EP0217429A1 - Cathode for the electrolytic refining of copper, and process for its manufacture - Google Patents

Cathode for the electrolytic refining of copper, and process for its manufacture Download PDF

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Publication number
EP0217429A1
EP0217429A1 EP86201440A EP86201440A EP0217429A1 EP 0217429 A1 EP0217429 A1 EP 0217429A1 EP 86201440 A EP86201440 A EP 86201440A EP 86201440 A EP86201440 A EP 86201440A EP 0217429 A1 EP0217429 A1 EP 0217429A1
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Prior art keywords
edge
cathode
groove
cathode according
liquid
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EP86201440A
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German (de)
French (fr)
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EP0217429B1 (en
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Adalbert Bartsch
Joachim Von Sawilski
Bernd Michalek
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Aurubis AG
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Norddeutsche Affinerie AG
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Priority to AT86201440T priority Critical patent/ATE43367T1/en
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    • 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 invention relates to a permanent cathode for the electrolytic refining of copper, which is immersed in an electrolyte in a vertical arrangement, and a method for its production.
  • copper output plates or sheets are usually used as cathodes and are connected to support rails.
  • the length of the support rails is greater than the width of the cathode sheet, so that the ends of the support rails can rest on the edge of the cell and the electrical contact is brought about.
  • the output plate is vertically immersed in the electrolyte of an electrolytic cell together with a pair of anode plates made of unrefined copper, or the output plate is located between a pair of non-soluble anodes and is immersed with them in the electrolyte of a cell for electrolytic metal recovery.
  • Starting plates made of copper so-called starting plates, have to be specially produced by electrolytic means and cannot be reused because the copper deposited on them cannot be removed.
  • the corners of the metal plate are rounded and the insulation is designed as a continuous insulating strip bent around the rounded corners, the material of the insulating strip being molded into along the edges Holes that are pressed in by hot pressing.
  • a cathode for the electrolytic deposition of metals which has a milled gap on the front side in its edge zones, into which an insulating strip of plastomers or elastomers is firmly introduced, for example by compression molding.
  • the outer part of the insulating strip extends beyond the bead-like border.
  • the cathode for the deposition of, for example, copper can be made of stainless steel.
  • the bead-like holding flanks for the insulating strip cause par due to different distance from the anode plate tial current density increases and undesired increased deposits in the edge area.
  • the arrangement has a lack of stability and the manufacture is complex.
  • the object of the invention is to provide a cathode for the galvanic deposition of copper, in which the advantages of the known electrodes with insulating edge strips are retained, but the known disadvantages, in particular the disadvantages indicated above, are avoided.
  • the invention is based on a cathode for the electrolytic refining of copper, with a support rod and a flat stainless steel starting sheet attached to it and at least provided with electrically insulating edge strips on the vertical longitudinal edges, the longitudinal edges having a groove on the end face with a fit therein and have the edge over their entire length projecting edge strips made of natural or synthetic polymers.
  • the object is achieved by designing a cathode of the aforementioned type in accordance with the invention in such a way that the insulating edge strip fitted into a dovetail-shaped groove is formed by longitudinal folding of a polymer film, in the fold (kink) of which a stainless steel wire is arranged and its congruence film halves lying one above the other are connected to one another in a liquid-tight manner.
  • the grooves advantageously have a flat or rounded base.
  • the flanks of the groove are chamfered on the outside and shaped into a dovetail profile by means of compression molding, the smaller opening of which corresponds approximately to the thickness of twice the film thickness.
  • the dovetail-shaped groove flanks and the insulated insulating edge strips are fitted in a form-fitting and liquid-tight manner in the critical area. The liquid-tight connection of the film halves prevents the penetration of electrolyte and crystalline deposits.
  • the liquid-tight connection can be an adhesive connection or a welded connection.
  • the method of connection depends on the type of material from which the edge strip is made.
  • the material of the edge strip is an electrically insulating material made of natural or synthetic polymers, for example natural or synthetic rubber, such as butadiene homopolymers, copolymers or block copolymers of butadiene with unsaturated monomers, such as styrene or acrylonitrile; halogenated rubbers such as polychloroprene; also thermoplastic polymers, such as polyolefins, polycarbonate; halogen-containing polymers, such as polymers or copolymers of vinyl chloride or vinylidene chloride; Polytetrafluoroethylene; Polyurethanes.
  • natural or synthetic rubber such as butadiene homopolymers, copolymers or block copolymers of butadiene with unsaturated monomers, such as styrene or acrylonitrile
  • halogenated rubbers such as polychloroprene
  • thermoplastic polymers such as polyolefins, polycarbonate
  • halogen-containing polymers such
  • thermoplastic elastomers such as block copolymers of butadiene with styrene, or thermoplastic polymers, such as halogen-containing vinyl polymers.
  • a material made of polyvinyl chloride is used which can be easily welded.
  • a PVC film of approximately 30 to 35 mm in width and approximately 0.4 to 0.6 mm in thickness.
  • a pocket-like sheath is initially obtained by, where appropriate, continuous, longitudinal longitudinal folding of the polymer film, preferably around a metal wire of approximately 0.8 to 1.2 mm in diameter, for example stainless steel wire.
  • foil and wire are removed from storage drums and brought together and folded by suitable devices.
  • the wire can also be retrofitted into the fold or folded and welded Foil sections are introduced.
  • the folded material with the wire in the kink is then expediently fed to a welding device.
  • the congruent, overlapping halves of the film are connected by line welding or surface welding.
  • the line weld is preferably carried out as an edge weld parallel and perpendicular to the fold edge, the weld carried out perpendicular to the fold edge being brought close to it.
  • the surface welding is also only brought close to the folded edge. In general, however, it is sufficient that only those parts of the film halves which are laterally projecting beyond the groove webs or groove flanks are surface-welded. If a gap-like opening remains between the wire insert and the fold, it is closed by injection of a low-viscosity synthetic resin that cures to the elastomer, for example by injection of a moisture-curing silicone resin.
  • the longitudinal edges that is to say the edges running perpendicular to the support rail, are provided with a groove on the end face, but the lower edge can also be provided with a groove for an insulating edge strip.
  • the depth of the groove is generally 4.5 to 6 mm, preferably 5.5 mm. The shallow groove depth ensures a favorable ratio of flank thickness to flank length and thus increased stability of the arrangement.
  • the edge overhang of the insulating edge strip is generally 5 to 20 mm.
  • a projection length of 8 to 15 mm is expediently provided.
  • a protrusion width of 10 mm is sufficient in many cases.
  • edges of the Katho the plate or groove flanks at the transition to the insulating strip are deburred on the inside to avoid damage when inserting the insulating strip into the groove.
  • the outside of the groove flanks is chamfered towards the edge strip with a positive angle to the precipitation cathode. This prevents jamming when stripping the precipitation cathode.
  • Stainless steels are expediently used as the material for the cathode, for example stainless steels with approx. 18% chromium, approx. 10% nickel, approx. 2% molybdenum and less than 0.1% carbon. Such steels ensure good adhesion of the deposited copper during the deposition process and, on the other hand, enable easy and automatic separation of the coating.
  • the support rail of the cathode according to the invention can consist of the same material as the cathode; However, the part of the mounting rail intended for the power supply is expediently made of copper.
  • the edge strip made of folded and welded foil with the inserted wire is preferably drawn in from the lower end of the grooved edge of the electrode sheet, optionally with the use of a lubricant.
  • the edge strip is pulled out over the upper horizontal edge of the electrode sheet so that a protruding part remains. This protruding part facilitates later replacement of the edge strip used by first pulling out the wire and then removing the film material from the groove. Due to the drawing process and the resulting frictional resistance, the edge strip is stretched with a reduced cross-section, so that after the tensile forces cease to exist, the strip contracts again and the narrow groove is closed in a liquid-tight manner.
  • the invention has a number of advantages. Compared to cathodes with conventional edge insulation, the effective cathode width is increased with the same cell dimensions. The material distortions caused by different expansion coefficients of the different materials of the cathode and insulating strips are avoided.
  • the edge strip is against migration or Pulled out of the wedge-shaped gap secured during operation by the inserted stainless steel wire. In the event of renewal, the wire can be easily pulled out lengthways and then the insulating strip removed. An increased service life of the cathode is achieved and thus downtimes and repair work are reduced.
  • the cathode 2 is welded to the support rail 1 via the webs 4.
  • the edge strip insulation 3 with inserted wire 5 is fitted into the side edge (longitudinal edge) running perpendicular to the mounting rail via a groove milled on the end face.
  • Fig. 2 shows a section along the line A-B of Fig. L.
  • the edge strip 3 with its parts 3a is positively fitted.
  • the edges of the cheeks 7 are deburred on the inside and chamfered on the outside towards the edge strip with a positive angle to the precipitation cathode.
  • the gap-like opening 9 with the inserted wire 5 is filled with an elastomer.
  • With 8 a surface weld is designated.
  • With l0 is still part of the original milling groove designated, which is filled completely liquid-tight with the deformable film material with the enclosed elastomeric resin and wire at a sufficiently high pressure.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
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Abstract

A cathode for use in the electrolytic refining of copper which comprises a carrying bar and a flat starting plate, which is secured to the carrying bar and made of special steel and provided with electrically insulating edge strips at least at its vertical longitudinal edges, which are formed in their edge faces with a groove, which contains an edge strip, that is made of a natural or synthetic polymer and fits into said groove and protrudes from the edge throughout its length. To prevent a deposition of metal in the critical region, the insulating edge strip which has been fitted into the dovetail groove has been formed by a longitudinal folding of a polymer film and contains at its fold line a wire of special steel, and the side portions of said film are coextensive and lie one over the other and are liquid-tightly joined to each other. The invention relates also to a process of manufacturing the cathode.

Description

Die Erfindung betrifft eine Dauerkathode für die elektro­lytische Raffination von Kupfer, die in senkrechter Anord­nung in einen Elektrolyten eintaucht, und ein Verfahren zu ihrer Herstellung.The invention relates to a permanent cathode for the electrolytic refining of copper, which is immersed in an electrolyte in a vertical arrangement, and a method for its production.

Bei der elektrolytischen Kupferraffination werden üb­licherweise als Kathoden Ausgangsplatten bzw. -bleche aus Kupfer verwendet, die mit Trageschienen verbunden sind. Die Länge der Trageschienen ist größer als die Breite des Kathodenbleches, so daß die Enden der Trageschienen auf dem Zellenrand aufliegen können und der elektrische Kon­takt herbeigeführt wird. Die Ausgangsplatte ist zusammen mit einem Paar von Anoden platten aus nichtraffiniertem Kupfer senkrecht in den Elektrolyten einer elektroly­tischen Zelle eingetaucht, oder aber die Ausgangsplatte befindet sich zwischen einem Paar nichtlöslicher Anoden und ist mit diesen in den Elektrolyten einer Zelle für die elektrolytische Metallgewinnung eingetaucht. Ausgangs­platten aus Kupfer, sogenannte Startbleche, müssen speziell auf elektrolytischem Wege hergestellt werden und können nicht wiederverwendet werden, da das auf ihnen niedergeschlagene Kupfer nicht abgezogen werden kann. Diesem Nachteil hat man im Stand der Technik durch die Bereitstellung von Ausgangsblechen aus Titan oder Edelstahl als Kathoden (Dauerkathoden) abgeholfen. Aus DE-OS 30 03 927 ist insbesondere eine derartige Kathode aus Edelstahl bekannt, deren dauerhafte Oxid­schicht das Entfernen des auf dem Blech niedergeschlagenen Kupfers erleichtert und vereinfacht und die dennoch die niedergeschlagene Kupferschicht während ihres Aufbaus genügend fixiert. Um das Kupfer einfach und insbesondere maschinell abheben zu können, darf der Kupferniederschlag nicht kontinuierlich die insbesondere senkrechten Katho­denkanten umgreifen. Zur Vermeidung dieser Schwierigkeiten ist es gemäß DE-OS 30 03 927 bekannt, zumindest die zur Trageschiene senkrecht verlaufenden Seitenkanten der Aus­gangsplatte mit einer längsgeschlitzten profilartigen Leiste aus Kunststoff abzudecken. Die Profilleiste wird mittels Stiften aus Kunststoff sowie über zusätzliche Klebeverbindungen an der Ausgangsstelle festgehalten. Der Kunststoff der vorbekannten Leiste ist ein Gemisch aus Polycarbonat und einem AN/BD/ST-Copolymerisat.In electrolytic copper refining, copper output plates or sheets are usually used as cathodes and are connected to support rails. The length of the support rails is greater than the width of the cathode sheet, so that the ends of the support rails can rest on the edge of the cell and the electrical contact is brought about. The output plate is vertically immersed in the electrolyte of an electrolytic cell together with a pair of anode plates made of unrefined copper, or the output plate is located between a pair of non-soluble anodes and is immersed with them in the electrolyte of a cell for electrolytic metal recovery. Starting plates made of copper, so-called starting plates, have to be specially produced by electrolytic means and cannot be reused because the copper deposited on them cannot be removed. This disadvantage has been remedied in the prior art by providing starting sheets made of titanium or stainless steel as cathodes (permanent cathodes). From DE-OS 30 03 927 such is in particular Cathode made of stainless steel known, the permanent oxide layer facilitates and simplifies the removal of the copper deposited on the sheet and which nevertheless fixes the deposited copper layer sufficiently during its construction. In order to be able to lift off the copper easily and in particular mechanically, the copper deposit must not continuously encompass the particularly vertical cathode edges. To avoid these difficulties, it is known according to DE-OS 30 03 927 to cover at least the side edges of the starting plate which run perpendicular to the mounting rail with a longitudinally slotted profile-like strip made of plastic. The profile strip is held in place by plastic pins and additional adhesive connections at the starting point. The plastic of the known strip is a mixture of polycarbonate and an AN / BD / ST copolymer.

Bei der aus DE-PS 28 43 279 bekannten Elektrode für die elektrolytische Abscheidung von Metallen, sind die Ecken der Metallplatte abgerundet und die Isolierung ist als durchgehender, um die abgerundeten Ecken gebogener Iso­lierstreifen ausgebildet, wobei das Material des Isolier­streifens, in entlang den Kanten eingeformte Bohrungen, durch Warmpressung eingedrückt ist.In the electrode known from DE-PS 28 43 279 for the electrolytic deposition of metals, the corners of the metal plate are rounded and the insulation is designed as a continuous insulating strip bent around the rounded corners, the material of the insulating strip being molded into along the edges Holes that are pressed in by hot pressing.

Aus FR-PS 2 388 062 ist eine Kathode für die elektroly­tische Abscheidung von Metallen bekannt, die in ihren Randzonen stirnseitig einen eingefrästen Spalt aufweist, in den ein isolierender Streifen aus Plastomeren oder Elastomeren fest eingebracht ist, z.B. durch Preßverfor­mung. Der Isolierstreifen überragt mit seinem äußeren Teil die wulstartige Einfassung. Die Kathode für die Abschei­dung von z.B. Kupfer kann aus Edelstahl bestehen. Die wulstartigen Halteflanken für den Isolierstreifen bewirken infolge unterschiedlichen Abstandes zur Anodenplatte par­ tielle Stromdichteerhöhungen und unerwünschte verstärkte Abscheidungen im Kantenbereich. Darüber hinaus hat die Anordnung mangelnde Stabilität und die Herstellung ist aufwendig.From FR-PS 2 388 062 a cathode for the electrolytic deposition of metals is known, which has a milled gap on the front side in its edge zones, into which an insulating strip of plastomers or elastomers is firmly introduced, for example by compression molding. The outer part of the insulating strip extends beyond the bead-like border. The cathode for the deposition of, for example, copper can be made of stainless steel. The bead-like holding flanks for the insulating strip cause par due to different distance from the anode plate tial current density increases and undesired increased deposits in the edge area. In addition, the arrangement has a lack of stability and the manufacture is complex.

Die vorbekannten Einrichtungen, bei denen isolierende Werkstoffe in der Regel als vorgeformte Profile aus Kunst­stoff klemmend und/oder klebend über die Außenkanten der Elektrodenplatten aufgebracht und zum Teil zusätzlich, z.B. durch Nietenreihen, mechanisch gesichert werden, weisen u.a. folgende Nachteile auf:
- Der zwischen Platte und Profil entstehende Spalt ist seiner Lage nach dem Ionenstrom zugekehrt.
- Kleber und Haftvermittler, die den Spalt zunächst füllen und die Haftung zwischen Metallplatte und Kunststoffprofil sicherstellen sollen, versagen bei längerem Einsatz chemisch, thermisch und mechanisch.
- Wegen der unterschiedlichen Wärmedehnung von Platten­werkstoff und Isolierwerkstoff (Kunststoffprofil) ent­stehen infolge des Temperaturwechsels im periodischen Betrieb der Elektrolysezelle Verformungen, Spaltbil­dung und Scherbrüche, hervorgerufen durch Spannungen, Kontraktion und Relaxation.
- Das Einwachsen des abgeschiedenen Kupfers unter das Isolierprofil und in den dem Ionenstrom zugekehrten Spalt führt zum Verhaken der gewonnenen Kathode und damit zu Schwierigkeiten beim Abziehen sowie zu einer zusätzlichen starken Belastung des Isoliermaterials.
- Wachstumsunregelmäßigkeiten sowie die Herausnahme defekter Elektroden führen zu Betriebszeitverlusten und einem relativ hohen Reparaturaufwand.The previously known devices, in which insulating materials are usually applied as preformed profiles made of plastic by clamping and / or adhesive over the outer edges of the electrode plates and in some cases additionally mechanically secured, for example by rows of rivets, have the following disadvantages, among others:
- The gap between the plate and the profile has turned towards the ion current.
- Adhesives and adhesion promoters, which initially fill the gap and are intended to ensure the adhesion between the metal plate and the plastic profile, fail chemically, thermally and mechanically when used for a long time.
- Due to the different thermal expansion of the plate material and the insulating material (plastic profile), the temperature change in the periodic operation of the electrolytic cell leads to deformation, gap formation and shear fractures, caused by stresses, contraction and relaxation.
- The ingrowth of the deposited copper under the insulating profile and in the gap facing the ion current leads to the hooking of the cathode obtained and thus to difficulties in stripping and to an additional heavy load on the insulating material.
- Growth irregularities and the removal of defective electrodes lead to loss of operating time and a relatively high repair effort.

Der Erfindung liegt die Aufgabe zugrunde, eine Kathode für die galvanische Abscheidung von Kupfer bereitzustellen, bei der zwar die Vorteile der bekannten Elektroden mit isolierendem Randstreifen erhalten bleiben, jedoch die bekannten Nachteile, insbesondere die vorstehend aufge­zeigten Nachteile, vermieden werden.The object of the invention is to provide a cathode for the galvanic deposition of copper, in which the advantages of the known electrodes with insulating edge strips are retained, but the known disadvantages, in particular the disadvantages indicated above, are avoided.

Zur Lösung der Aufgabe geht die Erfindung aus von einer Kathode für die elektrolytische Raffination von Kupfer, mit einer Tragestange und einem daran befestigten ebenen und zumindest an den vertikalen Längskanten mit elektrisch isolierendem Randstreifen versehenen Ausgangsblech aus Edelstahl, wobei die Längskanten stirnseitig eine Nut mit darin eingepaßtem und die Kante auf deren gesamter Länge überstehendem Randstreifen aus natürlichen oder synthe­tischen Polymeren aufweisen.To achieve the object, the invention is based on a cathode for the electrolytic refining of copper, with a support rod and a flat stainless steel starting sheet attached to it and at least provided with electrically insulating edge strips on the vertical longitudinal edges, the longitudinal edges having a groove on the end face with a fit therein and have the edge over their entire length projecting edge strips made of natural or synthetic polymers.

Die Aufgabe wird gelöst, indem eine Kathode der vorgenann­ten Art gemäß der Erfingung in der Weise ausgestaltet wird, daß der in einer schwalbenschwanzartig geformten Nut eingepaßte isolierende Randstreifen durch Längsfaltung einer Polymerfolie gebildet ist, in deren Faltung (Knick) ein Edelstahldraht angeordnet ist und deren deckungs­gleich übereinander liegende Folienhälften flüssigkeits­dicht miteinander verbunden sind.The object is achieved by designing a cathode of the aforementioned type in accordance with the invention in such a way that the insulating edge strip fitted into a dovetail-shaped groove is formed by longitudinal folding of a polymer film, in the fold (kink) of which a stainless steel wire is arranged and its congruence film halves lying one above the other are connected to one another in a liquid-tight manner.

Die Nuten haben zweckmäßig eine flache oder abgerundete Grundfläche. Die Nutflanken sind außen angefast und durch Preßverformung zu einem Schwalbenschwanzprofil gestaltet, dessen kleinere Öffnung etwa der Dicke der doppelten Folienstärke entspricht. Die schwalbenschwanzartig ver­formten Nutflanken und der einliegende isolierende Rand­streifen sind im kritischen Bereich formschlüssig und flüssigkeitsdicht eingepaßt. Mit der flüssigkeitsdichten Verbindung der Folienhälften werden ein Eindringen von Elektrolyt und kristalline Abscheidungen verhindert.The grooves advantageously have a flat or rounded base. The flanks of the groove are chamfered on the outside and shaped into a dovetail profile by means of compression molding, the smaller opening of which corresponds approximately to the thickness of twice the film thickness. The dovetail-shaped groove flanks and the insulated insulating edge strips are fitted in a form-fitting and liquid-tight manner in the critical area. The liquid-tight connection of the film halves prevents the penetration of electrolyte and crystalline deposits.

Die flüssigkeitsdichte Verbindung kann eine Klebeverbin­dung oder eine Schweißverbindung sein. Dabei richtet sich die Verbindungsweise nach der Art des Werkkstoffs, aus dem der Randstreifen gefertigt wird.The liquid-tight connection can be an adhesive connection or a welded connection. The method of connection depends on the type of material from which the edge strip is made.

Der Werkstoff des Randstreifens ist ein elektrisch isolie­rendes Material aus natürlichen oder synthetischen Poly­meren, beispielsweise Natur- oder Synthesekautschuk, wie Butadienhomopolymerisate, Copolymerisate oder Blockcopoly­merisate des Butadiens mit ungesättigten Monomeren, wie Styrol oder Acrylnitril; halogenhaltige Kautschuke, wie Polychloropren; ferner thermoplastische Polymere, wie Polyolefine, Polycarbonat; halogenhaltige Polymerisate, wie Polymerisate oder Copolymerisate des Vinylchlorids oder Vinylidenchlorids; Polytetrafluoräthylen; Poly­urethane.The material of the edge strip is an electrically insulating material made of natural or synthetic polymers, for example natural or synthetic rubber, such as butadiene homopolymers, copolymers or block copolymers of butadiene with unsaturated monomers, such as styrene or acrylonitrile; halogenated rubbers such as polychloroprene; also thermoplastic polymers, such as polyolefins, polycarbonate; halogen-containing polymers, such as polymers or copolymers of vinyl chloride or vinylidene chloride; Polytetrafluoroethylene; Polyurethanes.

Bevorzugtes verschweißbares Material für die Polymerfolie sind thermoplastische Elastomere, wie Blockcopolymerisate des Butadiens mit Styrol oder thermoplastische Polymere, wie halogenhaltige Vinylpolymerisate. Zweckmäßig wird ein Material aus Polyvinylchlorid verwendet, das sich leicht verschweißen läßt.Preferred weldable material for the polymer film are thermoplastic elastomers, such as block copolymers of butadiene with styrene, or thermoplastic polymers, such as halogen-containing vinyl polymers. A material made of polyvinyl chloride is used which can be easily welded.

Zur Herstellung des Randstreifens der Kathode gemäß der Erfindung wird zweckmäßig von einer PVC-Folie von ca. 30 bis 35 mm Breite und ca. 0,4 bis 0,6 mm Dicke ausgegan­gen. Durch ggf. kontinuierliches, hälftiges Längsfalten der Polymerfolie, vorzugsweise um einen Metalldraht von ca. 0,8 bis l,2 mm Durchmesser, beispielsweise Edelstahl­draht, wird zunächst eine taschenartige Hülle erhalten. Hierbei werden Folie und Draht von Vorrattrommeln abgezo­gen und durch geeignete Vorrichtungen zusammengeführt und gefaltet. Der Draht kann aber auch nachträglich in den Knick der gefalteten oder gefalteten und verschweißten Folienabschnitte eingebracht werden. Zweckmäßig wird das Faltmaterial mit dem im Knick befindlichen Draht anschlie­ßend einer Schweißvorrichtung zugeführt. Je nach den Erfordernissen werden die deckungsgleichen übereinander­liegenden Folienhälften durch eine Linienschweißung oder Flächenschweißung verbunden. Die Linienschweißung wird vorzugsweise als Randverschweißung parallel und senkrecht zur Faltkante ausgeführt, wobei die senkrecht zur Falt­kante vorgenommene Schweißung bis dicht an diese heran­geführt wird. Auch die Flächenverschweißung wird nur dicht an die Faltkante herangeführt. Im allgemeinen genügt es jedoch, daß nur die Teile der Folienhälften flächenver­schweißt sind, welche seitlich über die Nutstege oder Nutflanken hinausstehen. Soweit zwischen Drahteinlage und Faltung eine spaltartige Öffnung verbleibt, wird diese durch Injektion eines niedrig viskosen, zum Elastomeren härtenden Kunstharzes verschlossen, beispielsweise durch Injektion eines durch Feuchtigkeit härtenden Silikonharzes.To produce the edge strip of the cathode according to the invention, it is expedient to start from a PVC film of approximately 30 to 35 mm in width and approximately 0.4 to 0.6 mm in thickness. A pocket-like sheath is initially obtained by, where appropriate, continuous, longitudinal longitudinal folding of the polymer film, preferably around a metal wire of approximately 0.8 to 1.2 mm in diameter, for example stainless steel wire. Here, foil and wire are removed from storage drums and brought together and folded by suitable devices. However, the wire can also be retrofitted into the fold or folded and welded Foil sections are introduced. The folded material with the wire in the kink is then expediently fed to a welding device. Depending on the requirements, the congruent, overlapping halves of the film are connected by line welding or surface welding. The line weld is preferably carried out as an edge weld parallel and perpendicular to the fold edge, the weld carried out perpendicular to the fold edge being brought close to it. The surface welding is also only brought close to the folded edge. In general, however, it is sufficient that only those parts of the film halves which are laterally projecting beyond the groove webs or groove flanks are surface-welded. If a gap-like opening remains between the wire insert and the fold, it is closed by injection of a low-viscosity synthetic resin that cures to the elastomer, for example by injection of a moisture-curing silicone resin.

Im allgemeinen sind nur die Längskanten, also die senk­recht zur Trageschiene verlaufenden Kanten, stirnseitig mit einer Nut versehen, es kann jedoch auch die untere Kante mit einer Nut für einen isolierenden Randstreifen vorgesehen werden. Die Tiefe der Nut beträgt im allge­meinen 4,5 bis 6 mm, vorzugsweise 5,5 mm. Die geringe Nuttiefe gewährleistet ein günstiges Verhältnis von Flankenstärke zu Flankenlänge und damit eine erhöhte Stabilität der Anordnung.In general, only the longitudinal edges, that is to say the edges running perpendicular to the support rail, are provided with a groove on the end face, but the lower edge can also be provided with a groove for an insulating edge strip. The depth of the groove is generally 4.5 to 6 mm, preferably 5.5 mm. The shallow groove depth ensures a favorable ratio of flank thickness to flank length and thus increased stability of the arrangement.

Der Kantenüberstand des isolierenden Randstreifens beträgt im allgemeinen 5 bis 20 mm. Zweckmäßig wird eine Über­standsbreite von 8 bis l5 mm vorgesehen. Eine Überstands­breite von l0 mm ist in vielen Fällen ausreichend.The edge overhang of the insulating edge strip is generally 5 to 20 mm. A projection length of 8 to 15 mm is expediently provided. A protrusion width of 10 mm is sufficient in many cases.

Es ist des weiteren zweckmäßig, daß die Kanten des Katho­ denbleches bzw. Nutflanken am Übergang zum Isolierstreifen hin innen entgratet sind, um Beschädigungen beim Einbrin­gen des Isolierstreifens in die Nut zu vermeiden. Die Nutflanken sind außen zum Randstreifen hin angefast mit positivem Winkel zur Niederschlagskathode. Hierdurch wird ein Verhaken beim Strippen der Niederschlagskathode vermieden.It is also useful that the edges of the Katho the plate or groove flanks at the transition to the insulating strip are deburred on the inside to avoid damage when inserting the insulating strip into the groove. The outside of the groove flanks is chamfered towards the edge strip with a positive angle to the precipitation cathode. This prevents jamming when stripping the precipitation cathode.

Als Werkstoff für die Kathode werden zweckmäßig Edelstähle verwendet, beispielsweise Edelstähle mit ca. l8 % Chrom, ca. l0 % Nickel, ca. 2 % Molybdän und weniger als 0,l % Kohlenstoff. Derartige Stähle ergeben eine gute Haftung des abgeschiedenen Kupfers während des Abscheidevorgangs und ermöglichen andererseits eine leichte und automatische Abtrennung des Belages. Die Trageschiene der erfindungs­gemäßen Kathode kann aus demselben Werkstoff wie die Kathode bestehen; zweckmäßig besteht jedoch der für die Stromzufuhr bestimmte Teil der Tragschiene aus Kupfer.Stainless steels are expediently used as the material for the cathode, for example stainless steels with approx. 18% chromium, approx. 10% nickel, approx. 2% molybdenum and less than 0.1% carbon. Such steels ensure good adhesion of the deposited copper during the deposition process and, on the other hand, enable easy and automatic separation of the coating. The support rail of the cathode according to the invention can consist of the same material as the cathode; However, the part of the mounting rail intended for the power supply is expediently made of copper.

Die Erfindung betrifft des weiteren ein Verfahren zur Herstellung einer Kathode mit Randisolierung für die elektrolytische Raffination von Kupfer, mit einer Trag­stange und einem daran befestigten ebenen, zumindest an den vertikalen Längskanten mit elektrisch isolierenden Randstreifen versehenem Ausgangsblech aus Edelstahl, wobei die Längskanten stirnseitig eine Nut und einen darin ein­gepaßten und die Kante auf deren gesamter Länge überste­henden Randstreifen aus natürlichen oder synthetischen Polymeren aufweisen. Das erfindungsgemäße Verfahren besteht darin, daß

  • a) in die Stirnseiten des Ausgangsbleches Nuten mit vorzugsweise runder Basis eingeschnitten werden,
  • b) die Flanken der Nuten durch spanlose Formung schwalbenschwanzartig verformt werden,
  • c) in den gebildeten keilförmigen Spalt von einem Ende der Nut ausgehend in Längsrichtung ein über die Nutflanken hinausragender isolierender Randstreifen mit einliegendem Edelstahldraht eingezogen wird, wobei der kleinste Spaltabstand nicht größer als die Dicke des Randstreifens eingestellt wird, und wobei
  • d) der Edelmetalldraht in den Knick einer hälftig gefalteten Polymerfolie eingebracht wird und die deckungsgleich übereinander liegenden Folienhälften flüssigkeitsdicht miteinander verbunden werden.
The invention further relates to a method for producing a cathode with edge insulation for the electrolytic refining of copper, with a support rod and a flat starting plate made of stainless steel attached to it, at least on the vertical longitudinal edges with electrically insulating edge strips, the longitudinal edges having a groove and have a fitted in it and the edge over their entire length projecting edge strips made of natural or synthetic polymers. The inventive method is that
  • a) grooves with a preferably round base are cut into the end faces of the starting plate,
  • b) the flanks of the grooves are shaped in a dovetail-like manner by non-cutting shaping,
  • c) is drawn into the wedge-shaped gap formed from one end of the groove in the longitudinal direction an insulating edge strip projecting beyond the groove flanks with an inserted stainless steel wire, the smallest gap distance not being set greater than the thickness of the edge strip, and wherein
  • d) the noble metal wire is introduced into the kink of a half-folded polymer film and the film halves lying congruently one above the other are connected to one another in a liquid-tight manner.

Das Einziehen des Randstreifens aus gefalteter und geschweißter Folie mit dem einliegenden Draht erfolgt vorzugsweise vom unteren Ende der genuteten Kante des Elektrodenbleches her, ggf. unter Mitverwendung eines Gleitmittels. Dabei wird der Randstreifen bis über die obere waagerechte Elektrodenblechkante hinausgezogen, so daß ein überstehender Teil verbleibt. Dieser überstehende Teil erleichtert ein späteres Auswechseln des benutzten Randstreifens, indem zunächst der Draht herausgezogen und dann das Folienmaterial aus der Nut entfernt wird. Durch den Ziehvorgang und den dabei auftretenden Reibungswider­stand wird der Randstreifen unter Querschnittsverminderung gedehnt, so daß nach Wegfall der Zugkräfte der Streifen sich wieder zusammenzieht und die enge Nut flüssigkeits­dicht geschlossen wird.The edge strip made of folded and welded foil with the inserted wire is preferably drawn in from the lower end of the grooved edge of the electrode sheet, optionally with the use of a lubricant. The edge strip is pulled out over the upper horizontal edge of the electrode sheet so that a protruding part remains. This protruding part facilitates later replacement of the edge strip used by first pulling out the wire and then removing the film material from the groove. Due to the drawing process and the resulting frictional resistance, the edge strip is stretched with a reduced cross-section, so that after the tensile forces cease to exist, the strip contracts again and the narrow groove is closed in a liquid-tight manner.

Die Erfindung weist eine Reihe von Vorteilen auf. Gegen­über Kathoden mit herkömmlichen Randisolierungen wird die wirksame Kathodenbreite bei gleicher Zellenabmessung vergrößert. Die durch unterschiedliche Ausdehnungskoeffi­zienten der unterschiedlichen Werkstoffe von Kathode und Isolierstreifen bewirkten Materialverwerfungen werden vermieden. Der Randstreifen ist gegen Herauswandern oder Herausziehen aus dem keilförmigen Spalt während des Betriebs durch den eingelegten Edelstahldraht gesichert. Im Falle einer Erneuerung kann der Draht leicht in Längsrichtung herausgezogen und dann der Isolierstreifen entfernt werden. Es werden eine erhöhte Standzeit der Kathode erzielt und somit Ausfallzeiten und Reparaturauf­wand vermindert.The invention has a number of advantages. Compared to cathodes with conventional edge insulation, the effective cathode width is increased with the same cell dimensions. The material distortions caused by different expansion coefficients of the different materials of the cathode and insulating strips are avoided. The edge strip is against migration or Pulled out of the wedge-shaped gap secured during operation by the inserted stainless steel wire. In the event of renewal, the wire can be easily pulled out lengthways and then the insulating strip removed. An increased service life of the cathode is achieved and thus downtimes and repair work are reduced.

Die Erfindung wird anhand der schematischen Darstellung der Zeichnungen veranschaulicht.

  • Fig. l zeigt eine Seitenansicht der Kathode mit Rand­streifenisolierung gemäß der Erfindung.
  • Fig. 2 zeigt einen Schnitt gemäß der Linie A-B der Fig. l in vergrößertem Maßstab.
The invention is illustrated by the schematic representation of the drawings.
  • Fig. L shows a side view of the cathode with edge strip insulation according to the invention.
  • Fig. 2 shows a section along the line AB of FIG. 1 on an enlarged scale.

In Fig. l ist an die Trageschiene l die Kathode 2 über die Stege 4 angeschweißt. In die zur Trageschiene senkrecht verlaufende Seitenkante (Längskante) ist über eine stirn­seitig eingefräste Nut die Randstreifenisolierung 3 mit eingelegtem Draht 5 eingepaßt.In Fig. L, the cathode 2 is welded to the support rail 1 via the webs 4. The edge strip insulation 3 with inserted wire 5 is fitted into the side edge (longitudinal edge) running perpendicular to the mounting rail via a groove milled on the end face.

Fig. 2 zeigt einen Schnitt entlang der Linie A-B der Fig. l. In die Nutwangen 7 der Kante der Kathode 2 ist der Randstreifen 3 mit seinen Teilen 3a formschlüssig einge­paßt. Bei 6 sind die Kanten der Wangen 7 innen entgratet und außen zum Randstreifen hin angefast mit positivem Winkel zur Niederschlagskathode. Die spaltartige Öffnung 9 mit dem einliegenden Draht 5 ist mit einem Elastomeren ausgefüllt. Mit 8 ist eine Flächenschweißung bezeichnet. Mit l0 ist noch ein Teil der ursprünglichen Fräsnut be­zeichnet, die bei genügend hohem Preßdruck völlig durch das verformbare Folienmaterial mit dem eingeschlossenen elastomeren Harz und Draht flüssigkeitsdicht ausgefüllt wird.Fig. 2 shows a section along the line A-B of Fig. L. In the groove cheeks 7 of the edge of the cathode 2, the edge strip 3 with its parts 3a is positively fitted. At 6, the edges of the cheeks 7 are deburred on the inside and chamfered on the outside towards the edge strip with a positive angle to the precipitation cathode. The gap-like opening 9 with the inserted wire 5 is filled with an elastomer. With 8 a surface weld is designated. With l0 is still part of the original milling groove designated, which is filled completely liquid-tight with the deformable film material with the enclosed elastomeric resin and wire at a sufficiently high pressure.

Claims (10)

1. Kathode für die elektrolytische Raffination von Kupfer, mit einer Tragestange und einem daran befestigten ebenen und zumindest an den vertikalen Längskanten mit elektrisch isolierendem Randstreifen versehenen Ausgangsblech aus Edelstahl, wobei die Längskanten stirnseitig eine Nut mit darin eingepaßtem und die Kante auf deren gesamter Länge überstehendem Randstreifen aus natürlichen oder synthe­tischen Polymeren aufweisen, dadurch gekennzeichnet, daß der in einer schwalbenschwanzartig geformten Nut einge­paßte isolierende Randstreifen durch Längsfaltung einer Polymerfolie gebildet ist, in deren Faltung (Knick) ein Edelstahldraht angeordnet ist und deren deckungsgleich übereinanderliegenden Folienhälften flüssigkeitsdicht miteinander verbunden sind.1.Cathode for the electrolytic refining of copper, with a support rod and a flat stainless steel starting plate attached to it and at least on the vertical longitudinal edges provided with electrically insulating edge strips, the longitudinal edges having a groove on the end face and the edge projecting over their entire length Edge strips made of natural or synthetic polymers, characterized in that the insulating edge strip fitted into a dovetail-shaped groove is formed by longitudinal folding of a polymer film, in the fold (kink) of which a stainless steel wire is arranged and the film halves lying congruently one above the other are connected to one another in a liquid-tight manner. 2. Kathode nach Anspruch l, dadurch gekennzeichnet, daß die flüssigkeitsdichte Verbindung eine Klebeverbindung ist.2. Cathode according to claim l, characterized in that the liquid-tight connection is an adhesive connection. 3. Kathode nach Anspruch l, dadurch gekennzeichnet, daß die flüssigkeitsdichte Verbindung eine Schweißverbindung ist.3. Cathode according to claim l, characterized in that the liquid-tight connection is a welded connection. 4. Kathode nach den Ansprüchen l und 3, dadurch kennzeichnet, daß die Schweißverbindung eine Linienschweißung, vorzugs­weise Randverschweißung ist.4. Cathode according to claims l and 3, characterized in that the welded connection is a line weld, preferably edge weld. 5. Kathode nach den Ansprüchen l und 3, dadurch gekennzeich­net, daß die Schweißverbindung eine Flächenverschweißung ist.5. Cathode according to claims l and 3, characterized in that the welded connection is a surface weld. 6. Kathode nach den Ansprüchen l, 3 und 5, dadurch gekenn­zeichnet, daß zumindest die über die Nutkante hinauss­stehenden Folienteile flächig verschweißt sind.6. Cathode according to claims 1, 3 and 5, characterized in that at least the foil parts projecting beyond the groove edge are welded flat. 7. Kathode nach den Ansprüchen l bis 6, dadurch gekennzeich­net, daß im Bereich der Drahteinlage gebildete spaltartige Öffnungen mit zu einem Elastomer härtbaren niedrig visko­sen Harz ausgefüllt sind.7. Cathode according to claims 1 to 6, characterized in that gap-like openings formed in the area of the wire insert are filled with low-viscosity resin which is curable to an elastomer. 8. Kathode nach den Ansprüchen l bis 7, dadurch gekennzeich­net, daß der Randstreifen mit Drahteinlage mindestens die obere Elektrodenblechkante überragt.8. Cathode according to claims l to 7, characterized in that the edge strip with wire insert projects beyond at least the upper electrode sheet edge. 9. Kathode nach den Ansprüchen l bis 8, dadurch gekennzeich­net, daß schwalbenschwanzartig verformte Nutwangen und einliegender isolierender Randstreifen formschlüssig und flüssigkeitsdicht verbunden sind.9. Cathode according to claims l to 8, characterized in that dovetail-shaped groove cheeks and insulated insulating edge strips are positively and liquid-tightly connected. l0. Verfahren zur Herstellung einer Kathode mit Randisolierung der Art gemäß den Ansprüchen l bis 9, dadurch gekennzeich­net, daß a) in die Stirnseiten des Ausgangsbleches Nuten mit vor­zugsweise runder Basis eingeschnitten werden, b) die Flanken der Nuten durch spanlose Formung schwalben­schwanzartig verformt werden, c) in den gebildeten keilförmigen Spalt von einem Ende der Nut ausgehend in Längsrichtung ein über die Nutflanken hinausragender isolierender Randstreifen mit einliegen­dem Edelstahldraht eingezogen wird, wobei der kleinste Spaltabstand nicht größer als die Dicke des Randstrei­fens eingestellt wird, und wobei d) der Edelmetalldraht in den Knick einer hälftig gefalte­ten Polymerfolie eingebracht wird und die deckungs­gleich übereinander liegenden Folienhälften flüssig­keitsdicht miteinander verbunden werden. l0. Process for the production of a cathode with edge insulation of the type according to Claims 1 to 9, characterized in that a) grooves with a preferably round base are cut into the end faces of the starting plate, b) the flanks of the grooves are shaped in a dovetail-like manner by non-cutting shaping, c) is drawn into the wedge-shaped gap formed from one end of the groove in the longitudinal direction an insulating edge strip projecting beyond the groove flanks with an inserted stainless steel wire, the smallest gap distance not being set greater than the thickness of the edge strip, and wherein d) the noble metal wire is introduced into the kink of a half-folded polymer film and the film halves lying congruently one above the other are connected to one another in a liquid-tight manner.
EP86201440A 1985-08-31 1986-08-20 Cathode for the electrolytic refining of copper, and process for its manufacture Expired EP0217429B1 (en)

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AT86201440T ATE43367T1 (en) 1985-08-31 1986-08-20 CATHODE FOR THE ELECTROLYTIC REFINING OF COPPER AND PROCESS FOR THEIR PRODUCTION.

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DE19853531176 DE3531176A1 (en) 1985-08-31 1985-08-31 CATHODE FOR ELECTROLYTIC REFINING OF COPPER AND METHOD FOR THE PRODUCTION THEREOF
DE3531176 1985-08-31

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SE9502889D0 (en) * 1995-08-21 1995-08-21 Skega Ab Cathode element as well as process for making the cathode element
WO1997041280A1 (en) * 1996-04-26 1997-11-06 Marley Plastics Pty. Ltd. Improvements relating to cathode plate edge protectors
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GB2337995A (en) * 1998-06-05 1999-12-08 Creators Europ Limited Edge protected cathode plates used in the recovery of metals
US6231730B1 (en) * 1999-12-07 2001-05-15 Epvirotech Pumpsystems, Inc. Cathode frame
US6746581B2 (en) 2002-10-22 2004-06-08 William A. Ebert Edge protector systems for cathode plates and methods of making same
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CN106435649B (en) * 2016-11-07 2018-10-12 杨丹虹 Electrorefining permanent cathode plate vertical edge is assembled with concealed fastener type and recoverable wrapping strip
CN115071044A (en) * 2022-06-17 2022-09-20 深圳市宇盛光电有限公司 Manufacturing method of PN copper bar plastic-coated component

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AU6209786A (en) 1987-03-05
FI863244A (en) 1987-03-01
EP0217429B1 (en) 1989-05-24
AU580241B2 (en) 1989-01-05
US4670124A (en) 1987-06-02
FI863244A0 (en) 1986-08-08
ES2001284A6 (en) 1988-05-01
DE3663538D1 (en) 1989-06-29
PL261217A1 (en) 1987-09-21
JPS6256590A (en) 1987-03-12
ATE43367T1 (en) 1989-06-15

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