EP0046522B1 - Verfahren zum Regenerieren einer ammoniakalischen Ätzlösung - Google Patents

Verfahren zum Regenerieren einer ammoniakalischen Ätzlösung Download PDF

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Publication number
EP0046522B1
EP0046522B1 EP81106058A EP81106058A EP0046522B1 EP 0046522 B1 EP0046522 B1 EP 0046522B1 EP 81106058 A EP81106058 A EP 81106058A EP 81106058 A EP81106058 A EP 81106058A EP 0046522 B1 EP0046522 B1 EP 0046522B1
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EP
European Patent Office
Prior art keywords
etching
etching solution
activated carbon
solution
carbon powder
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
EP81106058A
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German (de)
English (en)
French (fr)
Other versions
EP0046522A1 (de
Inventor
Bertel Professor Dr. Kastening
Wolfgang Faul
Leander Fürst
Walter Holzer
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.)
Elo Chem Atztechnik GmbH
Forschungszentrum Juelich GmbH
Original Assignee
Elo Chem Atztechnik GmbH
Forschungszentrum Juelich GmbH
Kernforschungsanlage Juelich 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.)
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Publication date
Application filed by Elo Chem Atztechnik GmbH, Forschungszentrum Juelich GmbH, Kernforschungsanlage Juelich GmbH filed Critical Elo Chem Atztechnik GmbH
Priority to AT81106058T priority Critical patent/ATE22935T1/de
Publication of EP0046522A1 publication Critical patent/EP0046522A1/de
Application granted granted Critical
Publication of EP0046522B1 publication Critical patent/EP0046522B1/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 ammoniacal etching solution and for etching with this solution which is supplied with oxygen for the reoxidation of the etchant contained in the etching solution.
  • Alkaline etchants are used for etching metallic objects, in particular for the production of printed circuit boards, which are also known under the name "printed circuits", especially when the printed circuit boards to be etched are metal parts which are not resistant to acidic etching media, for example made of lead, tin or nickel exhibit.
  • a re-oxidation of the alkaline etching solution after etching off the metal is carried out with the addition of ammonia gas and / or ammonium chloride in the presence of oxygen or air.
  • waste solutions are also created that cannot be removed without prior detoxification treatment. Compare, for example, H. Bruch et al., "Printed circuit boards", Eugen G. Leutze-Verlag, Saulgau / Kunststoff, 1978.
  • the object of the invention is to provide a method for regenerating alkaline etching solutions in which no toxic residual solutions are obtained and in which the etching solution rapidly reoxidizes.
  • activated carbon powder particles suspended in aqueous solution for removing pollutants are used as catalysts for the oxidation of pollutants such as nitrite, cyanide or sulfite.
  • the invention is based on this known effect of the activated carbon powder particles. It is known to use activated carbon powder particles when regenerating chloride-containing etching solutions, cf. EP-A1-0 011 788. The activated carbon powder particles are used in this process to prevent chlorine formation in the electrolysis cell.
  • the activated carbon powder particles effective in the etching solution were previously annealed in a vacuum, in an inert, reducing atmosphere containing CO 2 or water vapor at a temperature between 900 and 1200 ° C.
  • the amount of CO 2 and water vapor is adjusted so that only a slight degradation of the activated carbon powder takes place during the treatment. It has proven to be advantageous to glow the activated carbon powder particles in the aforementioned manner for over an hour, claim 2.
  • concentrations of the activated carbon powder particles in the etching solution between 5 and 25% by weight, preferably between 10 and 12% by weight, is obtained a viscosity suitable for transport and for spraying the etching solution, claims 3 and 4.
  • measures specified in patent claims 5 and 6 serve to separate metal ions dissolved in the etching solution.
  • part of the etching solution is passed through the cathode compartment of an electrolysis cell.
  • the partial amount of the etching solution passed through the electrolytic cell and the electrolysis current are adjusted so that the metal concentration which results from the deposition of the metal ions on the cathode is sufficient for an optimal etching speed within the etching solution containing the suspended activated carbon powder parts.
  • the part of the etching solution passed through the electrolytic cell is returned to the etching solution circuit after flowing through the cathode space.
  • FIGS. 1 to 3 show the improvements achieved in the etching of copper using activated carbon powder.
  • An ammonium sulfate solution with a content of 150 g ammonium sulfate per liter is used as the etching solution, which is adjusted to a pH of 9 by adding gaseous ammonia.
  • etching rate as a function of the copper content in the solution
  • different copper contents are set and the dissolution rate of a copper plate sprayed with air in an etching solution is measured.
  • the etching speeds achieved in the case of etching solutions without activated carbon powder particles are shown in curve 1 in FIG. 1; the etching speed with 12% by weight of activated carbon powder particles suspended are shown in curve 11. From the course of the curve of curve 11 and 11 it can be seen that solutions with a copper content of about 20 g copper per liter or more when adding activated carbon powder have a considerably higher etching rate than etching solutions without activated carbon powder. It is particularly advantageous that the maximum of the etching speed in etching solutions with carbon powder particles compared to etching solutions without carbon powder particles is shifted towards higher copper contents in the solution.
  • a solution of 150 g ammonium sulfate and 30 g copper per liter was adjusted to a pH of 9 by adding gaseous ammonia.
  • the solution was sprayed in air for oxidation by means of a nozzle, collected in an upwardly open solvent tank and circulated.
  • the overpressure in the solution was 0.7 bar in front of the nozzle.
  • the potential of the solution was measured using a platinum pen against a mercury / mercury oxide reference electrode. 1.5 liters of this solution, which had been heated to 50 ° C., were passed in the circuit.
  • the etching system consists of an etching chamber 1, in which the objects 2 to be etched are sprayed with ammoniacal etching solution by means of a spray device 3.
  • the etching solution is circulated by a solvent pump 4 from the bottom of the etching chamber 1 via a pipeline 5 connected to the spray device 3.
  • a section of the pipeline 5 consists of a filter 6 which is permeable to the etching solution, but which retains the activated carbon powder particles suspended in the etching solution.
  • the part of the etching solution which passes through the filter 6 is led to the cathode chamber 7 of an electrolytic cell 8 and, after the etched metal has been deposited, through the anode chamber 9
  • a diaphragm 10, i in the circuit of the etching solution, in the exemplary embodiment is returned to the etching chamber 1 through the electrolysis cell between the cathode and anode areas of the electrolysis cell.
  • etching solution which contained 150 g of ammonium sulfate and 50 g of copper per liter and activated carbon powder in an amount of 10% by weight are circulated and by means of the spray device equipped with nozzles at an overpressure of 0 , 5 bar sprayed in air.
  • the etching solution had been heated to 50 ° C. and was adjusted to a pH of 9 by adding ammonia gas. Copper plates were etched. The etch rate was approximately 2.6 g copper per minute.
  • About 20 milliliters of the solution were continuously separated from the circuit through a diaphragm, which was used as a filter in the pipeline, and activated carbon powder was introduced into the cathode compartment of the electrolytic cell.
  • Copper was deposited from the etching solution on a stainless steel cathode with 30 ampere direct current, corresponding to a current density of 5 ampere per dm 2 .
  • the copper-depleted etching solution penetrated into the anode space of the electrolysis cell through the diaphragm separating the cathode and anode space of the electrolysis cell.
  • a plastic net resistant to the etching solution was used as the diaphragm.
  • the etching solution was returned from the anode compartment to the circuit of the etching solution containing the suspended activated carbon powder particles.
  • the cell voltage was 2.3 volts.
  • Brass was etched in the etching system shown in Figure 4 with an ammoniacal etching solution.
  • a portion of the aqueous solution containing 150 g of ammonium sulfate, 21 g of copper and 44 g of zinc per liter was introduced into the cathode chamber of the stainless steel cathode electrolytic cell.
  • a solution temperature of 20 ° C and a current density of 5 amperes per dm 2 an alloy of 66% copper and 34% zinc is separated in the electrolytic cell on the stainless steel cathode.
  • the current efficiency for metal deposition was 92%.
  • activated carbon powder particles were suspended in the etching solution in the same way as in the previous exemplary embodiments, and the etching solution was sprayed in air to come into contact with oxygen.

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Physical Water Treatments (AREA)
EP81106058A 1980-08-21 1981-08-03 Verfahren zum Regenerieren einer ammoniakalischen Ätzlösung Expired EP0046522B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81106058T ATE22935T1 (de) 1980-08-21 1981-08-03 Verfahren zum regenerieren einer ammoniakalischen aetzloesung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19803031567 DE3031567A1 (de) 1980-08-21 1980-08-21 Verfahren zum regenerieren einer ammoniakalischen aetzloesung
DE3031567 1980-08-21

Publications (2)

Publication Number Publication Date
EP0046522A1 EP0046522A1 (de) 1982-03-03
EP0046522B1 true EP0046522B1 (de) 1986-10-15

Family

ID=6110120

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81106058A Expired EP0046522B1 (de) 1980-08-21 1981-08-03 Verfahren zum Regenerieren einer ammoniakalischen Ätzlösung

Country Status (8)

Country Link
US (1) US4385969A (enrdf_load_stackoverflow)
EP (1) EP0046522B1 (enrdf_load_stackoverflow)
JP (1) JPS5773183A (enrdf_load_stackoverflow)
AT (1) ATE22935T1 (enrdf_load_stackoverflow)
AU (1) AU548856B2 (enrdf_load_stackoverflow)
CA (1) CA1175323A (enrdf_load_stackoverflow)
DE (1) DE3031567A1 (enrdf_load_stackoverflow)
DK (1) DK158156C (enrdf_load_stackoverflow)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2133806B (en) * 1983-01-20 1986-06-04 Electricity Council Regenerating solutions for etching copper
DE3348401C2 (en) * 1983-02-16 1993-08-26 Siemens Ag, 8000 Muenchen, De Electrolyte regeneration of ammoniacal etching soln.
DE3305319A1 (de) * 1983-02-16 1984-08-16 Siemens AG, 1000 Berlin und 8000 München Elektrolytisches vollregenerierverfahren einer ammoniakalischen aetzloesung
DE3340343A1 (de) * 1983-04-13 1984-10-18 Kernforschungsanlage Jülich GmbH, 5170 Jülich Verfahren und anlage zum regenerieren einer ammoniakalischen aetzloesung
EP0122963B1 (de) * 1983-04-13 1988-06-01 Forschungszentrum Jülich Gmbh Anlage zum Regenerieren einer ammoniakalischen Ätzlösung
DE3324450A1 (de) * 1983-07-07 1985-01-17 ELO-CHEM Ätztechnik GmbH, 7758 Meersburg Ammoniumsulfathaltige aetzloesung sowie verfahren zur regeneration der aetzloesung
DE3340342A1 (de) * 1983-11-08 1985-05-15 ELO-CHEM Ätztechnik GmbH, 7758 Meersburg Verfahren und anlage zum regenerieren einer ammoniakalischen aetzloesung
US4490224A (en) * 1984-04-16 1984-12-25 Lancy International, Inc. Process for reconditioning a used ammoniacal copper etching solution containing copper solute
FR2567914B1 (fr) * 1984-07-19 1989-04-07 Univ Languedoc Procede de recuperation de cations metalliques en continu a partir de solutions diluees et appareil pour sa mise en oeuvre
DE3539886A1 (de) * 1985-11-11 1987-05-14 Hoellmueller Maschbau H Verfahren und vorrichtung zum aetzen eines zumindest teilweise aus metall, vorzugsweise kupfer, bestehenden aetzguts
US20090106888A1 (en) * 2002-08-02 2009-04-30 Roy W. Mattson, Jr. Safety device
US6760931B1 (en) 2002-08-02 2004-07-13 Roy W. Mattson, Jr. Non-electric sanitation water vessel system
US7146659B2 (en) 2002-08-02 2006-12-12 Mattson Jr Roy W Hydromassage antimicrobial whirlpool bathtub
DE102006051952A1 (de) * 2006-11-01 2008-05-08 Merck Patent Gmbh Partikelhaltige Ätzpasten für Siliziumoberflächen und -schichten
CN108149249A (zh) * 2017-07-05 2018-06-12 叶涛 一种线路板碱性蚀刻废液的蒸氨回收循环工艺
CN115135806B (zh) * 2020-07-28 2023-12-05 叶涛 碱性蚀刻废液再生回用的方法及其设备

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL111200C (enrdf_load_stackoverflow) * 1958-07-31 1964-12-15
US3944487A (en) * 1974-02-06 1976-03-16 Thiokol Corporation Catalytic filtering-incinerating process and device for waste water
DE2714075C2 (de) * 1977-03-30 1980-04-17 Kernforschungsanlage Juelich Gmbh, 5170 Juelich Verfahren zur Oxidation von in wäßriger Lösung oxidierbaren Schadstoffen
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
DE2917597A1 (de) * 1979-04-30 1980-11-13 Siemens Ag Verfahren zur regenerierung ammoniakalischer aetzloesungen zum aetzen von metallischem kupfer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Elektrochemie und Elektronik" Dechema-Monographen Vol. 90, Verlag Chemie, Weinheim/New York 1981, pages 145-161 *

Also Published As

Publication number Publication date
JPS5773183A (en) 1982-05-07
ATE22935T1 (de) 1986-11-15
CA1175323A (en) 1984-10-02
DE3031567C2 (enrdf_load_stackoverflow) 1987-09-03
DE3031567A1 (de) 1982-04-29
AU548856B2 (en) 1986-01-02
AU7397581A (en) 1982-02-25
EP0046522A1 (de) 1982-03-03
DK158156B (da) 1990-04-02
DK158156C (da) 1990-09-03
JPH0329868B2 (enrdf_load_stackoverflow) 1991-04-25
US4385969A (en) 1983-05-31
DK368981A (da) 1982-02-22

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