EP1050607A2 - Procédé et dispositif pour le dépôt électrolytique d'or et d'alliages d'or - Google Patents

Procédé et dispositif pour le dépôt électrolytique d'or et d'alliages d'or Download PDF

Info

Publication number
EP1050607A2
EP1050607A2 EP00500086A EP00500086A EP1050607A2 EP 1050607 A2 EP1050607 A2 EP 1050607A2 EP 00500086 A EP00500086 A EP 00500086A EP 00500086 A EP00500086 A EP 00500086A EP 1050607 A2 EP1050607 A2 EP 1050607A2
Authority
EP
European Patent Office
Prior art keywords
gold
cathode
electrolyte
anode
electrolytic cell
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP00500086A
Other languages
German (de)
English (en)
Other versions
EP1050607B1 (fr
EP1050607A3 (fr
Inventor
Josep Ferre Torres
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of EP1050607A2 publication Critical patent/EP1050607A2/fr
Publication of EP1050607A3 publication Critical patent/EP1050607A3/fr
Application granted granted Critical
Publication of EP1050607B1 publication Critical patent/EP1050607B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C25D17/12—Shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/06—Suspending or supporting devices for articles to be coated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • C25D21/14—Controlled addition of electrolyte components
    • 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
    • C25D3/48—Electroplating: Baths therefor from solutions of gold

Definitions

  • the present invention relates to a method and to an equipment for the electrodeposition of gold or gold alloys, for example gold with silver or gold with copper and cadmium.
  • Electrodeposition of gold or gold alloys are known since long time ago, and are essentially based in the deposition of a layer of metal or alloy on cathodes immersed in an electrolyte of adequate composition. These methods can serve either to produce alloyed or pure gold hollow items (electroforming), and in this case the gold or alloy layer is plated on a model that is subsequently removed, or to clad objects with a layer of a certain thickness of gold or alloy.
  • cyano-complex solution mainly potassium dicyanoaurate K(Au(CN) 2 ), dissolved in deionized or distilled water to a specified concentration.
  • Free cyanide plays a very important roll in cathode kinetics. Gold, copper and cadmium in one electrolyte and gold and silver in another, all codeposit from cyano complexes, so that under the conditions in which the process is carried out, every atom-gram of metal plated out releases the following amounts of free potassium cyanide:
  • This free KCN released accumulates in the electrolyte, and is eliminated very slowly only through anodic oxidation, through hydrolysis and by the effect of the electrolyte temperature.
  • the KCN is released in the cathodic boundary layer to a rate that depends on the applied current density, and therefore its local concentration in this layer is higher than in the bulk electrolyte. Owing to this concentration gradient, the KCN released in the cathodic boundary layer is slowly transported to the bulk electrolyte where it accumulates. As the concentration gradient between the cathode boundary layer and the bulk electrolyte decreases, diffusion decreases too, and KCN tends to accumulate in the same place where it is produced.
  • the invention relates to a method for the electrodeposition of gold or gold alloys, comprising: arranging some objects, on which the gold or alloy has to be deposited, in a cathode of an electrolytic cell containing an alkali-cyanide electrolyte with gold in solution; causing the deposition of the gold or gold alloy on these objects by circulating current through the electrolyte between an anode and the cathode; and replenishing the gold consumed during the process.
  • the method is characterised in that the gold replenishing is carried out by continuously recirculating the electrolyte between the electrodeposition electrolytic cell and an auxiliary electrolytic cell in whose anode gold sheets are arranged, such that the free KCN formed in the electrolyte as a consequence of the electrodeposition process combines with gold in said auxiliary electrolytic cell to form the cyano-complex K(Au(CN) 2 ) (potassium dicyanoaurate).
  • the KCN released by the gold cathodic electrodeposition is withdrawn from the solution at the same rate at which it is produced, and combines in the auxiliary cell with pure gold as a cyano-complex, and the latter is replenished continuously to the electrolyte, at the same rate at which it is consumed in the process.
  • the described method allows to maintain constant the cyano-complex concentration in the electrolyte, and avoids the increase of free KCN and its accumulation in the cathode zone, improving the process stability; free KCN plays a very important role in the cathode kinetics, and to maintain its concentration within narrow margins is very advantageous.
  • Another advantage of the method according to the invention is that the electrolyte life is improved. This is due to the fact that gold gets into the process in form of pure metal and thus no impurities, that to a lower or higher degree are present in K(Au(CN) 2 ) solutions used in all the existing systems, are introduced in the electrolyte.
  • the electrodeposition process is carried out in several consecutive stages, in each one of which a layer is deposited out by passing through the electrolyte a current intensity and an electrical charge quantity both controlled, and that are previously determined before each stage depending on the total weight to be deposited and on the composition analysis and the weight of the layer deposited in the previous stage.
  • the electrodeposited alloy composition can be determined from its electrochemical equivalent or, alternatively, from its density.
  • the electrodeposited layer weight is determined by weighing the cathode immersed in the electrolyte.
  • This characteristic allows to make the control weighing very quickly, without extracting the cathode from the electrolyte nor drying it, and with less fluctuations due to thermal differences.
  • every stage are also calculated the current intensity and the electrical charge quantity to be applied in the auxiliary electrolytic cell, so that gold replenishing is always synchronised with its consumption, at each stage, and its concentration in the electrolyte is kept constant in every moment.
  • the invention in another aspect relates to an equipment for the electrodeposition of gold and gold alloys, comprising an electrolytic cell with an anode, a cathode where the objects to be electrodeposited with gold or alloy are arranged, and an alkali-cyanide electrolyte, and means to replenish the gold consumed during the electrodeposition process; it is characterised in that the means to replenish gold comprise an auxiliary electrolytic cell, connected to the electrolytic cell in which the electrodeposition process takes place through respective conduits that allow the recirculation of the electrolyte from one cell to another, said auxiliary electrolytic cell comprising an anode where the gold sheets are arranged.
  • the auxiliary electrolytic cell comprises an anode made of a metallic framework intended to hold gold sheets and a metallic mesh disc arranged horizontal at the bottom of the cell and connected to said framework, and a cathode made of a metallic mesh cylinder arranged in the middle of the cell, inside a semipermeable cylindrical diaphragm, and in that the inside of said semipermeable diaphragm is filled with a conductive solution.
  • the diaphragm avoids that any part of gold be lost by electrodepositing on the metallic mesh cylindrical cathode; the metallic mesh disc in the cell's bottom collects the gold fragments loosened from the gold sheets and transmits the anodic potential thereto, so that the fragments are also profited.
  • the electrolytic cell where the electrodeposition process takes place comprises an anode formed by two concentric pieces of metallic mesh, of generally cylindrical configuration, between which the cathode is rotatably arranged.
  • the inner piece of the anode has the shape of an elongate truncated revolution ellipsoid, convex towards the outside of the cell
  • the outer anode piece has the shape of an elongate one-sheet revolution hyperboloid convex towards the inside of the cell, such that the distance between both anodes is shorter in the central area than at the upper and lower ends.
  • the inner piece of the anode has the shape of two truncated cones superimposed with their larger bases in contact
  • the outer piece of the anode has the shape of two truncated cones superimposed with their smaller bases in contact, in such a way that the distance between both anodes is shorter in the central area of the cell than at the upper and lower ends.
  • the inner piece of the anode has an area factor higher than the outer piece. In this way the difference between the areas of both parts of the anode owing to its different diameters is compensated, and the currents reaching the inner and outer parts of the cathode are equal, and so are the characteristics of the coatings on both areas.
  • Another optional equipment characteristic that improves the current distribution on the objects mounted on the cathode, and therefore the coating's homogeneity, is that the cathode is placed closer to the inner piece of the anode than to the outer piece.
  • the cathode is suspended from a supporting and rotation driving device, that can be arranged an upper loading position, in which the cathode is out of the electrolyte, an intermediate operation position in which the part of the cathode that holds the objects is completely immersed in the electrolyte and the cathode engages the rotation driving means, and a lower control position in which the cathode is disengaged from the driving means and rests on a vertical projection of a scale placed in the middle of the electrolytic cell, in an are lacking in electrolyte.
  • a supporting and rotation driving device that can be arranged an upper loading position, in which the cathode is out of the electrolyte, an intermediate operation position in which the part of the cathode that holds the objects is completely immersed in the electrolyte and the cathode engages the rotation driving means, and a lower control position in which the cathode is disengaged from the driving means and rests on a vertical projection of a scale placed in the middle of the electrolytic cell
  • the main advantage of this cathode and scale arrangement is that it allows to weigh the cathode without extracting it from the electrolyte.
  • Figure 1 shows schematically an equipment according to the invention. It basically consists of one main electrolytic cell 1, in which the gold or gold alloys electrodeposition takes place on objects to clad or on models that will be subsequently removed from inside the hollow electroformed pieces, and one auxiliary electrolytic cell 2 used to continuously replenish the gold consumed in the electrodeposition process.
  • Electrodeposition cell 1 includes a process tank 3, for instance a vessel with the shape of a cube made of a non current-conductive plastic material, that contains an electrolyte of the alkaline-cyanide type, suitable for the electrodeposition of gold or gold alloys.
  • the electrolyte level in the main compartment 7 is higher than in the secondary compartment 8, and electrolyte can overflow from one to the other over the cylindrical wall 4.
  • a filtration and circulation pump B1 propels the electrolyte again towards the main compartment 7 through two pipes 9 (for the sake of clarity only one has been represented in the figure) arranged at the bottom of the main compartment 7 and provided with a plurality of output holes.
  • two metallic mesh pieces 10 and 11 essentially cylindrical and concentric, that are connected to the positive polarity of a power source, and that constitute the electrolytic cell anode.
  • the construction details of these mesh pieces are very important, and will be discussed later on.
  • a cathodic rack 12 also cylindrical, on which the objects to be electroplated are mounted.
  • the rack is made of titanium, and coated with a layer of isolating material on all its parts that remain immersed and should not be coated by gold or gold alloy.
  • the cathodic rack 12 is attached to a support 13 through which it receives both the rotation movement and the corresponding negative electric potential by means of a conventional system with brushes.
  • the support 13 has also ascent and descent means, and the rack can engage and disengage the rotation driving means, as will be explained later on.
  • the cathodic rack 12 presents a housing 14 suitable to rest on a projection 15 of a scale 16, that is located in the central area 6 of the process tank, to perform a weighing of the cathode during the process, as will be explained later on.
  • cell 1 is analogous to other electrodeposition electrolytic cells: a current is applied, pure direct or pulsating, and the electrodeposition of gold and other alloying metals if they are present, is produced on the cathode.
  • FIG 2 is schematically represented an anode according with an embodiment of the invention.
  • Every piece 10, 11 of the anode is made out of metallic mesh, advantageously of titanium coated with platinum or a mixture of ruthenium and iridium oxides, at least on the active parts.
  • the inner piece 10 and the outer piece 11 of the anode have a curved shape, so that the distance between both pieces in the central part is smaller than at the ends; more specifically, for an optimal current distribution in the vertical sense, the inner piece 10 is an elongate truncated revolution ellipsoid, while the outer piece 11 is an elongate one-sheet revolution hyperboloid.
  • the equations of the generatrix ellipse or generatrix hyperbola and of the eccentricities of pieces 10, 11 are functions of geometrical parameters of the system, such as cathode diameter and cathode working height, distances between cathode and each one of the anode pieces, and the electrolyte level above the cathode working part.
  • the pieces 10 and 11 are formed each one by two truncated cones; in the case of the outer piece 10, both truncated cones are in contact by their smaller bases, while in the inner piece 11 are in contact by their larger bases, so that the distance between both pieces is smaller in the central part.
  • the pieces 10, 11 can also be cylindrical, if appropriately dimensioned in height.
  • the mesh of the inner piece 11 is much thicker than that of the outer piece 10, that is, has a lower mesh size (higher area factor).
  • the deposited metals are consumed, giving rise to the free KCN formation and, on the other hand a number of products such as brightener compounds, wetting agents, complexing agents, etc. are also consumed.
  • Replenishing the alloying metals is done in a conventional way, and therefore will not be described in detail: copper, for instance, is added to the electrolyte at the end of every process, under the form of a solid mixture that includes also other consumed additives, since maintaining copper concentration in the electrolyte is not a critical factor, the deposition of this metal not being much influenced by mass transport.
  • Other metals such as silver or cadmium are added in an intermittent form by means of a high precision peristaltic pump, under the form of replenishing solutions that contain exactly known concentrations of the metals and other compounds consumed during the process.
  • gold replenishing is done according to the invention, in a new and original way.
  • gold replenishing has a great importance because most of the KCN released during the process is generated by the gold deposition.
  • the secondary compartment 8 of the process tank 1 is connected through two conduits 17, 18 with the auxiliary electrolytic cell 2 for gold replenishing.
  • a pump B2 that sucks in electrolyte from the electrodeposition cell 1 at a speed determined by the process being realised, and transport it to cell 2; the electrolyte that reaches a certain level in cell 2 goes back to cell 1 by gravity, through the conduit 18.
  • Cell 2 is made up by a vessel 20 of plastic material, for instance methyl methacrylate, polypropylene, or others, and contains a metallic framework 21, preferably of titanium, to which are fastened sheets 22 of 999,9 pure gold in a quantity adequate to the cyano-complex generation.
  • plastic material for instance methyl methacrylate, polypropylene, or others
  • metallic framework 21 preferably of titanium
  • a metallic mesh disc 23 that remains near the bottom of the cell, and that collects the gold fragments that can fall off from the sheets.
  • the whole assembly of framework 21, disc 23 and gold sheets 22 make up the anode of cell 2 and is connected to the positive pole of a current power supply.
  • the cell cathode connected to the negative pole, is made up of a stainless steel mesh cylinder 24 placed in the central part of the cell.
  • a semipermeable diaphragm 25 that prevents ions of gold and other heavy metals present in the electrolyte from penetrating inside it, and that is filled with a solution to allow conductivity, preferably KCN in deionized water.
  • the diaphragm 25 is portable and rests on the vessel 20 by means of three or more radial arms; the cathode 24 can have at least one radial arm resting on the diaphragm.
  • cell 2 The dimensions of cell 2 depend on the needs of cyano-complex generation.
  • the electrolyte that enters cell 2 has a relatively high free KCN concentration, the one initially present in the electrolyte plus the one generated in cell 1 because of the deposition of gold and other metals.
  • this free KCN reacts with the gold to form the cyano-complex K(Au(CN) 2 ) according to the global equation: 2Au + 4KCN + 2H 2 O ⁇ 2K(Au(CN) 2 ) + 2KOH + H 2
  • the gold anodic oxidation reaction takes place according to:
  • the electrolyte returns to cell 1 enriched with K(Au(CN) 2 ); the continuous or intermittent recirculation of electrolyte between cells 1 and 2, along with a strict step by step control of the operating parameters of both cells, guarantees the maintenance of a constant gold concentration in the electrolyte in the electrodeposition cell 1, so that the gold or gold alloy layer characteristics can be controlled with high precision.
  • the equipment includes control means (not shown), for instance a PC computer with an appropriate program, that carry out the control of all the electrodeposition process and products replenishing, and govern the operation of electrovalves, pumps, etc.
  • control means for instance a PC computer with an appropriate program, that carry out the control of all the electrodeposition process and products replenishing, and govern the operation of electrovalves, pumps, etc.
  • the process control method is represented in the essential in figure 4.
  • a first phase A the required data are inputted to the computer: the area of cathodes or models on which the metal is going to be deposited, the layer thickness, the desired gold content of the alloy that is going to be deposited, the cathode weight, the initial concentrations of metals in the electrolyte, the current density, and others.
  • phase B a first weighing of the cathode immersed inside the electrolyte is performed, in the way that will be explained forward, and after this the equipment calculates, in phase C, the total weight to be electrodeposited on the base of the alloy composition, the thickness, the cathode area, etc.
  • phase D are calculated the parameters of an initial electrodeposition stage or, in other words, the parameters that will be applied to cells 1 and 2 to deposit a first layer on the cathode.
  • These parameters are the current intensity to be applied to each cell, and the total charge that has to be consumed.
  • the intensity and the charge to be applied in cell 1 will be the appropriate to deposit roughly a fifth of the weight of material (although for the calculations the increase of cathode area between one stage and the following has to be borne in mind).
  • the calculated parameters are applied to cells 1 and 2, respectively.
  • the control means stop the stage in each cell once they check that the foreseen electric charge quantity has circulated through the electrolyte.
  • the function i x t that is, the circulating current intensity by the intensity circulation time, is integrated.
  • phase G a control weighing of the cathode is performed (phase G), to verify the deposited weight and to compare it with the foreseen result; if any discrepancy exists, this result is used to adjust the parameters in the following stages.
  • the method allows to control the composition of the electrodeposited alloy.
  • the composition control is based in the determination of the electrochemical equivalent of the alloy, since to each composition corresponds a well defined electrochemical equivalent.
  • control means determine the electrochemical equivalent of the deposited alloy, and, as a consequence, deduce its composition.
  • control means check if the five stages have already been completed, and, if it is not the case, return to calculation phase D and a new electrodeposition stage is started.
  • control means verify that the process has been completed, they go on to phase H, to make a final check balance, and the results are outputted to the user, the possibility existing of an additional stage, for instance if it is wished to deposit a greater gold or gold alloy quantity.
  • This control method guarantees optimal results of the electrodeposition process.
  • Figure 5a shows the cathode 12 hanging over the process tank, in a loading position.
  • the support 13 includes a motor 30 that allows to put the cathode 12 in rotation clock and anticlockwise, alternatively, during time periods fixed in advance and with a selected speed.
  • the motor 30 rotates a driving element 31 that, by friction, transfers the rotation to a driven element 32 integral with the rod 33 of the cathodic rack 12.
  • the negative polarity is also transmitted to cathode 12 through the support 13, for instance by a conventional system of brushes (not shown).
  • the support 13 is attached to a jamb 34 in such a way that it can slide vertically along it, propelled, for example, by a pneumatic piston (not shown).
  • the support 13 is lowered to the working position of figure 5b.
  • elements 31, 32 are engaged and the rotation of motor 30 is transmitted to the cathode 12; it should be noticed that, in this position, the seat 14 of the cathodic rack stays separate from the projection 15 of the scale 16.
  • the cathode can be weighed while immersed in the electrolyte.
  • the auxiliary electrolytic cell where the cyano-complex K(Au(CN) 2 ) (potassium dicyanoaurate) is produced could even function as an independent element, for the production of cyano-complexes in concentrated solution, if it is feeded directly with deionized water, KCN and metal; from this concentrated solution the cyano-complexes could be extracted by crystallisation or in liquid form.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Automation & Control Theory (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Contacts (AREA)
  • Electroplating Methods And Accessories (AREA)
EP00500086A 1999-05-06 2000-05-03 Dispositif pour le dépôt électrolytique d'or et d'alliages d'or Expired - Lifetime EP1050607B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES009900931A ES2166660B1 (es) 1999-05-06 1999-05-06 Procedimiento y equipo para la electrodeposicion de oro o aleaciones de oro.
ES9900931 1999-05-06

Publications (3)

Publication Number Publication Date
EP1050607A2 true EP1050607A2 (fr) 2000-11-08
EP1050607A3 EP1050607A3 (fr) 2002-11-13
EP1050607B1 EP1050607B1 (fr) 2005-10-05

Family

ID=8308255

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00500086A Expired - Lifetime EP1050607B1 (fr) 1999-05-06 2000-05-03 Dispositif pour le dépôt électrolytique d'or et d'alliages d'or

Country Status (4)

Country Link
EP (1) EP1050607B1 (fr)
AT (1) ATE305988T1 (fr)
DE (1) DE60022940D1 (fr)
ES (2) ES2166660B1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2383337A (en) * 2001-12-21 2003-06-25 Accentus Plc Electroplating plant and method
WO2008028311A1 (fr) * 2006-09-05 2008-03-13 Oerlikon Trading Ag, Trübbach Installation d'enlèvement de couche et procédé pour son utilisation
WO2012059300A3 (fr) * 2010-11-02 2012-09-07 Robert Bosch Gmbh Dispositif de revêtement et procédé de revêtement galvanique régulé d'un objet
CN105803512A (zh) * 2016-06-03 2016-07-27 东莞市艺神五金制品有限公司 一种中央阳极电镀设备及电镀方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH529843A (fr) * 1971-07-09 1972-10-31 Oxy Metal Finishing Europ S A Bain pour le dépôt électrolytique d'alliages d'or et son utilisation en galvanoplastie
US4075065A (en) * 1975-07-07 1978-02-21 Handy & Harman Gold plating bath and process
DE2852078A1 (de) * 1978-12-01 1980-06-12 Linde Ag Verfahren und vorrichtung zum abkuehlen von erdgas
US4288298A (en) * 1979-03-14 1981-09-08 Rogers Olbert W Method and apparatus for electroplating or electroforming metal objects
KR830003601A (ko) * 1979-09-06 1983-06-21 오. 이. 앨버 첨가제가 없는 강금 전기도금 및 그 산물
CA1180674A (fr) * 1981-02-17 1985-01-08 Kenneth D. Baker Bain et methode de dorure
JP3202375B2 (ja) * 1992-12-25 2001-08-27 株式会社徳力本店 ジシアノ金酸カリウムの製造方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2383337A (en) * 2001-12-21 2003-06-25 Accentus Plc Electroplating plant and method
WO2008028311A1 (fr) * 2006-09-05 2008-03-13 Oerlikon Trading Ag, Trübbach Installation d'enlèvement de couche et procédé pour son utilisation
CN101512050B (zh) * 2006-09-05 2012-05-02 奥尔利康贸易股份公司（特吕巴赫） 涂层去除装置及其操作方法
RU2460829C2 (ru) * 2006-09-05 2012-09-10 Эрликон Трейдинг Аг, Трюббах Установка для удаления покрытия и способ ее эксплуатации
US8361290B2 (en) 2006-09-05 2013-01-29 Oerlikon Trading, Ag, Trubbach Coating removal installation and method of operating it
WO2012059300A3 (fr) * 2010-11-02 2012-09-07 Robert Bosch Gmbh Dispositif de revêtement et procédé de revêtement galvanique régulé d'un objet
CN105803512A (zh) * 2016-06-03 2016-07-27 东莞市艺神五金制品有限公司 一种中央阳极电镀设备及电镀方法

Also Published As

Publication number Publication date
EP1050607B1 (fr) 2005-10-05
EP1050607A3 (fr) 2002-11-13
ES2166660A1 (es) 2002-04-16
DE60022940D1 (de) 2006-02-16
ATE305988T1 (de) 2005-10-15
ES2250092T3 (es) 2006-04-16
ES2166660B1 (es) 2003-02-16

Similar Documents

Publication Publication Date Title
US8920623B2 (en) Method for replenishing tin and its alloying metals in electrolyte solutions
KR100740817B1 (ko) 전해질 내의 금속 이온 농도의 조절 방법 및 장치, 및그의 용도
Madore et al. The rotating cylinder Hull cell: design and application
EP1050607B1 (fr) Dispositif pour le dépôt électrolytique d'or et d'alliages d'or
JPH0647759B2 (ja) 電気メッキ処理
US5308464A (en) Low temperature tin-bismuth electroplating system
JPH06158397A (ja) 金属の電気メッキ方法
CN1186875A (zh) 金属电积过程中在线控制有机添加剂的方法和装置
JPH05302199A (ja) 不溶性陽極を用いた銅めっき法における銅めっき浴の組成制御方法
Wilcox et al. Faraday's laws of electrolysis
JP2009185383A (ja) 銅めっき液供給機構並びにそれを用いた銅めっき装置および銅皮膜形成方法
US4634504A (en) Process for the electrodeposition of metals
JPS585997B2 (ja) 電鋳装置
CN204918821U (zh) 电镀槽
JP3903120B2 (ja) 硫酸銅めっき方法
EP0550002B1 (fr) Procédé d'étamage électrolytique
JPS6021398A (ja) 合金めつき方法及び合金めつき装置
Murase et al. Measurement of pH in the vicinity of a cathode during the chloride electrowinning of nickel
US2457021A (en) Palladium plating
JPS5941488A (ja) 鉄系電気メツキ浴濃度の自動制御方法
KR800000028B1 (ko) 전기주석 도금방법
JPS5976890A (ja) 鉄−亜鉛合金電気メツキ方法
Lapicque et al. Thick silver electrodeposits from ethaline and propeline deep eutectic solvents toward recovery of precious metals from waste
JPH0242911B2 (fr)
JP2023158843A (ja) 亜鉛系めっき皮膜の製造方法およびめっき装置

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

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

AX Request for extension of the european patent

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

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

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

AX Request for extension of the european patent

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

RIC1 Information provided on ipc code assigned before grant

Free format text: 7C 25D 21/14 A, 7C 25D 21/12 B, 7C 25D 17/12 B, 7C 25D 17/06 B

17P Request for examination filed

Effective date: 20030505

AKX Designation fees paid

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

17Q First examination report despatched

Effective date: 20041007

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RTI1 Title (correction)

Free format text: EQUIPMENT FOR THE ELECTROLYTIC DEPOSITION OF GOLD OR GOLD ALLOYS

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

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

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051005

Ref country code: FI

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

Effective date: 20051005

Ref country code: BE

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

Effective date: 20051005

Ref country code: AT

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

Effective date: 20051005

Ref country code: NL

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

Effective date: 20051005

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

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

Ref country code: SE

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

Effective date: 20060105

Ref country code: GR

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

Effective date: 20060105

Ref country code: DK

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

Effective date: 20060105

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

Ref country code: DE

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

Effective date: 20060106

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: KIRKER & CIE SA

REF Corresponds to:

Ref document number: 60022940

Country of ref document: DE

Date of ref document: 20060216

Kind code of ref document: P

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

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

Effective date: 20060306

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2250092

Country of ref document: ES

Kind code of ref document: T3

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

Ref country code: IE

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

Effective date: 20060503

Ref country code: GB

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

Effective date: 20060503

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

Ref country code: MC

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

Effective date: 20060531

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20060706

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

Ref country code: FR

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

Effective date: 20061020

EN Fr: translation not filed
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20060503

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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

Ref country code: LU

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

Effective date: 20060503

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

Ref country code: FR

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

Effective date: 20051005

Ref country code: CY

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

Effective date: 20051005

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

Ref country code: CH

Payment date: 20120514

Year of fee payment: 13

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: CH

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

Effective date: 20130531

Ref country code: LI

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

Effective date: 20130531

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

Ref country code: ES

Payment date: 20170612

Year of fee payment: 18

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20190913

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

Ref country code: ES

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

Effective date: 20180504