosphatschicht eingebaut und können unter speziellen Bedingungen zu einer Verbesserung der Schichtqualität führen.Another expedient embodiment of the invention provides for the phosphate coatings to be produced by bringing the surfaces into contact with an aqueous phosphating solution which additionally has one or more cations from the group Ni, Mn, Mg, Ca. The phosphating solutions should contain the aforementioned cations in amounts of 0.1 to 1.5 g / l. Some of these cations are built into the phosphate layer and, under special conditions, can lead to an improvement in the layer quality.
Die Phosphatierungslösungen können noch weitere, in der Phosphatiertechnik bekannte Zusätze zur Modifizierung der Verfahrensweise und der Schichteigenschaften enthalten. Als Beispiele seien genannt: Tenside, Polyhydroxycarbonsäuren, Polyphosphate, Ammonium-, Alkali-, Kupfer-, Kobaltionen und indifferente Anionen, wie Chlorid und Sulfat.The phosphating solutions can also contain further additives known in phosphating technology for modifying the procedure and the layer properties. Examples include: surfactants, polyhydroxycarboxylic acids, polyphosphates, ammonium, alkali, copper, cobalt ions and indifferent anions such as chloride and sulfate.
Die Phosphatierbadtemperatur wird üblicherweise zwischen 40 und 60°C und die Spritzzeit zwischen 1 und 3 min gewählt.The phosphating bath temperature is usually chosen between 40 and 60 ° C and the spraying time between 1 and 3 minutes.
Die mit dem erfindungsgemäßen Verfahren erzeugten Phosphatschichten besitzen ein Flächengewicht von etwa 1 bis 5 g/m2 und sind auf allen Gebieten, auf denen Phosphatüberzüge eingesetzt werden, gut einsetzbar. Ein besonders vorteilhafter Anwendungsfall liegt in der Vorbereitung der Metalloberflächen für die Lackierung. Als Vorbereitung für die Elektrotauchlackierung ist das Verfahren mit besonderem Vorteil anwendbar.The phosphate layers produced by the process according to the invention have a weight per unit area of approximately 1 to 5 g / m 2 and can be used well in all areas in which phosphate coatings are used. A particularly advantageous application is the preparation of the metal surfaces for painting. The method can be used with particular advantage as preparation for the electrocoating process.
Die Erfindung wird anhand der folgenden Beispiele näher und beispielsweise erläutert:The invention is explained in more detail and, for example, using the following examples:
Vier Serien von Verbundblechen mit Oberflächen aus AIMg3 und Stahl, AIMg3 und verzinktem Stahl, AIMgO, 4Sil, 2 und Stahl sowie AIMgO, 4Sii!, 2 und verzinktem Stahl wurden mit einem aktivierenden mildalkalischen Reiniger 2 min bei 50°C spritzentfettet, anschließend mit Wasser gespült und danach 2 min mit folgenden Phosphatierungslösungen im Spritzen phosphatiert:
Nach der Phosphatierung wurde mit Wasser gespült, mit Cr(VI)-haltigem Passivierungsmittel nachgespült, mit vollentsalztem Wasser abgebraust und getrocknet.After the phosphating, rinsing with water, rinsing with Cr (VI) -containing passivating agent, rinsing with demineralized water and drying.
Auf allen vier Blechserien wurden mit sämtlichen Phosphatiervarianten A, B und C gleichmäßig deckende Phosphatischichten erzeugt, die sich gut für eine anschließende Elektrotauchlackierung eigneten.With all phosphating variants A, B and C, uniformly opaque phosphate layers were produced on all four sheet metal series, which were well suited for subsequent electrocoating.
Claims (9)
as determined by a fluoride-sensitive electrode immersed into the bath solution and in which the content of free acid (FA) (in points) has been adjusted to and is maintained at a value corresponding to
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3631759 | 1986-09-18 | ||
DE19863631759 DE3631759A1 (en) | 1986-09-18 | 1986-09-18 | METHOD FOR PRODUCING PHOSPHATE COATINGS ON METAL SURFACES |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0261704A1 EP0261704A1 (en) | 1988-03-30 |
EP0261704B1 true EP0261704B1 (en) | 1991-01-23 |
Family
ID=6309850
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87201520A Expired - Lifetime EP0261704B1 (en) | 1986-09-18 | 1987-08-11 | Process for producing phosphate coatings on metal surfaces |
Country Status (7)
Country | Link |
---|---|
US (1) | US4849031A (en) |
EP (1) | EP0261704B1 (en) |
JP (1) | JP2604387B2 (en) |
CA (1) | CA1308338C (en) |
DE (2) | DE3631759A1 (en) |
ES (1) | ES2020259B3 (en) |
GB (1) | GB2195359B (en) |
Families Citing this family (18)
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 |
DE3918136A1 (en) * | 1989-06-03 | 1990-12-06 | Henkel Kgaa | METHOD FOR PRODUCING MANAGE-CONTAINING PHOSPHATE COATINGS ON METAL SURFACES |
DE3920296A1 (en) * | 1989-06-21 | 1991-01-10 | Henkel Kgaa | METHOD FOR PRODUCING ZINC PHOSPHATE CONTAINING MANGANE AND MAGNESIUM |
DE3927131A1 (en) * | 1989-08-17 | 1991-02-21 | Henkel Kgaa | METHOD FOR THE PRODUCTION OF MANGANIZED ZINC PHOSPHATE LAYERS ON GALVANIZED STEEL |
US5372656A (en) * | 1989-08-17 | 1994-12-13 | Henkel Kommanditgesellschaft Auf Aktien | Process for producing manganese-containing zinc phosphate coatings on galvanized steel |
KR100197145B1 (en) * | 1989-12-19 | 1999-06-15 | 후지이 히로시 | Method for phosphating metal surface with zinc phosphate |
CA2035048A1 (en) * | 1990-01-26 | 1991-07-27 | Thomas W. Cape | Phosphate coating composition and method of applying a zinc-nickel-manganese phosphate coating |
JP2695963B2 (en) * | 1990-03-16 | 1998-01-14 | マツダ株式会社 | Phosphating of metal surfaces |
JP2500010B2 (en) * | 1990-09-21 | 1996-05-29 | 株式会社神戸製鋼所 | Manufacturing method of aluminum alloy surface control plate for automobile panel |
DE4131382A1 (en) * | 1990-09-21 | 1992-03-26 | Kobe Steel Ltd | Surface treated aluminium@ alloy sheet for motor car construction - used in making decorative coloured items, zinc phosphate layer having fine grained structure of uniform thickness |
JP2794013B2 (en) * | 1990-10-24 | 1998-09-03 | 日本パーカライジング株式会社 | Phosphate chemical conversion treatment solution for iron-aluminum metal sheet metal construction |
JPH04341574A (en) * | 1991-05-18 | 1992-11-27 | Nippon Paint Co Ltd | Treatment of zinc phosphate onto metal surface |
DE4238242C2 (en) * | 1992-09-17 | 2003-04-24 | Rieger Franz Metallveredelung | Process for pretreating light metals according to patent DE 4231052 C2 |
JPH07173643A (en) * | 1993-12-21 | 1995-07-11 | Mazda Motor Corp | Method for phosphating metal surface and phosphating solution |
JP3417653B2 (en) * | 1994-05-11 | 2003-06-16 | 日本パーカライジング株式会社 | Pretreatment method for painting aluminum material |
US5728235A (en) * | 1996-02-14 | 1998-03-17 | Henkel Corporation | Moderate temperature manganese phosphate conversion coating composition and process |
DE10261014B4 (en) * | 2002-12-24 | 2005-09-08 | Chemetall Gmbh | Process for coating metal surfaces with an alkali phosphating solution, aqueous concentrate and use of the metal surfaces coated in this way |
DE102010030697A1 (en) * | 2010-06-30 | 2012-01-05 | Henkel Ag & Co. Kgaa | Process for the selective phosphating of a composite metal construction |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3619300A (en) * | 1968-11-13 | 1971-11-09 | Amchem Prod | Phosphate conversion coating of aluminum, zinc or iron |
US3660172A (en) * | 1970-08-19 | 1972-05-02 | Amchem Prod | Prepaint treatment for zinciferous surfaces |
US3681207A (en) * | 1970-12-28 | 1972-08-01 | Hooker Chemical Corp | Metal coating process |
GB1297715A (en) * | 1971-02-02 | 1972-11-29 | ||
GB1542222A (en) * | 1977-01-06 | 1979-03-14 | Pyrene Chemical Services Ltd | Phosphate coating compositions |
JPS5811515B2 (en) * | 1979-05-11 | 1983-03-03 | 日本ペイント株式会社 | Composition for forming a zinc phosphate film on metal surfaces |
US4673444A (en) * | 1981-03-16 | 1987-06-16 | Koichi Saito | Process for phosphating metal surfaces |
DE3118375A1 (en) * | 1981-05-09 | 1982-11-25 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR PHOSPHATING METALS AND ITS APPLICATION FOR PRE-TREATMENT FOR ELECTRO DIP PAINTING |
US4498935A (en) * | 1981-07-13 | 1985-02-12 | Parker Chemical Company | Zinc phosphate conversion coating composition |
DE3413905A1 (en) * | 1984-04-13 | 1985-10-24 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR MONITORING FLUORIDE-CONTAINING BATHS FOR THE SURFACE TREATMENT OF METALS |
US4595424A (en) * | 1985-08-26 | 1986-06-17 | Parker Chemical Company | Method of forming phosphate coating on zinc |
-
1986
- 1986-09-18 DE DE19863631759 patent/DE3631759A1/en not_active Withdrawn
-
1987
- 1987-08-11 DE DE8787201520T patent/DE3767631D1/en not_active Expired - Lifetime
- 1987-08-11 EP EP87201520A patent/EP0261704B1/en not_active Expired - Lifetime
- 1987-08-11 ES ES87201520T patent/ES2020259B3/en not_active Expired - Lifetime
- 1987-08-19 CA CA000544881A patent/CA1308338C/en not_active Expired - Lifetime
- 1987-09-04 US US07/092,951 patent/US4849031A/en not_active Expired - Lifetime
- 1987-09-16 JP JP62229917A patent/JP2604387B2/en not_active Expired - Lifetime
- 1987-09-18 GB GB8722064A patent/GB2195359B/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
GB2195359A (en) | 1988-04-07 |
CA1308338C (en) | 1992-10-06 |
ES2020259B3 (en) | 1991-08-01 |
GB8722064D0 (en) | 1987-10-28 |
DE3767631D1 (en) | 1991-02-28 |
DE3631759A1 (en) | 1988-03-31 |
JP2604387B2 (en) | 1997-04-30 |
US4849031A (en) | 1989-07-18 |
EP0261704A1 (en) | 1988-03-30 |
JPS63157879A (en) | 1988-06-30 |
GB2195359B (en) | 1990-06-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0261704B1 (en) | Process for producing phosphate coatings on metal surfaces | |
DE3879099T2 (en) | METHOD AND COMPOSITION FOR PRODUCING ZINC PHOSPHATE. | |
EP0304108B1 (en) | Metal-phosphating process | |
DE69108087T2 (en) | Phosphating process for metal surfaces for the production of a zinc phosphate coating. | |
DE3834480A1 (en) | METHOD OF APPLYING CONVERSION OVERHEADS | |
DE4013483A1 (en) | METHOD FOR PHOSPHATING METAL SURFACES | |
EP0069950B1 (en) | Process for phosphating metal surfaces | |
EP0056881A1 (en) | Method of phosphating metals | |
DE2155670A1 (en) | PHOSPHATE REPLACEMENT COATING ON ALUMINUM, ZINC OR IRON | |
EP0327153B1 (en) | Process for applying phosphate coatings to metals | |
EP0361375A1 (en) | Phosphate-coating process | |
EP0155547B1 (en) | Process for the zinc-calcium phosphatizing of metal surfaces at a low treating temperature | |
EP0656957B1 (en) | Process for phosphatizing steel zinc-coated on one side only | |
DE3408577A1 (en) | METHOD FOR PHOSPHATING METALS | |
EP0111223B1 (en) | Process for phosphatizing metallic surfaces, and solutions for use therein | |
DE2932822C2 (en) | Phosphate coating solution and method for creating phosphate coatings on surfaces of machined or tinned steel | |
EP0486576B1 (en) | Process for producing manganese-containing zinc phosphate coatings on galvanized steel | |
EP0264811B1 (en) | Process for producing phosphate coatings | |
DE19735314A1 (en) | Simultaneously pretreating different metal surfaces | |
EP1290242B1 (en) | Method for treating or pre-treating components comprising aluminium surfaces | |
EP0264151B1 (en) | Process for obtaining phosphate coatings | |
WO1994008074A1 (en) | Process for phosphating galvanised steel surfaces | |
EP0258922A1 (en) | Process for producing phosphate coatings and their use | |
DE1248427B (en) | Method and solution for applying coatings to aluminum and its alloys | |
DE1088311B (en) | Process for the production of firmly adhering protective coatings on surfaces made of titanium, zirconium or their alloys |
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): BE DE ES FR IT NL SE |
|
17P | Request for examination filed |
Effective date: 19880803 |
|
17Q | First examination report despatched |
Effective date: 19891120 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE ES FR IT NL SE |
|
REF | Corresponds to: |
Ref document number: 3767631 Country of ref document: DE Date of ref document: 19910228 |
|
ET | Fr: translation filed | ||
ITF | It: translation for a ep patent filed | ||
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: 87201520.1 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20010724 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20010801 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20010802 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20010803 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20010810 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20011016 Year of fee payment: 15 |
|
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: 20020812 Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020812 |
|
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: 20020831 |
|
BERE | Be: lapsed |
Owner name: *METALLGESELLSCHAFT A.G. Effective date: 20020831 |
|
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: 20030301 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030301 |
|
EUG | Se: european patent has lapsed | ||
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: 20030430 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20030301 |
|
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: 20030912 |
|
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: 20050811 |