US20140131221A1 - Permanent cathode and a method for treating the surface of a permanent cathode - Google Patents

Permanent cathode and a method for treating the surface of a permanent cathode Download PDF

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US20140131221A1
US20140131221A1 US14/127,484 US201214127484A US2014131221A1 US 20140131221 A1 US20140131221 A1 US 20140131221A1 US 201214127484 A US201214127484 A US 201214127484A US 2014131221 A1 US2014131221 A1 US 2014131221A1
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permanent cathode
cathode plate
permanent
metal
plate
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Mari Lindgren
Henri Virtanen
Ville Nieminen
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Outotec Oyj
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Outotec Oyj
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Assigned to OUTOTEC OYJ reassignment OUTOTEC OYJ ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: NIEMINEN, VILLE, LINDGREN, MARI, VIRTANEN, HENRI
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • 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
    • 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
    • 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
    • C25C7/06—Operating or servicing
    • C25C7/08—Separating of deposited metals from the cathode
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium

Definitions

  • the invention relates to a permanent cathode defined in the independent claims, for use in the electrolytic recovery and electrowinning of metals. Furthermore, the invention relates to a method for treating the surface of a permanent cathode plate.
  • hydrometallurgical methods such as electrolytic refining or recovery are used.
  • electrolytic refining impure copper anodes are dissolved electrochemically, and the copper dissolved from them is reduced onto the cathode.
  • electrolytic recovery the copper is reduced directly from the electrolytic solution, which is typically a copper sulphate solution.
  • the rate of deposit of the metal, such as copper, on the cathode surfaces depends mostly on the current density used.
  • the cathodes used in the process can be starter sheets made of the metal to be reduced, or permanent cathodes made of steel, for example.
  • a transition to the use of permanent cathodes has been the prevailing trend at electrolytic plants for a long time, and in practice, all new copper electrolysis processes are based on this technology.
  • a permanent cathode by itself is formed of a cathode plate and an attached suspension bar using which the cathode is suspended in the electrolytic bath.
  • the copper can be mechanically stripped from the permanent cathode's cathode plate, and the permanent cathodes can be reused.
  • Permanent cathodes can be used in both electrolytic refining and recovery of metals. The mere corrosion resistance of the steel grade used as a permanent cathode plate in the electrolyte is not enough to guarantee that the properties required of the cathode are fulfilled.
  • the surface properties of a permanent cathode plate must be appropriate so that the depositing metal does not spontaneously strip off from the surface during the electrolytic process but adheres sufficiently, however not preventing the deposited metal from being removed using a stripping machine, for example.
  • the most important properties required of a permanent cathode plate include corrosion resistance, straightness and surface properties with regard to the adhesion and removability of the deposit.
  • a prior art method is the manufacture of permanent cathode plates from stainless steel.
  • Stainless steel is an iron-based alloy containing more than 10.5% chromium and less than 1.2% carbon.
  • the chromium forms a thin oxide layer on the steel surface, known as the passive film, which substantially improves the corrosion resistance of the steel.
  • Other alloying elements can also be used to influence the properties of the passive film and thus corrosion resistance. For example, molybdenum improves the endurance of the passive film against pitting caused by chlorides, in which the protective passive film is damaged locally. Alloying elements are also used to influence other properties, for example mechanical properties and manufacturing properties such as weldability.
  • Stainless steels are widely used in applications requiring good corrosion resistance, such as the process industry, the chemical industry and the pulp and paper industry. Due to the large volume of use, stainless steels are usually manufactured by hot rolling. After this, the rolling scale is removed from the steel surface. When making thinner plates with tighter thickness tolerances, cold rolling is used. Processing after cold rolling depends on the desired surface quality. Standard SFS-EN 10088-2 defines, for example, that a surface of type 2B shall be cold rolled, heat treated, pickled and skinpass-rolled. 2B thus describes the manufacturing route of the material and therefore only specifies the surface properties at a very general level, with the basic parameters being surface smoothness and brightness.
  • Surface roughness is typically used to describe surfaces. Surface roughness can be defined in a myriad of different ways but, for example, the widely used R a index refers to the mean deviation of surface roughness. However, it does not address the surface profile at all—whether the surface roughness is formed by peaks or valleys. In other words, surfaces of very different qualities may have exactly the same R a index. This is illustrated in FIGS. 1 a , 1 b and 1 c.
  • a permanent cathode plate be made of an alloy at least partially comprised of duplex steel.
  • a duplex grade of steel refers to a steel containing 30% to 70% austenite with the remainder being of ferritic structure.
  • the desired structure can be created through appropriate alloying.
  • the roughness of the cathode plate surface is an essential factor for the adherence of the metal deposit.
  • the publication also presents structures to be made on the cathode plate surface for ensuring the adherence of the metal deposit. Such structures include, for example, various types of holes, grooves and ledges.
  • a permanent cathode plate be made of Grade 304 steel.
  • This grade is a universal stainless steel having a composition very close to the grade known as acid-proof steel and an austenitic structure.
  • the roughness of the cathode plate surface is an essential factor for the adherence of the metal deposit, and also this publication presents structures to be made on the cathode plate surface for ensuring the adherence of the metal deposit.
  • the steel be manufactured with 2B finish in order to achieve appropriate adhesion of the metal deposit.
  • An optimal surface is typically defined using parameters such as the surface roughness parameter R a .
  • a way of describing a surface with a certain finish is AISI 316 2B, describing a certain grade of steel that has been skinpass-rolled. The characteristic manufacturing route produces a smooth, semi-bright but not mirroring surface.
  • the publication U.S. Pat. No. 7,807,028 B2 proposes the parameter 2B for the cathode surface finish, meaning that the surface has been processed by methods including cold rolling, heat treatment and pickling. Material processing and the processing parameters are used to influence the properties of the final surface.
  • the above-mentioned ways of defining the surface cannot be considered sufficient for determining an optimal surface for a permanent cathode.
  • a further object of the invention is to provide an improved permanent cathode for electrodeposition of stiff metals.
  • the invention relates to a permanent cathode to be used as an electrode in the electrowinning of metals, including a permanent cathode plate at least partially made of steel and providing the possibility of electrochemically depositing metal from an electrolytic solution onto its surface.
  • the grain boundary dimensions of the permanent cathode plate surface have been arranged to be suitable for the adhesion of deposited metal on the surface and the stripping of metal from the surface at least in a part of the surface that is in contact with the electrolyte.
  • the size of the grains in the permanent cathode plate is 1 to 40 micrometres measured by the linear intercept method.
  • the average grain boundary width W in the permanent cathode plate is 1 to 3 micrometres.
  • the average grain boundary depth d in the permanent cathode plate is less than 1 micrometre. According to the invention, an optimal permanent cathode can be created by influencing the grain boundary properties of the permanent cathode plate surface.
  • the permanent cathode plate is at least partially ferritic steel. According to another embodiment of the invention, the permanent cathode plate is at least partially austenitic steel. According to an embodiment of the invention, the permanent cathode plate is at least partially duplex steel.
  • the permanent cathode plate material surface properties according to the invention make it possible to use different grades of steel for the electrowinning of metals.
  • the permanent cathode plate comprises a surface area provided with strong adhesion properties and a surface area provided with weak adhesion properties, said adhesion properties being dependent on the dimensions of the grain boundaries in said surface area.
  • the surface area with weak adhesion properties forms a part of the surface that is in contact with the electrolyte and said surface area is located at a point where the stripping of metal deposit is meant to start.
  • the invention also relates to an arrangement to be used for the electrowinning of metals, said arrangement containing an electrolytic bath of an electrolytic solution in which anodes and permanent cathodes are alternately arranged, and said permanent cathodes being supported in the bath by a support element, the permanent cathode according to the invention thus being a part of the arrangement.
  • the invention also relates to a method for treating the surface of a permanent cathode plate, in which the permanent cathode plate is formed at least partially of steel plate.
  • the grain boundaries of the permanent cathode plate surface at least on a part of the surface that is in contact with the electrolyte are treated chemically or electrochemically to achieve the desired surface properties for the adhesion of deposited metal on the surface and the stripping of metal from the surface.
  • the permanent cathode plate surface is treated until the desired separating force is achieved, for example by etching the surface of the permanent cathode plate.
  • different areas of the permanent cathode plate surface that are in contact with the electrolyte are treated differently to produce an area with strong adhesion and an area with weak adhesion.
  • the area with weak adhesion is produced on a part of the cathode plate surface where the stripping of metal deposit is meant to start.
  • FIGS. 1 a , 1 b and 1 c illustrate the roughness of a permanent cathode plate surface
  • FIG. 2 illustrates an arrangement according to the invention
  • FIG. 3 a illustrates a permanent cathode
  • FIG. 3 b illustrates the surface of the permanent cathode
  • FIG. 4 illustrates the surface of a sample piece from a permanent cathode plate
  • FIGS. 5 a and 5 b illustrate permanent cathodes with areas of different adhesion properties
  • FIG. 6 illustrates stripping of a deposit from the permanent cathode
  • FIG. 7 illustrates the preferred fracture path between a deposit and the cathode plate.
  • FIGS. 1 a , 1 b and 1 c illustrate different versions of the surface roughness of a cathode plate 4 in a permanent cathode 1 .
  • FIGS. 1 a , 1 b and 1 c have the same R a index describing surface roughness even though they look different in closer view, as schematically illustrated by the Figures. According to the invention, the mere surface roughness index is not enough to achieve a sufficiently optimal permanent cathode surface.
  • the permanent cathode 1 according to the invention is illustrated in its operating environment in FIG. 2 .
  • the permanent cathode is intended to be used for the electrowinning of metals.
  • the permanent cathode is placed in an electrolytic solution in the electrolytic bath 3 alternately with anodes 2 over the entire length of the bath, and the desired metal is deposited from the electrolytic solution onto the surface of the cathode plate 4 in the permanent cathodes 1 .
  • the permanent cathode plate 4 is supported in the bath using a support element 5 .
  • Prior art has described permanent cathodes in which the surface roughness constitutes a crucial factor for the adhesion of the metal deposit.
  • the metal surface also has grain boundaries that play an essential role in the adhesion of copper onto the surface.
  • Solid metal has a crystalline structure, which means that the atoms are tightly packed in a regular array, and the same array extends over a long distance compared to the interatomic distance. These crystals are collectively referred to as grains.
  • the grains form irregular volume areas because their growth is limited by adjacent grains growing at the same time. In multigranular metal, each grain is joined with its neighbouring grains tightly across its surface at the grain boundary.
  • the grain boundary is an area of high surface energy in which the depositing copper primarily nucleates. Therefore special attention must be paid to the number and properties of grain boundaries.
  • Grain boundaries can be seen with an optical microscope or a scanning electron microscope but examination of the dimensions of grain boundaries requires an atomic force microscope (AFM).
  • An AFM has a sharp probe connected to a flexible support arm. When the probe is moved on the surface of the sample under examination, interactions between the surface and the probe are registered as bending of the support arm. The bending can be measured with a laser beam, allowing the generation of a three-dimensional image of the surface profile of the sample.
  • An AFM can be used to measure the dimensions, depth and width, of the grain boundary. The width and depth of grain boundaries naturally vary to a certain extent. This variation can be represented as a normal deviation, allowing statistical processing of the dimensions.
  • the grain size of a material can be defined in several different ways.
  • One of the methods is the linear intercept method (Metals Handbook, Desk Edition, ASM International, Metals Park, Ohio, USA, 1998 pp. 1405-1409), in which the grain size I is
  • N L is the number of grain boundaries divided by the measurement distance. According to the formula, grain size is inversely proportional to the number of grain boundaries per unit length.
  • FIGS. 3 a and 3 b illustrate the surface 6 of a permanent cathode plate 4 in a permanent cathode 1 according to the invention, and the schematic drawing presents the width W and depth d of the grain boundary between grains 8 in the surface.
  • the grain boundary width can be estimated from an image taken using an optical microscope or a scanning electron microscope, or it can be measured from AFM results.
  • at least a part of the surface of the permanent cathode plate 6 that it is in contact with the electrolyte is treated.
  • the grain boundaries 7 between grains 8 in the permanent cathode plate surface 6 are treated so as to be suitable for the adhesion of deposited metal onto the surface and the stripping of metal from it.
  • An optimal surface for the growth of metal can be achieved in accordance with the invention.
  • the dimensions of grain boundaries 7 in the surface 6 are modified in order to achieve an optimal permanent cathode surface.
  • the grain size of grains 8 in the surface 6 of an optimal permanent cathode plate 4 measured by the linear intercept method, is 1 to 40 micrometres, the average grain boundary width W is 1 to 3 micrometres, and the grain boundary depth d is less than 1 micrometre.
  • a permanent cathode plate according to the invention can be manufactured of austenitic steel, for example.
  • the permanent cathode plate surface is treated by electroetching, for example, until the desired separating force is achieved. The separating force represents the separability of the deposited material from the surface. If the separating force is too small, the metal deposit will be prematurely self-stripped from the permanent cathode plate surface, while an excessively great separating force makes it difficult to strip the metal deposit from the permanent cathode plate surface.
  • FIG. 5 a illustrates a permanent cathode provided with three surface areas 6 a , 6 b and 6 c with different adhesion properties.
  • Line L indicates the level of electrolytic solution when the permanent cathode plate 4 is immersed in an electrolytic bath.
  • the main part of the cathode plate surface, area 6 a is etched in such a way that the desired relative dimensions of the grain boundaries are achieved to improve the adhesion of metal deposit onto the permanent cathode plate 4 .
  • the part of the permanent cathode plate 4 above the electrolyte level L, area 6 c may be non-etched or gently etched.
  • the permanent cathode plate 4 contains at least one area 6 a with strong adhesion and at least one area 6 b with weak adhesion, the area 6 b with weak adhesion at least partly lying below the electrolyte level L.
  • FIG. 5 b shows an alternative embodiment where the area 6 b with low adhesion is located in the central area of the width of the cathode plate 4 and the edges of the area below the electrolyte line L form a part of the more strongly etched area 6 a.
  • FIGS. 5 a and 5 b make it easy to start stripping when the main part 6 a of the permanent cathode plate 4 has strong deposit adhesion.
  • stripping can be easily started by flexing the permanent cathode plate 4 in order to loosen the adhesion of the deposition on the plate.
  • bending of the permanent cathode plate 4 may be difficult, because nickel is a stiff metal which does not deform easily.
  • Good adhesion properties are preferably achieved by etching at least a part of the cathode plate 4 .
  • the part 6 b of the cathode plate 4 located just below the electrolyte level L is kept non-etched or it is etched just gently to obtain an area 6 b with much weaker adhesion properties than the major part 6 a of the cathode plate 4 .
  • Manufacturing of this kind of permanent cathode plate 4 is in principle easy.
  • the areas 6 b , 6 c that are not to be etched are, for instance, covered by a tape, or even more simply, the plate is just immersed to a certain depth into an etching solvent.
  • FIG. 6 illustrates the operation of a permanent cathode plate 4 according to FIG. 5 a .
  • metal deposits 11 are on both sides of the cathode plate 4 , but for the sake of simplicity, only one metal deposit 11 is shown in FIG. 6 .
  • Stripping the metal deposit 11 off the permanent cathode plate 4 is started by pushing a knife 10 , or wedge, of a stripping machine between the permanent cathode plate 4 and the metal deposit 11 .
  • the major part of the metal deposit 11 is strongly adhered to the surface 6 a of the cathode plate 4 with strong adhesion.
  • the force F required will consequently be very high.
  • the force F can be reduced substantially.
  • FIG. 7 illustrates the self-alignment of the preferred fracture path 13 into the interface between the metal deposit 11 and the permanent cathode plate 4 when stripping in the presence of imperfections 12 in the upper end of the deposit 11 . Because the interface between the metal deposit 11 and the cathode plate 4 is the weakest point, the fracture will preferentially occur along the interface, even though the edges 12 of the metal deposit 11 were “feather-like”, as depicted in FIG. 7 .
  • the permanent cathode plates used having materials with different grain boundary properties were: AISI 316L (EN 1.4404) in delivery state 2B (sample 1), AISI 316L (EN 1.4404) heavily etched (sample 2), LDX 2101 (EN 1.4162) in delivery state 2E (sample 3) ja AISI 444 (EN 1.4521) 2B with two different degrees of etching (samples 4 and 5).
  • Material AISI 316L was etched to enlarge the grain boundaries, and material AISI 444 was etched to open the grain boundaries.
  • the etching method used was electrolytic etching. Small samples were cut off the permanent cathode plate materials and subjected to AFM inspection for determining the grain boundary dimensions of the materials. The measured dimensions are presented in Table 1. In the table, W refers to grain boundary width and d refers to grain boundary depth.
  • Sample Permanent cathode Grain boundary dimensions number plate material W/ ⁇ m d/ ⁇ m W/d d/W 1 AISI 316L 2B 2.2 0.5 4.2 0.2 2 AISI 316L 2B, etched 4.1 1.4 2.8 0.4 3 LDX 2101 2E 2.8 0.7 3.7 0.3 4 444 2B, etched 1.5 0.4 3.7 0.3 5 444 2B, etched 2.2 1.1 2.1 0.5
  • Laboratory-scale electrolysis experiments were conducted to deposit copper onto these selected permanent cathode surfaces.
  • the permanent cathode surface was covered with a perforated plastic sheet so that it was possible to deposit a total of four copper discs of 20 mm diameter onto each permanent cathode during one electrolysis experiment.
  • the anode used in the experiments was a plate cut from copper cathode sheet. The distance between the cathode and anode surfaces was 30 mm. After deposition, the copper discs were separated from the permanent cathode plate using a special stripping device that could measure the force required for separation.
  • the electrolysis equipment consisted of a 3-litre electrolytic cell and a 5-litre circulation tank.
  • the electrolyte was pumped from the circulation tank into the electrolytic cell, from which it returned back to the circulation tank by overflow at a solution circulation rate of 7 litres per minute.
  • the circulation tank was fitted with heating equipment and an agitator.
  • the electrolyte used for the experiments was made of copper sulphate and sulphuric acid and contained 50 g/l of copper and 150 g/l of sulphuric acid. Hydrochloric acid was also added to the electrolyte so that the electrolyte had a chloride content of 50 mg/l. Bone glue and thiourea were used as additives and were continuously fed into the circulation tank as an aqueous solution.
  • the electrolyte temperature in the electrolytic cell was maintained at 65° C. by regulating the electrolyte temperature in the circulation tank.
  • the cathodic current density in the experiments was 30 mA/cm 2 , which corresponds well to the current density used in production-scale electrolysis.
  • the electrolysis duration in each experiment was 20 hours.
  • the mask plate was removed from the permanent cathode, and the copper discs were separated from the permanent cathode after a fixed period of time from the end of the experiment.
  • the force required for separation was measured, and the forces are presented in Table 2 as relative forces where the reference is AISI 316L in delivery condition 2B.
  • the choice of reference is based on the fact that such permanent cathode material is generally used at copper electrolysis plants.
  • the magnitude of the separating force is clearly dependent on the grain boundary dimensions of the permanent cathode material. Etching can be used to further open the grain boundaries of the materials in both the width and the depth dimension.
  • the duplex material LDX 2101 was not treated in any way before the experiments, and also the separating force measured on that material is greater than the separating force measured on the reference material.
  • the surface roughnesses (R a indices) of the permanent cathode materials chosen for the separation experiments were also measured, and the measured values are presented in Table 3. It can be noted that etching treatment, among other things, has changed the surface roughness to some extent. However, no clear correlation can be found in a comparison of surface roughnesses and the measurement results from the separation experiments.
  • the surface roughness index does not measure the grain boundary dimensions. Therefore the roughness index alone cannot be considered a sufficient criterion for achieving the desired adhesion and separating force.
  • the surface structure of the permanent cathode plate immediately reveals that the grain boundaries of the material have opened too much during pickling, and no appropriate adhesion surface for copper can be found any longer.
  • the delivery state of the permanent cathode plate was 2B, and according to measurements, the R a index of its surface varied between 0.4 and 0.5 ⁇ m.
  • the grain boundary width of the sample, measured from a scanning electronic microscopic image, was 8 to 10 ⁇ m.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Metallurgy (AREA)
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  • Electrolytic Production Of Metals (AREA)
US14/127,484 2011-06-23 2012-06-19 Permanent cathode and a method for treating the surface of a permanent cathode Abandoned US20140131221A1 (en)

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PCT/FI2012/050637 WO2012175803A2 (en) 2011-06-23 2012-06-19 Permanent cathode and a method for treating the surface of a permanent cathode

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US20160312376A1 (en) * 2013-12-18 2016-10-27 Outotec (Finland) Oy Method for maintenance of used permanent cathode plates
CN109750322A (zh) * 2019-03-15 2019-05-14 北京矿冶科技集团有限公司 一种密闭式电解槽用永久阴极
US11001932B2 (en) 2015-01-27 2021-05-11 Outokumpu Oyj Method for manufacturing a plate material for electrochemical process

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US7807029B2 (en) * 2005-03-09 2010-10-05 Xstrata Queensland Limited Stainless steel electrolytic plates
US20100078319A1 (en) * 2007-02-13 2010-04-01 Outotec Oyj Method of manufacturing a cathode plate, and a cathode plate
US20100276281A1 (en) * 2009-04-29 2010-11-04 Phelps Dodge Corporation Anode structure for copper electrowinning

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US20160312376A1 (en) * 2013-12-18 2016-10-27 Outotec (Finland) Oy Method for maintenance of used permanent cathode plates
US9708725B2 (en) * 2013-12-18 2017-07-18 Outotec (Finland) Oy Method for maintenance of used permanent cathode plates
US11001932B2 (en) 2015-01-27 2021-05-11 Outokumpu Oyj Method for manufacturing a plate material for electrochemical process
CN109750322A (zh) * 2019-03-15 2019-05-14 北京矿冶科技集团有限公司 一种密闭式电解槽用永久阴极

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EP2723920A4 (en) 2015-04-29
FI20110210L (fi) 2012-12-24
RU2566119C2 (ru) 2015-10-20
KR20140024470A (ko) 2014-02-28
BG2816U1 (bg) 2017-11-15
WO2012175803A2 (en) 2012-12-27
CA2838877A1 (en) 2012-12-27
ES1186663Y (es) 2017-09-27
WO2012175803A3 (en) 2013-02-21
MX2013014910A (es) 2014-02-19
WO2012175803A4 (en) 2013-04-04
AT15652U1 (de) 2018-04-15
ES1186663U (es) 2017-07-03
RU2013155581A (ru) 2015-07-27
KR20160005798A (ko) 2016-01-15
EP2723920A2 (en) 2014-04-30
JP2014517159A (ja) 2014-07-17
CL2013003666A1 (es) 2014-08-01
FI20110210A0 (fi) 2011-06-23
AU2012273906A1 (en) 2014-02-06
BR112013033245A2 (pt) 2017-03-01
PE20142001A1 (es) 2014-12-24

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