EP0878561B1 - Procédé et dispositif pour la régéneration des solutions de plaçage d'étain - Google Patents

Procédé et dispositif pour la régéneration des solutions de plaçage d'étain Download PDF

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Publication number
EP0878561B1
EP0878561B1 EP98107584A EP98107584A EP0878561B1 EP 0878561 B1 EP0878561 B1 EP 0878561B1 EP 98107584 A EP98107584 A EP 98107584A EP 98107584 A EP98107584 A EP 98107584A EP 0878561 B1 EP0878561 B1 EP 0878561B1
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EP
European Patent Office
Prior art keywords
chamber
cathode
tin
solution
copper
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
EP98107584A
Other languages
German (de)
English (en)
Other versions
EP0878561A3 (fr
EP0878561A2 (fr
Inventor
Klaus Prof. Rer. Nat. Fischwasser
Hans-Wilhelm Prof. Dr.-Ing. Lieber
Ralph Dr. Rer. Nat. Blittersdorf
Annette Dipl.-Ing. Heuss (Fh)
Ulrich Dr.-Ing. Reiter
Werner Dr. Rer. Nat. Harnischmacher
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.)
KM Europa Metal AG
Original Assignee
KM Europa Metal AG
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 KM Europa Metal AG filed Critical KM Europa Metal AG
Publication of EP0878561A2 publication Critical patent/EP0878561A2/fr
Publication of EP0878561A3 publication Critical patent/EP0878561A3/fr
Application granted granted Critical
Publication of EP0878561B1 publication Critical patent/EP0878561B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1617—Purification and regeneration of coating baths
    • 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
    • C25D21/22—Regeneration of process solutions by ion-exchange
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S204/00—Chemistry: electrical and wave energy
    • Y10S204/13—Purification and treatment of electroplating baths and plating wastes

Definitions

  • the invention relates to a method and an apparatus for regenerating used tinning solutions.
  • the external tinning of copper workpieces using an aqueous tinning solution is a common process in surface coating technology. It is used, for example, for the internal tinning of copper pipes or tinning of circuit boards for integrated circuits application.
  • the tinning solution contains aqueous dissolved tin ions which, due to a chemical reduction using a suitable reducing agent on the copper be deposited. This takes place on the surface of the copper workpieces Exchange between the metals takes place through one in the tinning solution contained complexing agent is made possible.
  • Hypophosphite is the main reducing agent used, thiourea is mostly used as a complexing agent.
  • the used tinning solution then contains tin and copper ions, free and complexing agent bound to the copper ions, used and unused Reducing agents and, if appropriate, further constituents or in terms of process technology conditional contamination.
  • the DE 27 42 718 A1 proposed to first remove the tin ions by means of electrolysis and then the foreign metal ions in a cation exchanger remove.
  • DE 43 10 366 C1 counts a method and a device for regeneration from aqueous, external currentless coating solutions for metal coating using metal ions and a reducing agent to the prior art Technology.
  • a combination of an ion exchange process with the Electrode reactions of the electrolysis made.
  • the process takes place in an at least four-chamber electrolysis cell. It electrolytic regeneration is achieved by reducing the amount generated in the process Orthophosphite in a cathode chamber to hypophosphite and through Electrodialytic provision of counter ion-free resharpening chemicals.
  • the present invention comes in, the object of which is a method and to show a device that allow the accumulating interference component Separate copper by cathodic deposition and at the same time to supply the consumable component tin, so that the Service life or service life of tinning solutions that operate without external power for copper workpieces can be significantly extended.
  • the essence of the invention is the measure of tinning solution used regenerate strong dilution.
  • a combination of Electrode reactions of electrolysis with transport processes in ion exchange membranes performed.
  • copper is depleted by cathodic deposition from a dilution of the tinning solution and Enrichment of tin by anodic dissolution and transport through a cation exchange membrane.
  • the invention adopts the knowledge that in a regeneration solution, in which the tinning solution used in the tinning process is strong is present diluted, the separation ratios compared to the original concentrated Reverse tinning solution and prefer copper from the thermodynamic deposits disadvantaged copper complex. This can cause the interference component Copper depleted and the tin component required for the process can be supplied by anodic dissolution.
  • the regeneration solution is fed to an electrolysis cell, which has a cathode chamber with an inserted cathode, a middle chamber and one with a Anolyte-filled anode chamber with anode incorporated.
  • the cathode chamber is separated from the middle chamber by an anion exchange membrane, whereas a cation exchange membrane between the anode chamber and the middle chamber is incorporated.
  • the regeneration solution first reaches the cathode chamber and remains there with the deposition of copper on the cathode.
  • the dwell time depends on the total amount of metal supplied. Then will the copper-depleted regeneration solution is directed into the middle chamber, where a tin enrichment from the anolyte of the anode chamber through the cathode exchange membrane penetrated tin ions.
  • the prepared regeneration solution is expediently used in the tinning process returned where they also the water losses occurring there through evaporation balances.
  • the regeneration solution consists of a 5 to 50% dilution of the tinning solution. Being particularly advantageous considered a concentration range between 10 to 15%.
  • the electrolyte concentration preferably has 10 to 15% of the process solution then passed into the cathode chamber of the electrolytic cell.
  • the copper ions contained in the regeneration solution are deposited cathodically. To a small extent, they are also in the regeneration solution contained tin ions cathodically deposited with.
  • the ions of the reducing agent can diffuse through the ion exchange membranes into the middle chamber, in which the regeneration solution of the previous regeneration cycle is located. This is already depleted in copper.
  • the regeneration solution transferred to the central chamber in which the tin enrichment takes place.
  • tin ions which are anodically dissolved in the anode chamber, by diffusion from the anode chamber through the cation exchange membrane in the middle chamber.
  • the anions of the reducing agent are through the cation exchange membrane prevented from passing into the anode chamber, so that they remain in the middle chamber.
  • the regenerated solution is used in the tinning process returned and refreshes the tinning solution. This will the service life and useful life of the tinning solution are significantly extended.
  • tetrafluoroboric acid or methanesulfonic acid can also be used as the anolyte be, as provided for in claim 6.
  • the temperature in the electrolytic cell between 10 ° C and 60 ° C.
  • Cathodic depletion starts best Copper and tin enrichment in a temperature range between 30 ° C and 40 ° C.
  • the regeneration solution is moved in the electrolysis cell as claimed in claim 9 provides. This can be done, for example, by pumping from chamber to chamber take place or by stirring in the chambers. This causes polarization effects avoided in the chambers, especially on the membrane surfaces.
  • the temperature of the Electrolysis cell can be controlled (claim 10).
  • the method according to the invention can be used both in continuous cycle operation as well as in batch operation.
  • the regeneration solution can either run quasi continuously in two cycles the cathode chamber or middle chamber of the three-chamber membrane electrolysis led or there may be a portion of the tinning solution diluted in the batch Cell regenerated and then returned to the tinning solution.
  • the cathode material preferably consists of copper or stainless steel 11).
  • the anode material consists of tin. This is a requirement for that Tin enrichment during the regeneration process.
  • the prepared regeneration solution is the same this out. If necessary, a needs-based process-dependent correction can be made or adjustment of the regeneration solution. In this way is also a cheaper water cycle management by the inventive method reached.
  • Electrolytic cells in stacks one after the other (series connection) or in parallel next to each other (Parallel connection). This creates a high capacity provided for the processing of used tinning solutions.
  • the example concerns a tinning electrolyte for tinning without external current the fluoroborate-based with the complexing agent thiourea and the reducing agent Hypophosphite is built up.
  • the invention results in that in the regeneration solution in the tinning solution is present in the specified dilution, electrode kinetic effects (Breakdown reaction, exchange current density, overvoltage) an increasingly important Play role, so that preferred despite the unfavorable potential conditions Copper can be deposited.
  • FIG. 1 The course of the regeneration process of a tinning solution is illustrated in FIG. 1.
  • the reaction equilibria, redox potentials that are important for the system and complex stability constants can be found in the table above.
  • FIG. 1 in FIG. 1 is a system for tinning copper workpieces without external current referred to by means of an aqueous tinning solution.
  • the copper workpieces are made in one Rinsing process cleaned.
  • the flushing process is with SP, the water supply through the Arrow marked W.
  • the tinning solution is carried out by electrolyte extraction towed portion diluted by the rinse water.
  • the rinse water to a 10 to 15% dilution the process solution concentrated.
  • the regeneration solution produced in this way becomes a three-chamber electrolysis cell 2 forwarded.
  • the electrolytic cell comprises a cathode chamber 3, one Middle chamber 4 and an anode chamber 5.
  • cathode chamber 3 there is a cathode 6 made of copper, in the anode chamber 5 is an anode 7 made of tin. Between anode 7 and cathode 6 a potential difference is created.
  • the cathode chamber 3 is through an anion exchange membrane 8 and the anode chamber 5 through a cation exchange membrane 9 from the middle chamber 4 Cut.
  • the regeneration solution is first fed into the cathode chamber 3 (arrow P1).
  • the interfering component copper is then cathodically deposited from the thiourea complex at a current density of 0.4 to 0.6 A / dm 2 and thus removed from the system.
  • anions such as the tetrafluoroborate anion and the hypophosphite anion can pass through the anion exchange membrane 8 into the middle chamber 4.
  • the regenerated solution can be used in the tinning process be returned (arrow P3). This can also be used in the tinning process occurring evaporation losses can be compensated.
  • the in Evaporation occurring during the tinning process is indicated by the arrows V. If a need correction (arrow BK) of the prepared diluted solution made to the process engineering requirements of the tinning solution become.
  • the respective electrolyte solutions in the three reaction chambers are moved so that polarization effects in the reaction chambers 3, 4, 5, in particular on the membrane surfaces, are avoided.
  • the movement in the cathode chamber 3 and in the middle chamber 4 is indicated by the arrows B1 and B2.
  • the movement B1, B2 can take place, for example, by stirring.
  • the anolyte (H 2 SO 4 ) in the anode chamber 5 is conducted in a separate circuit. This is indicated by arrow B3.
  • the combination of electrode reactions of electrolysis with transport processes in ion exchange membranes thus enables a selective separation of the Interfering component copper from a diluted tinning solution with simultaneous Enrichment of tin via anodic dissolution and transport of the tin ions through the cation exchange membrane.
  • the regenerated solution is in the tinning solution of the tinning process. This will make the Service life or the useful life of the tinning solution significantly extended.
  • Electrolytic cells 2 in stacks one after the other (series connection) or in parallel next to each other (Parallel connection) are connected. In this way, each Capacity designed for the processing of tinning solutions reached.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Chemically Coating (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Claims (12)

  1. Procédé pour régénérer une solution d'étamage aqueuse, travaillant sans courant extérieur, pour des pièces en cuivre, contenant des ions libres d'étain et de cuivre, et des formateurs de complexe libres et liés aux ions de cuivre, ainsi que de l'agent réducteur consommé et non consommé,
    caractérisé en ce que
    on fournit à une cellule d'électrolyse (2) une cellule de régénération avec une solution ayant une teneur en étain plus faible que celle d'une solution d'étain fonctionnant sans courant extérieur ;
    cette cellule d'électrolyse comprenant une chambre cathodique (3) avec une cathode (6) intégrée, une chambre intermédiaire (4) et une chambre anodique (5) remplie d'un liquide anodique et intégrant une anode d'étain (7) ;
    on applique une différence de potentiel entre l'anode d'étain (7) et la cathode (6) et on sépare de la chambre intermédiaire (4) la chambre cathodique (3) par une membrane échangeuse d'anions (8) et la chambre anodique (5) par une membrane d'échange cationique (9) ;
    la solution de régénération est fournie d'abord à la chambre cathodique (3) et de là, avec séparation du cuivre, séjourne au niveau de la cathode (6) ; et
    après le temps de séjour, la solution de régénération, appauvrie en cuivre, est pompée dans la chambre intermédiaire (4) dans laquelle se fait un enrichissement en étain par les ions d'étain venant de la chambre anodique (5) à travers la membrane d'échange de cations (9).
  2. Procédé selon la revendication 1,
    caractérisé en ce que
    la solution de régénération contient entre 5 % et 50 % et de préférence entre 10 % et 15 % d'une solution d'étain.
  3. Procédé selon les revendications 1 ou 2,
    caractérisé en ce que
    la solution de régénération résulte d'un procédé de rinçage (SP) de pièces en cuivre.
  4. Procédé selon l'une des revendications 1 à 3,
    caractérisé en ce que
    l'anolyte circule dans un circuit (B3).
  5. Procédé selon l'une des revendications 1 à 4,
    caractérisé en ce que
    l'anolyte est une solution d'acide sulfurique à 3 - 6 %.
  6. Procédé selon l'une des revendications 1 à 4,
    caractérisé en ce que
    l'anolyte est une solution de tétrafluoroborique ou un acide métha-sulfonique.
  7. Procédé selon l'une des revendications 1 à 6,
    caractérisé en ce que
    la température de la cellule d'électrolyse (2) est comprise entre 10°C et 60°C de préférence entre 30°C et 40°C.
  8. Dispositif pour la mise en oeuvre du procédé selon une ou plusieurs des revendications 1 à 7,
    composé d'une cellule d'électrolyse (2) ayant une chambre cathodique (3) intégrant une cathode (6), une chambre intermédiaire (4) et une chambre anodique (5) intégrant une anode d'étain (7),
    la chambre cathodique (3) étant séparée de la chambre intermédiaire (4) par une membrane d'échange d'anions (8) et la chambre anodique (5) par une membrane échangeuse de cations (9), et on applique une différence de potentiel entre l'anode de zinc (7) et la cathode (6).
  9. Dispositif selon la revendication 8,
    caractérisé en ce que
    la solution de régénération de la cellule d'électrolyse (2) est en mouvement.
  10. Dispositif selon l'une des revendications 8 ou 9,
    caractérisé en ce qu'
    on commande la température de la cellule d'électrolyse (2).
  11. Dispositif selon l'une des revendications 8 à 10,
    caractérisé en ce que
    la cathode (6) est en cuivre ou en acier inoxydable.
  12. Dispositif selon l'une des revendications 8 à 11,
    caractérisé en ce que
    plusieurs cellules d'électrolyse sont branchées les unes derrière les autres et/ou en parallèle.
EP98107584A 1997-05-07 1998-04-25 Procédé et dispositif pour la régéneration des solutions de plaçage d'étain Expired - Lifetime EP0878561B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19719020 1997-05-07
DE19719020A DE19719020A1 (de) 1997-05-07 1997-05-07 Verfahren und Vorrichtung zum Regenerieren von Verzinnungslösungen

Publications (3)

Publication Number Publication Date
EP0878561A2 EP0878561A2 (fr) 1998-11-18
EP0878561A3 EP0878561A3 (fr) 1999-04-28
EP0878561B1 true EP0878561B1 (fr) 2003-09-03

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EP98107584A Expired - Lifetime EP0878561B1 (fr) 1997-05-07 1998-04-25 Procédé et dispositif pour la régéneration des solutions de plaçage d'étain

Country Status (12)

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US (1) US6120673A (fr)
EP (1) EP0878561B1 (fr)
JP (1) JPH10317154A (fr)
AR (1) AR010155A1 (fr)
AT (1) ATE248935T1 (fr)
AU (1) AU724854B2 (fr)
BR (1) BR9801580A (fr)
CA (1) CA2236393C (fr)
DE (2) DE19719020A1 (fr)
DK (1) DK0878561T3 (fr)
ES (1) ES2202686T3 (fr)
PT (1) PT878561E (fr)

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GB9901586D0 (en) * 1999-01-25 1999-03-17 Alpha Fry Ltd Process for the recovery of lead and/or tin or alloys thereof from substrate surfaces
JP3455709B2 (ja) * 1999-04-06 2003-10-14 株式会社大和化成研究所 めっき方法とそれに用いるめっき液前駆体
FR2801062B1 (fr) * 1999-11-12 2001-12-28 Lorraine Laminage Installation et procede de dissolution electrolytique par oxydation d'un metal
JP2002317275A (ja) * 2001-04-17 2002-10-31 Toto Ltd 無電解スズめっき液の長寿命化方法
DE10132478C1 (de) * 2001-07-03 2003-04-30 Atotech Deutschland Gmbh Verfahren zum Abscheiden einer Metallschicht sowie Verfahren zum Regenerieren einer Metallionen in einer hohen Oxidationsstufe enthaltenden Lösung
US7195702B2 (en) * 2003-06-06 2007-03-27 Taskem, Inc. Tin alloy electroplating system
US6942810B2 (en) * 2003-12-31 2005-09-13 The Boc Group, Inc. Method for treating metal-containing solutions
US20060096867A1 (en) * 2004-11-10 2006-05-11 George Bokisa Tin alloy electroplating system
EP1726683B1 (fr) * 2005-05-25 2008-04-09 Enthone Inc. Procédé et appareil pour ajuster la concentration d'ions d'un électrolyte
JP2006341213A (ja) * 2005-06-10 2006-12-21 Es Adviser:Kk 無電解銅めっき廃液の電解処理装置及びその電解処理方法
DE102006045157B4 (de) 2006-09-25 2020-06-18 Robert Bosch Gmbh Handwerkzeugmaschine
KR100934729B1 (ko) * 2007-10-29 2009-12-30 (주)화백엔지니어링 무전해 주석도금액 불순물 제거장치 및 방법
US20110226613A1 (en) 2010-03-19 2011-09-22 Robert Rash Electrolyte loop with pressure regulation for separated anode chamber of electroplating system
US9404194B2 (en) 2010-12-01 2016-08-02 Novellus Systems, Inc. Electroplating apparatus and process for wafer level packaging
JP5715411B2 (ja) 2010-12-28 2015-05-07 ローム・アンド・ハース電子材料株式会社 めっき液中から不純物を除去する方法
JP5830242B2 (ja) 2010-12-28 2015-12-09 ローム・アンド・ハース電子材料株式会社 めっき液中から不純物を除去する方法
JP5937320B2 (ja) 2011-09-14 2016-06-22 ローム・アンド・ハース電子材料株式会社 めっき液中から不純物を除去する方法
WO2013080326A1 (fr) 2011-11-30 2013-06-06 不二商事株式会社 Procédé de régénération de liquide de placage
EP2671968B1 (fr) * 2012-06-05 2014-11-26 ATOTECH Deutschland GmbH Procédé et appareil de régénération pour régénérer un composition de placage
US9534308B2 (en) 2012-06-05 2017-01-03 Novellus Systems, Inc. Protecting anodes from passivation in alloy plating systems
JP6706095B2 (ja) * 2016-03-01 2020-06-03 株式会社荏原製作所 無電解めっき装置および無電解めっき方法
KR20230125095A (ko) 2017-11-01 2023-08-28 램 리써치 코포레이션 전기화학적 도금 장치 상에서 도금 전해질 농도 제어
KR102523503B1 (ko) * 2018-05-09 2023-04-18 어플라이드 머티어리얼스, 인코포레이티드 전기도금 시스템들에서 오염을 제거하기 위한 시스템들 및 방법들
CN109467167B (zh) * 2018-10-30 2021-12-03 上海大学 一种去除不锈钢酸洗废水中重金属的方法
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
CN111676470A (zh) * 2020-05-29 2020-09-18 广东天承科技有限公司 一种简易可溶性的高价锡的还原方法

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CA2083196C (fr) * 1991-11-27 1998-02-17 Randal D. King Procede pour prolonger la duree de vie d'un bain de galvanoplastie par jet mobile
DE4310366C1 (de) * 1993-03-30 1994-10-13 Fraunhofer Ges Forschung Verfahren zum Regenerieren von wässrigen, außenstromlos arbeitenden Beschichtungsbädern

Also Published As

Publication number Publication date
US6120673A (en) 2000-09-19
AU6475798A (en) 1998-11-12
AR010155A1 (es) 2000-05-17
CA2236393A1 (fr) 1998-11-07
ATE248935T1 (de) 2003-09-15
BR9801580A (pt) 1999-07-06
DE59809451D1 (de) 2003-10-09
DE19719020A1 (de) 1998-11-12
DK0878561T3 (da) 2004-01-12
EP0878561A3 (fr) 1999-04-28
AU724854B2 (en) 2000-10-05
PT878561E (pt) 2004-02-27
ES2202686T3 (es) 2004-04-01
CA2236393C (fr) 2004-01-20
EP0878561A2 (fr) 1998-11-18
JPH10317154A (ja) 1998-12-02

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