EP0269138A1 - Process for producing phosphate coatings on metals - Google Patents
Process for producing phosphate coatings on metals Download PDFInfo
- Publication number
- EP0269138A1 EP0269138A1 EP87201890A EP87201890A EP0269138A1 EP 0269138 A1 EP0269138 A1 EP 0269138A1 EP 87201890 A EP87201890 A EP 87201890A EP 87201890 A EP87201890 A EP 87201890A EP 0269138 A1 EP0269138 A1 EP 0269138A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metals
- iron
- phosphating solution
- contact
- acid
- 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
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
- C23C22/34—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
- C23C22/364—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 manganese cations
Definitions
- the invention relates to a process for the production of phosphate coatings on at least partially iron or steel surfaces containing metals by means of aqueous phosphating solutions containing zinc, manganese, PO4, nitrate and - in the incorporated state - iron (II) ions, and its application on the preparation of metals for the subsequent cold forming.
- phosphate metals in particular iron and steel
- manganese and iron (II) -containing zinc phosphate solutions at temperatures from 50 to 98 ° C.
- the phosphate coatings produced here are suitable for all areas of application known in phosphating technology, e.g. Rust protection, primer for paints, electrical insulation as well as facilitating sliding processes and non-cutting cold forming (DE-OS 30 23 479, EP-PS 42 63l).
- the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the metals are brought into contact with a phosphating solution at a temperature in the range from 30 to 50 ° C.
- Zinc in amounts of 5 to 25 g / l
- Manganese in quantities from 1 to 10 g / l Iron (II) in quantities of 0.1 to 13 g / l
- Phosphate in amounts of 5 to 40 g / l (calculated as P2O5)
- Nitrate in amounts of 5 to 50 g / l as well as additionally 0.5 to 5 g / l fluoroborate (calculated as BF4)
- 0.05 to 3 g / l tartaric acid and / or citric acid contains, in which the weight ratios Zn: P2O5ank (0.5 to 3): l and Mn: Zn to (0.04 to 0.5): l and the ratio of free acid to total acid to (
- the method according to the invention is used in particular to treat iron and steel with alloy additives up to a maximum of about 5%.
- alloy additives up to a maximum of about 5%.
- other metals e.g. from zinc and zinc alloys, be it in the form of solid workpieces made of them or workpieces coated with them, successfully treated.
- the iron (II) removal can e.g. in a separate ventilation tank with a downstream filter.
- Bath components are consumed during the phosphating process, ie through coating formation, sludge formation and mechanical discharge of phosphating solution. These must over the phosphating solution the individual components or via supplementary concentrates which contain several or all of the individual components are fed back.
- the supplement is particularly advantageous if the phosphating solution is supplemented with regard to the components zinc, manganese, phosphate and nitrate ions by adding at least one concentrate in which the weight ratios of Zn: P2O5 to (0.3 to 0.8) : l, from Mn: Zn to (0.0l to 0.05): l and from NO3: P2O5 to (0.2 to l): l are set.
- the other components should be in the weight ratio Ca: Zn as (0.005 to 0.1): 1, Ni: Zn as (0.005 to 0.05): 1, Cu: Zn as (0.00l to 0 , 03): l and the components (tartaric acid and / or citric acid): P2O2 as (0.05 to 0.3): l and BF4: P2O5 as (0.008 to 0.04): l are added.
- the metals can come into contact with the phosphating solution by dipping, flooding or spraying.
- the application is usually done in diving, with treatment times of e.g. 5 to 15 minutes should be observed.
- the phosphate layers produced by the processes according to the invention have a layer weight of approximately 3 to 15 g / m 2.
- the pretreatment of the metals before the actual phosphating is done in a conventional manner.
- degreasing can be carried out using aqueous, alkaline cleaners which advantageously contain surfactant.
- scale or rust can be removed by pickling treatment, e.g. with sulfuric acid or hydrochloric acid.
- the workpieces can be formed prior to phosphating to form fine crystalline phosphate coatings in a manner known per se, e.g. with an activation bath containing titanium phosphate.
- after the phosphating treatment is usually with Rinsed water, treated if necessary and dried if necessary.
- aftertreatment can be carried out, for example, with chromic acid and / or corrosion protection emulsions.
- an aftertreatment can be carried out, for example, with a soap bath.
- the basis weight of the phosphate coating was 8 to 10 g / m2.
- the phosphate coating was uniformly opaque and finely crystalline despite the absence of an activating pre-rinse with titanium phosphate.
- the bath was supplemented with a supplement concentrate containing the total acid points 11.4% by weight Zn 0.26 wt% Mn 0.13% by weight approx 0.1% by weight of Ni 0.025 wt% Cu 22.9% by weight of P2O5 l0.3 wt .-% NO3 2.6% by weight tartaric acid 0.38 wt% BF4 0.26% by weight urea
- the consumption of supplemental concentrate was about 20 g / m2 metal surface and was therefore very low.
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)
Abstract
Bei einem Verfahren zur Erzeugung von Phosphatüberzügen auf mindestens teilweise Eisen oder Stahloberflächen aufweisenden Metallen bringt man die Metalle mit einer Phosphatierungslösung einer Temperatur im Bereich von 30 bis 50°C in Kontakt, die Zink in Mengen von 5 bis 25 g/l Mangan in Mengen von l bis l0 g/l Eisen(II) in Mengen von 0,l bis l3 g/l Phosphat in Mengen von 5 bis 40 g/l ( ber. als P2O5) Nitrat in Mengen von 5 bis 50 g/l sowie zusätzlich 0,5 bis 5 g/l Fluoroborat (ber. als BF4) 0,05 bis 3 g/l Weinsäure und/oder Zitronensäure enthält, in der die Gewichtsverhältnisse Zn : P2O5 auf (0,5 bis 3) : l und Mn : Zn auf (0,04 bis 0,5) : l und das Verhältnis von Freier Säure zu Gesamtsäure auf (0,04 bis 0,2) : l eingestellt sind. Vorzugsweise setzt man der Phosphatierungslösung Nickel, Kupfer und/oder Kalzium zu und stellt den Gehalt an Fe(II) auf maximal l0 g/l ein. Das Verfahren ist insbesondere für die Vorbereitung von Metallen für die Kaltumformung geeignet.In a process for producing phosphate coatings on at least partially iron or steel surfaces, the metals are brought into contact with a phosphating solution at a temperature in the range from 30 to 50 ° C., the zinc in amounts of 5 to 25 g / l of manganese in amounts of 1 to 10 g / l iron (II) in quantities of 0.1 to 13 g / l phosphate in quantities of 5 to 40 g / l (calc. as P2O5) nitrate in quantities of 5 to 50 g / l and additionally 0 , 5 to 5 g / l fluoroborate (calculated as BF4) contains 0.05 to 3 g / l tartaric acid and / or citric acid, in which the weight ratios Zn: P2O5 to (0.5 to 3): l and Mn: Zn are set to (0.04 to 0.5): 1 and the ratio of free acid to total acid is set to (0.04 to 0.2): 1. Nickel, copper and / or calcium are preferably added to the phosphating solution and the Fe (II) content is adjusted to a maximum of 10 g / l. The process is particularly suitable for the preparation of metals for cold forming.
Description
Die Erfindung betrifft ein Verfahren zur Erzeugung von Phosphatüberzügen auf mindestens teilweise Eisen oder Stahloberflächen aufweisenden Metallen mittels wäßriger Phosphatierungslösungen, die Zink-, Mangan-, PO₄-, Nitrat- und - in eingearbeitetem Zustand - Eisen(II)-ionen enthalten, sowie dessen Anwendung auf die Vorbereitung von Metallen für die anschließende Kaltumformung.The invention relates to a process for the production of phosphate coatings on at least partially iron or steel surfaces containing metals by means of aqueous phosphating solutions containing zinc, manganese, PO₄, nitrate and - in the incorporated state - iron (II) ions, and its application on the preparation of metals for the subsequent cold forming.
Es ist bekannt, Metalle, insbesondere Eisen und Stahl, mit Mangan und Eisen(II)-haltigen Zinkphosphatlösungen bei Temperaturen von 50 bis 98°C zu phosphatieren. Die hierbei erzeugten Phosphatüberzüge eignen sich für alle in der Phosphatiertechnik bekannten Anwendungsgebiete, z.B. Rostschutz, Haftgrund für Lacke, elektrische Isolation sowie Erleichterung von Gleitvorgängen und der spanlosen Kaltumformung (DE-OS 30 23 479, EP-PS 42 63l).It is known to phosphate metals, in particular iron and steel, with manganese and iron (II) -containing zinc phosphate solutions at temperatures from 50 to 98 ° C. The phosphate coatings produced here are suitable for all areas of application known in phosphating technology, e.g. Rust protection, primer for paints, electrical insulation as well as facilitating sliding processes and non-cutting cold forming (DE-OS 30 23 479, EP-PS 42 63l).
Bei der Anwendung der bekannten Verfahren im Bereich niedriger Temperaturen, z.B. zwischen 30 und 50°C, treten jedoch häufig Schwierigkeiten auf, die sich u.a. in der Ausbildung unvollständig deckender und mit zunehmendem Eisen(II)-Gehalt in der Phosphatierungslösung gröber werdenden Phosphatüberzügen äußern. Durch Anwendung einer aktivierenden Vorspülung, z.B. auf Basis von Titanphosphat, lassen sich zwar gewisse Verbesserungen erzielen, ohne jedoch zu voll befriedigenden Ergebnissen zu gelangen. Andererseits besteht wegen der damit verbundenen Energieersparnis ein dringender Bedarf an Niedrigtemperatur-Verfahren. Ferner bringen die auf der Eisen(II)-Seite betriebenen Verfahren im Vergleich zu den Verfahren, die mit praktisch eisen(II)-freien Phosphatierungslösungen arbeiten, den Vorteil, daß sie wesentlich weniger Badschlamm liefern und günstige Verbrauchswerte aufweisen.When using the known processes in the range of low temperatures, for example between 30 and 50 ° C, difficulties often arise which are manifested, among other things, in the formation of incompletely opaque phosphate coatings which become coarser with increasing iron (II) content in the phosphating solution. By using an activating pre-rinse, for example based on titanium phosphate, certain improvements can be achieved without achieving completely satisfactory results. On the other hand, there is an urgent need because of the associated energy savings Low temperature process. Furthermore, the processes operated on the iron (II) side have the advantage, compared to the processes which work with practically iron (II) -free phosphating solutions, that they deliver significantly less bath sludge and have favorable consumption values.
Aufgabe der Erfindung ist es, ein Verfahren zur Erzeugung von Phosphatüberzügen auf mindestens teilweise Eisen- oder Stahloberflächen aufweisenden Metallen bereitzustellen, das im Niedrigtemperaturbereich und auf der Eisen(II)-Seite arbeitet, gleichmäßig deckende Phosphatüberzüge entstehen läßt und keinen unüblichen verfahrensmäßigen Aufwand erfordert.The object of the invention is to provide a process for the production of phosphate coatings on at least partially iron or steel surfaces containing metals, which works in the low temperature range and on the iron (II) side, allows uniformly covering phosphate coatings and does not require any unusual procedural effort.
Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man die Metalle mit einer Phosphatierungslösung einer Temperatur im Bereich von 30 bis 50°C in Kontakt bringt, die
Zink in Mengen von 5 bis 25 g/l
Mangan in Mengen vonl bis l0 g/l
Eisen(II) in Mengen von 0,l bis l3 g/l
Phosphat in Mengen von 5 bis 40 g/l
(ber. als P₂O₅)
Nitrat in Mengen von 5 bis 50 g/l
sowie zusätzlich
0,5 bis 5 g/l Fluoroborat (ber. als BF₄)
0,05 bis 3 g/l Weinsäure und/oder Zitronensäure
enthält, in der die Gewichtsverhältnisse Zn : P₂O₅auf (0,5 bis 3) : l und Mn : Zn auf (0,04 bis 0,5) : l und das Verhältnis von Freier Säure zu Gesamtsäure auf (0,04 bis 0,2) : l eingestellt sind.The object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the metals are brought into contact with a phosphating solution at a temperature in the range from 30 to 50 ° C.
Zinc in amounts of 5 to 25 g / l
Manganese in quantities from 1 to 10 g / l
Iron (II) in quantities of 0.1 to 13 g / l
Phosphate in amounts of 5 to 40 g / l
(calculated as P₂O₅)
Nitrate in amounts of 5 to 50 g / l
as well as additionally
0.5 to 5 g / l fluoroborate (calculated as BF₄)
0.05 to 3 g / l tartaric acid and / or citric acid
contains, in which the weight ratios Zn: P₂O₅auf (0.5 to 3): l and Mn: Zn to (0.04 to 0.5): l and the ratio of free acid to total acid to (0.04 to 0, 2): l are set.
Das erfindungsgemäße Verfahren dient insbesondere der Behandlung von Eisen und Stahl mit Legierungszusätzen bis maximal etwa 5 %. Außerdem lassen sich zusammen mit Eisen und Stahl auch andere Metalle, z.B. aus Zink und Zinklegierungen, sei es in Form hieraus bestehender massiver Werkstücke oder hiermit beschichteter Werkstücke, mit Erfolg behandeln.The method according to the invention is used in particular to treat iron and steel with alloy additives up to a maximum of about 5%. In addition, together with iron and steel, other metals, e.g. from zinc and zinc alloys, be it in the form of solid workpieces made of them or workpieces coated with them, successfully treated.
Die einzelnen Komponenten der Phosphatierungslösung, z.B. Zink, Mangan, Phosphat etc., werden meist, wie in der Phosphatiertechnik üblich, gemeinsam als saures Phosphatierkonzentrat vorgelöst und in dieser Form in die Phosphatierungslösung eingebracht. Die Bemessung der einzelnen Bestandteile erfolgt in der Weise, daß die geforderten Konzentrationsbereiche in der Phosphatierungslösung resultieren. Um das notwendige Verhältnis von Freier Säure zu Gesamtsäure einzustellen, müssen gegebenenfalls weitere Kationen aus der Alkali- und/oder Ammoniumgruppe mitverwendet werden.The individual components of the phosphating solution, e.g. Zinc, manganese, phosphate etc. are usually, as is customary in phosphating technology, pre-dissolved together as an acidic phosphating concentrate and introduced into the phosphating solution in this form. The individual components are dimensioned in such a way that the required concentration ranges result in the phosphating solution. In order to set the necessary ratio of free acid to total acid, additional cations from the alkali and / or ammonium group may have to be used.
Bevorzugte Ausführungsformen der Erfindung sehen vor, die Metalle mit einer Phosphatierungslösung in Kontakt zu bringen, die zusätzlich 0,05 bis 2 g/l Ni und/oder 0,00l bis 0,l g/l Cu und/oder 0,5 bis 2 g/l Ca enthält. Durch den Nickelgehalt wird die Schichtbildung, insbesondere auf schwerer angreifbaren Materialien und auf Zink, unterstützt. Durch die Zugabe von Kupferionen findet eine Beschleunigung des Phosphatierprozesses statt. Mit Hilfe des Zusatzes von Kalziumionen wird der Phosphatüberzug modifizert und der - allerdings geringe - Badschlamm so konditioniert, daß er im Phosphatierungsbad noch weniger stört und sich leichter aus dem System entfernen läßt.Preferred embodiments of the invention provide for the metals to be brought into contact with a phosphating solution which additionally contains 0.05 to 2 g / l of Ni and / or 0.001 to 0.1 g / l of Cu and / or 0.5 to 2 g / l Ca contains. The nickel content supports the layer formation, especially on materials that are more difficult to attack and on zinc. By adding copper ions one finds Acceleration of the phosphating process instead. With the addition of calcium ions, the phosphate coating is modified and the bath sludge - albeit low - is conditioned in such a way that it is less disruptive in the phosphating bath and is easier to remove from the system.
Die im erfindungsgemäßen Verfahren einzusetzenden Phosphatierungslösungen enthalten nicht notwendigerweise vom Start an Eisen(II)-ionen. Diese Komponente reichert sich vielmehr zwangsläufig bei der Behandlung von Eisen und Stahl im Bad an. Vorzugsweise werden die Phosphatierungslösungen derart eingesetzt, daß die Konzentration von Eisen(II)-ionen l0 g/l nicht übersteigt.The phosphating solutions to be used in the process according to the invention do not necessarily contain iron (II) ions from the start. Rather, this component inevitably accumulates in the treatment of iron and steel in the bathroom. The phosphating solutions are preferably used in such a way that the concentration of iron (II) ions does not exceed 10 g / l.
Um einen Anstieg der Konzentration darüber hinaus zu vermeiden, ist es zweckmäßig, einen Teil des durch Beizangriff in Lösung gegangenen Eisen(II)-ions zu Eisen(III)-ionen zu oxidieren und damit in Form von schwer löslichem Eisen(III)-phosphat-Schlamm auszufällen. Bevorzugte Ausgestaltungen der Erfindung sehen vor, den überschüssigen Eisen(II)-gehalt durch Kontakt mit sauerstoffhaltigem Gas oder mit Hilfe von Chlorat in die dreiwertige Form zu überführen und als Eisen(III)-phosphat-Schlamm auszufällen. In der ersten Ausführungsform kann die Eisen(II)-Entfernung z.B. in einem separaten Belüftungsbehälter mit nachgeschaltetem Filter erfolgen.In order to avoid an increase in the concentration, it is advisable to oxidize part of the iron (II) ion dissolved in the pickling attack to iron (III) ions and thus in the form of poorly soluble iron (III) phosphate - precipitate sludge. Preferred refinements of the invention provide for the excess iron (II) content to be converted into the trivalent form by contact with oxygen-containing gas or with the aid of chlorate and to be precipitated as iron (III) phosphate sludge. In the first embodiment, the iron (II) removal can e.g. in a separate ventilation tank with a downstream filter.
Während des Phosphatierverfahrens, d.h. durch Überzugsausbildung, Schlammbildung und mechanischen Austrag von Phosphatierungslösung, werden Badkomponenten verbraucht. Diese müssen der Phosphatierungslösung über die Einzelkomponenten oder über Ergänzungskonzentrate, die mehrere oder alle Einzelkomponenten enthalten, wieder zugeführt werden. Besonders vorteilhaft gestaltet sich die Ergänzung, wenn man die Phosphatierungslösung hinsichtlich der Komponenten Zink-, Mangan-, Phosphat- und Nitrationen durch Zugabe von mindestens einem Konzentrat ergänzt, bei dem die Gewichtsverhältnisse von Zn : P₂O₅ auf (0,3 bis 0,8) : l, von Mn : Zn auf (0,0l bis 0,05) : l und von NO₃ : P₂O₅ auf (0,2 bis l) : l eingestellt sind. Sofern in der Phosphatierungslösung enthalten, sollten die weiteren Komponenten im Gewichtsverhältnis Ca : Zn wie (0,005 bis 0,l) : l, Ni : Zn wie (0,005 bis 0,05) : l, Cu : Zn wie (0,00l bis 0,03) : l sowie die Bestandteile (Weinsäure und/oder Zitronensäure) : P₂O₅ wie (0,05 bis 0,3) : l und BF₄ : P₂O₅ wie (0,008 bis 0,04) : l ergänzt werden.Bath components are consumed during the phosphating process, ie through coating formation, sludge formation and mechanical discharge of phosphating solution. These must over the phosphating solution the individual components or via supplementary concentrates which contain several or all of the individual components are fed back. The supplement is particularly advantageous if the phosphating solution is supplemented with regard to the components zinc, manganese, phosphate and nitrate ions by adding at least one concentrate in which the weight ratios of Zn: P₂O₅ to (0.3 to 0.8) : l, from Mn: Zn to (0.0l to 0.05): l and from NO₃: P₂O₅ to (0.2 to l): l are set. If contained in the phosphating solution, the other components should be in the weight ratio Ca: Zn as (0.005 to 0.1): 1, Ni: Zn as (0.005 to 0.05): 1, Cu: Zn as (0.00l to 0 , 03): l and the components (tartaric acid and / or citric acid): P₂O₂ as (0.05 to 0.3): l and BF₄: P₂O₅ as (0.008 to 0.04): l are added.
Zur Einstellung des anspruchsgemäß geforderten Verhältnisses an Freier Säure zu Gesamtsäure eignen sich vorzugsweise Mangankarbonat, Zinkoxid und/oder Zinkkarbonat, die der Phosphatierungslösung in Pulverform oder als wäßrige Aufschlemmung zugegeben werden. Zur Ermittlung der Freien bzw. der Gesamtsäure werden je l0 ml Badprobe mit n/l0 NaOH gegen den ersten bzw. zweiten Umschlag der Phosphorsäure titriert, wobei als Indikator z.B. der Farbumschlag von Dimethylgelb (Freie Säure) bzw. von Phenolphthalein (Gesamtsäure) dient. Die verbrauchten ml an n/l0 NaOH entsprechen der Freien Säure bzw. der Gesamtsäure in Punkten.Manganese carbonate, zinc oxide and / or zinc carbonate, which are added to the phosphating solution in powder form or as an aqueous slurry, are preferably suitable for setting the ratio of free acid to total acid required according to the claims. To determine the free or total acid, titrate each 10 ml bath sample with n / 10 NaOH against the first or second change in phosphoric acid. the color change of dimethyl yellow (free acid) or of phenolphthalein (total acid) serves. The ml of n / l0 NaOH consumed correspond to the free acid or total acid in points.
Es hat sich ferner als vorteilhaft erwiesen, die Metalle mit einer Phosphatierungslösung in Kontakt zu bringen, die nitritzerstörende Substanzen, z.B. Harnstoff oder Amidosulfosäure, enthält. Hierdurch wird eine autokatalytische Nitritbildung aus dem enthaltenen Nitrat unterbunden und ein "Umkippen" des Bades von der Eisenseite auf die Nitritseite ausgeschlossen.It has also proven advantageous to bring the metals into contact with a phosphating solution which contains nitrite-interfering substances, for example urea or amidosulfonic acid. This prevents autocatalytic nitrite formation from the nitrate contained and prevents the bath from "tipping over" from the iron side to the nitrite side.
Der Kontakt der Metalle mit der Phosphatierungslösung kann im Tauchen, Fluten oder Spritzen erfolgen. Meist erfolgt die Applikation jedoch im Tauchen, wobei Behandlungszeiten von z.B. 5 bis l5 min eingehalten werden sollten.The metals can come into contact with the phosphating solution by dipping, flooding or spraying. However, the application is usually done in diving, with treatment times of e.g. 5 to 15 minutes should be observed.
Die mit den erfindungsgemäßen Verfahren erzeugten Phosphatschichten besitzen - je nach spezieller Badzusammensetzung, Behandlungstemperatur, Behandlungszeit und Arbeitsgang - ein Schichtgewicht von etwa 3 bis l5 g/m².Depending on the particular bath composition, treatment temperature, treatment time and operation, the phosphate layers produced by the processes according to the invention have a layer weight of approximately 3 to 15 g / m 2.
Die Vorbehandlung der Metalle vor der eigentlichen Phosphatierung geschieht in konventioneller Weise. Beispielsweise kann eine Entfettung mittels wäßriger, alkalischer Reiniger, die zweckmäßigerweise Tensid enthalten, vorgenommen werden. Sofern vorhanden, sind Zunder oder Rost durch eine Beizbehandlung, z.B. mit Schwefelsäure oder Salzsäure, zu entfernen.The pretreatment of the metals before the actual phosphating is done in a conventional manner. For example, degreasing can be carried out using aqueous, alkaline cleaners which advantageously contain surfactant. If present, scale or rust can be removed by pickling treatment, e.g. with sulfuric acid or hydrochloric acid.
Obgleich nicht zwingend notwendig, können die Werkstücke vor der Phosphatierung zur Ausbildung feinkristalliner Phosphatüberzüge in an sich bekannter Weise, z.B. mit einem Titanphosphat enthaltenden Aktivierungsbad, vorgespült werden.Although not absolutely necessary, the workpieces can be formed prior to phosphating to form fine crystalline phosphate coatings in a manner known per se, e.g. with an activation bath containing titanium phosphate.
Nach der Phosphatierbehandlung wird üblicherweise mit Wasser gespült, gegebenenfalls nachbehandelt und bei Bedarf getrocknet. Zum Zweck der Verbesserung des Korrosionsschutzes kann z.B. mit Chromsäure und/oder Korrosionsschutzemulsionen nachbehandelt werden. Für den Fall, daß eine Kaltumformung beabsichtigt ist, kann eine Nachbehandlung z.B. mit einem Beseifungsbad erfolgen.After the phosphating treatment is usually with Rinsed water, treated if necessary and dried if necessary. For the purpose of improving the corrosion protection, aftertreatment can be carried out, for example, with chromic acid and / or corrosion protection emulsions. In the event that cold forming is intended, an aftertreatment can be carried out, for example, with a soap bath.
Die nach dem erfindungsgemäßen Verfahren erzeugten Phosphatüberzüge sind auf allen Gebieten, auf dem Phosphatüberzüge Verwendung finden, mit Vorteil einsetzbar. Vorzugsweise sind sie jedoch für die Vorbereitung von Metallen für die anschließende Kaltumformung geeignet.The phosphate coatings produced by the process according to the invention can be used advantageously in all fields in which phosphate coatings are used. However, they are preferably suitable for the preparation of metals for the subsequent cold forming.
Die Erfindung wird anhand des Beispiels beispielsweise und näher beschrieben.The invention is described by way of example and in more detail.
Stahldraht mit einem Kohlenstoffgehalt von 0,5 bis 0,9 Gew.-% wurde im Tauchen durch Behandeln mit Salzsäure von Rost und Zunder befreit und nach gründlichem Wasserspülen 6 bis l0 min bei 45°C in einer Phosphatierungslösung nachstehender Zusammensetzung phosphatiert:
l0,9 g/l Zn
2,l g/l Mn
2,0 g/l Fe(II)
0,5 g/l Ca
0,5 g/l Ni
0,0l g/l Cu
0,3 g/l Na
24,0 g/l NO₃
l0,6 g/l P₂O₅
l,6 g/l BF₄
l,6 g/l Weinsäure
0,5 g/l Harnstoff
Freie Säure: 4,7 Punkte
Gesamtsäure: 40,7 PunkteSteel wire with a carbon content of 0.5 to 0.9% by weight was freed of rust and scale in immersion by treatment with hydrochloric acid and, after thorough water rinsing, phosphated for 6 to 10 minutes at 45 ° C. in a phosphating solution of the following composition:
0.9 g / l Zn
2.1g / l Mn
2.0 g / l Fe (II)
0.5 g / l approx
0.5 g / l Ni
0.0l g / l Cu
0.3 g / l Na
24.0 g / l NO₃
l0.6 g / l P₂O₅
1.6 g / l BF₄
1.6 g / l tartaric acid
0.5 g / l urea
Free acidity: 4.7 points
Total acidity: 40.7 points
Im Anschluß daran wurde wiederum mit Wasser gespült, in einer wäßrigen, heißen Borax-Lösung neutralisiert und im Ofen getrocknet. Nach diesem Arbeitsgang ergab sich ein Flächengewicht des Phosphatüberzuges von 8 bis l0 g/m². Der Phosphatüberzug war trotz des Fehlens einer aktivierenden Vorspülung mit Titanphosphat gleichmäßig deckend und feinkristallin.This was followed by rinsing again with water, neutralizing in an aqueous, hot borax solution and drying in the oven. After this operation, the basis weight of the phosphate coating was 8 to 10 g / m². The phosphate coating was uniformly opaque and finely crystalline despite the absence of an activating pre-rinse with titanium phosphate.
Die so vorbehandelten Drähte ließen sich in bis zu l0 Zügen mit einer maximalen Querschnittsabnahme von 93,5 % einwandfrei bei nur sehr niedrigem Verschleiß der Ziehwerkzeuge umformen. Die Drahtoberfläche wies nach dem Ziehen noch eine gleichmäßige Restphosphatschicht auf und war frei von Riefen.The wires pretreated in this way could easily be formed in up to 10 passes with a maximum cross-sectional decrease of 93.5% with very little wear on the drawing tools. The wire surface still had a uniform layer of residual phosphate after drawing and was free of scoring.
Während des Durchsatzes wurde in das Phosphatierbad Luft eingeblasen und damit der Eisen(II)-ionen-Gehalt unter den gegebenen Durchsatzbedingungen im Bereich von 2 bis 7 g/l gehalten. Die Ergänzung des Bades erfolgte auf Konstanz der Gesamtsäurepunkte mit einem Ergänzungskonzentrat, enthaltend
ll,4 Gew.-% Zn
0,26 Gew.-% Mn
0,l3 Gew.-% Ca
0,ll Gew.-% Ni
0,025 Gew.-% Cu
22,9 Gew.-% P₂O₅
l0,3 Gew.-% NO₃
2,6 Gew.-%Weinsäure
0,38 Gew.-% BF₄
0,26 Gew.-% Harnstoff
Entsprechend der Verfahrensführung auf der Eisenseite bildete sich nur wenig Badschlamm. Der Verbrauch an Ergänzungskonzentrat betrug etwa 20 g/m² Metalloberfläche und war damit sehr niedrig.Air was blown into the phosphating bath during the throughput and the iron (II) ion content was thus kept in the range from 2 to 7 g / l under the given throughput conditions. The bath was supplemented with a supplement concentrate containing the total acid points
11.4% by weight Zn
0.26 wt% Mn
0.13% by weight approx
0.1% by weight of Ni
0.025 wt% Cu
22.9% by weight of P₂O₅
l0.3 wt .-% NO₃
2.6% by weight tartaric acid
0.38 wt% BF₄
0.26% by weight urea
According to the procedure on the iron side, only a little bath sludge was formed. The consumption of supplemental concentrate was about 20 g / m² metal surface and was therefore very low.
Claims (10)
Zink in Mengen von 5 bis 25 g/l
Mangan in Mengen von l bis l0 g/l
Eisen(II) in Mengen von 0,l bis l3 g/l
Phosphat in Mengen von 5 bis 40 g/l
( ber. als P₂O₅)
Nitrat in Mengen von 5 bis 50 g/l
sowie zusätzlich
0,5 bis 5 g/l Fluoroborat (ber. als BF₄)
0,05 bis 3 g/l Weinsäure und/oder Zitronensäure
enthält, in der die Gewichtsverhältnisse Zn : P₂O₅ auf (0,5 bis 3) : l und Mn : Zn auf (0,04 bis 0,5) : l und das Verhältnis von Freier Säure zu Gesamtsäure auf (0,04 bis 0,2) : l eingestellt sind.1. A process for producing phosphate coatings on at least partially iron or steel surfaces having metals by means of aqueous phosphating solutions which contain zinc, manganese, PO,, nitrate and - in the incorporated state - iron (II) ions, characterized in that the metals in contact with a phosphating solution at a temperature in the range of 30 to 50 ° C, the
Zinc in amounts of 5 to 25 g / l
Manganese in quantities of 1 to 10 g / l
Iron (II) in quantities of 0.1 to 13 g / l
Phosphate in amounts of 5 to 40 g / l
(calculated as P₂O₅)
Nitrate in amounts of 5 to 50 g / l
as well as additionally
0.5 to 5 g / l fluoroborate (calculated as BF₄)
0.05 to 3 g / l tartaric acid and / or citric acid
contains, in which the weight ratios Zn: P₂O₅ to (0.5 to 3): l and Mn: Zn to (0.04 to 0.5): l and the ratio of free acid to total acid to (0.04 to 0 , 2): l are set.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19863636390 DE3636390A1 (en) | 1986-10-25 | 1986-10-25 | METHOD FOR PRODUCING PHOSPHATE COATINGS ON METALS |
DE3636390 | 1986-10-25 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0269138A1 true EP0269138A1 (en) | 1988-06-01 |
EP0269138B1 EP0269138B1 (en) | 1990-11-28 |
Family
ID=6312485
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87201890A Expired - Lifetime EP0269138B1 (en) | 1986-10-25 | 1987-10-03 | Process for producing phosphate coatings on metals |
Country Status (10)
Country | Link |
---|---|
US (1) | US4824490A (en) |
EP (1) | EP0269138B1 (en) |
JP (1) | JP2700061B2 (en) |
AU (1) | AU8003887A (en) |
BR (1) | BR8705698A (en) |
CA (1) | CA1308629C (en) |
DE (2) | DE3636390A1 (en) |
ES (1) | ES2018535B3 (en) |
GB (1) | GB2203453B (en) |
ZA (1) | ZA877980B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0327153A2 (en) * | 1988-02-03 | 1989-08-09 | Metallgesellschaft Ag | Process for applying phosphate coatings to metals |
WO1995004842A1 (en) * | 1993-08-06 | 1995-02-16 | Metallgesellschaft Aktiengesellschaft | Phosphate treatment process for steel strip with one galvanised surface |
WO1996009422A1 (en) * | 1994-09-23 | 1996-03-28 | Henkel Kommanditgesellschaft Auf Aktien | No-rinse phosphatising process |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3800834A1 (en) * | 1988-01-14 | 1989-07-27 | Henkel Kgaa | METHOD AND MEANS FOR SIMULTANEOUS SLICING, CLEANING AND PASSIVATING OF METALLIC WORKSTUFFS |
DE3828676A1 (en) * | 1988-08-24 | 1990-03-01 | Metallgesellschaft Ag | PHOSPHATING PROCESS |
JPH02101174A (en) * | 1988-10-06 | 1990-04-12 | Nippon Paint Co Ltd | Treatment with zinc phosphate for cold working |
DE3927613A1 (en) * | 1989-08-22 | 1991-02-28 | Metallgesellschaft Ag | METHOD FOR PRODUCING PHOSPHATE COATINGS ON METAL SURFACES |
DE4004914A1 (en) * | 1990-02-16 | 1991-08-22 | Zwez Chemie Gmbh | USE OF BRUENIER BATH SLUDGE |
US5378292A (en) * | 1993-12-15 | 1995-01-03 | Henkel Corporation | Phosphate conversion coating and compositions and concentrates therefor with stable internal accelerator |
US5954892A (en) * | 1998-03-02 | 1999-09-21 | Bulk Chemicals, Inc. | Method and composition for producing zinc phosphate coatings on metal surfaces |
JP4630326B2 (en) * | 1999-08-09 | 2011-02-09 | 新日本製鐵株式会社 | Method for producing phosphate-treated zinc-plated steel sheet with excellent workability |
US20040221924A1 (en) * | 1999-09-30 | 2004-11-11 | Klaus-Dieter Nittel | Method for applying manganese phosphate layers |
JP2001170557A (en) * | 1999-12-21 | 2001-06-26 | Nisshin Steel Co Ltd | Surface treatment liquid for plated steel plate and treating method therefor |
CA2467751A1 (en) * | 2001-12-13 | 2003-07-03 | Henkel Kommanditgesellschaft Auf Aktien | Use of substituted hydroxylamines in metal phosphating processes |
US7037384B2 (en) * | 2003-06-23 | 2006-05-02 | Bulk Chemicals, Inc. | Lubricating chemical coating for metalworking |
JP5347295B2 (en) * | 2008-03-26 | 2013-11-20 | Jfeスチール株式会社 | Zinc-based plated steel sheet and method for producing the same |
CN102978598B (en) * | 2012-12-06 | 2015-07-22 | 三达奥克化学股份有限公司 | General phosphate agent for cast iron, hot steel, hot-rolled plate, pickling board and cold-rolled plate and preparation method thereof |
RU2572688C1 (en) * | 2014-09-10 | 2016-01-20 | Закрытое акционерное общество "ФК" | Solution for metal surface phosphating |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1144991B (en) * | 1958-10-03 | 1963-03-07 | Metallgesellschaft Ag | Process for applying phosphate coatings to ferrous metals |
US3860455A (en) * | 1973-03-16 | 1975-01-14 | Oxy Metal Finishing Corp | Method for phosphatizing ferrous surfaces |
FR2235203A1 (en) * | 1973-06-29 | 1975-01-24 | Parker Ste Continentale | |
FR2389683A1 (en) * | 1977-05-03 | 1978-12-01 | Parker Ste Continentale | Phosphating soln. contg. boron fluoride - for phosphating ferrous and non-ferrous surfaces, e.g. steel, zinc and aluminium |
EP0036689A1 (en) * | 1980-03-21 | 1981-09-30 | Metallgesellschaft Ag | Method of applying phosphate coatings |
EP0045110A1 (en) * | 1980-07-25 | 1982-02-03 | Metallgesellschaft Ag | Method for the production of phosphate coatings on iron and steel surfaces, and its use |
DE3345498A1 (en) * | 1983-12-16 | 1985-06-27 | Metallgesellschaft Ag, 6000 Frankfurt | Process for producing phosphate coatings |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2479564A (en) * | 1945-09-14 | 1949-08-23 | Lloyd O Gilbert | Phosphate coating of metallic articles |
US2850418A (en) * | 1953-04-28 | 1958-09-02 | Amchem Prod | Composition for use in preparing metal for a deforming operation and method of deforming |
DE1107481B (en) * | 1959-06-10 | 1961-05-25 | Dr Stefan Klinghoffer | Process for the pretreatment of wires for the purpose of drawing |
DE1184592B (en) * | 1960-12-02 | 1964-12-31 | Metallgesellschaft Ag | Process for phosphating iron and steel |
US3166444A (en) * | 1962-04-26 | 1965-01-19 | Lubrizol Corp | Method for cleaning metal articles |
US3297494A (en) * | 1963-08-05 | 1967-01-10 | Amchem Prod | Concentrated material for use in preparing and preplenishing zinc phosphate coating solutions |
US3338755A (en) * | 1963-09-03 | 1967-08-29 | Hooker Chemical Corp | Production of phosphate coatings on metals |
DE2100021A1 (en) * | 1971-01-02 | 1972-09-07 | Collardin Gmbh Gerhard | Process for applying phosphate layers to steel, iron and zinc surfaces |
GB1297715A (en) * | 1971-02-02 | 1972-11-29 | ||
GB1374963A (en) * | 1973-04-27 | 1974-11-20 | Pyrene Chemical Services Ltd | Production of phosphate coatings on metals |
JPS5343043A (en) * | 1976-10-01 | 1978-04-18 | Nippon Packaging Kk | Solution for forming conversion coating of zinc phosphate |
GB1591039A (en) * | 1977-05-03 | 1981-06-10 | Pyrene Chemical Services Ltd | Processes and compositions for coating metal surfaces |
DE2907094A1 (en) * | 1979-02-23 | 1980-09-04 | Metallgesellschaft Ag | PHOSPHATION SOLUTIONS |
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 |
DE3023479A1 (en) * | 1980-06-24 | 1982-01-14 | Metallgesellschaft Ag, 6000 Frankfurt | PHOSPHATING PROCESS |
CA1257527A (en) * | 1984-12-20 | 1989-07-18 | Thomas W. Tull | Cold deformation process employing improved lubrication coating |
-
1986
- 1986-10-25 DE DE19863636390 patent/DE3636390A1/en not_active Withdrawn
-
1987
- 1987-10-03 EP EP87201890A patent/EP0269138B1/en not_active Expired - Lifetime
- 1987-10-03 DE DE8787201890T patent/DE3766477D1/en not_active Expired - Lifetime
- 1987-10-03 ES ES87201890T patent/ES2018535B3/en not_active Expired - Lifetime
- 1987-10-07 CA CA000548749A patent/CA1308629C/en not_active Expired - Lifetime
- 1987-10-20 US US07/110,949 patent/US4824490A/en not_active Expired - Lifetime
- 1987-10-21 JP JP62264067A patent/JP2700061B2/en not_active Expired - Lifetime
- 1987-10-22 AU AU80038/87A patent/AU8003887A/en not_active Abandoned
- 1987-10-23 ZA ZA877980A patent/ZA877980B/en unknown
- 1987-10-23 BR BR8705698A patent/BR8705698A/en unknown
- 1987-10-26 GB GB8725035A patent/GB2203453B/en not_active Expired - Fee Related
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1144991B (en) * | 1958-10-03 | 1963-03-07 | Metallgesellschaft Ag | Process for applying phosphate coatings to ferrous metals |
US3860455A (en) * | 1973-03-16 | 1975-01-14 | Oxy Metal Finishing Corp | Method for phosphatizing ferrous surfaces |
FR2235203A1 (en) * | 1973-06-29 | 1975-01-24 | Parker Ste Continentale | |
FR2389683A1 (en) * | 1977-05-03 | 1978-12-01 | Parker Ste Continentale | Phosphating soln. contg. boron fluoride - for phosphating ferrous and non-ferrous surfaces, e.g. steel, zinc and aluminium |
EP0036689A1 (en) * | 1980-03-21 | 1981-09-30 | Metallgesellschaft Ag | Method of applying phosphate coatings |
EP0045110A1 (en) * | 1980-07-25 | 1982-02-03 | Metallgesellschaft Ag | Method for the production of phosphate coatings on iron and steel surfaces, and its use |
DE3345498A1 (en) * | 1983-12-16 | 1985-06-27 | Metallgesellschaft Ag, 6000 Frankfurt | Process for producing phosphate coatings |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0327153A2 (en) * | 1988-02-03 | 1989-08-09 | Metallgesellschaft Ag | Process for applying phosphate coatings to metals |
EP0327153A3 (en) * | 1988-02-03 | 1990-04-25 | Metallgesellschaft Ag | Process for applying phosphate coatings to metals |
WO1995004842A1 (en) * | 1993-08-06 | 1995-02-16 | Metallgesellschaft Aktiengesellschaft | Phosphate treatment process for steel strip with one galvanised surface |
WO1996009422A1 (en) * | 1994-09-23 | 1996-03-28 | Henkel Kommanditgesellschaft Auf Aktien | No-rinse phosphatising process |
US5976272A (en) * | 1994-09-23 | 1999-11-02 | Henkel Kommanditgesellschaft Auf Aktien | No-rinse phosphating process |
Also Published As
Publication number | Publication date |
---|---|
GB2203453B (en) | 1990-12-05 |
BR8705698A (en) | 1988-05-31 |
EP0269138B1 (en) | 1990-11-28 |
GB8725035D0 (en) | 1987-12-02 |
ES2018535B3 (en) | 1991-04-16 |
ZA877980B (en) | 1989-06-28 |
GB2203453A (en) | 1988-10-19 |
DE3766477D1 (en) | 1991-01-10 |
DE3636390A1 (en) | 1988-04-28 |
JP2700061B2 (en) | 1998-01-19 |
US4824490A (en) | 1989-04-25 |
AU8003887A (en) | 1988-04-28 |
CA1308629C (en) | 1992-10-13 |
JPS63190178A (en) | 1988-08-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0269138B1 (en) | Process for producing phosphate coatings on metals | |
EP0045110B1 (en) | Method for the production of phosphate coatings on iron and steel surfaces, and its use | |
EP0287133B1 (en) | Phosphating treatment before electrophoretic dip painting | |
EP0414301B1 (en) | Process for obtaining phosphate coatings on metal surfaces | |
EP0478648B1 (en) | Process for producing zinc phosphate coatings containing manganese and magnesium | |
EP1929070A1 (en) | Phosphatising solution with hydrogen peroxide and chelating carboxylic acids | |
EP0327153B1 (en) | Process for applying phosphate coatings to metals | |
EP0155547B1 (en) | Process for the zinc-calcium phosphatizing of metal surfaces at a low treating temperature | |
EP0134895B1 (en) | Process and compounds for applying accelerated and grain-refined phosphate coatings to metallic surfaces | |
EP0656957A1 (en) | Process for phosphatizing steel zinc-coated on one side only. | |
DE19808440C2 (en) | Aqueous solution and method for phosphating metallic surfaces and use of the solution and method | |
EP0111223B1 (en) | Process for phosphatizing metallic surfaces, and solutions for use therein | |
EP0486576B1 (en) | Process for producing manganese-containing zinc phosphate coatings on galvanized steel | |
EP0603921B1 (en) | Process for forming phosphate coatings | |
EP1005578B1 (en) | Phosphating method accelerated by n-oxides | |
EP0219779A2 (en) | Phosphatizing process for electrolytically galvanized metal objects | |
EP0121274A1 (en) | Process for phosphating metal surfaces | |
EP0258922A1 (en) | Process for producing phosphate coatings and their use | |
DE2213781C3 (en) | Process for the phosphating of steel | |
EP0711849A1 (en) | Process for applying phosphate coatings | |
EP0866888B1 (en) | Method of phosphating metal surfaces | |
EP1155163B1 (en) | Method for phosphatizing zinc or aluminium surfaces | |
DE19733978A1 (en) | Acid phosphating solution, stable in presence of copper ions | |
WO2001023638A1 (en) | Method for applying manganese phosphate layers | |
DE19716075A1 (en) | Phosphating process accelerated with hydroxylamine and chlorate |
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: 19881104 |
|
17Q | First examination report despatched |
Effective date: 19900226 |
|
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: 3766477 Country of ref document: DE Date of ref document: 19910110 |
|
ET | Fr: translation filed | ||
ITF | It: translation for a ep patent filed |
Owner name: STUDIO JAUMANN |
|
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 |
|
ITTA | It: last paid annual fee | ||
26N | No opposition filed | ||
EAL | Se: european patent in force in sweden |
Ref document number: 87201890.8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20010925 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: 20011001 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: 20011011 Year of fee payment: 15 Ref country code: BE Payment date: 20011011 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: 20011024 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: 20021004 Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20021004 |
|
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: 20021031 |
|
BERE | Be: lapsed |
Owner name: *METALLGESELLSCHAFT A.G. Effective date: 20021031 |
|
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: 20030501 |
|
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: 20030630 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20030501 |
|
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: 20031112 |
|
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: 20051003 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20061220 Year of fee payment: 20 |