EP0115791A1 - Procédé et appareil pour la régénération d'une solution de décapage contenant du cuivre - Google Patents

Procédé et appareil pour la régénération d'une solution de décapage contenant du cuivre Download PDF

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Publication number
EP0115791A1
EP0115791A1 EP84100326A EP84100326A EP0115791A1 EP 0115791 A1 EP0115791 A1 EP 0115791A1 EP 84100326 A EP84100326 A EP 84100326A EP 84100326 A EP84100326 A EP 84100326A EP 0115791 A1 EP0115791 A1 EP 0115791A1
Authority
EP
European Patent Office
Prior art keywords
copper
cathode
anode
chloride
etching solution
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
EP84100326A
Other languages
German (de)
English (en)
Other versions
EP0115791B1 (fr
Inventor
Rudi Dr. Dipl.-Chem. Ott
Heribert Reith
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.)
OFFERTA DI LICENZA AL PUBBLICO
Original Assignee
Robert Bosch 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 Robert Bosch GmbH filed Critical Robert Bosch GmbH
Publication of EP0115791A1 publication Critical patent/EP0115791A1/fr
Application granted granted Critical
Publication of EP0115791B1 publication Critical patent/EP0115791B1/fr
Expired legal-status Critical Current

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    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/46—Regeneration of etching compositions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions

Definitions

  • the invention is based on a method for the regeneration of a copper-containing etching solution according to the preamble of claim 1 and on an apparatus for carrying out the method according to claim 5.
  • a copper (II ) it is known to etch a copper (II ) to use chloride-containing etching solution which contains an alkali chloride, in particular potassium chloride, as complexing agent.
  • chloride-containing etching solution which contains an alkali chloride, in particular potassium chloride, as complexing agent.
  • Such an etching solution which is used in particular in the manufacture of printed circuit boards, has the advantage over the conventional etching solutions which contain hydrochloric acid as a complexing agent that it has a higher etching speed, that no hydrochloric acid mist in the exhaust air and no signs of corrosion occur on the machines.
  • the method according to the invention with the characterizing features of the main claim has the advantage that the composition of the CuCl 2 / KCl etching solution is kept optimally constant with the aid of an electrolysis cell, ie in principle only the etched metal is removed from the solution removed while keeping the CuI / II redox potential constant. There is no consumption of chemicals, the regeneration system can be built very compactly and is therefore very well suited for inclusion in a production line.
  • the device according to the invention for carrying out the above-mentioned method with the characteristic features Cathode surface on carbon brushes, also not shown, on the rotating copper shaft and from there on the insulated copper disk on the end face made of titanium.
  • the anode 4 which consists of titanium, niobium or tantalum and is coated with platinum, iridium or non-stoichiometric platinum metal oxide compounds, is arranged parallel to the end face of the disk 3 and at a short distance from the end face, wherein either solid material or expanded metal can be used .
  • the partition Between the copper disk 3 serving as the cathode and the anode 4 there is a porous intermediate wall 5 made of electrically non-conductive material such as a coarse-pored plastic material made of polypropylene or polyethylene, which serves to keep the strong bath movement caused by the circulation pump 16 away from the cathode 3, without hindering the electrolyte exchange, the partition therefore has no diaphragm function, but only serves as a flow stabilizer.
  • the disc 3 rotates, the copper sludge deposited on the cathode is stripped off and slips into a collecting container (not shown) with the aid of a water spray.
  • the spray rinse water is used in the circuit. After reaching a predetermined amount of copper sludge and a certain salt concentration in the rinsing water, the contents of the collecting container are pumped on for solid-liquid separation (decanter, filter).
  • the etching solution to be regenerated is fed from the etching system via the inlet 14 to the regeneration system and flows back in via the outlet 15 of the etching system.
  • In Painting of claim 5 has the advantage that it can be built in a compact unit and that the type of execution of the cathode, the metal powder that is deposited on this cathode, can be removed continuously from the circuit.
  • FIG. 1 shows a perspective view of the regeneration system and FIG. 2 shows a partial section through the disk-shaped cathode.
  • the regeneration system consists of a container 1 made of plastic or insulated metal with an inlet 14 and an outlet 15 to the etching system as well as two connections 7 and 8 for a circulating pump 16.
  • the container 1 there is a circular, fixed with a serving as cathodic power supply Copper shaft 2 connected copper disc 3, which serves as a cathode.
  • the copper disk 10 has a copper ring 12 on its circumference, the whole is covered with PVC insulation 11 and a titanium ring 13 as contact material for the etching solution has been shrunk onto the non-insulated end face. Copper cannot serve as a contact material here because it dissolves in the etching medium.
  • the copper shaft 2 is rotatably mounted on the container edge, as indicated in the figure.
  • the disk is driven by a plastic gear (not shown) attached to the copper shaft as electrical insulation, while the power supply to the regeneration system was achieved with the etching solution described at cathodic current densities between 50 and 150 A / dm 2 and temperatures between 30 and 50 ° C current yields between 0.9 and 1.15 g / Ah copper in powder form.
  • the regeneration system forms metallic copper as a very fine crystalline copper sludge when current flows through the cathode 3 by discharging the copper ions at very high current densities.
  • Discharge of the chloride ions forms chlorine at the anode, which dissolves well in water and is quickly distributed throughout the container by the strong bath movement caused by the circulation pump 16.
  • This chlorine oxidizes existing copper (I) chloride to copper (II) chloride.
  • the electrochemical process is controlled by detecting the copper (I) ions with the aid of the redox potential and switching off the current at a limit value which is approximately 390 mV.
  • the regeneration system as used here has a volume of 210 1, the cathode 3 has a disk diameter of 500 mm with an immersed cathode surface of 2 dm 2, while the anode surface is 25 dm 2 .
  • the circulation pump 16 pumps the entire container volume 25 times an hour.

Landscapes

  • 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)
  • ing And Chemical Polishing (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
EP84100326A 1983-02-03 1984-01-13 Procédé et appareil pour la régénération d'une solution de décapage contenant du cuivre Expired EP0115791B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3303594 1983-02-03
DE19833303594 DE3303594A1 (de) 1983-02-03 1983-02-03 Verfahren und vorrichtung zur regenerierung einer kupferhaltigen aetzloesung

Publications (2)

Publication Number Publication Date
EP0115791A1 true EP0115791A1 (fr) 1984-08-15
EP0115791B1 EP0115791B1 (fr) 1988-06-01

Family

ID=6189908

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84100326A Expired EP0115791B1 (fr) 1983-02-03 1984-01-13 Procédé et appareil pour la régénération d'une solution de décapage contenant du cuivre

Country Status (4)

Country Link
US (1) US4508599A (fr)
EP (1) EP0115791B1 (fr)
JP (1) JPS59143072A (fr)
DE (2) DE3303594A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991014801A1 (fr) * 1990-03-29 1991-10-03 Hans Höllmüller Maschinenbau GmbH & Co. Dispositif de regeneration electrolytique d'un reactif d'attaque contenant du metal, en particulier du cuivre
EP0539792A1 (fr) * 1991-10-28 1993-05-05 Nittetsu Mining Co., Ltd. Procédé de régénération d'agents de décapage
CN110306209A (zh) * 2019-08-09 2019-10-08 郑州金泉矿冶设备有限公司 电解法生产超细银粉的设备

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0227689A1 (fr) * 1985-06-27 1987-07-08 Cheminor A/S Procede de production de metaux par electrolyse
DE3832674A1 (de) * 1988-09-27 1990-03-29 Kodak Ag Metallrueckgewinnungs-vorrichtung
GB2293390A (en) * 1994-09-20 1996-03-27 British Tech Group Simultaneous etchant regeneration and metal deposition by electrodialysis
JP2941741B2 (ja) * 1997-06-03 1999-08-30 核燃料サイクル開発機構 使用済核燃料の乾式再処理方法及び乾式再処理装置

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD45299A (fr) *
FR1213119A (fr) * 1957-10-28 1960-03-29 Western Electric Co Bain pour corroder du cuivre et régénération de ce bain
DE1223653B (de) * 1960-01-11 1966-08-25 Siemens Ag Vorrichtung zum kontinuierlichen elektro-lytischen Regenerieren von Kupferchlorid-AEtzloesungen
FR2156249A1 (fr) * 1971-10-12 1973-05-25 Shipley Co
US3825484A (en) * 1971-04-29 1974-07-23 N Fronsman Electrolytic regenerator for chemical etchants including scraper means and rotating cathodes
DE2650912A1 (de) * 1976-11-06 1978-05-18 Hoellmueller Maschbau H Elektrolytische regeneration eines aetzmittels

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1959376A (en) * 1930-09-26 1934-05-22 Nichols Copper Co Process for producing metal powders
JPS5124537A (en) * 1974-08-26 1976-02-27 Hitachi Ltd Etsuchinguyokuno saiseihoho
SU548051A1 (ru) * 1975-03-17 1977-10-05 Горьковский политехнический институт им.А.А.Жданова Способ регенерации железо-меднохлоридны' травильных растворов
DE2641905C2 (de) * 1976-09-17 1986-03-20 Geb. Bakulina Galina Aleksandrovna Batova Verfahren zur Regenerierung verbrauchter Ätzlösungen
DE2850564C2 (de) * 1978-11-22 1982-12-23 Kernforschungsanlage Jülich GmbH, 5170 Jülich Verfahren und Vorrichtung zum Regenerieren einer Kupfer(II)-Chlorid und/oder Eisen(III)-Chlorid enthaltenden Ätzlösung in einer Elektrolysezelle
JPS5629686A (en) * 1979-08-17 1981-03-25 Kazuo Ogawa Electrolytic cathode plate for copper recovery
JPS5914097B2 (ja) * 1980-07-30 1984-04-03 新日本製鐵株式会社 靭性を改良せるフェライト系耐熱鋼

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD45299A (fr) *
FR1213119A (fr) * 1957-10-28 1960-03-29 Western Electric Co Bain pour corroder du cuivre et régénération de ce bain
DE1223653B (de) * 1960-01-11 1966-08-25 Siemens Ag Vorrichtung zum kontinuierlichen elektro-lytischen Regenerieren von Kupferchlorid-AEtzloesungen
US3825484A (en) * 1971-04-29 1974-07-23 N Fronsman Electrolytic regenerator for chemical etchants including scraper means and rotating cathodes
FR2156249A1 (fr) * 1971-10-12 1973-05-25 Shipley Co
DE2650912A1 (de) * 1976-11-06 1978-05-18 Hoellmueller Maschbau H Elektrolytische regeneration eines aetzmittels

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Band 98, Nr. 2, 10. Januar 1983, Seiten 160,161, Nr. 7189a, Columbus, Ohio, USA *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991014801A1 (fr) * 1990-03-29 1991-10-03 Hans Höllmüller Maschinenbau GmbH & Co. Dispositif de regeneration electrolytique d'un reactif d'attaque contenant du metal, en particulier du cuivre
EP0539792A1 (fr) * 1991-10-28 1993-05-05 Nittetsu Mining Co., Ltd. Procédé de régénération d'agents de décapage
CN110306209A (zh) * 2019-08-09 2019-10-08 郑州金泉矿冶设备有限公司 电解法生产超细银粉的设备

Also Published As

Publication number Publication date
US4508599A (en) 1985-04-02
DE3303594A1 (de) 1984-08-09
JPS59143072A (ja) 1984-08-16
JPH0472910B2 (fr) 1992-11-19
DE3471692D1 (en) 1988-07-07
EP0115791B1 (fr) 1988-06-01

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