EP0011799B1 - Verfahren und Vorrichtung zum Regenerieren einer Kupfer(II)-Chlorid und/oder Eisen(III)-Chlorid enthaltenden Ätzlösung in einer Elektrolysezelle - Google Patents

Verfahren und Vorrichtung zum Regenerieren einer Kupfer(II)-Chlorid und/oder Eisen(III)-Chlorid enthaltenden Ätzlösung in einer Elektrolysezelle Download PDF

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Publication number
EP0011799B1
EP0011799B1 EP79104574A EP79104574A EP0011799B1 EP 0011799 B1 EP0011799 B1 EP 0011799B1 EP 79104574 A EP79104574 A EP 79104574A EP 79104574 A EP79104574 A EP 79104574A EP 0011799 B1 EP0011799 B1 EP 0011799B1
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EP
European Patent Office
Prior art keywords
etching solution
etching
copper
anode
chloride
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
Application number
EP79104574A
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German (de)
English (en)
French (fr)
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EP0011799A1 (de
Inventor
Wolfgang Faul
Bertel Prof. Dr. Kastening
Harald Luft
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.)
Forschungszentrum Juelich GmbH
Original Assignee
Forschungszentrum Juelich GmbH
Kernforschungsanlage Juelich GmbH
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Publication date
Application filed by Forschungszentrum Juelich GmbH, Kernforschungsanlage Juelich GmbH filed Critical Forschungszentrum Juelich GmbH
Priority to AT79104574T priority Critical patent/ATE1071T1/de
Publication of EP0011799A1 publication Critical patent/EP0011799A1/de
Application granted granted Critical
Publication of EP0011799B1 publication Critical patent/EP0011799B1/de
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

Definitions

  • the invention relates to a method for regenerating an etching solution used in the chemical processing of metallic surfaces, which contains copper (II) chloride and / or iron (III) chloride, in a diaphragm or an ion exchange membrane having an ion exchange membrane between the anode and the cathode. which is flowed through by the etching solution for anodic oxidation of the copper (1) and / or iron (11) ions formed during the etching of the metallic surface, and to a device for carrying out the method.
  • Copper (II) chloride and / or iron (III) chloride are known as oxidizing agents in etching solutions for processing metallic surfaces. They are used for the production of printed circuit boards or printed circuits. Plastic plates, which are copper-clad on one or both sides, are to be etched off the remaining part of the copper cladding after covering the surfaces forming the circuit with a protective layer. The etching solutions are also used to form the surface relief of printing rollers. In addition to surfaces made of copper or copper alloys, steel or hard metals are also etched.
  • etching solutions are regenerated and reprocessed, see Bruch et al, "Printed Circuit Boards", Leuze Verlag, Saulgau, 1978.
  • the aim is to recover the copper contained in the etching solution.
  • Electrochemical processes are suitable for continuous reprocessing of the etching solution, the etching solution being introduced into an electrolytic cell, at the anode of which the oxidizing agent used for the etching is regenerated.
  • iron (III) chloride is used as the etchant
  • the iron (11) chloride formed during the etching is oxidized to iron (III) chloride.
  • etching solutions containing copper (II) chloride as an oxidizing agent can be regenerated.
  • the copper (I) chloride contained in the electrolytic solution after removal of the copper surface is converted back to copper (II) chloride at the anode of the electrolytic cell.
  • the disadvantage here is the development of chlorine at the anode, which leads to considerable pollution of the environment and to the consumption of the oxidizing agent.
  • the object of the invention is to regenerate the etching solution by introducing it into an electrolysis cell while avoiding the development of chlorine in such a way that no toxic substances are produced which are harmful to the environment and the method is easy to handle.
  • the activated carbon powder particles suspended in the etching solution in the anode chamber of the electrolytic cell react with the chlorine formed after regeneration of the oxidizing agent to form chloride ions, the activated carbon powder being oxidized.
  • the concentration of copper (II) and / or iron (III) chloride in the etching solution can be kept relatively high in the presence of activated carbon particles. It is also advantageous that metal-coated workpieces machined with etching solutions according to the invention have a slight undercut of the covered surface areas.
  • Activated carbon powder particles are preferably added to the etching solution in a concentration between 5 and 25% by weight.
  • Activated carbon powder particles characterized in claims 3 and 4 are particularly suitable for the regeneration of the etching solutions.
  • a suitable device for performing the method according to the invention is indicated in the drawing.
  • the etching solution containing the activated carbon powder particles is circulated between the etching chamber and the anode space, so that in addition to continuous etching with an etching solution that remains unchanged in its composition, especially in the case of processing copper surfaces, a continuous recovery of copper is made possible.
  • the copper that has gone into solution separates again at the cathode of the electrolysis.
  • Another advantage is the slight under-etching of the metal-coated workpieces treated in the etching chamber with an etching solution containing activated carbon powder particles.
  • the device has an etching chamber 1 and an electrolysis cell 2, between which an etching solution 3 is circulated.
  • the etching solution is applied to the surface of a workpiece 5 to be processed by means of a spray nozzle 4.
  • the used etching solution flows to the bottom of the etching chamber 1. From there it is sucked off by a solvent pump 7 via a suction line 6 and pumped into the electrolytic cell 2.
  • a diaphragm or an ion exchange membrane 10 is inserted in the electrolytic cell, which separates the cathode compartment 11 of the electrolytic cell from the anode compartment 12.
  • An overflow 13, which opens into the etching chamber 1, is provided on the cathode compartment 11 for the solution contained in the cathode compartment.
  • the anode 8 consists of graphite and is designed as a tube through which the etching solution flows.
  • the wall of the graphite tube has openings 14 in order to bring the etching solution to the diaphragm or the ion exchange membrane and to enable the ion exchange between the anode space 12 and the cathode space 11.
  • the oxidizing agent of the etching solution is regenerated at the anode 8, and the removed copper can be deposited on the cathode 9 if the machined surface consists of copper or a copper alloy.
  • the recycled etching solution flows back from the anode chamber 12 to the etching chamber 1 via a pressure line 15.
  • Activated carbon powder particles corresponding to a concentration of 15% by weight activated carbon powder based on the weight of the etched solution were suspended in etching solutions with different iron chloride contents. A total of 1, 4 1 etching solution were circulated in the device. A constant current of 5 A was set at the graphite anode with the aid of a galvanostat. The etching solution was removed from the anode compartment at a temperature of approximately 50 ° C. and sprayed onto a stainless steel sheet from a distance of approximately 4 cm by means of the spray nozzle 4 under a pressure of 1.5 bar.
  • the weight loss of the stainless steel sheet per minute was measured as a function of the iron content in the etching solution. With an iron content of 5 g / l in the etching solution, 42 mg of stainless steel were etched away per minute. The etching rate increased with increasing iron content and reached a metal removal of 221 mg / min with an iron content of 50 g / l. In all experiments, even after complete oxidation of iron (II) to iron (III) ions, chlorine could not be escaped from the electrolysis cell with a constant current of 5 A. The weight loss of activated carbon powder was less than 1% during the processing time up to 5 hours.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
EP79104574A 1978-11-22 1979-11-19 Verfahren und Vorrichtung zum Regenerieren einer Kupfer(II)-Chlorid und/oder Eisen(III)-Chlorid enthaltenden Ätzlösung in einer Elektrolysezelle Expired EP0011799B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT79104574T ATE1071T1 (de) 1978-11-22 1979-11-19 Verfahren und vorrichtung zum regenerieren einer kupfer(ii)-chlorid und/oder eisen(iii)-chlorid enthaltenden aetzloesung in einer elektrolysezelle.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2850564A DE2850564C2 (de) 1978-11-22 1978-11-22 Verfahren und Vorrichtung zum Regenerieren einer Kupfer(II)-Chlorid und/oder Eisen(III)-Chlorid enthaltenden Ätzlösung in einer Elektrolysezelle
DE2850564 1978-11-22

Publications (2)

Publication Number Publication Date
EP0011799A1 EP0011799A1 (de) 1980-06-11
EP0011799B1 true EP0011799B1 (de) 1982-05-19

Family

ID=6055294

Family Applications (1)

Application Number Title Priority Date Filing Date
EP79104574A Expired EP0011799B1 (de) 1978-11-22 1979-11-19 Verfahren und Vorrichtung zum Regenerieren einer Kupfer(II)-Chlorid und/oder Eisen(III)-Chlorid enthaltenden Ätzlösung in einer Elektrolysezelle

Country Status (7)

Country Link
US (1) US4269678A (enrdf_load_stackoverflow)
EP (1) EP0011799B1 (enrdf_load_stackoverflow)
JP (1) JPS5573900A (enrdf_load_stackoverflow)
AT (1) ATE1071T1 (enrdf_load_stackoverflow)
AU (1) AU528323B2 (enrdf_load_stackoverflow)
CA (1) CA1160592A (enrdf_load_stackoverflow)
DE (1) DE2850564C2 (enrdf_load_stackoverflow)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3031567A1 (de) * 1980-08-21 1982-04-29 Elochem Ätztechnik GmbH, 7758 Meersburg Verfahren zum regenerieren einer ammoniakalischen aetzloesung
CS218296B1 (en) * 1980-10-30 1983-02-25 Antonin Stehlik Method of continuous regeneration of the iron trichloride solution
DE3245474A1 (de) * 1982-12-08 1984-06-14 Vladimir Petrovič Šustov Verfahren zur regenerierung einer eisenchlorid-kupferchlorid-aetzloesung
GB2133806B (en) * 1983-01-20 1986-06-04 Electricity Council Regenerating solutions for etching copper
DE3303594A1 (de) * 1983-02-03 1984-08-09 Robert Bosch Gmbh, 7000 Stuttgart Verfahren und vorrichtung zur regenerierung einer kupferhaltigen aetzloesung
DE3324450A1 (de) * 1983-07-07 1985-01-17 ELO-CHEM Ätztechnik GmbH, 7758 Meersburg Ammoniumsulfathaltige aetzloesung sowie verfahren zur regeneration der aetzloesung
DE3330349A1 (de) * 1983-08-23 1985-03-14 Robert Bosch Gmbh, 7000 Stuttgart Verfahren zur elektrochemischen kompensation der luftoxidation bei der elektrochemischen regenerierung von chloridhaltigen kupferaetzloesungen
US4600483A (en) * 1984-11-19 1986-07-15 Chevron Research Company Electrolytic reduction of cobaltic ammine
US4752364A (en) * 1986-05-19 1988-06-21 Delphi Research, Inc. Method for treating organic waste material and a catalyst/cocatalyst composition useful therefor
US5035778A (en) * 1989-05-12 1991-07-30 International Business Machines Corporation Regeneration of spent ferric chloride etchants
US5145553A (en) * 1991-05-06 1992-09-08 International Business Machines Corporation Method of making a flexible circuit member
DE4407448C2 (de) * 1994-03-07 1998-02-05 Mib Metallurg Und Oberflaechen Elektrolyseverfahren zum Regenerieren einer Eisen-III-Chlorid- oder Eisen-III-Sulfatlösung, insbesondere zum Sprühätzen von Stahl
GB2293390A (en) * 1994-09-20 1996-03-27 British Tech Group Simultaneous etchant regeneration and metal deposition by electrodialysis
US5660712A (en) * 1995-06-07 1997-08-26 Carus, Iii; Paul Electrolytic production of potassium permanganate using a cationic membrane in an electrolytic cell
IT1282979B1 (it) * 1996-05-09 1998-04-03 Novamax Itb S R L Procedimento per il decapaggio dell'acciaio nel quale la ossidazione dello ione ferroso formatosi viene effettuata per via elettrochimica
US7470361B2 (en) 2003-11-14 2008-12-30 Eberly Christopher N System for stormwater environmental control
TWI633206B (zh) 2013-07-31 2018-08-21 卡利拉股份有限公司 使用金屬氧化物之電化學氫氧化物系統及方法
CN103556211B (zh) * 2013-10-14 2016-08-10 刘刚 一种印制电路板铜表面微蚀粗化方法及其设备
WO2017075443A1 (en) 2015-10-28 2017-05-04 Calera Corporation Electrochemical, halogenation, and oxyhalogenation systems and methods
US10556848B2 (en) 2017-09-19 2020-02-11 Calera Corporation Systems and methods using lanthanide halide
CN110857470B (zh) * 2018-08-24 2022-02-08 沈阳师范大学 一种三氯化铁蚀刻液的再生与循环方法
CN114855171B (zh) * 2022-04-01 2024-03-26 安徽中科冉图环保科技有限公司 一种酸性蚀刻液废液处理系统和方法
CN114702191B (zh) * 2022-05-25 2022-11-22 山东凤鸣桓宇环保有限公司 一种含油压舱水处理系统

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE436084C (de) * 1925-07-21 1926-10-23 Siemens & Halske Akt Ges Verfahren zur elektrolytischen Raffination zinnhaltigen Kupfers
US2748071A (en) * 1951-08-30 1956-05-29 Technograph Printed Circuits L Apparatus for regeneration of etching media
US3033793A (en) * 1958-08-13 1962-05-08 Photo Engravers Res Inc Powderless etching of copper photoengraving plates
GB1353960A (en) * 1971-09-21 1974-05-22 Rolls Royce Method of etching a partially masked surface
US3974050A (en) * 1971-10-12 1976-08-10 Kernforschungsanlage Julich Gesellschaft Mit Beschrankter Haftung Method of and apparatus for processing the surface of bodies
US3788915A (en) * 1972-02-09 1974-01-29 Shipley Co Regeneration of spent etchant
US4153531A (en) * 1976-08-21 1979-05-08 Kernforschungsanlage Julich Gesellschaft Mit Beschrankter Haftung Apparatus for electrochemically processing metallic surfaces
DE2641905C2 (de) * 1976-09-17 1986-03-20 Geb. Bakulina Galina Aleksandrovna Batova Verfahren zur Regenerierung verbrauchter Ätzlösungen
DE2650912A1 (de) * 1976-11-06 1978-05-18 Hoellmueller Maschbau H Elektrolytische regeneration eines aetzmittels
DE2655137C2 (de) * 1976-12-04 1978-06-08 Kernforschungsanlage Juelich Gmbh, 5170 Juelich Verfahren zur elektrochemischen Bearbeitung metallischer Oberflächen

Also Published As

Publication number Publication date
JPS5573900A (en) 1980-06-03
EP0011799A1 (de) 1980-06-11
DE2850564A1 (de) 1980-06-04
ATE1071T1 (de) 1982-06-15
CA1160592A (en) 1984-01-17
JPS6327427B2 (enrdf_load_stackoverflow) 1988-06-02
US4269678A (en) 1981-05-26
AU5309279A (en) 1980-05-29
DE2850564C2 (de) 1982-12-23
AU528323B2 (en) 1983-04-21

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