EP0878561A2 - Process and apparatus for the regeneration of tin plating solutions - Google Patents

Process and apparatus for the regeneration of tin plating solutions Download PDF

Info

Publication number
EP0878561A2
EP0878561A2 EP98107584A EP98107584A EP0878561A2 EP 0878561 A2 EP0878561 A2 EP 0878561A2 EP 98107584 A EP98107584 A EP 98107584A EP 98107584 A EP98107584 A EP 98107584A EP 0878561 A2 EP0878561 A2 EP 0878561A2
Authority
EP
European Patent Office
Prior art keywords
chamber
copper
cathode
tin
anode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP98107584A
Other languages
German (de)
French (fr)
Other versions
EP0878561B1 (en
EP0878561A3 (en
Inventor
Klaus Prof. Rer. Nat. Fischwasser
Hans-Wilhelm Prof. Dr.-Ing. Lieber
Ralph Dr. Rer. Nat. Blittersdorf
Annette Dipl.-Ing. Heuss (Fh)
Ulrich Dr.-Ing. Reiter
Werner Dr. Rer. Nat. Harnischmacher
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
KM Europa Metal AG
Original Assignee
KM Europa Metal AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by KM Europa Metal AG filed Critical KM Europa Metal AG
Publication of EP0878561A2 publication Critical patent/EP0878561A2/en
Publication of EP0878561A3 publication Critical patent/EP0878561A3/en
Application granted granted Critical
Publication of EP0878561B1 publication Critical patent/EP0878561B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1617—Purification and regeneration of coating baths
    • 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
    • C25D21/16—Regeneration of process solutions
    • C25D21/22—Regeneration of process solutions by ion-exchange
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S204/00—Chemistry: electrical and wave energy
    • Y10S204/13—Purification and treatment of electroplating baths and plating wastes

Definitions

  • the invention relates to a method and an apparatus for regenerating used tinning solutions.
  • the external tinning of copper workpieces using an aqueous tinning solution is a common process in surface coating technology. It is used, for example, for the internal tinning of copper pipes or tinning of printed circuit boards for integrated circuits application.
  • the tinning solution contains aqueous dissolved tin ions which, due to a chemical reduction using a suitable reducing agent on the copper be deposited. This takes place on the surface of the copper workpieces Exchange between the metals takes place through one in the tinning solution contained complexing agent is made possible.
  • Hypophosphite is the main reducing agent used, thiourea is usually used as a complexing agent.
  • the used tinning solution then contains tin and copper ions, free and complexing agent bound to the copper ions, used and unused Reducing agents and, if appropriate, further constituents or in terms of process technology conditional contamination.
  • DE 43 10 366 C1 counts a method and a device for regeneration from aqueous, external currentless coating solutions for metal coating using metal ions and a reducing agent to the prior art Technology.
  • a combination of an ion exchange process with the Electrode reactions of the electrolysis made.
  • the process takes place in an at least four-chamber electrolysis cell. It electrolytic regeneration is achieved by reducing the amount generated in the process Orthophosphite in a cathode chamber to hypophosphite and through Electrodialytic provision of counter ion-free resharpening chemicals.
  • the present invention comes in, the object of which is a method and to show a device that allow the accumulating interference component Separate copper by cathodic deposition and at the same time to supply the consumable component tin, so that the Service life or service life of tinning solutions that operate without external power for copper workpieces can be significantly extended.
  • the essence of the invention is the measure of tinning solution used regenerate strong dilution.
  • a combination of Electrode reactions of electrolysis with transport processes in ion exchange membranes performed.
  • copper is depleted by cathodic deposition from a dilution of the tinning solution and Enrichment of tin by anodic dissolution and transport through a cation exchange membrane.
  • the invention adopts the knowledge that in a regeneration solution, in which the tinning solution used in the tinning process is strong is present diluted, the deposition ratio compared to the original concentrated Reverse tinning solution and prefer copper from the thermodynamic deposits disadvantaged copper complex. This can cause the interference component Copper depleted and the tin component required for the process can be supplied by anodic dissolution.
  • the regeneration solution is fed to an electrolysis cell, which has a cathode chamber with an inserted cathode, a middle chamber and one with a Anolyte filled anode chamber with incorporated anode.
  • the cathode chamber is separated from the middle chamber by an anion exchange membrane, whereas a cation exchange membrane between the anode chamber and the middle chamber is incorporated.
  • the regeneration solution first reaches the cathode chamber and rests there depositing copper on the cathode.
  • the dwell time depends on the total amount of metal supplied. Then will the copper-depleted regeneration solution is fed into the middle chamber, where a tin enrichment from the anolyte of the anode chamber through the cathode exchange membrane penetrated tin ions.
  • the prepared, tin-enriched regeneration solution can then be removed from the Middle chamber are fed for further use.
  • the prepared regeneration solution is expediently used in the tinning process returned where they also the water losses occurring there through evaporation compensates.
  • the regeneration solution consists of a 5 to 50% dilution of the tinning solution. Being particularly advantageous considered a concentration range between 10 to 15%.
  • the electrolyte concentration preferably has 10 to 15% of the process solution then passed into the cathode chamber of the electrolytic cell.
  • the copper ions contained in the regeneration solution are deposited cathodically. To a small extent, they are also in the regeneration solution contained tin ions cathodically deposited with.
  • the ions of the reducing agent can diffuse through the ion exchange membranes into the middle chamber, in which the regeneration solution of the previous regeneration cycle is located. This is already depleted in copper.
  • the regeneration solution transferred to the middle chamber in which the tin enrichment takes place.
  • tin ions which are anodically dissolved in the anode chamber, by diffusion from the anode chamber through the cation exchange membrane in the middle chamber.
  • the anions of the reducing agent are through the cation exchange membrane prevented from passing into the anode chamber, so that they remain in the middle chamber.
  • the combination of electrode reactions of electrolysis with transport processes in ion exchange membranes enables selective deposition according to the invention the interfering component copper from a regeneration solution in the form of diluted tinning solution.
  • the regenerated solution is used in the tinning process returned and refreshes the tinning solution. This will the service life and useful life of the tinning solution are significantly extended.
  • tetrafluoroboric acid or methanesulfonic acid can also be used as the anolyte be, as provided for in claim 6.
  • the temperature in the electrolytic cell between 10 ° C and 60 ° C.
  • the cathodic depletion starts best Copper and enrichment in tin in a temperature range between 30 ° C and 40 ° C.
  • the regeneration solution is moved in the electrolysis cell as claimed in claim 9 provides. This can be done, for example, by pumping from chamber to chamber take place or by stirring in the chambers. This causes polarization effects avoided in the chambers, especially on the membrane surfaces.
  • the temperature of the Electrolysis cell can be controlled (claim 10).
  • the method according to the invention can be used both in continuous cycle operation as well as in batch operation.
  • the regeneration solution can either quasi continuously in two cycles the cathode chamber or middle chamber of the three-chamber membrane electrolysis led or it can be a portion of the tinning solution diluted in the batch Cell regenerated and then returned to the tinning solution.
  • the cathode material preferably consists of copper or stainless steel 11).
  • the anode material consists of tin. This is a requirement for that Tin enrichment during the regeneration process.
  • the prepared regeneration solution is the same this out. If necessary, a needs-based process-dependent correction can be made or adjustment of the regeneration solution. In this way is also a cheaper water cycle management by the inventive method reached.
  • Electrolytic cells in stacks one after the other (series connection) or in parallel next to each other (Parallel connection). This creates a high capacity provided for the processing of used tinning solutions.
  • the example concerns a tinning electrolyte for tinning without external current the fluoroborate-based with the complexing agent thiourea and the reducing agent Hypophosphite is built up.
  • the invention leads to that in the regeneration solution in the tinning solution is present in the specified dilution, electrode kinetic effects (Breakdown reaction, exchange current density, overvoltage) an increasingly important Play role, so preferred despite the unfavorable potential conditions Copper can be deposited.
  • FIG. 1 The course of the regeneration process of a tinning solution is illustrated in FIG. 1.
  • the reaction equilibria, redox potentials that are important for the system and complex stability constants can be found in the table above.
  • FIG. 1 in FIG. 1 is a system for tinning copper workpieces without external current referred to by means of an aqueous tinning solution.
  • the copper workpieces are made in one Rinsing process cleaned.
  • the flushing process is with SP, the water supply through the Arrow marked W.
  • the tinning solution is carried out by electrolyte extraction towed portion diluted by the rinse water.
  • the rinse water to a 10 to 15% dilution the process solution concentrated.
  • the regeneration solution produced in this way becomes a three-chamber electrolysis cell 2 forwarded.
  • the electrolytic cell comprises a cathode chamber 3, one Middle chamber 4 and an anode chamber 5.
  • cathode chamber 3 there is a cathode 6 made of copper, in the anode chamber 5 is an anode 7 made of tin. Between anode 7 and cathode 6 a potential difference is created.
  • the cathode chamber 3 is through an anion exchange membrane 8 and the anode chamber 5 through a cation exchange membrane 9 from the middle chamber 4 Cut.
  • the regeneration solution is first fed into the cathode chamber 3 (arrow P1).
  • the interfering component copper is then cathodically separated from the thiourea complex at a current density of 0.4 to 0.6 A / dm 2 and thus removed from the system.
  • anions such as the tetrafluoroborate anion and the hypophosphite anion can pass through the anion exchange membrane 8 into the middle chamber 4.
  • the regenerated solution can be used in the tinning process be returned (arrow P3). This can also be used in the tinning process occurring evaporation losses can be compensated.
  • the in Evaporation occurring during the tinning process is indicated by the arrows V. If required, a need correction (arrow BK) of the prepared diluted solution made to the process engineering requirements of the tinning solution will.
  • the respective electrolyte solutions in the three reaction chambers are moved so that polarization effects in the reaction chambers 3, 4, 5, in particular on the membrane surfaces, are avoided.
  • the movement in the cathode chamber 3 and in the middle chamber 4 is indicated by the arrows B1 and B2.
  • the movement B1, B2 can take place, for example, by stirring.
  • the anolyte (H 2 SO 4 ) in the anode chamber 5 is conducted in a separate circuit. This is indicated by arrow B3.
  • the combination of electrode reactions of electrolysis with transport processes in ion exchange membranes thus enables a selective separation of the Interfering component copper from a diluted tinning solution with simultaneous Enrichment of tin via anodic dissolution and transport of the tin ions through the cation exchange membrane.
  • the regenerated solution is in the tinning solution of the tinning process. This will make the Service life or the useful life of the tinning solution significantly extended.
  • Electrolytic cells 2 in stacks one after the other (series connection) or in parallel next to each other (Parallel connection) are connected. This way, each Capacity designed for the processing of tinning solutions reached.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Chemically Coating (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

Die Erfindung betrifft ein Verfahren und eine Vorrichtung zum Regenerieren von verbrauchten Verzinnungslösungen, welche Zinn und Kupferionen, freien und an die Kupferionen gebundenen Komplexbildner sowie verbrauchtes und unverbrauchtes Reduktionsmittel enthalten. Durch eine entsprechende Spültechnik wird das Spülwasser des Verzinnungsprozesses auf eine 10 bis 15 %ige Verdünnung der Prozeßlösung konzentriert. Diese so hergestellte Regenerationslösung wird einer Elektrolysezelle (2) zugeleitet. Diese umfaßt eine Kathodenkammer (3), eine Mittelkammer (4) und eine Anodenkammer (5). Die Kathodenkammer (3) ist durch eine Anionenaustauschermembran (8) und die Anodenkammer (5) ist durch eine Kationenaustauschermembran (9) von der Mittelkammer (4) getrennt. Die Regenerationslösung wird zunächst in die Kathodenkammer (3) geleitet. Hier wird die Störkomponente Kupfer kathodisch abgeschieden. Nach einer entsprechenden Verweilzeit wird die an Kupfer abgereicherte Regenerationslösung in die Mittelkammer (4) umgepumpt, wo eine Zinnanreicherung von aus der Anodenkammer (5) durch die Kationenaustauschermembran (9) diffundierten Zinnionen erfolgt. Die regenerierte Lösung wird anschließend in den Verzinnungsprozeß zurückgeführt.The invention relates to a method and a device for regenerating used tinning solutions which contain tin and copper ions, free complexing agents bound to the copper ions and used and unused reducing agents. Using a suitable rinsing technique, the rinsing water from the tinning process is concentrated to a 10 to 15% dilution of the process solution. This regeneration solution thus produced is fed to an electrolysis cell (2). This comprises a cathode chamber (3), a middle chamber (4) and an anode chamber (5). The cathode chamber (3) is separated from the central chamber (4) by an anion exchange membrane (8) and the anode chamber (5) is separated by a cation exchange membrane (9). The regeneration solution is first fed into the cathode chamber (3). The interfering component copper is deposited cathodically here. After a corresponding dwell time, the copper-depleted regeneration solution is pumped into the middle chamber (4), where there is a tin enrichment of tin ions diffused from the anode chamber (5) through the cation exchange membrane (9). The regenerated solution is then returned to the tinning process.

Description

Die Erfindung betrifft ein Verfahren und eine Vorrichtung zum Regenerieren von verbrauchten Verzinnungslösungen.The invention relates to a method and an apparatus for regenerating used tinning solutions.

Die außenstromlose Verzinnung von Kupferwerkstücken mittels einer wäßrigen Verzinnungslösung ist ein gängiges Verfahren in der Oberflächenbeschichtungstechnik. Es findet beispielsweise bei der Innenverzinnung von Kupferrohren oder der Verzinnung von Platinen für integrierte Schaltkreise Anwendung.The external tinning of copper workpieces using an aqueous tinning solution is a common process in surface coating technology. It is used, for example, for the internal tinning of copper pipes or tinning of printed circuit boards for integrated circuits application.

Die Verzinnungslösung enthält wäßrig gelöste Zinnionen, welche aufgrund einer chemischen Reduktion mittels eines geeigneten Reduktionsmittels auf dem Kupfer abgeschieden werden. Hierbei findet an der Oberfläche der Kupferwerkstücke ein Austausch zwischen den Metallen statt, der durch einen in der Verzinnungslösung enthaltenen Komplexbildner ermöglicht wird. Als Reduktionsmittel wird vor allem Hypophosphit eingesetzt, als Komplexbildner findet meist Thioharnstoff Anwendung.The tinning solution contains aqueous dissolved tin ions which, due to a chemical reduction using a suitable reducing agent on the copper be deposited. This takes place on the surface of the copper workpieces Exchange between the metals takes place through one in the tinning solution contained complexing agent is made possible. Hypophosphite is the main reducing agent used, thiourea is usually used as a complexing agent.

Durch die Herabsetzung des Redoxpotentials von Kupfer in der komplexgebundenen Form, geht Kupfer in Lösung und Zinn scheidet sich auf der Oberfläche des Kupferwerkstücks ab. Da bei chemischen Reaktionen keine freien Elektronen auftreten, ist die Oxidation eines Reaktionspartners stets von der Reduktion eines anderen begleitet. By reducing the redox potential of copper in the complex-bound Form, copper goes into solution and tin separates on the surface of the copper workpiece from. Since there are no free electrons in chemical reactions the oxidation of one reactant is always accompanied by the reduction of another.

Mit dem Prozeß der außenstromlosen Verzinnung ist folglich eine Anreicherung von Kupfer und eine Abreicherung von Zinn in der Verzinnungslösung verbunden. Im konventionellen Betrieb muß daher Zinn und Komplexbildner nachdosiert werden, bis eine Kupfergrenzkonzentration erreicht ist, bei der die Lösung unbrauchbar ist und ausgetauscht werden muß. Desweiteren muß von Zeit zu Zeit Reduktionsmittel nachdosiert werden, da sich dieses verbraucht, wenn nach dem Erreichen einer vollständigen Zinnschicht noch weiteres Metall abgeschieden werden soll.With the process of electroless tinning is therefore an enrichment of Copper and a depletion of tin in the tinning solution. in the conventional operation must therefore be replenished with tin and complexing agents, until a copper limit concentration is reached at which the solution is unusable and needs to be replaced. Furthermore, reducing agents must be used from time to time be replenished, as this is used up if after reaching one complete metal layer, additional metal is to be deposited.

Die verbrauchte Verzinnungslösung enthält dann Zinn- und Kupferionen, freien und an die Kupferionen gebundenen Komplexbildner, verbrauchtes und unverbrauchtes Reduktionsmittel und gegebenenfalls weitere Bestandteile oder prozeßtechnisch bedingte Verunreinigungen.The used tinning solution then contains tin and copper ions, free and complexing agent bound to the copper ions, used and unused Reducing agents and, if appropriate, further constituents or in terms of process technology conditional contamination.

Zur Regenerierung eines galvanischen Verzinnungselektrolyten wird durch die DE 27 42 718 A1 vorgeschlagen, zuerst die Zinnionen mittels Elektrolyse zu entfernen und dann im Anschluß die Fremdmetallionen in einem Kationenaustauscher zu entfernen.For the regeneration of a galvanic tinning electrolyte DE 27 42 718 A1 proposed to first remove the tin ions by means of electrolysis and then the foreign metal ions in a cation exchanger remove.

Durch die DE 43 10 366 C1 zählt ein Verfahren und eine Vorrichtung zum Regenerieren von wäßrigen, außenstromlos arbeitenden Beschichtungslösungen zur Metallbeschichtung mittels Metallionen und eines Reduktionsmittels zum Stand der Technik. Hierbei wird eine Kombination eines Ionenaustauscher-Prozesses mit den Elektrodenreaktionen der Elektrolyse vorgenommen.DE 43 10 366 C1 counts a method and a device for regeneration from aqueous, external currentless coating solutions for metal coating using metal ions and a reducing agent to the prior art Technology. Here, a combination of an ion exchange process with the Electrode reactions of the electrolysis made.

Der Vorgang findet in einer mindestens vierkammerigen Elektrolysezelle statt. Es wird eine elektrolytische Regeneration erreicht durch Reduktion von im Prozeß entstehendem Orthophosphit in einer Kathodenkammer zu Hypophosphit und durch elektrodialytische Bereitstellung von gegenionenfreien Nachschärfchemikalien. The process takes place in an at least four-chamber electrolysis cell. It electrolytic regeneration is achieved by reducing the amount generated in the process Orthophosphite in a cathode chamber to hypophosphite and through Electrodialytic provision of counter ion-free resharpening chemicals.

Eine elektrolytische Regeneration von außenstromlos arbeitenden Verzinnungslösungen konnte bislang nicht erfolgreich praktiziert werden, da bereits die thermodynamischen Potentiale des komplexgebundenen Kupfers und des Zinns gegen eine Kupferabscheidung sprechen.An electrolytic regeneration of tinning solutions that operate without external current could not be practiced successfully because the thermodynamic Potentials of complex-bound copper and tin against one Speak copper deposition.

Hier setzt die vorliegende Erfindung ein, deren Aufgabe es ist, ein Verfahren und eine Vorrichtung aufzuzeigen, welche es ermöglichen, die sich anreichernde Störkomponente Kupfer durch kathodische Abscheidung abzutrennen und gleichzeitig die sich verbrauchende Komponente Zinn nachzuliefern, so daß hierdurch die Nutzungsdauer bzw. Standzeit von außenstromlos arbeitenden Verzinnungslösungen für Kupferwerkstücke deutlich verlängert werden kann.This is where the present invention comes in, the object of which is a method and to show a device that allow the accumulating interference component Separate copper by cathodic deposition and at the same time to supply the consumable component tin, so that the Service life or service life of tinning solutions that operate without external power for copper workpieces can be significantly extended.

Die Lösung des verfahrensmäßigen Teils dieser Aufgabe besteht in den Merkmalen des Anspruchs 1.The solution to the procedural part of this task consists in the features of claim 1.

Die Lösung des gegenständlichen Teils dieser Aufgabe ist in den Merkmalen des Anspruchs 8 zu sehen.The solution of the objective part of this task is in the characteristics of the Claim 8 to see.

Vorteilhafte Weiterbildungen des erfindungsgemäßen Verfahrens sind in den abhängigen Ansprüchen 2 bis 7 charakterisiert. Vorteilhafte Ausgestaltungen der erfindungsgemäßen Vorrichtung bilden den Gegenstand der abhängigen Ansprüche 9 bis 12.Advantageous developments of the method according to the invention are in the dependent Claims 2 to 7 characterized. Advantageous embodiments of the invention Device form the subject of dependent claims 9 until 12.

Kernpunkt der Erfindung bildet die Maßnahme, verbrauchte Verzinnungslösung in starker Verdünnung zu regenerieren. Erfindungsgemäß wird eine Kombination von Elektrodenreaktionen der Elektrolyse mit Transportprozessen in Ionenaustauschermembranen vorgenommen. Hierbei erfolgt eine Abreicherung von Kupfer durch kathodische Abscheidung aus einer Verdünnung der Verzinnungslösung und Anreicherung von Zinn durch anodische Auflösung und Transport durch eine Kationenaustauschermembran. The essence of the invention is the measure of tinning solution used regenerate strong dilution. According to the invention, a combination of Electrode reactions of electrolysis with transport processes in ion exchange membranes performed. Here, copper is depleted by cathodic deposition from a dilution of the tinning solution and Enrichment of tin by anodic dissolution and transport through a cation exchange membrane.

Die Erfindung macht sich dabei die Erkenntnis zu eigen, daß bei einer Regenerationslösung, in der die im Verzinnungsprozeß verwendete Verzinnungslösung stark verdünnt vorliegt, sich die Abscheideverhältnisse gegenüber der originalkonzentrierten Verzinnungslösung umkehren und sich bevorzugt Kupfer aus dem thermodynamisch benachteiligten Kupferkomplex abscheidet. Dadurch kann die Störkomponente Kupfer abgereichert und die für den Prozeß notwendige Komponente Zinn durch anodische Auflösung nachgeliefert werden.The invention adopts the knowledge that in a regeneration solution, in which the tinning solution used in the tinning process is strong is present diluted, the deposition ratio compared to the original concentrated Reverse tinning solution and prefer copper from the thermodynamic deposits disadvantaged copper complex. This can cause the interference component Copper depleted and the tin component required for the process can be supplied by anodic dissolution.

Die Regenerationslösung wird einer Elektrolysezelle zugeleitet, welche eine Kathodenkammer mit eingegliederter Kathode, eine Mittelkammer und eine mit einem Anolyten gefüllte Anodenkammer mit eingegliederter Anode umfaßt. Die Kathodenkammer ist durch eine Anionenaustauschermembran von der Mittelkammer getrennt, wohingegen zwischen Anodenkammer und Mittelkammer eine Kationenaustauschermembran eingegliedert ist. Zwischen Anode und Kathode ist eine elektrische Potentialdifferenz angelegt.The regeneration solution is fed to an electrolysis cell, which has a cathode chamber with an inserted cathode, a middle chamber and one with a Anolyte filled anode chamber with incorporated anode. The cathode chamber is separated from the middle chamber by an anion exchange membrane, whereas a cation exchange membrane between the anode chamber and the middle chamber is incorporated. There is an electrical one between the anode and the cathode Potential difference created.

In der Elektrolysezelle gelangt die Regenerationslösung zunächst in die Kathodenkammer und verweilt dort unter Abscheidung von Kupfer an die Kathode. Die Verweilzeit ist abhängig von der zugeführten Gesamtmetallmenge. Anschließend wird die an Kupfer abgereicherte Regenerationslösung in die Mittelkammer geleitet, wo eine Zinnanreicherung von aus dem Anolyten der Anodenkammer durch die Kathodenaustauschermembran durchgetretenen Zinnionen erfolgt.In the electrolysis cell, the regeneration solution first reaches the cathode chamber and rests there depositing copper on the cathode. The dwell time depends on the total amount of metal supplied. Then will the copper-depleted regeneration solution is fed into the middle chamber, where a tin enrichment from the anolyte of the anode chamber through the cathode exchange membrane penetrated tin ions.

Danach kann die aufbereitete, mit Zinn angereicherte Regenerationslösung aus der Mittelkammer der Weiterverwendung zugeführt werden.The prepared, tin-enriched regeneration solution can then be removed from the Middle chamber are fed for further use.

Zweckmäßigerweise wird die aufbereitete Regenerationslösung in den Verzinnungsprozeß zurückgeführt, wo sie auch die dort durch Verdunstung auftretenden Wasserverluste ausgleicht. The prepared regeneration solution is expediently used in the tinning process returned where they also the water losses occurring there through evaporation compensates.

Gemäß den Merkmalen des Anspruchs 2 besteht die Regenerationslösung aus einer 5 bis 50 %igen Verdünnung der Verzinnungslösung. Als besonders vorteilhaft wird ein Konzentrationsbereich zwischen 10 bis 15 % angesehen.According to the features of claim 2, the regeneration solution consists of a 5 to 50% dilution of the tinning solution. Being particularly advantageous considered a concentration range between 10 to 15%.

Auch wenn es grundsätzlich möglich ist, die Regenerationslösung durch Abziehen von Verzinnungslösung aus dem Beschichtungsprozeß und Zumischen einer entsprechend hohen Menge von Wasser zu erhalten, ist eine besonders vorteilhafte Weiterbildung des erfindungsgemäßen Verfahrens in den Merkmalen des Anspruchs 3 zu sehen. Danach wird die Regenerationslösung aus einem Spülprozeß der Kupferwerkstücke gewonnen.Even if it is basically possible to withdraw the regeneration solution of tinning solution from the coating process and admixing one accordingly Getting high amounts of water is a particularly beneficial one Further development of the method according to the invention in the features of the claim 3 to see. The regeneration solution then becomes a rinsing process for the copper workpieces won.

Das durch eine geeignete Spültechnik aufkonzentrierte Spülwasser, das eine Elektrolytkonzentration von vorzugsweise 10 bis 15 % der Prozeßlösung besitzt, wird dann in die Kathodenkammer der Elektrolysezelle geleitet.The rinsing water concentrated by a suitable rinsing technique, the electrolyte concentration preferably has 10 to 15% of the process solution then passed into the cathode chamber of the electrolytic cell.

Die Verdünnung der Verzinnungslösung, die sich automatisch beim Spülprozeß ergibt und durch geeignete Spültechniken auf den geforderten Konzentrationsbereich gebracht wird, ermöglicht die kathodische Abscheidung von Kupfer aus dem Komplex gegenüber Zinn, und zwar obwohl die thermodynamischen Redoxpotentiale dies nicht erwarten lassen.The dilution of the tinning solution that results automatically during the rinsing process and through suitable flushing techniques to the required concentration range brought, the cathodic deposition of copper from the complex compared to tin, even though the thermodynamic redox potentials do not expect this.

Die in der Regenerationslösung enthaltenen Kupferionen werden kathodisch abgeschieden. In geringem Maße werden auch die ebenfalls in der Regenerationslösung enthaltenen Zinnionen kathodisch mit abgeschieden. Die Ionen des Reduktionsmittels können durch die Ionenaustauschermembranen in die Mittelkammer diffundieren, in der sich die Regenerationslösung des vorhergehenden Regeneriertakts befindet. Diese ist bereits an Kupfer abgereichert.The copper ions contained in the regeneration solution are deposited cathodically. To a small extent, they are also in the regeneration solution contained tin ions cathodically deposited with. The ions of the reducing agent can diffuse through the ion exchange membranes into the middle chamber, in which the regeneration solution of the previous regeneration cycle is located. This is already depleted in copper.

Nach der Kupferanreicherung in der Kathodenkammer wird die Regenerationslösung in die Mittelkammer überführt, in der die Zinnanreicherung stattfindet. After the copper enrichment in the cathode chamber, the regeneration solution transferred to the middle chamber in which the tin enrichment takes place.

Hierbei gelangen Zinnionen, die in der Anodenkammer anodisch aufgelöst werden, durch Diffusion aus der Anodenkammer durch die Kationenaustauschermembran in die Mittelkammer. Die Anionen des Reduktionsmittels werden durch die Kationenaustauschermembran an einem Durchtritt in die Anodenkammer gehindert, so daß sie in der Mittelkammer verbleiben.Here tin ions, which are anodically dissolved in the anode chamber, by diffusion from the anode chamber through the cation exchange membrane in the middle chamber. The anions of the reducing agent are through the cation exchange membrane prevented from passing into the anode chamber, so that they remain in the middle chamber.

Die Kombination von Elektrodenreaktionen der Elektrolyse mit Transportprozessen in Ionenaustauschermembranen ermöglicht erfindungsgemäß eine selektive Abscheidung der Störkomponente Kupfer aus einer Regenerationslösung in Form von verdünnter Verzinnungslösung.The combination of electrode reactions of electrolysis with transport processes in ion exchange membranes enables selective deposition according to the invention the interfering component copper from a regeneration solution in the form of diluted tinning solution.

Im Anschluß an die Zinnanreicherung wird die regenerierte Lösung in den Verzinnungsprozeß zurückgeführt und frischt die Verzinnungslösung auf. Hierdurch wird die Standzeit und Nutzungsdauer der Verzinnungslösung deutlich verlängert.Following the tin enrichment, the regenerated solution is used in the tinning process returned and refreshes the tinning solution. This will the service life and useful life of the tinning solution are significantly extended.

Als Anolyt, der in einem eigenen Kreislauf geführt wird (Anspruch 4), kommt Schwefelsäure zur Anwendung, vorzugsweise in einer Konzentration zwischen 3 % und 6 % (Anspruch 5). Hier verläuft eine anodische Auflösung des Zinns ohne Polarisationseffekt mit nahezu 100 %iger Stromausbeute.As an anolyte, which is carried out in a separate circuit (claim 4) Sulfuric acid for use, preferably in a concentration between 3% and 6% (claim 5). Anodic dissolution of the tin takes place here without a polarization effect with almost 100% current efficiency.

Alternativ kann als Anolyt auch Tetrafluoroborsäure oder Methansulfonsäure eingesetzt werden, wie dies Anspruch 6 vorsieht.Alternatively, tetrafluoroboric acid or methanesulfonic acid can also be used as the anolyte be, as provided for in claim 6.

Nach den Merkmalen des Anspruchs 7 liegt die Temperatur in der Elektrolysezelle zwischen 10 °C und 60 °C. Am besten verläuft die kathodische Abreicherung an Kupfer und Anreicherung an Zinn in einem Temperaturbereich zwischen 30 °C und 40 °C.According to the features of claim 7, the temperature in the electrolytic cell between 10 ° C and 60 ° C. The cathodic depletion starts best Copper and enrichment in tin in a temperature range between 30 ° C and 40 ° C.

Die Regenerationslösung wird in der Elektrolysezelle bewegt, wie dies Anspruch 9 vorsieht. Dies kann beispielsweise durch das Umpumpen von Kammer zu Kammer erfolgen oder durch ein Rühren in den Kammern. Hierdurch werden Polarisationseffekte in den Kammern, insbesondere an den Membranoberflächen, vermieden. The regeneration solution is moved in the electrolysis cell as claimed in claim 9 provides. This can be done, for example, by pumping from chamber to chamber take place or by stirring in the chambers. This causes polarization effects avoided in the chambers, especially on the membrane surfaces.

Zur Gewährleistung optimaler Regenerationsbedingungen kann die Temperatur der Elektrolysezelle steuerbar sein (Anspruch 10).To ensure optimal regeneration conditions, the temperature of the Electrolysis cell can be controlled (claim 10).

Das erfindungsgemäße Verfahren läßt sich sowohl im kontinuierlichen Taktbetrieb als auch im Chargenbetrieb durchführen.The method according to the invention can be used both in continuous cycle operation as well as in batch operation.

Die Regenerationslösung kann entweder quasi kontinuierlich in zwei Takten durch die Kathodenkammer bzw. Mittelkammer der dreikammerigen Membranelektrolyse geführt oder es kann ein Anteil der Verzinnungslösung als Charge verdünnt in der Zelle regeneriert und anschließend wieder der Verzinnungslösung zugeführt werden.The regeneration solution can either quasi continuously in two cycles the cathode chamber or middle chamber of the three-chamber membrane electrolysis led or it can be a portion of the tinning solution diluted in the batch Cell regenerated and then returned to the tinning solution.

Vorzugsweise besteht das Kathodenmaterial aus Kupfer oder Edelstahl (Anspruch 11). Das Anodenmaterial besteht aus Zinn. Dies ist eine Voraussetzung für die Zinnanreicherung während des Regenerationsprozesses.The cathode material preferably consists of copper or stainless steel 11). The anode material consists of tin. This is a requirement for that Tin enrichment during the regeneration process.

Da ein Verzinnungsprozeß üblicherweise bei Temperaturen zwischen 70 °C und 80 °C durchgeführt wird, treten entsprechend hohe Verdunstungsverluste in der Verzinnungslösung auf. Die zugeführte aufbereitete Regenerationslösung gleicht diese aus. Falls erforderlich, kann eine bedarfsgerechte prozeßabhängige Korrektur bzw. Einstellung der Regenerationslösung vorgenommen werden. Auf diese Weise wird durch das erfindungsgemäße Verfahren auch eine günstigere Wasserkreislaufführung erreicht.Since a tinning process usually takes place at temperatures between 70 ° C and 80 ° C is carried out, correspondingly high evaporation losses occur in the Tinning solution. The prepared regeneration solution is the same this out. If necessary, a needs-based process-dependent correction can be made or adjustment of the regeneration solution. In this way is also a cheaper water cycle management by the inventive method reached.

Gemäß den Merkmalen des Anspruchs 12 können zwei oder mehrere Elektrolysezellen stapelweise hintereinander (Reihenschaltung) oder parallel nebeneinander (Parallelschaltung) geschaltet werden. Damit wird eine hohe Kapazität für die Aufbereitung verbrauchter Verzinnungslösungen bereitgestellt.According to the features of claim 12, two or more Electrolytic cells in stacks one after the other (series connection) or in parallel next to each other (Parallel connection). This creates a high capacity provided for the processing of used tinning solutions.

Die Erfindung ist nachstehend durch ein Beispiel und eine Abbildung näher erläutert. The invention is explained in more detail below by an example and an illustration.

Das Beispiel betrifft einen Verzinnungselektrolyten zur außenstromlosen Verzinnung der auf Fluoroboratbasis mit dem Komplexbildner Thioharnstoff und dem Reduktionsmittel Hypophosphit aufgebaut ist.The example concerns a tinning electrolyte for tinning without external current the fluoroborate-based with the complexing agent thiourea and the reducing agent Hypophosphite is built up.

Für das Beispiel gelten die in der nachfolgenden Tabelle aufgeführten Daten:The data listed in the table below apply to the example:

Redoxpotentiale:Redox potential:

Figure 00080001
Figure 00080001

Stabilitätskonstanten:Stability constants:

Ks (Cu(TH)2 +)
= 2,0 x 1012
Ks (Cu(TH)3 +)
= 2,0 x 1014
Ks (Cu(TH)4 +)
= 3,4 x 1015 bzw. 2,4 x 1015
aus [Inorg. Chem., 15, 940, (1976)] und [J. Am. Chem. Soc., 72, 4724, (1950)]
K s (Cu (TH) 2 + )
= 2.0 x 10 12
K s (Cu (TH) 3 + )
= 2.0 x 10 14
K s (Cu (TH) 4 + )
= 3.4 x 10 15 or 2.4 x 10 15
from [Inorg. Chem., 15, 940, (1976)] and [J. At the. Chem. Soc., 72, 4724, (1950)]

In der Tabelle sind außer den Reaktionsgleichgewichten für das System aus Zinnionen, komplexgebundenen Kupferionen und Anionen des Reduktionsmittels auch diejenigen der chemischen Wasserzersetzung aufgeführt, da diese bei der Membranelektrolyse, insbesondere bei stark verdünnten Lösungen, mit berücksichtigt werden müssen.In addition to the reaction equilibria for the tin ion system, complex-bound copper ions and anions of the reducing agent too those of chemical water decomposition, as these are used in membrane electrolysis, especially with very dilute solutions Need to become.

Es zeigt sich anhand der Daten, daß freies Kupfer, sowohl als Cu(I) als auch als Cu(II) bevorzugt gegenüber Zinn abgeschieden werden könnte. Da das Kupfer aber ausschließlich als komplexgebundenes Kupfer vorliegt, erfolgt eine Zinnabscheidung. Dies ist in konzentrierten Lösungen auch der Fall. The data show that free copper, both as Cu (I) and as Cu (II) could preferably be deposited over tin. Since the copper Tin is only deposited as complex-bound copper. This is also the case in concentrated solutions.

Die Erfindung führt dazu, daß bei der Regenerationslösung in der Verzinnungslösung in der angegebenen Verdünnung vorliegt, elektrodenkinetische Effekte (Durchtrittsreaktion, Austauschstromdichte, Überspannung) eine zunehmend wichtigere Rolle spielen, so daß trotz der ungünstigen Potentialverhältnisse bevorzugt Kupfer abgeschieden werden kann.The invention leads to that in the regeneration solution in the tinning solution is present in the specified dilution, electrode kinetic effects (Breakdown reaction, exchange current density, overvoltage) an increasingly important Play role, so preferred despite the unfavorable potential conditions Copper can be deposited.

Der Ablauf des Regenerationsprozesses einer Verzinnungslösung ist in Figur 1 verdeutlicht. Die für das System wichtigen Reaktionsgleichgewichte, Redoxpotentiale und Komplexstabilitätskonstanten finden sich in vorstehender Tabelle.The course of the regeneration process of a tinning solution is illustrated in FIG. 1. The reaction equilibria, redox potentials that are important for the system and complex stability constants can be found in the table above.

Mit 1 ist in der Figur 1 eine Anlage zur außenstromlosen Verzinnung von Kupferwerkstücken mittels einer wäßrigen Verzinnungslösung bezeichnet.1 in FIG. 1 is a system for tinning copper workpieces without external current referred to by means of an aqueous tinning solution.

Im Anschluß an den Verzinnungsprozeß werden die Kupferwerkstücke in einem Spülvorgang gereinigt. Der Spülvorgang ist mit SP, die Wasserzuführung durch den Pfeil W gekennzeichnet. Hierbei wird der aus der Verzinnungslösung durch Elektrolytausschleppung ausgeschleppte Anteil durch das Spülwasser verdünnt. Durch eine entsprechende Spültechnik wird das Spülwasser auf eine 10 bis 15 %ige Verdünnung der Prozeßlösung konzentriert.Following the tinning process, the copper workpieces are made in one Rinsing process cleaned. The flushing process is with SP, the water supply through the Arrow marked W. Here, the tinning solution is carried out by electrolyte extraction towed portion diluted by the rinse water. By a appropriate rinsing technology, the rinse water to a 10 to 15% dilution the process solution concentrated.

Die so hergestellte Regenerationslösung wird einer dreikammerigen Elektrolysezelle 2 zugeleitet. Die Elektrolysezelle umfaßt eine Kathodenkammer 3, eine Mittelkammer 4 und eine Anodenkammer 5.The regeneration solution produced in this way becomes a three-chamber electrolysis cell 2 forwarded. The electrolytic cell comprises a cathode chamber 3, one Middle chamber 4 and an anode chamber 5.

In der Kathodenkammer 3 befindet sich eine Kathode 6 aus Kupfer, in der Anodenkammer 5 ist eine Anode 7 aus Zinn angeordnet. Zwischen Anode 7 und Kathode 6 ist eine Potentialdifferenz angelegt.In the cathode chamber 3 there is a cathode 6 made of copper, in the anode chamber 5 is an anode 7 made of tin. Between anode 7 and cathode 6 a potential difference is created.

Die Kathodenkammer 3 ist durch eine Anionenaustauschermembran 8 und die Anodenkammer 5 durch eine Kationenaustauschermembran 9 von der Mittelkammer 4 getrennt. The cathode chamber 3 is through an anion exchange membrane 8 and the anode chamber 5 through a cation exchange membrane 9 from the middle chamber 4 Cut.

Die Regenerationslösung wird zunächst in die Kathodenkammer 3 geleitet (Pfeil P1). Die Störkomponente Kupfer wird dann aus dem Thioharnstoffkomplex bei einer Stromdichte von 0,4 bis 0,6 A/dm2 zu über 95 % kathodisch abgeschieden und damit aus dem System entfernt. Gleichzeitig können Anionen, wie das Tetrafluoroboratanion und das Hypophosphitanion durch die Anionenaustauschermembran 8 in die Mittelkammer 4 durchtreten.The regeneration solution is first fed into the cathode chamber 3 (arrow P1). The interfering component copper is then cathodically separated from the thiourea complex at a current density of 0.4 to 0.6 A / dm 2 and thus removed from the system. At the same time, anions such as the tetrafluoroborate anion and the hypophosphite anion can pass through the anion exchange membrane 8 into the middle chamber 4.

Als Nebenreaktionen können eine Mitabscheidung des Zinns von weniger als 35 %, die Zersetzung von Wasser durch Wasserstoffentwicklung und eine Reduktion von Orthophosphitanteilen zu Hypophosphit über den entstehenden Wasserstoff eintreten. Insbesondere die Wasserzersetzung aufgrund der Verdünnung führt zu einer geringeren Stromausbeute (ca. 40 %) bezüglich der Metallabscheidung.As a side reaction, tin co-deposition of less than 35%, the decomposition of water through hydrogen evolution and a reduction of Orthophosphite parts to hypophosphite occur via the hydrogen formed. In particular, the water decomposition due to the dilution leads to a lower current efficiency (approx. 40%) with regard to metal deposition.

Nach einer der abzuscheidenden Metallmenge entsprechenden Verweilzeit wird der Inhalt der Kathodenkammer 3 in die Mittelkammer 4 umgepumpt (siehe Pfeil P 2). Hier findet eine Zinnanreicherung durch Zinnionen statt, die aus der Anodenkammer 5 durch die Kationenaustauschermembran 9 diffundieren. Die Tetrafluoroborat- und Hypophospitionen können wegen der Kationenaustauschermembran 9 nicht in die Anodenkammer 5 durchtreten.After a dwell time corresponding to the amount of metal to be deposited, the Pumped contents of the cathode chamber 3 into the middle chamber 4 (see arrow P 2). Here a tin enrichment by tin ions takes place, which comes from the anode chamber 5 diffuse through the cation exchange membrane 9. The tetrafluoroborate and Hypophospitations can not because of the cation exchange membrane 9 in the Step through anode chamber 5.

Im Anschluß an die Zinnanreicherung kann die regenerierte Lösung in den Verzinnungsprozeß zurückgeführt werden (Pfeil P3). Hierdurch können auch die im Verzinnungsprozeß auftretenden Verdunstungsverluste ausgeglichen werden. Die im Verzinnungsprozeß auftretende Verdunstung ist durch die Pfeile V angedeutet. Falls erforderlich, kann eine Bedarfskorrektur (Pfeil BK) der aufbereiteten verdünnten Lösung auf die prozeßtechnischen Anforderungen der Verzinnungslösung vorgenommen werden. Following the tin enrichment, the regenerated solution can be used in the tinning process be returned (arrow P3). This can also be used in the tinning process occurring evaporation losses can be compensated. The in Evaporation occurring during the tinning process is indicated by the arrows V. If required, a need correction (arrow BK) of the prepared diluted solution made to the process engineering requirements of the tinning solution will.

Die jeweiligen Elektrolytlösungen in den drei Reaktionskammern (Kathodenkammer 3, Mittelkammer 4, Anodenkammer 5) werden bewegt, damit Polarisationseffekte in den Reaktionskammern 3, 4, 5, insbesondere an den Membranoberflächen, vermieden werden. Die Bewegung in der Kathodenkammer 3 und in der Mittelkammer 4 ist durch die Pfeile B1 und B2 angedeutet. Die Bewegung B1, B2 kann beispielsweise durch Rühren erfolgen. Der Anolyt (H2SO4) in der Anodenkammer 5 wird in einem eigenen Kreislauf geführt. Dieser ist durch den Pfeil B3 gekennzeichnet.The respective electrolyte solutions in the three reaction chambers (cathode chamber 3, middle chamber 4, anode chamber 5) are moved so that polarization effects in the reaction chambers 3, 4, 5, in particular on the membrane surfaces, are avoided. The movement in the cathode chamber 3 and in the middle chamber 4 is indicated by the arrows B1 and B2. The movement B1, B2 can take place, for example, by stirring. The anolyte (H 2 SO 4 ) in the anode chamber 5 is conducted in a separate circuit. This is indicated by arrow B3.

Die Kombination von Elektrodenreaktionen der Elektrolyse mit Transportprozessen in Ionenaustauschermembranen ermöglicht somit eine selektive Abscheidung der Störkomponente Kupfer aus einer verdünnten Verzinnungslösung bei gleichzeitiger Anreicherung von Zinn über anodische Auflösung und Transport der Zinnionen durch die Kationenaustauschermembran. Die regenerierte Lösung wird in die Verzinnungslösung des Verzinnungsprozesses zurückgeführt. Hierdurch wird die Standzeit bzw. die Nutzungsdauer der Verzinnungslösung deutlich verlängert.The combination of electrode reactions of electrolysis with transport processes in ion exchange membranes thus enables a selective separation of the Interfering component copper from a diluted tinning solution with simultaneous Enrichment of tin via anodic dissolution and transport of the tin ions through the cation exchange membrane. The regenerated solution is in the tinning solution of the tinning process. This will make the Service life or the useful life of the tinning solution significantly extended.

Erfindungsgemäß ist es möglich, daß zwei oder mehrere der vorbeschriebenen Elektrolysezellen 2 stapelweise hintereinander (Reihenschaltung) oder parallel nebeneinander (Parallelschaltung) geschaltet sind. Auf diese Weise wird die jeweils bedarfsgerecht gestaltete Kapazität für die Aufbereitung von Verzinnungslösungen erreicht. According to the invention it is possible that two or more of the above Electrolytic cells 2 in stacks one after the other (series connection) or in parallel next to each other (Parallel connection) are connected. This way, each Capacity designed for the processing of tinning solutions reached.

BezugszeichenaufstellungList of reference symbols

  • 1 - Verzinnungsanlage1 - Tinning plant
  • 2 - Elektrolysezelle2 - Electrolysis cell
  • 3 - Kathodenkammer3 - cathode chamber
  • 4 - Mittelkammer4 - middle chamber
  • 5 - Anodenkammer5 - anode chamber
  • 6 - Kathode6 - cathode
  • 7 - Anode7 - anode
  • 8 - Anionenaustauschermembran8 - Anion exchange membrane
  • 9 - Kationenaustauschermembran9 - cation exchange membrane
  • B1 - PfeilB1 - arrow
  • B2 - PfeilB2 - arrow
  • B3 - PfeilB3 - arrow
  • BK - BedarfskorrekturBK - need correction
  • P1 - PfeilP1 - arrow
  • P2 - PfeilP2 - arrow
  • P3 - PfeilP3 - arrow
  • SP - SpülvorgangSP - flushing process
  • V - VerdunstungV - evaporation

    • Claims (12)

    Verfahren zum Regenerieren einer wäßrigen, außenstromlos arbeitenden Verzinnungslösung für Kupferwerkstücke, welche Zinn- und Kupferionen, freien und an die Kupferionen gebundenen Komplexbildner sowie verbrauchtes und unverbrauchtes Reduktionsmittel enthält, dadurch gekennzeichnet, daß eine verdünnte Verzinnungslösung enthaltende Regenerationslösung einer Elektrolysezelle (2) zugeleitet wird, welche eine Kathodenkammer (3) mit eingegliederter Kathode (6), eine Mittelkammer (4) und eine mit einem Anolyten gefüllte Anodenkammer (5) mit eingegliederter Anode (7) umfaßt, wobei zwischen Anode (7) und Kathode (6) eine Potentialdifferenz angelegt ist und die Kathodenkammer (3) durch eine Anionenaustauschermembran (8) und die Anodenkammer (5) durch eine Kationenaustauschermembran (9) von der Mittelkammer (4) getrennt sind, wobei die Regenerationslösung zunächst in die Kathodenkammer (3) geleitet wird und dort unter Abscheidung von Kupfer an die Kathode (6) verweilt, und daß nach der Verweilzeit die an Kupfer abgereicherte Regenerationslösung in die Mittelkammer (4) geleitet wird, wo eine Zinnanreicherung von aus der Anodenkammer (5) durch die Kationenaustauschermembran (9) durchgetretenen Zinnionen erfolgt.A process for regenerating an aqueous tin-plating solution for copper workpieces which works without external current and which contains tin and copper ions, free complexing agent bound to the copper ions and used and unused reducing agent, characterized in that a regeneration solution containing diluted tin-plating solution is fed to an electrolysis cell (2) which comprises a cathode chamber (3) with an integrated cathode (6), a central chamber (4) and an anode chamber (5) filled with an anolyte with an anode (7) incorporated, a potential difference being applied between the anode (7) and the cathode (6) and the cathode chamber (3) are separated from the middle chamber (4) by an anion exchange membrane (8) and the anode chamber (5) by a cation exchange membrane (9), the regeneration solution first being fed into the cathode chamber (3) and separated from it Copper lingers on the cathode (6), and that na After the residence time, the regeneration solution depleted in copper is passed into the middle chamber (4), where a tin enrichment of tin ions which have passed from the anode chamber (5) through the cation exchange membrane (9) takes place. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Regenerationslösung zwischen 5 % und 50 %, vorzugsweise 10 % bis 15 % Verzinnungslösung enthält. A method according to claim 1, characterized in that the regeneration solution contains between 5% and 50%, preferably 10% to 15%, of the tinning solution. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Regenerationslösung aus einem Spülprozeß (SP) der Kupferwerkstücke gewonnen wird.Method according to claim 1 or 2, characterized in that the regeneration solution is obtained from a rinsing process (SP) of the copper workpieces. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß der Anolyt in einem Kreislauf (B3) geführt wird.Method according to one of claims 1 to 3, characterized in that the anolyte is conducted in a circuit (B3). Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß als Anolyt eine 3 bis 6 %ige Schwefelsäure verwendet wird.Method according to one of claims 1 to 4, characterized in that a 3 to 6% sulfuric acid is used as the anolyte. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß als Anolyt eine Tetrafluoroborsäure oder eine Methansulfonsäure verwendet wird.Method according to one of claims 1 to 4, characterized in that a tetrafluoroboric acid or a methanesulfonic acid is used as the anolyte. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Temperatur in der Elektrolysezelle (2) zwischen 10 °C und 60 °C, vorzugsweise zwischen 30 °C und 40 °C, liegt.Method according to one of claims 1 to 6, characterized in that the temperature in the electrolysis cell (2) is between 10 ° C and 60 ° C, preferably between 30 ° C and 40 ° C. Vorrichtung zur Durchführung des Verfahrens nach einem oder mehreren der Ansprüche 1 bis 7, gekennzeichnet durch eine Elektrolysezelle (2), welche eine Kathodenkammer (3) mit eingegliederter Kathode (6), eine Mittelkammer (4) und eine Anodenkammer (5) mit eingegliederter Anode (7) umfaßt, wobei die Kathodenkammer (3) durch eine Anionenaustauschermembran (8) und die Anodenkammer (5) durch eine Kationenaustauschermembran (9) von der Mittelkammer (4) getrennt sind und zwischen Anode (7) und Kathode (6) eine Potentialdifferenz anlegbar ist.Device for carrying out the method according to one or more of claims 1 to 7, characterized by an electrolytic cell (2) which has a cathode chamber (3) with an integrated cathode (6), a central chamber (4) and an anode chamber (5) with an anode (7), the cathode chamber (3) being separated from the central chamber (4) by an anion exchange membrane (8) and the anode chamber (5) by a cation exchange membrane (9) and a potential difference between the anode (7) and cathode (6) can be created. Vorrichtung nach Anspruch 8, dadurch gekennzeichnet, daß die Regenerationslösung in der Elektrolysezelle (2) bewegbar ist.Device according to claim 8, characterized in that the regeneration solution can be moved in the electrolysis cell (2). Vorrichtung nach Anspruch 8 oder 9, dadurch gekennzeichnet, daß die Temperatur der Elektrolysezelle (2) steuerbar ist. Device according to claim 8 or 9, characterized in that the temperature of the electrolytic cell (2) can be controlled. Vorrichtung nach einem der Ansprüche 8 bis 10, dadurch gekennzeichnet, daß die Anode (7) aus Zinn und die Kathode (6) aus Kupfer oder Edelstahl besteht.Device according to one of Claims 8 to 10, characterized in that the anode (7) consists of tin and the cathode (6) consists of copper or stainless steel. Vorrichtung nach einem der Ansprüche 8 bis 11, dadurch gekennzeichnet, daß mehrere Elektrolysezellen hintereinander und/oder parallel geschaltet sind.Device according to one of claims 8 to 11, characterized in that several electrolytic cells are connected in series and / or in parallel.
    EP98107584A 1997-05-07 1998-04-25 Process and apparatus for the regeneration of tin plating solutions Expired - Lifetime EP0878561B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE19719020A DE19719020A1 (en) 1997-05-07 1997-05-07 Method and device for regenerating tinning solutions
    DE19719020 1997-05-07

    Publications (3)

    Publication Number Publication Date
    EP0878561A2 true EP0878561A2 (en) 1998-11-18
    EP0878561A3 EP0878561A3 (en) 1999-04-28
    EP0878561B1 EP0878561B1 (en) 2003-09-03

    Family

    ID=7828719

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP98107584A Expired - Lifetime EP0878561B1 (en) 1997-05-07 1998-04-25 Process and apparatus for the regeneration of tin plating solutions

    Country Status (12)

    Country Link
    US (1) US6120673A (en)
    EP (1) EP0878561B1 (en)
    JP (1) JPH10317154A (en)
    AR (1) AR010155A1 (en)
    AT (1) ATE248935T1 (en)
    AU (1) AU724854B2 (en)
    BR (1) BR9801580A (en)
    CA (1) CA2236393C (en)
    DE (2) DE19719020A1 (en)
    DK (1) DK0878561T3 (en)
    ES (1) ES2202686T3 (en)
    PT (1) PT878561E (en)

    Families Citing this family (26)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    GB9901586D0 (en) * 1999-01-25 1999-03-17 Alpha Fry Ltd Process for the recovery of lead and/or tin or alloys thereof from substrate surfaces
    JP3455709B2 (en) 1999-04-06 2003-10-14 株式会社大和化成研究所 Plating method and plating solution precursor used for it
    FR2801062B1 (en) * 1999-11-12 2001-12-28 Lorraine Laminage INSTALLATION AND METHOD FOR ELECTROLYTIC DISSOLUTION BY OXIDATION OF A METAL
    JP2002317275A (en) * 2001-04-17 2002-10-31 Toto Ltd Method for elongating service life of electroless tinning solution
    DE10132478C1 (en) * 2001-07-03 2003-04-30 Atotech Deutschland Gmbh Process for depositing a metal layer and process for regenerating a solution containing metal ions in a high oxidation state
    US7195702B2 (en) * 2003-06-06 2007-03-27 Taskem, Inc. Tin alloy electroplating system
    US6942810B2 (en) * 2003-12-31 2005-09-13 The Boc Group, Inc. Method for treating metal-containing solutions
    US20060096867A1 (en) * 2004-11-10 2006-05-11 George Bokisa Tin alloy electroplating system
    DE502005003655D1 (en) * 2005-05-25 2008-05-21 Enthone Method and device for adjusting the ion concentration in electrolytes
    JP2006341213A (en) * 2005-06-10 2006-12-21 Es Adviser:Kk Apparatus and method for electrolyzing waste electroless copper plating liquid
    DE102006045157B4 (en) 2006-09-25 2020-06-18 Robert Bosch Gmbh Hand tool
    KR100934729B1 (en) * 2007-10-29 2009-12-30 (주)화백엔지니어링 Electroless Tin Plating Solution Impurity Removal Apparatus and Method
    US20110226613A1 (en) 2010-03-19 2011-09-22 Robert Rash Electrolyte loop with pressure regulation for separated anode chamber of electroplating system
    US9404194B2 (en) 2010-12-01 2016-08-02 Novellus Systems, Inc. Electroplating apparatus and process for wafer level packaging
    JP5715411B2 (en) 2010-12-28 2015-05-07 ローム・アンド・ハース電子材料株式会社 Method for removing impurities from plating solution
    JP5830242B2 (en) 2010-12-28 2015-12-09 ローム・アンド・ハース電子材料株式会社 Method for removing impurities from plating solution
    JP5937320B2 (en) 2011-09-14 2016-06-22 ローム・アンド・ハース電子材料株式会社 Method for removing impurities from plating solution
    WO2013080326A1 (en) * 2011-11-30 2013-06-06 不二商事株式会社 Method of regenerating plating solution
    US9534308B2 (en) 2012-06-05 2017-01-03 Novellus Systems, Inc. Protecting anodes from passivation in alloy plating systems
    EP2671968B1 (en) * 2012-06-05 2014-11-26 ATOTECH Deutschland GmbH Method and regeneration apparatus for regenerating a plating composition
    JP6706095B2 (en) * 2016-03-01 2020-06-03 株式会社荏原製作所 Electroless plating apparatus and electroless plating method
    CN111630211B (en) 2017-11-01 2024-05-24 朗姆研究公司 Controlling plating electrolyte concentration on electrochemical plating equipment
    US20190345624A1 (en) * 2018-05-09 2019-11-14 Applied Materials, Inc. Systems and methods for removing contaminants in electroplating systems
    CN109467167B (en) * 2018-10-30 2021-12-03 上海大学 Method for removing heavy metals in stainless steel pickling wastewater
    EP3875638A1 (en) * 2020-03-04 2021-09-08 AT & S Austria Technologie & Systemtechnik Aktiengesellschaft Method for preparing a medium containing foreign metal and metal salt from printed circuit board and / or substrate production
    CN111676470A (en) * 2020-05-29 2020-09-18 广东天承科技有限公司 Simple and soluble high-valence tin reduction method

    Citations (3)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP0347016A2 (en) * 1985-01-14 1989-12-20 Macdermid Incorporated Electrodialysis apparatus for the chemical maintenance of electroless copper plating baths
    EP0545216A2 (en) * 1991-11-27 1993-06-09 Mcgean-Rohco, Inc. Process for extending the life of a displacement plating bath
    DE4310366C1 (en) * 1993-03-30 1994-10-13 Fraunhofer Ges Forschung Method for regenerating aqueous coating baths operating in an electroless manner

    Family Cites Families (3)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US3764503A (en) * 1972-01-19 1973-10-09 Dart Ind Inc Electrodialysis regeneration of metal containing acid solutions
    DE2742718C2 (en) * 1977-09-22 1984-04-19 ESTEL HOOGOVENS B.V., 1970 Ijmuiden Method and device for regenerating a tin-plating electrolyte
    US4330377A (en) * 1980-07-10 1982-05-18 Vulcan Materials Company Electrolytic process for the production of tin and tin products

    Patent Citations (3)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP0347016A2 (en) * 1985-01-14 1989-12-20 Macdermid Incorporated Electrodialysis apparatus for the chemical maintenance of electroless copper plating baths
    EP0545216A2 (en) * 1991-11-27 1993-06-09 Mcgean-Rohco, Inc. Process for extending the life of a displacement plating bath
    DE4310366C1 (en) * 1993-03-30 1994-10-13 Fraunhofer Ges Forschung Method for regenerating aqueous coating baths operating in an electroless manner

    Also Published As

    Publication number Publication date
    JPH10317154A (en) 1998-12-02
    AU724854B2 (en) 2000-10-05
    PT878561E (en) 2004-02-27
    EP0878561B1 (en) 2003-09-03
    US6120673A (en) 2000-09-19
    BR9801580A (en) 1999-07-06
    AR010155A1 (en) 2000-05-17
    ES2202686T3 (en) 2004-04-01
    EP0878561A3 (en) 1999-04-28
    DE59809451D1 (en) 2003-10-09
    DK0878561T3 (en) 2004-01-12
    ATE248935T1 (en) 2003-09-15
    CA2236393C (en) 2004-01-20
    CA2236393A1 (en) 1998-11-07
    AU6475798A (en) 1998-11-12
    DE19719020A1 (en) 1998-11-12

    Similar Documents

    Publication Publication Date Title
    EP0878561B1 (en) Process and apparatus for the regeneration of tin plating solutions
    EP1102875B1 (en) Alkali zinc nickel bath
    DE19748905A1 (en) Treatment of alkaline effluent from nuclear fuel reprocessing
    DE10025551C2 (en) Cathode for the electrochemical regeneration of permanganate etching solutions, process for their preparation and electrochemical regeneration device
    EP0638664A1 (en) Process and apparatus for regenerating solutions containing metal ions and sulfuric acid
    DE10261493A1 (en) Anode for electroplating
    EP1264010A1 (en) Method and device for the regulation of the concentration of metal ions in an electrolyte and use thereof
    DE4310366C1 (en) Method for regenerating aqueous coating baths operating in an electroless manner
    DE10240350B4 (en) Apparatus and method for regenerating an electroless plating bath
    EP0240589B1 (en) Process and apparatus for regenerating an electroless copper-plating bath
    DE2713392C2 (en) Process for the preparation of metal complex solutions
    DE2607512C2 (en) Process for the production of a metal powder, electrolysis cell for carrying out the process and application of the process
    WO2022229175A1 (en) Device and method for coating a component or semi-finished product with a chromium layer
    DE3943142A1 (en) ELECTROLYSIS PROCESS FOR PROCESSING METALION-CONTAINING OLD Stains or Product Streams
    DE1931123B2 (en) METHOD OF REMOVING CYANIDES FROM CYANIDE-CONTAINING Aqueous ALKALINE ELECTROLYTES BY ELECTROLYTIC OXYDATION OF THE CYANIDE
    DE2818306A1 (en) PROCEDURE FOR IN-SITU REDUCTION OF ELECTRODE OVERVOLTAGE AND ELECTROLYSIS CELL FOR PERFORMING THE PROCEDURE
    WO2000026440A2 (en) Circular method for pickling copper and copper alloys
    EP0746640A1 (en) Method of electrolytically depositing metals from electrolytes containing organic additives
    EP2384800B1 (en) Regeneration of alkaline zinc nickel electrolytes by removing cyanide ions
    DE2929305C2 (en) Process and device for the continuous electrodeposition of manganese on steel
    DE4218916C2 (en) Use of a grid anode for electrolytic detoxification or regeneration of an aqueous solution containing cyanide
    DE4229917C1 (en) Electrolytic bath for meter coating - has sec. anode contg. alkaline or ammonium soln. with acid added to electrolyte to compensate for pH rise
    DE2940741C2 (en)
    EP0079032B1 (en) Apparatus for electroplating a metallic workpiece
    DE19829274A1 (en) Process for the recovery of precious metals

    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: A2

    Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

    AX Request for extension of the european patent

    Free format text: AL;LT;LV;MK;RO;SI PAYMENT 980507

    PUAL Search report despatched

    Free format text: ORIGINAL CODE: 0009013

    AK Designated contracting states

    Kind code of ref document: A3

    Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

    AX Request for extension of the european patent

    Free format text: AL;LT;LV;MK;RO;SI PAYMENT 19980507

    17P Request for examination filed

    Effective date: 19991014

    AKX Designation fees paid

    Free format text: AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

    AXX Extension fees paid

    Free format text: SI PAYMENT 19980507

    17Q First examination report despatched

    Effective date: 20010419

    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

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

    AX Request for extension of the european patent

    Extension state: SI

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

    Ref country code: CY

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20030903

    RBV Designated contracting states (corrected)

    Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: FG4D

    Free format text: NOT ENGLISH

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: EP

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

    Ref document number: 59809451

    Country of ref document: DE

    Date of ref document: 20031009

    Kind code of ref document: P

    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: FG4D

    Free format text: GERMAN

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: NV

    Representative=s name: PA ALDO ROEMPLER

    REG Reference to a national code

    Ref country code: SE

    Ref legal event code: TRGR

    REG Reference to a national code

    Ref country code: GR

    Ref legal event code: EP

    Ref document number: 20030404580

    Country of ref document: GR

    REG Reference to a national code

    Ref country code: DK

    Ref legal event code: T3

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FG2A

    Ref document number: 2202686

    Country of ref document: ES

    Kind code of ref document: T3

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

    Ref country code: MC

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

    Effective date: 20040430

    ET Fr: translation 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

    Effective date: 20040604

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

    Ref country code: NL

    Payment date: 20070403

    Year of fee payment: 10

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

    Ref country code: SE

    Payment date: 20070404

    Year of fee payment: 10

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

    Ref country code: IE

    Payment date: 20070412

    Year of fee payment: 10

    Ref country code: AT

    Payment date: 20070412

    Year of fee payment: 10

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

    Ref country code: FI

    Payment date: 20070413

    Year of fee payment: 10

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

    Ref country code: DK

    Payment date: 20070416

    Year of fee payment: 10

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

    Ref country code: DE

    Payment date: 20070419

    Year of fee payment: 10

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

    Ref country code: CH

    Payment date: 20070427

    Year of fee payment: 10

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

    Ref country code: LU

    Payment date: 20070430

    Year of fee payment: 10

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

    Ref country code: ES

    Payment date: 20070521

    Year of fee payment: 10

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: PFA

    Owner name: KME GERMANY AG

    Free format text: KM EUROPA METAL AKTIENGESELLSCHAFT#POSTFACH 3320#D-49023 OSNABRUECK (DE) -TRANSFER TO- KME GERMANY AG#KLOSTERSTRASSE 29#49074 OSNABRUECK (DE)

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

    Ref country code: GB

    Payment date: 20070425

    Year of fee payment: 10

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

    Ref country code: IT

    Payment date: 20070522

    Year of fee payment: 10

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

    Ref country code: FR

    Payment date: 20080312

    Year of fee payment: 11

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: PCAR

    Free format text: ALDO ROEMPLER PATENTANWALT;BRENDENWEG 11 POSTFACH 154;9424 RHEINECK (CH)

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

    Ref country code: PT

    Payment date: 20080404

    Year of fee payment: 11

    Ref country code: BE

    Payment date: 20080616

    Year of fee payment: 11

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: PL

    REG Reference to a national code

    Ref country code: DK

    Ref legal event code: EBP

    EUG Se: european patent has lapsed
    GBPC Gb: european patent ceased through non-payment of renewal fee

    Effective date: 20080425

    NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

    Effective date: 20081101

    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: 20081101

    Ref country code: LI

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

    Effective date: 20080430

    Ref country code: DE

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

    Effective date: 20081101

    Ref country code: CH

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

    Effective date: 20080430

    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: MM4A

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

    Ref country code: FI

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

    Effective date: 20080425

    Ref country code: AT

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

    Effective date: 20080425

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

    Ref country code: GR

    Payment date: 20080313

    Year of fee payment: 11

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

    Ref country code: IE

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

    Effective date: 20080425

    Ref country code: DK

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

    Effective date: 20080430

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FD2A

    Effective date: 20080426

    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: 20080425

    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: 20080426

    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

    Effective date: 20080425

    BERE Be: lapsed

    Owner name: *KM EUROPA METAL A.G.

    Effective date: 20090430

    REG Reference to a national code

    Ref country code: PT

    Ref legal event code: MM4A

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

    Effective date: 20091026

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: ST

    Effective date: 20091231

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

    Ref country code: PT

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

    Effective date: 20091026

    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: 20091222

    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: 20090430

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

    Ref country code: LU

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

    Effective date: 20080425

    Ref country code: GR

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

    Effective date: 20091104

    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: 20080426