EP0034391A1 - Use of a lead alloy for the anodes in the electrolytic production of zinc - Google Patents
Use of a lead alloy for the anodes in the electrolytic production of zinc Download PDFInfo
- Publication number
- EP0034391A1 EP0034391A1 EP81200163A EP81200163A EP0034391A1 EP 0034391 A1 EP0034391 A1 EP 0034391A1 EP 81200163 A EP81200163 A EP 81200163A EP 81200163 A EP81200163 A EP 81200163A EP 0034391 A1 EP0034391 A1 EP 0034391A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- anodes
- zinc
- lead
- weight
- alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C11/00—Alloys based on lead
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
Definitions
- the wet metallurgical extraction of zinc usually takes place according to the process principle of zinc blende roasting, leaching of the roasted material, lye cleaning, electrolytic deposition of zinc and remelting of the zinc previously drawn off from the cathodes. Electrolytic deposition takes place practically exclusively from sulfuric acid solutions with the help of aluminum cathodes and lead anodes.
- Anode materials are primarily ternary lead alloys with mostly silver contents that are between 0.5 and 1.0% by weight.
- the third alloy component studies are available on thallium, tellurium, selenium, bismuth, calcium, gold, mercury, strontium, barium, arsenic, tin and cobalt (The Journal of Applied Chemistry of the USSR -english translation- Vol. 24 (1951) P. 1429 ff) and magnesium and silicon (The Journal of Applied Chemistry of the USSR -english translation- Vol. 26 (1953) p. 847 ff).
- the object of the invention is to provide an alloy for anodes in the electrolytic extraction of zinc from acidic solutions which do not have the disadvantages of the known alloys, have advantageous electrical and mechanical properties and can be produced as inexpensively as possible.
- the solution to the problem lies in the use of a lead alloy consisting of 0.05 to 0.25% by weight of strontium and / or 0.05 to 0.1% by weight of calcium and 0.1 to 0.5% by weight. % Silver, balance lead for anodes in the electrolytic extraction of zinc from acidic solutions.
- strontium-containing alloys those in which the strontium content is 0.05 to 0.1% by weight are preferably used.
- the anodes made from the aforementioned alloys have considerable hardness and high elasticity. They are dimensionally stable, so that they can be produced in a smaller thickness than conventional anodes. This saves alloy material in general and silver in particular. Due to the low weight of the anodes, the connection elements, in particular the support rods, can also be constructed more easily.
- the high dimensional stability of the anodes allows the electrode spacing to be reduced, so that a reduction in energy consumption is achieved.
- Alloys containing calcium or strontium are expediently used for reasons of simpler production. With regard to their properties, however, those that have both alloy components are also equivalent.
- the anodes can be produced by rolling or casting.
- the possibility of casting is advantageous insofar as the anodes are immediately given their final dimensions and - if desired - passage openings for the electrolyte can already be provided during the casting.
- the strength of the metal alloy is so high that even in the manufacture of anodes with through openings, a greater thickness - for reasons of stability, for example - is not necessary.
- the corrosion resistance of the anodes is so high that there is practically no removal even after months of operation. This is particularly surprising because there was a fear that a reduction in the silver content in the alloy would be associated with an increase in corrosion.
- the anodes obtained are used under the usual electrolysis conditions, ie for example at a current density of 160 to 630 A / m 2, a temperature of 30 to 46 ° C and a sulfuric acid content of the electrolyte of 165 to 220 g / 1 and a zinc content of the electrolyte of 40 to 70 g / l.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
Innerhalb des Naßmetallurgischen Verfahrensganges zur Gewinnung von Zink ist eine wesentliche Stufe dessen elektrolytische Abscheidung. Hierfür sind als Anodenmaterialien vorwiegend ternäre Bleilegierungen gebräuchlich, die neben Silber in Mengen von 0,5 bis 1,0 Gew.-% als dritte Leigierungskomponente, unterschiedlichste Metalle enthalten können. Hinsichtlich der elektrischen und mechanischen Eigenschaffen sowie aus Kostengründen wird für Anoden bei der elektrolytischen Gewinnung von Zink aus sauren Lösungen die Verwendung einer Blei-Legierung vorgeschlagen, die aus 0,05 bis 0,25 Gew.-%Strontium und/oder 0,05 bis 0,1 Gew.-% Calcium sowie 0.1 bis 0,5 Gew.-% Silber, Rest Blei besteht.An important step in the wet metallurgical process for the production of zinc is its electrolytic deposition. For this purpose, mainly ternary lead alloys are used as anode materials, which, in addition to silver in quantities of 0.5 to 1.0% by weight as a third alloy component, can contain a wide variety of metals. With regard to the electrical and mechanical properties and for reasons of cost, the use of a lead alloy is proposed for anodes in the electrolytic extraction of zinc from acidic solutions, which consists of 0.05 to 0.25% by weight of strontium and / or 0.05 to 0.1 wt .-% calcium and 0.1 to 0.5 wt .-% silver, the rest of lead.
Description
Die naßmetallurgische Gewinnung von Zink erfolgt üblicherweise nach dem Verfahrensprinzip Zinkblenderöstung, Laugung des Röstgutes, Laugenreinigung, elektrolytische Abscheidung von Zink und Umschmelzen des zuvor von den Kathoden abgezogenen Zinks. Die elektrolytische Abscheidung geschieht dabei praktisch ausschließlich aus schwefelsauren Lösungen mit Hilfe von Aluminiumkathoden und Bleianoden.The wet metallurgical extraction of zinc usually takes place according to the process principle of zinc blende roasting, leaching of the roasted material, lye cleaning, electrolytic deposition of zinc and remelting of the zinc previously drawn off from the cathodes. Electrolytic deposition takes place practically exclusively from sulfuric acid solutions with the help of aluminum cathodes and lead anodes.
Anodenmaterialien sind vorwiegend ternäre Blei-Legierungen mit meist Silber-Gehalten, die zwischen 0,5 bis 1,0 Gew.% liegen. Hinsichtlich der dritten Legierungskomponente liegen Untersuchungen über Thallium, Tellur, Selen, Wismut, Calzium, Gold, Quecksilber, Strontium, Barium, Arsen, Zinn und Kobalt vor (The Journal of Applied Chemistry of the UdSSR -english translation- Vol. 24 (1951) S. 1429 ff) sowie Magnesium und Silizium (The Journal of Applied Chemistry of the UdSSR -english translation- Vol. 26 (1953) S. 847 ff).Anode materials are primarily ternary lead alloys with mostly silver contents that are between 0.5 and 1.0% by weight. Regarding the third alloy component, studies are available on thallium, tellurium, selenium, bismuth, calcium, gold, mercury, strontium, barium, arsenic, tin and cobalt (The Journal of Applied Chemistry of the USSR -english translation- Vol. 24 (1951) P. 1429 ff) and magnesium and silicon (The Journal of Applied Chemistry of the USSR -english translation- Vol. 26 (1953) p. 847 ff).
Dabei zeigt sich, daß Anoden aus verschiedenen Legierungen während des Elektrolysebetriebes einen beträchtlichen Gewichtsverlust erleiden, der - abgesehen vom schnellen Verbrauch des Anodenmaterials - auch insofern nachteilig ist, als sich beträchtliche Schlammengen bilden können oder aber das kathodisch abgeschiedene Zink stark verunreinigt wird. Eine zusätzliche Problematik ergibt sich aus dem Umstand, daß verschiedene Legierungen nicht die erforderliche mechanische Festigkeit aufweisen oder während des Gebrauchs die anfänglich vorhandene Festigkeit verlieren. Es kann dann zu Verwerfungen und als Folge hiervon zu Kurzschlüssen und Brennern kommen.It is shown that anodes made of different alloys suffer a considerable weight loss during electrolysis operation, which - apart from the rapid consumption of the anode material - is also disadvantageous in that considerable amounts of sludge can form or the cathodically deposited zinc can be very strong is contaminated. An additional problem arises from the fact that various alloys do not have the required mechanical strength or lose the initially existing strength during use. This can lead to faults and, as a result, short circuits and burners.
Wie insbesondere auch die Ausführungen in "Blei und Blei- legierungen" von W. Hofmann, Springer-Verlag 1962, S. 285 ff zeigen, sind die Einflüsse der von Blei verschiedenen Legierungskomponenten vielfältig, zum Teil widersprüchlich und praktisch nicht vorhersehbar. Schließlich sind auch die mit der Herstellung der Legierung verbundenen Kosten von beträchtlicher Bedeutung, insbesondere wenn man berücksichtigt, daß sich in der Bäderhalle moderner Zinkelektrolysen Bleilegierungsmengen in der Größenordnung von 1.000 t und mehr befinden.As especially the explanations in "Lead and Lead Alloys" by W. Hofmann, Springer-Verlag 1962, p. 285 ff. Show, the influences of the alloy components other than lead are diverse, partly contradictory and practically unpredictable. Finally, the costs associated with the production of the alloy are also of considerable importance, especially if one takes into account that there are quantities of lead alloy in the order of 1,000 t and more in the bath hall of modern zinc electrolysis.
Aufgabe der Erfindung ist es, eine Legierung für Anoden bei der elektrolytischen Gewinnung von Zink aus sauren Lösungen bereitzustellen, die die Nachteile der bekannten Legierungen nicht aufweisen, vorteilhafte elektrische und mechanische Eigenschaften besitzen und möglichst kostengünstig herstellbar sind.The object of the invention is to provide an alloy for anodes in the electrolytic extraction of zinc from acidic solutions which do not have the disadvantages of the known alloys, have advantageous electrical and mechanical properties and can be produced as inexpensively as possible.
Die Lösung der Aufgabe liegt in der Verwendung einer Blei-Legierung, bestehend aus 0,05 bis 0,25 Gew.% Strontium und/oder 0,05 bis 0,1 Gew.% Calzium sowie 0,1 bis 0,5 Gew.% Silber, Rest Blei für Anoden bei der elektrolytischen Gewinnung von Zink aus sauren Lösungen.The solution to the problem lies in the use of a lead alloy consisting of 0.05 to 0.25% by weight of strontium and / or 0.05 to 0.1% by weight of calcium and 0.1 to 0.5% by weight. % Silver, balance lead for anodes in the electrolytic extraction of zinc from acidic solutions.
Sofern strontiumhaltige Legierungen vorgesehen sind, kommen vorzugsweise solche zur Anwendung, in denen der Strontium-Gehalt 0,05 bis 0,1 Gew.% beträgt.If strontium-containing alloys are provided, those in which the strontium content is 0.05 to 0.1% by weight are preferably used.
Die aus den vorgenannten Legierungen hergestellten Anoden besitzen eine beträchtliche Härte und eine hohe Elastizität. Sie sind formbeständig, so daß sie - verglichen mit üblichen Anoden - in geringerer Dicke hergestellt werden können. Hiermit verbunden ist eine Einsparung an Legierungsmaterial generell und insbesondere an Silber möglich. Infolge des geringen Gewichtes der Anoden können auch die Anschlußelemente, insbesondere die Tragestangen, leichter konstruiert werden.The anodes made from the aforementioned alloys have considerable hardness and high elasticity. They are dimensionally stable, so that they can be produced in a smaller thickness than conventional anodes. This saves alloy material in general and silver in particular. Due to the low weight of the anodes, the connection elements, in particular the support rods, can also be constructed more easily.
Die hohe Formbeständigkeit der Anoden läßt es zu, daß der Elektrodenabstand verkleinert werden kann, so daß eine Verringerung des Energieverbrauchs erzielt wird.The high dimensional stability of the anodes allows the electrode spacing to be reduced, so that a reduction in energy consumption is achieved.
Aus Gründen der einfacheren Herstellung werden zweckmäßigerweise Legierungen eingesetzt, die Calzium oder Strontium enthalten. Hinsichtlich ihrer Eigenschaften sind jedoch auch solche, die beide Legierungsbestandteile aufweisen, gleichwertig.Alloys containing calcium or strontium are expediently used for reasons of simpler production. With regard to their properties, however, those that have both alloy components are also equivalent.
Die Herstellung der Anoden kann durch Walzen oder Gießen erfolgen. Insbesondere die Möglichkeit des Gießens ist insofern vorteilhaft, als die Anoden unmittelbar ihre endgültigen Abmessungen erhalten und - sofern erwünscht - bereits beim Guß Durchtrittsöffnungen für den Elektrolyt vorgesehen werden können. Die Festigkeit der Metalllegierung ist so hoch, daß auch bei der Herstellung von Anoden mit Durchtrittsöffnungen eine größere Dicke - etwa aus Stabilitätsgründen - nicht erforderlich ist.The anodes can be produced by rolling or casting. In particular, the possibility of casting is advantageous insofar as the anodes are immediately given their final dimensions and - if desired - passage openings for the electrolyte can already be provided during the casting. The strength of the metal alloy is so high that even in the manufacture of anodes with through openings, a greater thickness - for reasons of stability, for example - is not necessary.
Bei der Herstellung von Gußanoden, die generell eine höhere Härte als Walzanoden aufweisen, empfiehlt sich eine langsame Abkühlung, weil hierdurch im Vergleich zur schnellen Abkühlung eine zusätzliche Erhöhung der Härte und der Korrosionsbeständigkeit erzielt wird.In the production of cast anodes, which generally have a higher hardness than rolled anodes, slow cooling is recommended because this makes a comparison an additional increase in hardness and corrosion resistance is achieved for rapid cooling.
Die Korrosionsbeständigkeit der Anoden ist so hoch, daß ein Abtrag selbst nach monatelangem Betrieb praktisch nicht vorhanden ist. Dies ist insbesondere deswegen überraschend als zu befürchten war, daß eine Reduktion des Silber-Gehaltes in der Legierung mit einer Vergrößerung der Korrosion verbunden sein würde.The corrosion resistance of the anodes is so high that there is practically no removal even after months of operation. This is particularly surprising because there was a fear that a reduction in the silver content in the alloy would be associated with an increase in corrosion.
Die erhaltenen Anoden werden unter den üblicherweise angewendeten Elektrolysebedingungen eingesetzt, d.h. beispielsweise
bei einer Stromdichte von 160 bis 630 A/m2 einer Temperatur von 30 bis 46°C und bei einem Schwefelsäuregehalt des Elektrolyten von 165 bis 220 g/1 und
einem Zinkgehalt des Elektrolyten von 40 bis 70 g/l.The anodes obtained are used under the usual electrolysis conditions, ie for example
at a current density of 160 to 630 A / m 2, a temperature of 30 to 46 ° C and a sulfuric acid content of the electrolyte of 165 to 220 g / 1 and
a zinc content of the electrolyte of 40 to 70 g / l.
Claims (2)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3005674 | 1980-02-15 | ||
| DE19803005674 DE3005674A1 (en) | 1980-02-15 | 1980-02-15 | USE OF A LEAD ALLOY FOR ANODES IN THE ELECTROLYTIC EXTRACTION OF ZINC |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0034391A1 true EP0034391A1 (en) | 1981-08-26 |
| EP0034391B1 EP0034391B1 (en) | 1983-08-24 |
Family
ID=6094697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP81200163A Expired EP0034391B1 (en) | 1980-02-15 | 1981-02-11 | Use of a lead alloy for the anodes in the electrolytic production of zinc |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4364807A (en) |
| EP (1) | EP0034391B1 (en) |
| JP (1) | JPS56127743A (en) |
| AU (1) | AU538729B2 (en) |
| DE (2) | DE3005674A1 (en) |
| ES (1) | ES8704552A1 (en) |
| FI (1) | FI65821C (en) |
| NO (1) | NO153976C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0052106A1 (en) * | 1980-03-10 | 1982-05-26 | KNIGHT, Bill J. | Process for electrowinning of metals |
| EP0090435A1 (en) * | 1982-02-18 | 1983-10-05 | Eltech Systems Corporation | Electroplating method |
| FR2575109A1 (en) * | 1984-12-21 | 1986-06-27 | Samim Soc Azionaria Minero Met | COMPOSITE MATERIAL AND ITS USE AS MATERIAL FOR ELECTRODES AND AS ACOUSTIC INSULATION |
| FR2691649A1 (en) * | 1992-05-29 | 1993-12-03 | Extramet Sa | Method for decontaminating soil polluted by metals. |
| WO2000042241A1 (en) * | 1999-01-13 | 2000-07-20 | Rsr Technologies, Inc. | Electrowinning anodes which rapidly produce a protective oxide coating |
| WO2014029848A1 (en) | 2012-08-24 | 2014-02-27 | Novartis Ag | Nep inhibitors for treating diseases characterized by atrial enlargement or remodeling |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1133952B (en) * | 1980-10-20 | 1986-07-24 | Samim Spa | UNATTACKABLE ANODE IN ALLIGATED LEAD |
| JPS5959891A (en) * | 1982-09-28 | 1984-04-05 | Akita Seiren Kk | Anode for electrowinning metal |
| US4439288A (en) * | 1983-07-11 | 1984-03-27 | Exxon Research & Engineering Company | Process for reducing Zn consumption in zinc electrolyte purification |
| JPH0652737U (en) * | 1992-12-26 | 1994-07-19 | 合資会社榊原 | Insulation for canned food |
| US5648286A (en) * | 1996-09-03 | 1997-07-15 | Advanced Micro Devices, Inc. | Method of making asymmetrical transistor with lightly doped drain region, heavily doped source and drain regions, and ultra-heavily doped source region |
| US6139705A (en) * | 1998-05-06 | 2000-10-31 | Eltech Systems Corporation | Lead electrode |
| JP5048981B2 (en) * | 2006-08-29 | 2012-10-17 | アシスト株式会社 | Mist sauna equipment |
| US7458902B2 (en) * | 2007-03-14 | 2008-12-02 | Eaton Corporation | Changeable golf grip |
| BG110844A (en) * | 2011-02-04 | 2012-10-31 | "Кцм" Ад | A method and a device for electroextraction of zinc out of sulphate solutions |
| CN103042031B (en) * | 2011-10-12 | 2016-06-08 | 云南大泽电极科技有限公司 | The casting-rolling production method of metal sheet material |
| CN106319565A (en) * | 2016-09-21 | 2017-01-11 | 东莞市联洲知识产权运营管理有限公司 | Method for preparing zinc electrodeposit under ammoniac system |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4272339A (en) * | 1980-03-10 | 1981-06-09 | Knight Bill J | Process for electrowinning of metals |
-
1980
- 1980-02-15 DE DE19803005674 patent/DE3005674A1/en not_active Withdrawn
-
1981
- 1981-02-06 NO NO810416A patent/NO153976C/en unknown
- 1981-02-11 FI FI810395A patent/FI65821C/en not_active IP Right Cessation
- 1981-02-11 EP EP81200163A patent/EP0034391B1/en not_active Expired
- 1981-02-11 US US06/233,491 patent/US4364807A/en not_active Expired - Fee Related
- 1981-02-11 DE DE8181200163T patent/DE3160775D1/en not_active Expired
- 1981-02-13 ES ES499435A patent/ES8704552A1/en not_active Expired
- 1981-02-13 JP JP2001281A patent/JPS56127743A/en active Granted
- 1981-02-13 AU AU67286/81A patent/AU538729B2/en not_active Ceased
Non-Patent Citations (2)
| Title |
|---|
| CHEMICAL ABSTRACTS, vol 84, no. 16, 19 April 1976, Columsbus, Ohio USA G.Z. KIRYAKOV " Lead alloy" page 293, column 1, abstract no. 110019e & ussr 473, 756 (Cl.C22C), 14 june 1975, appl. 1, 956, 571 21 august 1973 * |
| chemical abstracts, vol. 82, no. 20, 19th may 1975, columbus , ohio,usa g.z. kiryakov " prospective improvements in lead-based anodes" page 398, column 1, abstract no. 130938r & Tsvetn. Met 1975, (1), 21-2 (RUSS) * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0052106A1 (en) * | 1980-03-10 | 1982-05-26 | KNIGHT, Bill J. | Process for electrowinning of metals |
| EP0052106A4 (en) * | 1980-03-10 | 1982-07-20 | Bill J Knight | Process for electrowinning of metals. |
| EP0090435A1 (en) * | 1982-02-18 | 1983-10-05 | Eltech Systems Corporation | Electroplating method |
| FR2575109A1 (en) * | 1984-12-21 | 1986-06-27 | Samim Soc Azionaria Minero Met | COMPOSITE MATERIAL AND ITS USE AS MATERIAL FOR ELECTRODES AND AS ACOUSTIC INSULATION |
| FR2691649A1 (en) * | 1992-05-29 | 1993-12-03 | Extramet Sa | Method for decontaminating soil polluted by metals. |
| WO1993024250A1 (en) * | 1992-05-29 | 1993-12-09 | Entreprises Vibec Inc. | Method for decontaminating soils polluted by metals |
| WO1993024249A1 (en) * | 1992-05-29 | 1993-12-09 | Unimetal - Societe Française Des Aciers Longs | Process for decontamination of metal-polluted earth |
| US5549811A (en) * | 1992-05-29 | 1996-08-27 | Unimetal Societe Francaise Des Aciers Longs | Process for decontamination soils polluted with metals |
| WO2000042241A1 (en) * | 1999-01-13 | 2000-07-20 | Rsr Technologies, Inc. | Electrowinning anodes which rapidly produce a protective oxide coating |
| WO2014029848A1 (en) | 2012-08-24 | 2014-02-27 | Novartis Ag | Nep inhibitors for treating diseases characterized by atrial enlargement or remodeling |
Also Published As
| Publication number | Publication date |
|---|---|
| ES499435A0 (en) | 1987-06-01 |
| DE3160775D1 (en) | 1983-09-29 |
| NO153976C (en) | 1986-06-25 |
| AU6728681A (en) | 1981-08-20 |
| FI65821C (en) | 1984-07-10 |
| JPS56127743A (en) | 1981-10-06 |
| DE3005674A1 (en) | 1981-08-20 |
| US4364807A (en) | 1982-12-21 |
| JPS6323274B2 (en) | 1988-05-16 |
| ES8704552A1 (en) | 1987-06-01 |
| FI810395L (en) | 1981-08-16 |
| NO153976B (en) | 1986-03-17 |
| NO810416L (en) | 1981-08-17 |
| AU538729B2 (en) | 1984-08-23 |
| FI65821B (en) | 1984-03-30 |
| EP0034391B1 (en) | 1983-08-24 |
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