EP1581673B1 - Anode pour electrodeposition - Google Patents

Anode pour electrodeposition Download PDF

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Publication number
EP1581673B1
EP1581673B1 EP03813909A EP03813909A EP1581673B1 EP 1581673 B1 EP1581673 B1 EP 1581673B1 EP 03813909 A EP03813909 A EP 03813909A EP 03813909 A EP03813909 A EP 03813909A EP 1581673 B1 EP1581673 B1 EP 1581673B1
Authority
EP
European Patent Office
Prior art keywords
anode
shield
electroplating
metal
active layer
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.)
Expired - Lifetime
Application number
EP03813909A
Other languages
German (de)
English (en)
Other versions
EP1581673A2 (fr
Inventor
Jörg WURM
Stephane Menard
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.)
Metakem Gesellschaft fur Schichtchemie der Metalle mbH
Micropulse Plating Concepts SAS MPC
Original Assignee
Metakem Gesellschaft fur Schichtchemie der Metalle mbH
Micropulse Plating Concepts SAS MPC
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 Metakem Gesellschaft fur Schichtchemie der Metalle mbH, Micropulse Plating Concepts SAS MPC filed Critical Metakem Gesellschaft fur Schichtchemie der Metalle mbH
Publication of EP1581673A2 publication Critical patent/EP1581673A2/fr
Application granted granted Critical
Publication of EP1581673B1 publication Critical patent/EP1581673B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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

Definitions

  • the invention relates to an anode for electroplating.
  • insoluble anodes are known in the art. These generally consist of a carrier material and an active layer.
  • a carrier material usually titanium, niobium and others are used. In any case, however, materials are used which are self-passivating under the electrolysis conditions, so, for example, it is also possible to use nickel in alkaline baths.
  • the active layer is usually an electron-conducting layer. It usually consists of materials such as platinum, iridium, mixed oxides with platinum metals or diamond.
  • the active layer may be located directly on the surface of the carrier material, but it may also be located on a substrate which is attached to the carrier material spaced therefrom. As a substrate, for example, such materials can be used, which also come into consideration as a carrier material.
  • additives are added to the baths which act as brighteners, increase the hardness and increase the scattering. These are mostly organic compounds.
  • Anodes are often used here, whose base body consists of titanium and whose active layer consists of platinum or mixed oxide. This active layer is during operation very fast (related calculated on the power conversion in Ah / m 2 ) compared to active layers in the base metal electroplating. This is due, for the most part, to the attack of additives on this active layer, which dissolve the platinum metals of the layer by complex formation. Moreover, certain types of baths can also interfere with cyanate and carbonate formation.
  • the EP 0 471 577 A1 discloses an electrolyzer having an upper electrode and a lower electrode and wherein each of the opposing surfaces of the two electrodes is covered by a respective membrane. Each electrode and the adjacent membrane are mounted in a support structure.
  • the invention also relates to the method of electroplating according to claim 8 and to the use of the anode according to claim 9.
  • the anode for electroplating according to the invention is characterized in that it comprises an anode base body and a shield, wherein the anode base body has a carrier material and an active layer, the shield is attached to the anode base body spaced therefrom and the substance -transport reduced to the anode base body and away from it, the shield is made of metal or plastic and metal and the shield is electrically connected to the anode main body.
  • the anode according to the invention is preferably an anode in which the carrier material is self-passivating under electrolysis conditions.
  • the active layer is preferably electron-conducting.
  • the shield consists of metal. This metal should be largely corrosion resistant under anode conditions. It is further particularly preferred if the shield consists of a metal mesh, an expanded metal or a perforated plate.
  • the shield is made of plastic and metal, as it allows different desirable material properties to be combined.
  • the metallic shielding can bring about an additional potential effect, while with plastic, an effective transport obstacle is more easily achieved.
  • a combination of two metal meshes and an interposed fine tissue or membrane of plastic therefore constitutes a preferred embodiment of the present invention.
  • a particular advantage of this arrangement the very simple installation proves.
  • the shield of the anode according to the invention is electrically conductively connected to the anode base body.
  • positively charged additives must overcome an electrostatic barrier in addition to the mechanical barrier.
  • the efficiency of shielding This can be significantly increased.
  • Such a charged metallic shield acts electrostatically, but can not act electrochemically due to the oxide layer forming on the surface of the shield.
  • the shielding in particular has a distance to the anode base of 0.01 to 100 mm, preferably from 0.05 to 50 mm, more preferably from 0.1 to 20 mm and most preferably from 0.5 to 10 mm.
  • the shield is not parallel to the anode body, e.g. in the case of a corrugated metal sheet used as a shielding, the above-mentioned values relate to the mean distance between the shielding and the anode base body.
  • the effect of a shield located at this distance from the anode base body is particularly great since the additive molecules or ions must first travel a certain distance. This is a particular advantage e.g. against a shield applied directly to the anode-body surface and only a few microns thick.
  • a reduction in the surface area of the active layer of the anode base body is not present in the anode according to the invention, which represents a further advantage over the aforementioned anode with a shield located directly on the active layer.
  • a shield of the anode base body is also possible, but this is preferably also front and rear attached.
  • Another preferred embodiment of the present invention is an anode in which the configuration of the shield in its shape, the arrangement and the distance to the anode base body is such that the gas bubbles produced at the anode during operation are brought together.
  • the gases produced at the anode rise in the form of small bubbles up.
  • the number of bubbles increases towards the top and therefore leads to an inhomogeneous shielding of the anode.
  • the anode according to the invention leads to a reduction in the number of bubbles, since the bubbles are brought together and thus are larger. Since the additive degradation is in part a gas-liquid reaction, this change in the surface to volume ratio causes a further reduction in additive degradation.
  • By decreasing the shielding caused by the bubbles advantageously, there is also an increase in the deposition rate.
  • Another advantage is that the layer of metal deposited on the cathode side becomes more homogeneous as the inhomogeneity of the shielding caused by the bubbles is reduced.
  • the anode according to the invention thus also helps to save material.
  • the gradient caused by the remaining bubbles on the height of the anode and thus also the cathode can advantageously be compensated, for example, by the fact that the active layer of the anode base body tapers towards the bottom, or can also be compensated by using expanded metals with different surface factors.
  • the anode according to the invention advantageously allows use even in strongly alkaline solutions, since the anode in operation by the above-described local pH lowering of the anode environment in the resulting medium is essentially corrosion resistant.
  • the anode in operation by the above-described local pH lowering of the anode environment in the resulting medium is essentially corrosion resistant.
  • the anode described above may be connected according to the invention as a cathode.
  • the shield In cathodic switching of the anode, the shield is non-self-passivating. It is therefore advantageous if a large surface is present, since this reduces the current density and thus the cathodic overvoltage. This leads to a longer service life of the cathode connected as an anode.
  • the invention further relates to methods of electroplating in which an anode is used as described above.
  • a cathodic circuit of the anode ie, the anode is the cathode, of importance, - this is the case, inter alia, in so-called reverse pulse method.
  • the polarity reversal can occur at different times of the galvanization process.
  • a series of pulses are initially applied to the printed circuit board lying at cathodic potential and the anode according to the invention lying at anodic potential.
  • the polarization is reversed for a few milliseconds, so the circuit board is then at anodic potential, while the anode according to the invention acts as a cathode.
  • the iron object is first set to anodic potential to cause activation of the surface.
  • the anode according to the invention is the cathode.
  • the polarization is reversed and the anode according to the invention, which is now at anodic potential, is used in the usual way for the galvanization of the iron object, which is now at cathodic potential.
  • the shielding of the anode causes a reduction in the current density at the polarity reversal, which is advantageous for the life of the anode.
  • the additive degradation was investigated under the operating conditions of a sulfuric acid copper bath in DC operation.
  • the additive used was a sulfur compound.
  • As anodes two DC plates with an active layer of mixed oxide were used. In this case, the first consisted only of the anode body and the second anode according to the invention of anode body and shield.
  • As the cathode a brass plate was used in each case.
  • the additive consumption when using the two anodes would be measured cyclovoltametrisch and is in FIG. 1 applied against the flowed ampere hours. It can be clearly seen that the additive degradation when using the second anode according to the invention is reduced by a factor of 2.5 to 3 compared with the additive degradation when using the first anode.
  • Bubble formation under production conditions in a sulfuric acid copper bath was investigated for the copper plating of wells under reverse pulse plating conditions.
  • the first anode consisted only of an anode base composed of a titanium support material and an active layer of mixed oxide having a size of 1100 mm ⁇ 500 mm ⁇ 1.5 mm.
  • the second anode according to the invention also consisted of a base body which consisted of titanium as a carrier material and a mixed oxide as the active layer and had the same size as the main body of the first anode, and a shield of titanium expanded metal.
  • the same stream was passed through both anodes, and at the first anode the usual bubbling and a vigorously agitated bath were observed.
  • the second anode according to the invention however, the formation of bubbles was greatly reduced.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Magnetic Heads (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)

Claims (9)

  1. Anode pour galvanisation, qui comporte un corps de base d'anode et un élément protecteur, dans laquelle le corps de base d'anode comporte un matériau support et une couche de matière active, et l'élément protecteur est attaché au corps de base d'anode, à une certaine distance de celui-ci, et réduit les transports de matière vers le corps de base d'anode et à partir de celui-ci, et l'élément protecteur est en métal, ou en matière synthétique et métal, et se trouve raccordé au corps de base d'anode d'une manière permettant le passage d'un courant électrique.
  2. Anode conforme à la revendication 1, dans laquelle le matériau support est auto-passivant dans les conditions d'électrolyse.
  3. Anode conforme à la revendication 1 ou 2, dans laquelle la couche de matière active est conductrice par électrons.
  4. Anode conforme à l'une des revendications 1 à 3, dans laquelle l'élément protecteur est formé d'une toile métallique, d'une pièce de métal déployé ou d'une tôle perforée.
  5. Anode conforme à l'une des revendications 1 à 4, dans laquelle l'élément protecteur se trouve, par rapport au corps de base d'anode, à une distance de 0,01 à 100 mm, de préférence de 0,05 à 50 mm, mieux encore de 0,1 à 20 mm et surtout de 0,5 à 10 mm.
  6. Anode conforme à l'une des revendications 1 à 5, dans laquelle l'élément protecteur a été façonné et disposé de telle sorte, et placé à une telle distance du corps de base d'anode, que les bulles de gaz qui se forment sur l'anode pendant une opération de galvanisation sont amenées à se rassembler.
  7. Anode conforme à l'une des revendications 1 à 6, qui est montée en tant que cathode.
  8. Procédé de galvanisation dans lequel on utilise une anode conforme à l'une des revendications 1 à 7.
  9. Utilisation d'une anode conforme à l'une des revendications 1 à 7 dans une opération de galvanisation.
EP03813909A 2002-12-23 2003-12-23 Anode pour electrodeposition Expired - Lifetime EP1581673B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10261493A DE10261493A1 (de) 2002-12-23 2002-12-23 Anode zur Galvanisierung
DE10261493 2002-12-23
PCT/EP2003/014785 WO2004059045A2 (fr) 2002-12-23 2003-12-23 Anode pour electrodeposition

Publications (2)

Publication Number Publication Date
EP1581673A2 EP1581673A2 (fr) 2005-10-05
EP1581673B1 true EP1581673B1 (fr) 2011-03-23

Family

ID=32478077

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03813909A Expired - Lifetime EP1581673B1 (fr) 2002-12-23 2003-12-23 Anode pour electrodeposition

Country Status (10)

Country Link
US (1) US7943032B2 (fr)
EP (1) EP1581673B1 (fr)
JP (1) JP4346551B2 (fr)
KR (1) KR101077000B1 (fr)
CN (1) CN101027432B (fr)
AT (1) ATE503043T1 (fr)
AU (1) AU2003296716A1 (fr)
DE (2) DE10261493A1 (fr)
ES (1) ES2363278T3 (fr)
WO (1) WO2004059045A2 (fr)

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EP1712660A1 (fr) 2005-04-12 2006-10-18 Enthone Inc. Anode insoluble
EP1717351A1 (fr) * 2005-04-27 2006-11-02 Enthone Inc. Bain de galvanisation
DE102005051632B4 (de) 2005-10-28 2009-02-19 Enthone Inc., West Haven Verfahren zum Beizen von nicht leitenden Substratoberflächen und zur Metallisierung von Kunststoffoberflächen
US20090095927A1 (en) * 2005-11-04 2009-04-16 Mccarthy Matthew Thermally actuated valves, photovoltaic cells and arrays comprising same, and methods for producing same
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FR2927909B1 (fr) * 2008-02-26 2010-03-26 Serme Cache souple pour support galvanique, support et procede de mise en oeuvre
EP2848714B1 (fr) * 2008-04-22 2016-11-23 Rohm and Haas Electronic Materials LLC Procédé de régénération d'ions indium dans des compositions de dépôt électrique d'indium
DE202008006707U1 (de) 2008-05-16 2008-08-07 Saueressig Gmbh & Co. Vorrichtung zum Glavanisieren von Werkstücken
US8236163B2 (en) * 2009-09-18 2012-08-07 United Technologies Corporation Anode media for use in electroplating processes, and methods of cleaning thereof
TWI422714B (zh) * 2010-11-24 2014-01-11 Intech Electronics Co Ltd 電鍍裝置及其電鍍槽中的電極板結構
CN102477576A (zh) * 2010-11-30 2012-05-30 加贺开发科技有限公司 电镀装置及其电镀槽中的电极板结构
CN103820839A (zh) * 2014-01-14 2014-05-28 杭州三耐环保科技有限公司 一种高效抑制电积酸雾的阴阳极板结构及其实现方法
CN104073862A (zh) * 2014-07-11 2014-10-01 张钰 一种用于碱性锌镍合金电镀的不溶性阳极装置
US10428439B2 (en) * 2015-11-16 2019-10-01 Intel Corporation Predictive capability for electroplating shield design
MX2021008925A (es) * 2019-01-24 2021-08-24 Atotech Deutschland Gmbh Sistema de anodo de membrana para deposito electrolitico de aleacion de cinc-niquel.
CN110029381B (zh) * 2019-04-25 2020-12-15 首钢集团有限公司 一种高镀锡量镀锡板的生产方法
CN113106527B (zh) * 2021-04-19 2024-09-10 深圳铱创科技有限公司 不溶性阳极及脉冲电镀设备

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Also Published As

Publication number Publication date
KR20050085863A (ko) 2005-08-29
US7943032B2 (en) 2011-05-17
AU2003296716A1 (en) 2004-07-22
ES2363278T3 (es) 2011-07-28
JP4346551B2 (ja) 2009-10-21
KR101077000B1 (ko) 2011-10-26
CN101027432B (zh) 2010-09-29
DE50313572D1 (de) 2011-05-05
DE10261493A1 (de) 2004-07-08
WO2004059045A2 (fr) 2004-07-15
JP2006511712A (ja) 2006-04-06
EP1581673A2 (fr) 2005-10-05
ATE503043T1 (de) 2011-04-15
AU2003296716A8 (en) 2004-07-22
US20060124454A1 (en) 2006-06-15
CN101027432A (zh) 2007-08-29
WO2004059045A3 (fr) 2005-02-24

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