WO1997015704A2 - Installation galvanoplastique - Google Patents

Installation galvanoplastique Download PDF

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Publication number
WO1997015704A2
WO1997015704A2 PCT/DE1996/001936 DE9601936W WO9715704A2 WO 1997015704 A2 WO1997015704 A2 WO 1997015704A2 DE 9601936 W DE9601936 W DE 9601936W WO 9715704 A2 WO9715704 A2 WO 9715704A2
Authority
WO
WIPO (PCT)
Prior art keywords
auxiliary
electrolyte
electroplating
metal
anolyte
Prior art date
Application number
PCT/DE1996/001936
Other languages
German (de)
English (en)
Other versions
WO1997015704A3 (fr
Inventor
Karl Hans Fuchs
Original Assignee
Lea Ronal Gmbh
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 Lea Ronal Gmbh filed Critical Lea Ronal Gmbh
Priority to EP96945489A priority Critical patent/EP0801692A2/fr
Priority to JP9512202A priority patent/JPH10511743A/ja
Publication of WO1997015704A2 publication Critical patent/WO1997015704A2/fr
Publication of WO1997015704A3 publication Critical patent/WO1997015704A3/fr

Links

Classifications

    • 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
    • C25D21/16—Regeneration of process solutions
    • C25D21/18—Regeneration of process solutions of electrolytes
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/24—Reinforcing the conductive pattern
    • H05K3/241—Reinforcing the conductive pattern characterised by the electroplating method; means therefor, e.g. baths or apparatus

Definitions

  • the invention relates to a galvanic system according to the preamble of patent claim 1.
  • insoluble anodes in the previously known continuous electroplating system requires that the electrolyte be enriched with the metal ions provided for coating the electroplating material.
  • this is to be done by using a redox agent whose oxidized stage is present in the regeneration chamber and there causes the dissolution of the metal and thus the metal accumulation of the electrolyte.
  • the metal is thus dissolved outside the electrolytic cell by adding a special electrochemical reagent that is not specified in detail.
  • US Pat. No. 5,100,517 also shows a galvanic system, which involves the production of coatings on steel reinforcements, for example in tires or drive belts. Such coatings can in particular also consist of copper or zinc, it also being possible for several layers to be superimposed.
  • the basic idea of the new process proposed in this document is to avoid the consumption of the copper anode customary in standard copper coating processes by using an insoluble anode in the electroplating bath, whereas the necessary provision of copper ions for coating the object takes place in a regeneration room.
  • a basket with copper balls is provided as an anode and a cathode 27, with a membrane 26 being held between the two, which prevents the released copper ions from being deposited on the cathode 27 again, instead of via the circuit in the electroplating bath object to be coated.
  • this solution is an alternative to the solution to this problem indicated in the generic DE 44 05 741 Cl by a purely electrochemical route and also enables the use of insoluble anodes in the electroplating cell (in the example, a titanium grid coated with iridium oxide) .
  • an alkaline electroplating bath is used for coating, in which the copper ion is present in a copper pyrophosphate solution, ie the positive copper ions are shielded by the ligands and the overall complex has a negative charge and thus a certain movement characteristic; this is also expressed in the design of the membrane 26 in the regeneration space, which prevents the flow of such molecular complexes.
  • a copper layer with a thickness of 1 +/- 0.5 ⁇ can be applied to a steel wire.
  • this layer is not subject to any gloss or leveling requirements, since the steel wires coated in this way are only intended as reinforcements for further components (tires).
  • 5,100,517 would have the immediate consequence, for example, that in the selection of the process chemistry and electrode materials provided there, amounts of oxidizing substances such as oxygen or Chlorine is formed, with the oxygen in particular leading to uncontrolled oxidation processes on such organic additives, some of which are attacked by intermediates and depending on parameters such as flow conditions, the amount of current that is enforced, in particular the usual organic brighteners and are oxidatively destroyed in an uncontrollable manner .
  • oxidizing substances such as oxygen or Chlorine
  • a further embodiment of the electroplating system according to the invention provides that methods such as those described in electroplating baths with soluble anodes, for example in GB-22 14 520 A, are used to operate the circuit of the electroplating bath, in particular the so-called “pulse plating" -Procedure or “periodic reverse plating", or any combination of these processes with the desired specification of the positive and negative voltages independently of one another.
  • the coating results can thus be improved, the use of this method also enables the use of high current intensities, which in turn has an advantageous effect on the deposition rate or the duration of the electroplating bath.
  • Further advantageous embodiments, in particular of the diaphragms used can be found in the subclaims.
  • FIG. 1 a schematic representation of the first exemplary embodiment of the electroplating system
  • Figure 2 is a schematic representation of the second embodiment of the electroplating system.
  • a galvanizing container A there is a cathode 1, which is formed by the object to be coated with metal, for example a circuit board to be copper-plated.
  • the metal ions symbolically marked with circled plus signs are deposited on its surface (copper ions Cu ⁇ + in the example) and separate as metal.
  • the associated insoluble anodes 3 are not in the metal salt electrolyte 9 (in the example an acidic copper bath), but in an auxiliary anolyte 4.
  • An anode diaphragm 2, which is designed to be impermeable to anions, is used to separate the electrolyte 9 from the auxiliary anolyte 4.
  • a supply container B there is also electrolyte liquid 9, which is held by means of a pump 10 in a continuous electrolyte circuit K1A, K1B between galvanizing container A and supply container B.
  • the "loss" of metal ions which are deposited on the cathode for coating is at least partially replaced, with the help of a soluble anode 5, which is shown in the drawing as an anode basket with copper balls.
  • An auxiliary cathode 7, which is surrounded by an auxiliary catholyte 8, is also located in the supply container B.
  • a metal ion-impermeable diaphragm 6 serves to separate the auxiliary catholyte 8 from the metal salt electrolyte 9, which prevents the metal ions from attaching to the auxiliary cathode 7, which is symbolized by the reversing arrow.
  • the auxiliary catholyte 8 used in the supply container B typically consists of an acid solution of the same acid that is used in the electrolyte 9 in the same concentration.
  • the auxiliary catholyte contains no process organics, apart from a small amount that can diffuse through the diaphragm 6.
  • the auxiliary anolyte 4 in the electroplating tank A typically consists of the acid of the electrolyte 9 in approximately the same concentration; here too, practically no components of the process organics are contained.
  • auxiliary anolyte is thus compatible with the auxiliary anode and that the action of the diaphragm 2 prevents certain anions of the electrolyte 9 from being in the auxiliary anolyte and that there is an undesirable gas development, for example of chlorine gas, there through corresponding deposits.
  • electrolyte 9 In the case of copper electrolysis, as is preferably used for the coating of printed circuit boards, the following can be used, for example, as electrolyte 9:
  • Plastic material can be used as material for the diaphragms 2 and 6, which are designed as an anion exchanger in the case of the metal ion-impermeable diaphragm 6 and as a cation exchanger in the case of the anion-impermeable diaphragm 2.
  • the effect is based on the fact that the current conduction is effected by anion transport and the migration of metal ions is excluded, in the latter case that only cations, in particular protons, are transported.
  • a diaphragm made of porous ceramic can also be used, the effect of which is improved by adding suitable chemicals; in the case of an acidic copper bath as the electrolyte, this additive can be, for example, potassium hexacyanoferrate (yellow blood lye salt).
  • this additive can be, for example, potassium hexacyanoferrate (yellow blood lye salt).
  • the effect of this addition is that the interfering copper ions in the form of the corresponding copper salt (Copper hexacyanoferrate) in the pores of the diaphragm. This makes the diaphragm even more effective. In addition to the improved mechanical function of the diaphragm, any remaining copper ions are trapped.
  • acids other than electrolytes are used, for example methanesulfonic acid or borofluorohydric acid.
  • other acids can also be used as auxiliary catholyte or other acids of this electrolytic acid can be added, whereby in principle the same failure reaction takes place (sulfuric acid, the lead precipitates as lead sulfate, phosphoric acid, the tin IV as tin acid or similar compounds) .
  • the solution according to the invention it is relatively easy to maintain a balance of metal ions in the electrolyte, i.e. an exact possible approximation of the dissolution rate in the area of the soluble anode 5 to the deposition rate at the cathode 1.
  • a common circuit for the electroplating container and the supply container can be provided, or alternatively a metal content measurement can be carried out, for example the electrolyte 9 can be colored with a suitable sensor (for example a photocell) can be determined and its signal used as a control signal of a control circuit, the control variable of which is, for example, the on-time of the power supply in the supply container B.
  • the current consumption of the two circuits in the electroplating tank A and the supply tank B can also be measured and then an adjustment can be made via the duty cycle and / or the current strength.
  • the metal ions required for the deposition process on the electroplating material 1 to be coated are preferably or at least partially obtained in the supply container B by the processes described;
  • the auxiliary anolyte 4 with the associated diaphragm 2 according to the invention there is an additional or possibly also exclusive possibility of Introduce additional metal ions into the cathode compartment of the electroplating container A if this appears necessary, for example, to maintain a desired metal ion concentration:
  • the solution according to the invention is based on the idea that the anion-impermeable diaphragm 2, which shields the insoluble anodes 3, is by definition permeable to metal ions which are added to the auxiliary anolyte 4.
  • this is shown schematically by a circuit K2A, K2B, in which the auxiliary anolyte 4 is fed via a regeneration chamber C via a pump 11.
  • auxiliary anolyte for example in the form of a salt, a hydroxide, an oxide or a carbonate of the desired metal of the electrolyte, the recycling being appropriate depending on the regeneration material used and the chemical-physical composition of the overall system of the anolyte for reasons of equilibrium in the recycle circuit to be carried out only partially, ie to withdraw part of the overflowing auxiliary anolyte from the circuit.
  • this supplementary or predominantly used method for supplementing metal ion consumption is that the additives (metal salts, metal hydroxides, etc.) that can be used do not have to be obtained from raw materials or raw materials, but through well-known, simple chemical reactions (precipitation, crystallization) ) can be produced from substances that fall off, for example, in the processing of printed circuit boards, in particular in the case of etching processes, and whose use or disposal has hitherto been problematic.
  • This solution thus opens up a way of returning at least some of these products, which were previously regarded as waste, to the coating process in the circuit board processing, thus showing a recycling path for the respective coating metal in the circuit board production.
  • DC voltage sources Q are used for the voltage or power supply of the electroplating container A and the supply container B.
  • the power supply to the cathode 1 and auxiliary anodes 3 can be provided via a control unit S, which can be constructed, for example, as in FIG 4a of GB 22 14 520 A mentioned at the outset, and which is used to generate a voltage profile at cathode 1 and auxiliary anodes 3 shown there under FIG. 4c, with the aforementioned aim of improving the coating quality, in particular in the case of profiled objects, such as printed circuit boards with holes.
  • FIG. 2 shows a second exemplary embodiment, which corresponds in its basic principle to the first exemplary embodiment explained in detail above, so that identical components have been provided with the same reference numerals.
  • a circuit K3A, K3B is established, which runs between the auxiliary anolyte 4 in the electrolytic cell A and the auxiliary catholyte 8 in the regeneration chamber B, for the maintenance of which a pump 12 is provided.
  • This training is based on the following idea:
  • the auxiliary catholyte 8 would increase its pH in static operation and a lower acid content or a higher alkali content would result compared to the starting solution.
  • the auxiliary anolytes 4 would have the reverse development in static operation. This is avoided by the common circuit K3A.K3B of auxiliary anolyte 4 and auxiliary catholyte 8, since the mixing of these two substances eliminates the opposite shifts in pH, so that the circulation of these two auxiliary electrolytes is far greater than in static operation constant composition can be operated.
  • the auxiliary anolyte 4 can either flow back into the space of the auxiliary catholyte 8 in free fall via overflows (as shown in the drawing), or optionally via a further pump (not shown).

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)
  • Electroplating Methods And Accessories (AREA)

Abstract

L'invention concerne une installation galvanoplastique comprenant une cuve de galvanoplastie et une cuve d'alimentation entre lesquelles circule l'électrolyte. Dans la cuve d'alimentation, la teneur en métal de l'électrolyte est complétée par une anode soluble à laquelle est associée une cathode auxiliaire située dans un catholyte auxiliaire séparé de l'électrolyte par un diaphragme imperméable aux ions métalliques. Les anodes non solubles de la cuve de galvanoplastie se trouvent dans un anolyte auxiliaire séparé de l'électrolyte par l'intermédiaire de diaphragmes imperméables aux anions. Le principal avantage de cette invention réside dans la possibilité d'utiliser des anodes non solubles, mais également des additifs organiques indispensables, par exemple dans le domaine des cartes de circuits, pour des revêtements précis. Dans une variante perfectionnée particulièrement avantageuse, il est prévu que le catholyte auxiliaire et l'anolyte auxiliaire soient guidés dans un circuit commun, afin que les écarts opposés du pH du catholyte auxiliaire et de l'anolyte auxiliaire soient largement compensés par leur mélange continu.
PCT/DE1996/001936 1995-10-26 1996-10-11 Installation galvanoplastique WO1997015704A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP96945489A EP0801692A2 (fr) 1995-10-26 1996-10-11 Installation galvanoplastique
JP9512202A JPH10511743A (ja) 1995-10-26 1996-10-11 メッキ設備

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1995139865 DE19539865A1 (de) 1995-10-26 1995-10-26 Durchlauf-Galvanikanlage
DE19539865.3 1995-10-26

Publications (2)

Publication Number Publication Date
WO1997015704A2 true WO1997015704A2 (fr) 1997-05-01
WO1997015704A3 WO1997015704A3 (fr) 1997-07-10

Family

ID=7775839

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE1996/001936 WO1997015704A2 (fr) 1995-10-26 1996-10-11 Installation galvanoplastique

Country Status (4)

Country Link
EP (1) EP0801692A2 (fr)
JP (1) JPH10511743A (fr)
DE (1) DE19539865A1 (fr)
WO (1) WO1997015704A2 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1264918B1 (fr) 2001-06-07 2011-11-23 Shipley Co. L.L.C. Méthode de placage électrolytique de cuivre
ITMI20011374A1 (it) * 2001-06-29 2002-12-29 De Nora Elettrodi Spa Cella di elettrolisi per il ripristino della concentrazione di ioni metallici in processi di elettrodeposizione
DE10341998A1 (de) * 2003-09-04 2005-03-31 Gramm Gmbh & Co. Kg Vorrichtung und Verfahren zur Oberflächenbehandlung von Werkstücken in einem Kreislaufsystem
ES2546065T3 (es) * 2011-07-20 2015-09-18 Enthone Inc. Aparato para la deposición electroquímica de un metal
DE102012024758B4 (de) * 2012-12-18 2024-02-01 Maschinenfabrik Niehoff Gmbh & Co Kg Vorrichtung und Verfahren zum elektrolytischen Beschichten eines Gegenstandes und deren Verwendung
JP6079368B2 (ja) * 2013-03-28 2017-02-15 三菱マテリアル株式会社 Ｓｎ合金めっき方法及びＳｎ合金めっき液のリサイクル方法、並びにこれらの装置
US9765443B2 (en) * 2015-09-02 2017-09-19 Applied Materials, Inc. Electroplating processor with current thief electrode
CN105755510B (zh) * 2015-12-14 2018-12-07 南京航空航天大学 一种带镍离子补充装置的电铸镍系统及其工作方法
US11174564B2 (en) * 2018-10-31 2021-11-16 Unison Industries, Llc Electroforming system and method
EP3875642A1 (fr) * 2020-03-04 2021-09-08 AT & S Austria Technologie & Systemtechnik Aktiengesellschaft Procédé de traitement des eaux de rinçage provenant de la fabrication de cartes de circuit imprimé et/ou de substrats

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1293648A (en) * 1969-06-06 1972-10-18 Australian Iron Steel Pty Ltd Addition of metal ions to electrolytic plating baths
US4038160A (en) * 1975-07-03 1977-07-26 Albright & Wilson Limited Method of regenerating a chromium electroplating bath
FR2479856A1 (fr) * 1980-04-04 1981-10-09 Electricite De France Installation de traitement de surface par depot metallique et procede de regeneration des bains de depot metallique par voie electrolytique
US4469564A (en) * 1982-08-11 1984-09-04 At&T Bell Laboratories Copper electroplating process
US5100517A (en) * 1991-04-08 1992-03-31 The Goodyear Tire & Rubber Company Process for applying a copper layer to steel wire
GB2254859A (en) * 1991-04-18 1992-10-21 Nippon Cmk Kk In printed wiring board manufacturing use of waste etchant as copper ion sourcefor electroplating bath
DE4221970A1 (de) * 1992-06-30 1994-01-05 Schering Ag Verwendung von Alkenylen und Alkinylen als Zusätze in galvanischen Metallabscheidungsbädern

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8801827D0 (en) * 1988-01-27 1988-02-24 Jct Controls Ltd Improvements in electrochemical processes
DE4405741C1 (de) * 1994-02-23 1995-06-01 Atotech Deutschland Gmbh Verfahren zur elektrolytischen Abscheidung von Metallen aus Elektrolyten mit Prozeßorganik

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1293648A (en) * 1969-06-06 1972-10-18 Australian Iron Steel Pty Ltd Addition of metal ions to electrolytic plating baths
US4038160A (en) * 1975-07-03 1977-07-26 Albright & Wilson Limited Method of regenerating a chromium electroplating bath
FR2479856A1 (fr) * 1980-04-04 1981-10-09 Electricite De France Installation de traitement de surface par depot metallique et procede de regeneration des bains de depot metallique par voie electrolytique
US4469564A (en) * 1982-08-11 1984-09-04 At&T Bell Laboratories Copper electroplating process
US5100517A (en) * 1991-04-08 1992-03-31 The Goodyear Tire & Rubber Company Process for applying a copper layer to steel wire
GB2254859A (en) * 1991-04-18 1992-10-21 Nippon Cmk Kk In printed wiring board manufacturing use of waste etchant as copper ion sourcefor electroplating bath
DE4221970A1 (de) * 1992-06-30 1994-01-05 Schering Ag Verwendung von Alkenylen und Alkinylen als Zusätze in galvanischen Metallabscheidungsbädern

Also Published As

Publication number Publication date
EP0801692A2 (fr) 1997-10-22
JPH10511743A (ja) 1998-11-10
WO1997015704A3 (fr) 1997-07-10
DE19539865A1 (de) 1997-04-30

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