CN103946428A - Anodic structure for horizontal cells for processes of metal electrodeposition - Google Patents

Anodic structure for horizontal cells for processes of metal electrodeposition Download PDF

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Publication number
CN103946428A
CN103946428A CN201280056364.0A CN201280056364A CN103946428A CN 103946428 A CN103946428 A CN 103946428A CN 201280056364 A CN201280056364 A CN 201280056364A CN 103946428 A CN103946428 A CN 103946428A
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CN
China
Prior art keywords
electrode
anode
row
electroplating
pond
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Pending
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CN201280056364.0A
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Chinese (zh)
Inventor
J·E·戈麦斯德阿布瑞
T·欧伊什
A·卡尔德拉拉
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Industrie de Nora SpA
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Industrie de Nora SpA
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Publication of CN103946428A publication Critical patent/CN103946428A/en
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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
    • 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
    • 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
    • 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
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
    • 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
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0607—Wires
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • C25D7/0642—Anodes

Abstract

The present invention concerns an electrode for oxygen evolution in electroplating plants comprising a valve metal substrate and an outer catalytic layer, the substrate consisting of a metal plate provided with slits of area ranging from 2 to 8 cm2, said slits being spaced apart by a distance of 5 to 25 cm. The invention also concerns a horizontal electrochemical cell for electroplating processes comprising at least one of said electrodes, and an electroplating plant equipped with at least one of said cells. The invention also concerns an electroplating process comprising the step of anodically evolving oxygen on the surface of said electrode.

Description

Be used for the anode construction in the horizontal pond of metal electrodeposition technique
Technical field
The present invention relates to the electrode structure for analysing oxygen (oxygen evolution), described electrode structure is suitable for being equipped with the electrochemical electrodeposition apparatus of horizontal pond (horizontal cell).
Background technology
In the electrochemical electrodeposition technology of metal, in horizontal pond, use nonexpendable anode to substitute the lead anode of heavier and poor-performing, be the practice of knowing in this area.In fact, insoluble anode has higher handiness in equipment design and operational mode subsequently.Nonexpendable anode can also move than lead anode under higher current density, thereby has advantage aspect productivity.In traditional metal electrodeposition, for example close in unanimous plating at electrochemical zinc or zinc, oxygen has been generated as the result of anodic reaction.But, utilize nonexpendable anode to move under higher current density and cause the oxygen producing on anode surface to increase.Under many circumstances, electrodeposition apparatus is equipped with horizontal pond; In this case, through electrolytic bath (electrolytic bath), between the anode being arranged in parallel with each other, transmission is used as metal strip or the line of negative electrode.In this case, the oxygen output of increase generally means the problem relevant to gas hold-up, and result local current densities increases, and it causes negative impact to deposition uniformity.
Therefore, expecting provides a kind of electrode, and it has the mechanical property of improvement, thereby is applicable to promoting the release of oxygen and improves solution renewal rate-be conducive to providing enough positively charged ion-and be conducive to the contact of electrode-solution to negative electrode.
Summary of the invention
Different aspect of the present invention is illustrated in appended claim.
In one aspect, the present invention relates in the electroplating device that is equipped with horizontal pond for analysing the electrode of oxygen, described electrode package is containing valve metal (valve metal) base material and outer Catalytic Layer, and described base material comprises that having area is 2cm 2to 8cm 2the tinsel of seam (slit), described seam is spaced with the distance of 5em to 25em.In one embodiment, seam is arranged with the configuration evenly separating.
Contriver is surprised to find, and adds the seam of the suitable dimension of arranging with suitable distance, has the effect of remarkable increase electrode operation life, described electrode in electroplating technology for thering is the Oxygen anodic evolution of equipment in horizontal pond.
In one embodiment, electrode has the shape of rectangle, and described sewer has elongated shape, and wherein the long limit of seam is configured to be parallel to the minor face of electrode alternatively.
In another embodiment, in the electroplating device that is equipped with horizontal pond, for analysing the electrode of oxygen, to have spaced apart and area be regularly 3cm 2to 5cm 2seam.
Contriver is surprised to find, compared with having specific and compared with the seam of large-spacing distance, the metal output with the seam of reduced size does not demonstrate any advantage.This situation can be because seam too little and spaced apart cannot allow enough air releases and circulation.By contrast, seam too large and tight spacing causes active area loss, and it causes negative impact to deposition uniformity.
In yet another aspect, the valve metal of analysing oxygen electrode in the electroplating device that is equipped with horizontal pond is that titanium and Catalytic Layer comprise iridium, tantalum and titanyl compound.
In yet another aspect, the present invention relates to the horizontal electrochemical cell for electroplating technology, described horizontal electrochemical cell comprises at least one foregoing electrode.As long as the structure of anode part is the parallel anodes of two rows, wherein metal strip or line are used as negative electrode and transmit therebetween, and seam just can exist only on row's anode, preferably upper row.In yet another aspect, the present invention relates to the pond that comprises row's anode and lower row's anode, a row is arranged on another row; And by carry out the continous metal strip of forward movement or the negative electrode that line forms between upper row's anode and lower row's anode, described working direction is parallel to the parallel rows of described anode, and described at least one electrode anode that is described upper row's anode.In yet another aspect, the present invention relates to have the pond of seam, described in sew to arrange and make its long limit perpendicular to the working direction of metal strip or line that is used as negative electrode.
In yet another aspect, the present invention relates to be equipped with the electroplating device at least one horizontal electrochemical cell of electroplating technology, described horizontal electrochemical cell comprises at least one foregoing electrode.
Illustrate some embodiments of the present invention and be described in connection with accompanying drawing now, its sole purpose is the mutual arrangement of the different elements that explaination is relevant to described specific implementations of the present invention; Particularly, accompanying drawing needn't proportionally draw.
Brief description of the drawings
Fig. 1 illustrates according to the vertical view of the possible embodiment of the anode with 12 seams of the present invention.
Fig. 2 illustrates according to the side-view of the possible embodiment in horizontal pond of the present invention.
Embodiment
Fig. 1 demonstrates the vertical views of possible embodiment of the anode A with 12 seam B, wherein stitch B apart from one another by distance C and with peripheral spacing distance D.
Fig. 2 demonstrates the side-view of the possible embodiment in the horizontal pond with eight anode L, and anode has 12 seams separately, is arranged in two parallel rows, from be used as the metal strip I of negative electrode between two parallel rows through transmission.Also demonstrate electrolytic bath entrance E, discarded electrolytic bath outlet F, the oxygen discharge outlet G producing and the horizontal H of electrolytic bath on anode.
Following example is used for illustrating specific implementations of the present invention, and in claimed numerical range, its feasibility has been confirmed largely.It will be appreciated by those skilled in the art that disclosed carefully closing and carefully closing and technology operational excellence in practice of the present invention that technology represents to be found by the present inventor in example below; But, it will be understood by those of skill in the art that according to the present invention openly, in disclosed specific implementations, can make multiple variation, and in the scope of the invention, still can obtain same or analogous result not departing from.
Example 1
16 anodes that are of a size of 1380mm x200mm x6mm comprise the titanium base material with catalyst coatings, catalyst coatings comprises two different layers, that is: first (interior) layer, its oxide compound based on tantalum and iridium, the weight ratio of tantalum and iridium is 65: 35 (corresponding to the mol ratio that is about 63.6: 36.4), and wherein total iridium loading capacity is 10g/m 2; And second (outward) layer, based on iridium, tantalum and titanyl compound, the weight ratio of iridium, tantalum and titanium is 78: 20: 2 (corresponding to the mol ratio that is about 72.6: 19.9: 7.5), wherein total iridium loading capacity is 35g/m 2, 16 anodes are divided into two groups of eight anodes separately, and are arranged in parallel into corresponding two rows on the both sides of wanting zinc-plated sheet.It is 400mm that each anode has 12 areas 2elongate slot, described elongate slot is arranged the length that minor face is oriented as be parallel to sheet, elongate slot space 198mm and with the peripheral interval 25mm of sheet.Under the temperature of 50 DEG C and pH2 condition, in the electrolytic bath that comprises 100g/L zinc at 13kA/m 2current density under, in the galvanizing equipment with horizontal pond, test anode.After the zinc of 210 tons of depositions, anode deactivates and has occurred.In the scope of this specification sheets and according to the convention of conventionally accepting in many galvanizing equipments, in the time that the slope of the ohmmic drop in electrolytic bath (Ohmie drop) increases by 20% in time with respect to initial value, anode is considered to deactivate.In fact,, in the time that anode part deactivates beginning, along with current concentration is in the region activating most corresponding to anode, it is inhomogeneous that distribution of current becomes; Current concentration has determined the increase of the ohmmic drop in electrolytic bath, ohmmic drop thereby become the exemplary parameter of anode maintaining condition.
Comparative example 1
16 anodes that are of a size of 1380mm x200mm x6mm comprise the titanium base material with catalyst coatings, catalyst coatings comprises two different layers, that is: first (interior) layer, its oxide compound based on tantalum and iridium, the weight ratio of tantalum and iridium is 65: 35 (corresponding to the about mol ratio of 63.6: 36.4), and wherein total iridium loading capacity is 10g/m 2; And second (outward) layer, it is based on iridium, tantalum and titanyl compound, and the weight ratio of iridium, tantalum and titanium is 78: 20: 2 (corresponding to the about mol ratio of 72.6: 19.9: 7.5), and wherein total iridium loading capacity is 35g/m 2, above-mentioned 16 anodes are divided into two groups of eight anodes separately, and are arranged in parallel into corresponding two rows on the both sides of wanting zinc-plated sheet.Under the temperature of 50 DEG C and pH2 condition, in the electrolytic bath that comprises 100g/L zinc at 13kA/m 2current density under, in the galvanizing equipment with horizontal pond, test anode.After the deposition zinc of 100 tons, the anode generation of deactivating.
Example 2
16 anodes that are of a size of 1380mm x200mm x6mm comprise the titanium base material with catalyst coatings, catalyst coatings comprises two different layers, that is: first (interior) layer, its oxide compound based on tantalum and iridium, the weight ratio of tantalum and iridium is 65: 35 (corresponding to the about mol ratio of 63.6: 36.4), and wherein total iridium loading capacity is 10g/m 2; And second (outward) layer, it is based on iridium, tantalum and titanyl compound, and the weight ratio of iridium, tantalum and titanium is 78: 20: 2 (corresponding to the about mol ratio of 72.6: 19.9: 7.5), and wherein total iridium loading capacity is 35g/m 2, above-mentioned 16 anodes are divided into two groups of eight anodes separately, and are arranged in parallel into corresponding two rows on the both sides of wanting zinc-plated sheet.It is 400mm that each anode has 12 areas 2elongate slot, described elongate slot is arranged the length that minor face is oriented as be parallel to sheet, elongate slot space 198mm and with the peripheral interval 25mm of sheet.Under the temperature of 50 DEG C and pH2 condition, in the electrolytic bath that comprises 100g/L zinc at 10kA/m 2current density under, in the galvanizing equipment with horizontal pond, test anode.After the deposition zinc of 180 tons, the anode generation of deactivating.
Comparative example 2
16 anodes that are of a size of 1380mm x200mm x6mm comprise the titanium base material with catalyst coatings, catalyst coatings comprises two different layers, that is: first (interior) layer, its oxide compound based on tantalum and iridium, the weight ratio of tantalum and iridium is 65: 35 (corresponding to the about mol ratio of 63.6: 36.4), and wherein total iridium loading capacity is 10g/m 2; And second (outward) layer, based on iridium, tantalum and titanyl compound, the weight ratio of iridium, tantalum and titanium is 78: 20: 2 (corresponding to the about mol ratio of 72.6: 19.9: 7.5), wherein total iridium loading capacity is 35g/m 2, above-mentioned 16 anodes are divided into two groups of eight anodes separately, and are arranged in parallel into corresponding two rows on the both sides of wanting zinc-plated sheet.Under the temperature of 50 DEG C and pH2 condition, in the electrolytic bath that comprises 100g/L zinc at 10kA/m 2current density under, in the galvanizing equipment with horizontal pond, test anode.After the deposition zinc of 140 tons, the anode generation of deactivating.
Noted earlier is not of the present invention for limiting, and it can use according to different embodiment in the situation that not departing from its scope, and its scope is only by appended claim is limited.
In whole specification sheets of the present invention and claims, term " comprises " and changes and for example " comprises " and " comprising " is not the existence for repelling other element, component or additional process steps.
Document, behavior, material, device, article, and the like discussion be included in this specification sheets, be only used to provide the object of background of the present invention.Before not advising or be not illustrated in the application's the priority date of each claim, any or all these materials form a very part for plinth of prior art, or the common sense of technical field related to the present invention.

Claims (10)

  1. In electroplating device for analysing an electrode for oxygen, described electrode package is containing valve metal substrates and outer Catalytic Layer, base material comprises that to have area be 2cm 2to 8cm 2the metal sheet of seam, described in sew with the distance of 5cm to 25cm spaced apart.
  2. 2. electrode according to claim 1, wherein said sew spaced apart regularly.
  3. 3. electrode according to claim 1 and 2, wherein said sewer has elongated shape.
  4. 4. according to the electrode one of claim 1-3 Suo Shu, wherein said sewer has 3cm 2to 5cm 2area.
  5. 5. according to the electrode one of claim 1-4 Suo Shu, wherein valve metal is that titanium and described Catalytic Layer comprise iridium, tantalum and titanyl compound.
  6. 6. for a horizontal electrochemical cell for electroplating technology, comprise according at least one electrode one of aforementioned claim Suo Shu.
  7. 7. pond according to claim 6, wherein said at least one electrode package is containing elongate slot, and described elongate slot is arranged and makes long limit perpendicular to being used as the described metal strip of negative electrode or the working direction of line.
  8. 8. pond according to claim 6, comprises:
    A. upper row's anode and lower row's anode, a row is arranged on another row; And
    B. carry out the continous metal strip of forward movement or the negative electrode that line forms by arranging between anode and described lower row's anode on described, this working direction is parallel to the parallel rows of described anode,
    Wherein said at least one electrode is an anode in described upper row's anode.
  9. 9. one kind is equipped with according to the electroplating device at least one pond described in claim 6,7 or 8.
  10. 10. an electroplating technology, is included according to the surperficial Anodic of the electrode one of claim 1-5 Suo Shu and analyses the step of oxygen.
CN201280056364.0A 2011-11-24 2012-11-23 Anodic structure for horizontal cells for processes of metal electrodeposition Pending CN103946428A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
IT002136A ITMI20112136A1 (en) 2011-11-24 2011-11-24 ANODIC STRUCTURE FOR HORIZONTAL CELLS FOR METAL ELECTROPLATE PROCESSES
ITMI2011A002136 2011-11-24
PCT/EP2012/073527 WO2013076277A2 (en) 2011-11-24 2012-11-23 Anodic structure for horizontal cells for processes of metal electrodeposition

Publications (1)

Publication Number Publication Date
CN103946428A true CN103946428A (en) 2014-07-23

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CN201280056364.0A Pending CN103946428A (en) 2011-11-24 2012-11-23 Anodic structure for horizontal cells for processes of metal electrodeposition

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US (1) US20140231267A1 (en)
EP (1) EP2783027A2 (en)
JP (1) JP2015501880A (en)
KR (1) KR20140098155A (en)
CN (1) CN103946428A (en)
AR (1) AR088980A1 (en)
AU (1) AU2012342392A1 (en)
BR (1) BR112014011550A2 (en)
CA (1) CA2851076A1 (en)
EA (1) EA201491025A1 (en)
IL (1) IL232099A0 (en)
IN (1) IN2014KN00725A (en)
IT (1) ITMI20112136A1 (en)
MX (1) MX2014005832A (en)
WO (1) WO2013076277A2 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4310403A (en) * 1980-03-07 1982-01-12 Nippon Steel Corporation Apparatus for electrolytically treating a metal strip
US4964965A (en) * 1987-10-01 1990-10-23 Furukawa Circuit Foil Co., Ltd. Insoluble electrode device for treatment of metallic material
US6251254B1 (en) * 1998-09-30 2001-06-26 Permelec Electrode Ltd. Electrode for chromium plating
CN2832836Y (en) * 2005-06-14 2006-11-01 东元电机股份有限公司 Anode metal plate structure for electrophoretic deposition
US20070278107A1 (en) * 2006-05-30 2007-12-06 Northwest Aluminum Technologies Anode for use in aluminum producing electrolytic cell

Family Cites Families (6)

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Publication number Priority date Publication date Assignee Title
DE2135873B2 (en) * 1971-07-17 1980-05-14 Conradty Gmbh & Co Metallelektroden Kg, 8505 Roethenbach Cell top for amalgam high-load cells
JPS57101692A (en) * 1980-12-16 1982-06-24 Nippon Steel Corp Horizontal electroplating method by insoluble electrode
AU540287B2 (en) * 1982-02-10 1984-11-08 Nippon Steel Corporation Continuous electrolytic treatment of metal strip using horizontal electrodes
DE3421480A1 (en) * 1984-06-08 1985-12-12 Conradty GmbH & Co Metallelektroden KG, 8505 Röthenbach COATED VALVE METAL ELECTRODE FOR ELECTROLYTIC GALVANIZATION
US6322673B1 (en) * 1999-12-18 2001-11-27 Electroplating Technologies, Ltd. Apparatus for electrochemical treatment of a continuous web
US7273535B2 (en) * 2003-09-17 2007-09-25 Applied Materials, Inc. Insoluble anode with an auxiliary electrode

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4310403A (en) * 1980-03-07 1982-01-12 Nippon Steel Corporation Apparatus for electrolytically treating a metal strip
US4964965A (en) * 1987-10-01 1990-10-23 Furukawa Circuit Foil Co., Ltd. Insoluble electrode device for treatment of metallic material
US6251254B1 (en) * 1998-09-30 2001-06-26 Permelec Electrode Ltd. Electrode for chromium plating
CN2832836Y (en) * 2005-06-14 2006-11-01 东元电机股份有限公司 Anode metal plate structure for electrophoretic deposition
US20070278107A1 (en) * 2006-05-30 2007-12-06 Northwest Aluminum Technologies Anode for use in aluminum producing electrolytic cell

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AU2012342392A1 (en) 2014-04-17
CA2851076A1 (en) 2013-05-30
MX2014005832A (en) 2014-06-04
JP2015501880A (en) 2015-01-19
AR088980A1 (en) 2014-07-23
IN2014KN00725A (en) 2015-10-02
EA201491025A1 (en) 2014-09-30
BR112014011550A2 (en) 2017-05-09
EP2783027A2 (en) 2014-10-01
WO2013076277A3 (en) 2013-08-01
US20140231267A1 (en) 2014-08-21
ITMI20112136A1 (en) 2013-05-25
IL232099A0 (en) 2014-05-28
WO2013076277A2 (en) 2013-05-30
KR20140098155A (en) 2014-08-07

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