EP0969125A1 - Process for bringing zinc into solution in a ZnNi-electrolyte - Google Patents
Process for bringing zinc into solution in a ZnNi-electrolyte Download PDFInfo
- Publication number
- EP0969125A1 EP0969125A1 EP99112486A EP99112486A EP0969125A1 EP 0969125 A1 EP0969125 A1 EP 0969125A1 EP 99112486 A EP99112486 A EP 99112486A EP 99112486 A EP99112486 A EP 99112486A EP 0969125 A1 EP0969125 A1 EP 0969125A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zinc
- electrolyte
- znni
- nickel
- granules
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
- C25D21/14—Controlled addition of electrolyte components
Definitions
- the invention relates to a method for dissolving zinc from zinc granules in a weakly acidic ZnNi electrolyte with a pH of> 1.6.
- Cold rolled thin sheets are used for many purposes, e.g. For Body parts in automotive construction, in galvanized design used to increase corrosion resistance. Zinc alloy coatings containing 10 to 12% nickel contains, proved to be significantly more corrosion-resistant as a coating of pure zinc.
- the coating of the Thin sheets covered with a nickel-zinc alloy is done in practice by the cold rolled Steel strips continuously through a ZnNi electrolyte liquid bath about current rollers and Guide rollers are guided.
- a coherent K.-P. have an overview of this technique. Imlau and others in Stahl and Eisen 113 (1993), No. 5, pp. 69-76.
- the invention is based, in which Enrichment of a ZnNi electrolyte with zinc ions Dissolve zinc from a zinc granule fill mentioned surface nickel cementation on the To avoid zinc granules and the surface of the Zinc granules free of nickel deposited from the Keep ZnNi electrolytes. In the case of nickel cementation Zinc granules provided can thereby further nickel deposits can be prevented.
- FIG. 3 schematically shows the enrichment of the ZnNi electrolyte with zinc ions.
- a sieve tray 2 is arranged at a distance from the bottom.
- a ZnNi electrolyte acts through a tube 3 acting as an axis of rotation Air supplied from above flows through the Tube 3 down and through openings in the below the sieve plate 2 located agitator 4 against the sieve plate 2.
- the rotation of the stirring arm 4 promotes the even Ventilation of those located above the sieve tray 2
- Zinc granule fill 5 Up to the level of the bath level 6 is the container 1 with ZnNi electrolyte liquid 7 filled. When flowing through the zinc granules 5 the electrolyte absorbs zinc ions.
- the electrolyte can accumulate zinc ions either discontinuously or continuously.
- the ZnNi electrolyte contains 30 - 50 g / l zinc and 50 - 70 g / l nickel in a weakly acidic solution that contains 1.0 - 5.0 g / l H 2 SO 4 .
- the zinc granules used in the test only have an extremely low nickel coating of 1.4%.
- Nickel cementation during the enrichment of the ZnNi electrolyte Zinc ions from zinc granules are deposited by cementing up to 5.5% nickel on the surface the zinc granules from (row 1 of Table 1).
- the pH of the Electrolytes in the preferred range from 1.7 to 2.3 or can be kept at a value within this range become. Sulfuric acid electrolytes are preferred used.
Abstract
Description
Die Erfindung betrifft ein Verfahren zum Lösen von Zink aus Zinkgranalien in einem schwachsauren ZnNi-Elektrolyten mit einem pH-Wert von > 1,6.The invention relates to a method for dissolving zinc from zinc granules in a weakly acidic ZnNi electrolyte with a pH of> 1.6.
Kaltgewalzte Feinbleche werden für viele Zwecke, z.B. für Karosserieteile im Automobilbau, in verzinkter Ausführung zur Steigerung der Korrosionsbeständigkeit eingesetzt. Überzüge aus einer Zinklegierung, die 10 bis 12 % Nickel enthält, erwiesen sich als deutlich korrosionsbeständiger als ein Überzug aus reinem Zink. Die Beschichtung der Feinbleche mit einem Überzug aus einer Nickel-Zink-Legierung erfolgt in der Praxis, indem die kaltgewalzten Stahlbänder kontinuierlich durch ein ZnNi-Elektrolytflüssigkeits-bad über Stromrollen und Umlenkrollen geführt werden. Einen zusammenhängenden Überblick über diese Technik haben K.-P. Imlau u.a. in Stahl und Eisen 113 (1993), Nr. 5, S. 69-76, gegeben.Cold rolled thin sheets are used for many purposes, e.g. For Body parts in automotive construction, in galvanized design used to increase corrosion resistance. Zinc alloy coatings containing 10 to 12% nickel contains, proved to be significantly more corrosion-resistant as a coating of pure zinc. The coating of the Thin sheets covered with a nickel-zinc alloy is done in practice by the cold rolled Steel strips continuously through a ZnNi electrolyte liquid bath about current rollers and Guide rollers are guided. A coherent K.-P. have an overview of this technique. Imlau and others in Stahl and Eisen 113 (1993), No. 5, pp. 69-76.
Bei der Erzeugung einer Nickel-Zink-Legierungsschicht auf kaltgewalzten Stahlbändern mittels unlöslicher Anoden aus schwachsauren ZnNi-Elektrolyten mit einem pH-Wert > 1,6 haben sich Probleme bei der Elektrolytkonditionierung ergeben. Diese entstehen bei Verwendung von feinkörnigen Zinkgranalien zur Nachlieferung von Zink-Ionen in das Elektrolytbad zum Ausgleich von auf die Stahlbandoberfläche abgeschiedenem Zink aus dem Elektrolysebad. Zur Anreicherung mit Zink-Ionen wird der ZnNi-Elektrolyt in einem Nebenkreislauf durch eine Zink-Granalienschüttung geleitet. Bei diesem Lösungsvorgang zur Aufnahme von Zink-Ionen in den Elektrolyten kommt es zu einer unerwünschten stromlosen Beschichtung der Zinkgranalien mit dem edleren Nickel. Solche oberflächlichen Nickel-Zementationen auf Zinkgranalien sind in den Schliffbildern Fig. 1 in 50-facher Vergrößerung und Fig. 2 in 500-facher Vergrößerung gezeigt. Durch diese oberflächliche Nickel-Zementation wird die reaktive Fläche der Zinkgranalien nach und nach reduziert, wodurch die benötigte Anreicherung an Zink-Ionen im Elektrolyten beeinträchtigt wird. Um dies zu vermeiden, müssen die Zinkgranalien vorzeitig ausgetauscht werden. Das ist kostenaufwendig und stört den kontinuierlichen Beschichtungsbetrieb. Weiter wird das zementierte Nickel nicht wieder aufgelöst und somit dem Prozeß entzogen.When creating a nickel-zinc alloy layer cold-rolled steel strips using insoluble anodes weakly acidic ZnNi electrolytes with a pH> 1.6 have problems with electrolyte conditioning surrender. These arise when using fine-grained Zinc granules for the subsequent supply of zinc ions in the Electrolytic bath to compensate for that Steel strip surface deposited zinc from the Electrolysis bath. For enrichment with zinc ions, the ZnNi electrolyte in a secondary circuit through a bed of zinc granules headed. In this solution process Zinc ions are absorbed in the electrolytes to an undesired electroless coating of the Zinc granules with the nobler nickel. Such superficial nickel cementations on zinc granules are 50 times in the micrographs Fig. 1 Magnification and Fig. 2 in 500 times magnification shown. This superficial nickel cementation gradually the reactive surface of the zinc granules reduced, thereby increasing the required concentration of zinc ions in the electrolyte is impaired. To do this avoid the zinc granules prematurely be replaced. This is expensive and bothersome the continuous coating operation. Will continue the cemented nickel does not dissolve and therefore withdrawn from the process.
Der Erfindung liegt die Aufgabe zugrunde, bei der Anreicherung eines ZnNi-Elektrolyten mit Zink-Ionen durch Lösen von Zink aus einer Zink-Granalienschüttung die erwähnte oberflächliche Nickel-Zementation auf den Zinkgranalien zu vermeiden und die Oberfläche der Zinkgranalien frei von abgeschiedenem Nickel aus dem ZnNi-Elektrolyten zu halten. Im Falle bereits mit Nickel-Zementation versehener Zinkgranalien können hierdurch weitere Nickelablagerungen verhindert werden.The invention is based, in which Enrichment of a ZnNi electrolyte with zinc ions Dissolve zinc from a zinc granule fill mentioned surface nickel cementation on the To avoid zinc granules and the surface of the Zinc granules free of nickel deposited from the Keep ZnNi electrolytes. In the case of nickel cementation Zinc granules provided can thereby further nickel deposits can be prevented.
Zur Lösung dieser Aufgabe wird bei dem gattungsgemäßen Verfahren erfindungsgemäß vorgeschlagen, daß während des Lösungsvorgangs eine Zinkgranalienschüttung feinperlig von Luft gleichmäßig durchströmt wird.To solve this problem is the generic Method proposed according to the invention that during the A granular fill of fine granules is evenly flowed through by air.
Überraschenderweise wurde festgestellt, daß Nickel-Zementationen auf Zinkgranalien weitgehend unterbleiben bzw. auf bereits mit Nickel überzogenen Zinkgranalien weitere Nickel-Zementationen unterdrückt werden, wenn in erfindungsgemäßer Weise Luft feinperlig und gleichmäßig durch die Zink-Granalienschüttung hindurchgeleitet wird. Der Wirkungsmechanismus besteht darin, daß der im Vergleich zu den Nickel-Ionen elektrochemisch edlere Luftsauerstoff an der Zinkgranalienoberfläche angeboten wird und damit die Nickelzementation verhindert.Surprisingly, it was found that nickel cementations largely avoided on zinc granules or on zinc granules already coated with nickel further nickel cementations can be suppressed if in Air according to the invention fine-pearled and uniform is passed through the bed of zinc granules. The mechanism of action is that the im Compared to the nickel ions electrochemically nobler Atmospheric oxygen offered on the zinc granule surface is prevented and thus the nickel cementation.
Neben der Freihaltung der Zinkgranalien von oberflächlichen Zink-Zementationen und dadurch bedingte Konstanthaltung der Konzentration an Nickel- und Zink-Ionen im Elektrolyten ergibt sich der weitere Vorteil bei Anwendung des erfindungsgemäßen Verfahrens, daß das im Elektrolyten enthaltene Nickel in ionisierter Form erhalten bleibt. Nickel geht nicht - wie bisher - durch den Austausch von nickelzementierten Zinkgranalien (= Nickelsand) verloren.In addition to keeping the zinc granules free of superficial zinc cementations and related Keeping the concentration of nickel and zinc ions constant in the electrolyte there is another advantage Application of the method according to the invention that the Electrolytes contain nickel in ionized form preserved. Nickel does not go through - as before the exchange of nickel-cemented zinc granules (= Nickel sand) lost.
Ein weiterer Vorteil ergibt sich daraus, daß nun die Zinkgranalien vollständig aufgelöst werden können und nicht - wie bisher - nach erfolgter Nickel-Zementation an der Oberfläche vorzeitig ausgetauscht werden müssen.Another advantage arises from the fact that now the Zinc granules can be completely dissolved and not - as before - after nickel cementation the surface must be replaced prematurely.
Fig. 3 zeigt schematisch die Anreicherung des ZnNi-Elektrolyten
mit Zink-Ionen. In dem Lösungsbehälter 1 ist
in einem Abstand vom Boden ein Siebboden 2 angeordnet.
Durch eine als Drehachse wirkendes Rohr 3 wird dem ZnNi-Elektrolyten
von oben Luft zugeführt, strömt durch das
Rohr 3 nach unten und durch Öffnungen in den unterhalb
des Siebbodens 2 gelegenen Rührarm 4 gegen den Siebboden
2. Die Drehung des Rühr-arms 4 fördert die gleichmäßige
Belüftung der oberhalb des Siebbodens 2 befindlichen
Zink-Granalienschüttung 5. Bis zur Höhe des Badspiegels 6
ist der Behälter 1 mit ZnNi-Elektrolytflüssigkeit 7
gefüllt. Beim Durchströmen der Zink-Granalienschüttung 5
nimmt der Elektrolyt Zink-Ionen auf.3 schematically shows the enrichment of the ZnNi electrolyte
with zinc ions. In the
Die Anreicherung des Elektrolyten an Zink-Ionen kann entweder diskontinuierlich oder kontinuierlich erfolgen.The electrolyte can accumulate zinc ions either discontinuously or continuously.
Der sich für die Anwendung des erfindungsgemäßen
Verfahrens ergebende Erfolg kann auch durch die Angaben
in Tabelle 1 dokumentiert werden.
Im Ausgangszustand enthält der ZnNi-Elektrolyt 30 - 50 g/l Zink und 50 - 70 g/l Nickel in einer schwachsauren Lösung, die 1,0 - 5,0 g/l H2SO4 enthält. Die im Versuch eingesetzten Zinkgranalien weisen nur einen außerordentlich geringen Belag an Nickel von 1,4 % auf.In the initial state, the ZnNi electrolyte contains 30 - 50 g / l zinc and 50 - 70 g / l nickel in a weakly acidic solution that contains 1.0 - 5.0 g / l H 2 SO 4 . The zinc granules used in the test only have an extremely low nickel coating of 1.4%.
Durch die bei herkömmlicher Verfahrensweise entstehende
Nickel-Zementation bei der Anreicherung des ZnNi-Elektrolyten
an Zink-Ionen aus Zinkgranalien lagert sich
durch Zementation bis zu 5,5 % Nickel an der Oberfläche
der Zinkgranalien ab (Zeile 1 von Tabelle 1).The result of the conventional procedure
Nickel cementation during the enrichment of the ZnNi electrolyte
Zinc ions from zinc granules are deposited
by cementing up to 5.5% nickel on the surface
the zinc granules from (
Wenn erfindungsgemäß bei der Zink-Anreicherung des Elektrolyten feinperlige Luft durch die Granalienschüttung geleitet wird, so kann diese Nickel-Zementation weitgehend vermieden und der Nickelgehalt der Zinkgranalien auf dem Ausgangswert von 1,4 % gehalten werden. Die Zink-Nickel-Konzentration verschiebt sich dabei nicht zuungunsten des Nickelgehalts.If according to the invention in the zinc enrichment of the Electrolytes through the air Granular bulk is passed, so this nickel cementation largely avoided and the nickel content of the Zinc granules kept at baseline at 1.4% become. The zinc-nickel concentration is shifting not to the disadvantage of the nickel content.
Im Laborversuch ist durch Säurezugabe der pH-Wert des Elektrolyten im bevorzugten Bereich von 1,7 bis 2,3 bzw. kann auf einem Wert innerhalb dieses Bereiches gehalten werden. Bevorzugt werden schwefelsaure Elektrolyte eingesetzt.In the laboratory test, the pH of the Electrolytes in the preferred range from 1.7 to 2.3 or can be kept at a value within this range become. Sulfuric acid electrolytes are preferred used.
Claims (3)
dadurch gekennzeichnet, daß
während des Lösungsvorgangs eine Zinkgranalienschüttung feinperlig von Luft gleichmäßig durchströmt wird.Process for dissolving zinc from zinc granules in a weakly acidic ZnNi electrolyte with a pH> 1.6
characterized in that
during the dissolving process, a fine-bubbled layer of zinc granules is evenly flowed through by air.
dadurch gekennzeichnet, daß
schwefel- oder salzsaure Elektrolyte verwendet werden.Method according to claim 1,
characterized in that
sulfuric or hydrochloric acid electrolytes can be used.
dadurch gekennzeichnet, daß
der pH-Wert des ZnNi-Elektrolyten während des Lösungsvorgangs auf einen Wert im Bereich von 1,7 bis 2,3 gehalten wird.Method according to claim 1 or 3,
characterized in that
the pH of the ZnNi electrolyte is maintained in the range 1.7 to 2.3 during the dissolving process.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19829768A DE19829768C1 (en) | 1998-07-03 | 1998-07-03 | Process for dissolving zinc in a ZnNi electrolyte |
| DE19829768 | 1998-07-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0969125A1 true EP0969125A1 (en) | 2000-01-05 |
| EP0969125B1 EP0969125B1 (en) | 2002-06-05 |
Family
ID=7872881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP99112486A Expired - Lifetime EP0969125B1 (en) | 1998-07-03 | 1999-07-01 | Process for bringing zinc into solution in a ZnNi-electrolyte |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0969125B1 (en) |
| AT (1) | ATE218630T1 (en) |
| DE (2) | DE19829768C1 (en) |
| ES (1) | ES2177172T3 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2389188B1 (en) | 2011-03-29 | 2013-09-02 | Rovalma Sa | CATHODIC PROTECTION THROUGH COATING FOR COOLING CIRCUITS OR OTHER HOLES OR CHANNELS. |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5162555A (en) * | 1989-12-18 | 1992-11-10 | Cassella Aktiengesellschaft | Process and apparatus for preparing a solution of a non-ferrous metal sulphonate |
| US5609747A (en) * | 1995-08-17 | 1997-03-11 | Kawasaki Steel Corporation | Method of dissolving zinc oxide |
-
1998
- 1998-07-03 DE DE19829768A patent/DE19829768C1/en not_active Expired - Fee Related
-
1999
- 1999-07-01 DE DE59901594T patent/DE59901594D1/en not_active Expired - Fee Related
- 1999-07-01 AT AT99112486T patent/ATE218630T1/en not_active IP Right Cessation
- 1999-07-01 ES ES99112486T patent/ES2177172T3/en not_active Expired - Lifetime
- 1999-07-01 EP EP99112486A patent/EP0969125B1/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5162555A (en) * | 1989-12-18 | 1992-11-10 | Cassella Aktiengesellschaft | Process and apparatus for preparing a solution of a non-ferrous metal sulphonate |
| US5609747A (en) * | 1995-08-17 | 1997-03-11 | Kawasaki Steel Corporation | Method of dissolving zinc oxide |
Non-Patent Citations (1)
| Title |
|---|
| KAMMERECK H. E.A.: "Neues Elektrolytisches Verfahren zur Zinc-Nickel-Beschichtung von Feinblech", STAHL UND EISEN, vol. 109, no. 6, 28 March 1989 (1989-03-28), pages 67 - 72, XP002116008 * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE59901594D1 (en) | 2002-07-11 |
| ATE218630T1 (en) | 2002-06-15 |
| DE19829768C1 (en) | 2000-04-27 |
| ES2177172T3 (en) | 2002-12-01 |
| EP0969125B1 (en) | 2002-06-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE2644035C3 (en) | Process for the electrodeposition of a dispersion layer | |
| DE2611267A1 (en) | CHROMED, GALVANIZED STEEL SHEETS AND THE PROCESS FOR THEIR PRODUCTION | |
| DE3005159C2 (en) | Process for the plating of steel strips with a zinc-nickel alloy | |
| DE202016007550U1 (en) | Electroplated copper alloys with high strength and conductivity | |
| DD201812A5 (en) | METHOD OF SEPARATING METAL LAYERS ON THE CHOKES OF COCKENS | |
| EP0969125B1 (en) | Process for bringing zinc into solution in a ZnNi-electrolyte | |
| DE882168C (en) | Bath and process for the electrolytic production of zinc coatings | |
| DE2646881C3 (en) | Process for the galvanic deposition of a dispersion layer | |
| DE2226699A1 (en) | Electroplating bath for the deposition of rhodium-platinum alloys | |
| DE2636552C3 (en) | Use of ferro-nickel granules | |
| DE1521040B2 (en) | PROCESS FOR GALVANIC SOFT CHROMING OF METAL OBJECTS, IN PARTICULAR CAST IRON | |
| EP0061130B1 (en) | Process for the galvanic deposit of a zinc-nickel-alloy layer on a metal object, in particular on steel strip | |
| DE2032867A1 (en) | Gold bath and its application | |
| DE3132269C2 (en) | ||
| DE1764799A1 (en) | Magnetic storage | |
| AT277696B (en) | Galvanic nickel bath | |
| DE4122543C2 (en) | ||
| DE1032636B (en) | Supplementary solution to reduce the increase in alkalinity in cyanidic baths for the galvanic deposition of gold alloys | |
| DE1496923A1 (en) | Process for the galvanic deposition or deposition of a decorative glossy chrome plating or a decorative glossy chrome coating | |
| DE2242503C3 (en) | Aqueous acid bath and process for the electrodeposition of rhodium coatings | |
| AT216855B (en) | Process for direct nickel plating and nickel plating solution for carrying out the process | |
| DE3139640A1 (en) | "BATH AND METHOD FOR THE GALVANIC DEPOSITION OF BLACK NICKEL" | |
| AT377791B (en) | METHOD AND DEVICE FOR CONTINUOUSLY COATING ON ONE OR BOTH SIDES OF A METAL STRIP | |
| DE1919544A1 (en) | Process for the electrolytic deposition of alloys of two metals, in particular nickel and silver | |
| DE1247802B (en) | Acid galvanic tin-nickel bath |
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 |
|
| 17P | Request for examination filed |
Effective date: 19991109 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE DE ES GB |
|
| AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
| AKX | Designation fees paid |
Free format text: AT BE DE ES GB |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| 17Q | First examination report despatched |
Effective date: 20010806 |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: THYSSENKRUPP STAHL AG |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE DE ES GB |
|
| REF | Corresponds to: |
Ref document number: 218630 Country of ref document: AT Date of ref document: 20020615 Kind code of ref document: T |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
| REF | Corresponds to: |
Ref document number: 59901594 Country of ref document: DE Date of ref document: 20020711 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20020801 Year of fee payment: 4 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20020819 Year of fee payment: 4 |
|
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20020830 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2177172 Country of ref document: ES Kind code of ref document: T3 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed |
Effective date: 20030306 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030701 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030702 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20030730 Year of fee payment: 5 |
|
| 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: 20030731 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20030819 Year of fee payment: 5 |
|
| BERE | Be: lapsed |
Owner name: *THYSSENKRUPP STAHL A.G. Effective date: 20030731 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20030701 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040701 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20030702 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050201 |