EP0018592A1 - Process for the regeneration of ammoniacal etching solutions for etching metallic copper - Google Patents
Process for the regeneration of ammoniacal etching solutions for etching metallic copper Download PDFInfo
- Publication number
- EP0018592A1 EP0018592A1 EP80102194A EP80102194A EP0018592A1 EP 0018592 A1 EP0018592 A1 EP 0018592A1 EP 80102194 A EP80102194 A EP 80102194A EP 80102194 A EP80102194 A EP 80102194A EP 0018592 A1 EP0018592 A1 EP 0018592A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- etching
- copper
- ammoniacal
- regeneration
- poorly soluble
- 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.)
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- 239000010949 copper Substances 0.000 title claims abstract description 34
- 238000005530 etching Methods 0.000 title claims abstract description 33
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000008929 regeneration Effects 0.000 title claims abstract description 6
- 238000011069 regeneration method Methods 0.000 title claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract 4
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000010953 base metal Substances 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 239000001099 ammonium carbonate Substances 0.000 claims 1
- 235000012501 ammonium carbonate Nutrition 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
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
- 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 ammoniacal etching solutions for etching metallic copper, in particular for etching galvanized printed circuit boards.
- Atmospheric oxygen is meant as 0 2 .
- Air oxidation from Gu + to Cu ++ takes place spontaneously in the spray etching machine. A separate air supply is not necessary.
- mixtures of NH 4 Cl and (NH 4 ) 2 CO 3 are preferably used as NH 4 salts.
- the overall reaction for example with chloride, looks as follows:
- the metallic copper is oxidized to [Cu (NH 3 ) 4 ] ++ ion using ammonia, ammonium salts and atmospheric oxygen.
- the chemicals NH 3 and NH 4 salts are metered into the etching machine as aqueous solutions, so-called “supplementary solutions", during the etching process.
- the resulting highly copper-containing etching concentrates are collected as an overflow and given to a relevant copper processing company, where, to our knowledge, the NH 3 is destroyed with chlorine and the copper is cemented with scrap iron (Fe). The transfer of the overflow to this company is associated with transport and processing costs.
- the invention has for its object to provide a method for the regeneration of the ammoniacal etching solutions with which the NH 3 and NH 4 salts and the etched copper can be recovered in a relatively simple manner.
- the recycling- developed to solve the task Veriahren consists in that with the help of a metal that is less noble than copper and forms a poorly soluble hydroxide in the pH range of the etching medium, the Cu ++ ion is reduced to metallic copper and the etching chemicals are re-formed, the metal itself becoming one poorly soluble hydroxide is oxidized.
- Al is preferably used, since it does not form soluble amine complexes and does not release any toxic ions. The following reactions take place:
- the decoupled solution is separated from the Cu and Al (OH) 3 sludge by filtration and reused as a supplementary solution for the etching process.
- the cement copper is a heavy powder and is relatively easy to separate from the lighter hydroxide.
- the ammonia property of dissolving some Al (OH) 3 as aluminate is completely prevented by the presence of the NH 4 salts.
- the copper cementation is carried out in the form of an internal electrolysis, the deposited materials copper and aluminum hydroxide being obtained separately. This facilitates the regeneration process.
- the anode compartment 3 is filled with supplementary solution and the cathode compartment 4 with a mixture of supplementary solution and etching solution.
- An Al plate 5 is immersed in the anode compartment 3 as a base electrode as a soluble anode and a Cu plate 6 is immersed in the cathode compartment 4 as a nobler electrode.
- electrolysis without an external power source internal electrolysis
- the Al plate 5 emits electrons to the Cu plate 6 and decays itself into Al (OH) 3 after the following reaction:
- the liquid in the cathode compartment 4 is completely decoupled, pure supplementary solution is formed. Part of it is removed and replaced with an etching solution.
- the supplementary solution removed is metered into the etching machine for the etching process.
- the overflow of the etching machine is decoupled in batches in the cathode space 4 and converted into supplementary solution.
- the cathode liquid preferably consists of approx. 95% supplementary solution and 5% etching solution. This is necessary because of the difference in density (1.05 g / ml for the supplementary solution and 1.2 g / ml for the etching solution with approx.
- the supplementary solution in the anode compartment 3 is separated from the Al (OH) 3 sludge by filtration and used again as the anode liquid.
- the deposited Al (OH) 3 can be discarded.
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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)
- Removal Of Specific Substances (AREA)
Abstract
Das erfindungsgemäße Recycling-Verfahren für ammoniakalische Ätzlösungen, welche außer den ätzfähigen Tetramminkupfer(II)-Ionen, Ammoniak und Ammoniumchlorid enthalten, besteht darin, daß mit Hilfe eines Metalls, das unedler ist als Kupfer und im pH-Bereich des Ätzmediums ein schwerlösliches Hydroxid bildet, das Cu<+><+>- Ion zu metallischem Kupfer reduziert wird und die Ätzchemikalien zurückgebildet werden, wobei das Metall selbst zu einem schwerlöslichen Hydroxid oxidiert wird. Der Regenerierprozeß wird vorzugsweise mit Hilfe eines Diaphragmas (2) als Elektrolyseprozeß ohne äußere Stromquelle durchgeführt, wobei das geätzte Kupfer im Kathodenraum (4) und das Al(OH)3 im Anodenraum (3) getrennt abgeschieden werden.The recycling process according to the invention for ammoniacal etching solutions which, in addition to the etchable tetrammin copper (II) ions, contain ammonia and ammonium chloride, consists in that with the aid of a metal which is less noble than copper and forms a poorly soluble hydroxide in the pH range of the etching medium , the Cu <+> <+> ion is reduced to metallic copper and the etching chemicals are regressed, the metal itself being oxidized to a poorly soluble hydroxide. The regeneration process is preferably carried out using a diaphragm (2) as an electrolysis process without an external power source, the etched copper in the cathode compartment (4) and the Al (OH) 3 in the anode compartment (3) being separated.
Description
Die Erfindung bezieht sich auf ein Verfahren zur Regenerierung ammoniakalischer Ätzlösungen zum Ätzen von metallischem Kupfer, insbesondere zum Ätzen von galvanisierten Leiterplatten.The invention relates to a method for regenerating ammoniacal etching solutions for etching metallic copper, in particular for etching galvanized printed circuit boards.
Beispielsweise ist aus der DE-OS 26 25 869 bekannt, zum Ätzen von kupferkaschierten Leiterplatten wäßrige Lösungen zu verwenden, welche neben Tetramminkupfer(II)-Ionen noch Ammoniak und Ammoniumsalze enthalten. Beim Ätzen von metallischem Kupfer laufen hierbei folgende Reaktionen ab:
Die Summe a) + b) ergibt die Gesamtreaktion c):
Als 02 ist Luftsauerstoff gemeint. Die Luftoxidation von Gu+ zu Cu++ findet in der Sprühätzmaschine spontan statt. Eine gesonderte Luftzufuhr ist nicht erforderlich.Atmospheric oxygen is meant as 0 2 . Air oxidation from Gu + to Cu ++ takes place spontaneously in the spray etching machine. A separate air supply is not necessary.
Als NH4-Salze werden nach DE-OS 26 25 869 vorzugsweise Gemische aus NH4Cl und (NH4)2CO3 verwendet. In Salzform sieht die Gesamtreaktion z.B. beim Chlorid wie folgt aus:
Daraus ist zu ersehen, daß das metallische Kupfer unter Verbrauch von Ammoniak, Ammoniumsalzen und Luftsauerstoff zu [Cu(NH3)4] ++-Ion oxidiert wird. Die Chemikalien NH3 und NH4-Salze werden in der Praxis als wäßrige Lösungen, sog. "Ergänzungslösungen", der Ätzmaschine während des Ätzprozesses zudosiert.It can be seen from this that the metallic copper is oxidized to [Cu (NH 3 ) 4 ] ++ ion using ammonia, ammonium salts and atmospheric oxygen. In practice, the chemicals NH 3 and NH 4 salts are metered into the etching machine as aqueous solutions, so-called "supplementary solutions", during the etching process.
Die hierbei entstehenden stark kupferhaltigen Ätzkonzentrate werden als Überlauf gesammelt und einem ein- schlägigen Kupferverarbeitungsbetrieb abgegeben, wo, unseres Wissens nach, das NH3 mit Chlor zerstört und das Kupfer mit Schrott (Fe) auszementiert wird. Die Abgabe des Überlaufs an diesen Betrieb ist mit Transport-und Verarbeitungskosten verbunden.The resulting highly copper-containing etching concentrates are collected as an overflow and given to a relevant copper processing company, where, to our knowledge, the NH 3 is destroyed with chlorine and the copper is cemented with scrap iron (Fe). The transfer of the overflow to this company is associated with transport and processing costs.
Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Regenerierung der ammoniakalischen Ätzlösungen zu schaffen, mit dem auf relativ einfache Weise die beim Kupferätzen verbrauchten Stoffe NH3 und NH4-Salze sowie das geätzte Kupfer zurückgewonnen werden können. Das zur Lösung der gestellten Aufgabe entwickelte Recycling-Veriahren besteht darin, daß mit Hilfe eines Metalls, das unedler ist als Kupfer und im pH-Bereich des Ätznediums ein schwerlösliches Hydroxid bildet, das Cu++-Ion zu metallischem Kupfer reduziert wird und die Ätzchemikalien zurückgebildet werden, wobei das Metall selbst zu einem schwerlöslichen Hydroxid oxidiert wird.The invention has for its object to provide a method for the regeneration of the ammoniacal etching solutions with which the NH 3 and NH 4 salts and the etched copper can be recovered in a relatively simple manner. The recycling- developed to solve the task Veriahren consists in that with the help of a metal that is less noble than copper and forms a poorly soluble hydroxide in the pH range of the etching medium, the Cu ++ ion is reduced to metallic copper and the etching chemicals are re-formed, the metal itself becoming one poorly soluble hydroxide is oxidized.
Von den für den Kupferzementationsprozeß geeigneten unedlen Metallen Al, Zn, Mg und Fe wird bevorzugt Al verwendet, da es keine löslichen Amminkomplexe bildet und keine toxischen Ionen abgibt. Es laufen hierbei folgende Reaktionen ab:
Die Summe von e) und f) ergibt die Gesantreaktion g):
Aus der Gleichung g) ist zu ersehen, daß mit Hilfe von Al praktisch die Umkehrung des Ätzprozesses nach Gleichung c) erreicht wird.From equation g) it can be seen that the inversion of the etching process according to equation c) is practically achieved with the aid of Al.
Die Rea.ktion g) sieht in der Chloridform wie folgt aus:
Ähnlich verläuft die Reaktion mit Fe:
Durch Filtrieren wird die entkupferte Lösung vom Cu und Al(OH)3-Schlamm getrennt und als Ergänzungslösung für den Ätzprozeß wiederverwendet. Das Zementkupfer liegt als schweres Pulver vor und läßt sich von dem leichteren Hydroxid relativ leicht abtrennen. Ergänzend soll betont werden, daß die Eigenschaft des Ammoniaks, etwas Al(OH)3 als Aluminat aufzulösen, durch die Anwesenheit der NH4-Salze völlig unterbunden wird. Durch die vorzugsweise Verwendung eines Diaphragmas wird die Kupferzementation in Form einer inneren Elektrolyse durchgeführt, wobei die abgeschiedenen Stoffe Kupfer und Aluminiumhydroxid getrennt erhalten werden. Dies erleichtert den Regenerierprozeß.The decoupled solution is separated from the Cu and Al (OH) 3 sludge by filtration and reused as a supplementary solution for the etching process. The cement copper is a heavy powder and is relatively easy to separate from the lighter hydroxide. In addition, it should be emphasized that the ammonia property of dissolving some Al (OH) 3 as aluminate is completely prevented by the presence of the NH 4 salts. By preferably using a diaphragm, the copper cementation is carried out in the form of an internal electrolysis, the deposited materials copper and aluminum hydroxide being obtained separately. This facilitates the regeneration process.
Eine zur Durchführung des erfindungsgemäßen Verfahrens geeignete Apparatur ist in der Zeichnung dargestellt.An apparatus suitable for carrying out the method according to the invention is shown in the drawing.
Sie besteht aus einem Behälter 1, der mittels eines Diaphragmas 2 in einem Anodenraum 3 und einem Kathodenraum 4 unterteilt ist. Der Anodenraum 3 ist mit Ergänzungslösung und der Kathodenraum 4 mit einem Gemisch aus Ergänzungslösung und Ätzlösung gefüllt. In den Anodenraum 3 wird als unedle Elektrode eine Al-Platte 5 als lösliche Anode und in den Kathodenraum 4 als edlere Elektrode eine Cu-Platte 6 eingetaucht. Durch Verbinden beider Platten mit einem Metalldraht 7 beginnt sofort eine Elektrolyse ohne äußere Stromquelle (innere Elektrolyse). Hierbei gibt die Al-Platte 5 an die Cu-Platte 6 Elektronen ab und zerfällt selbst in Al(OH)3 nach folgender Reaktion:
An der Cu-Elektrode wird gleichzeitig fest haftendes Kupfer abgeschieden:
Als Gesamtreaktion ergibt sich die bereits erwähnte Gleichung g).The above-mentioned equation g) results as the overall reaction.
Auf diese Weise wird die Flüssigkeit im Kathodenraum 4 völlig entkupfert, es entsteht reine Ergänzungslösung. Ein Teil davon wird herausgenommen und durch Ätzlösung ersetzt. Die entnommene Ergänzungslösung wird der Ätzmaschine für den Ätzprozeß zudosiert. Der Überlauf der Ätzmaschine wird, wie oben beschrieben, im Kathodenraun 4 chargenweise entkupfert und in Ergänzungslösung umgewandelt. Die Kathodenflüssigkeit besteht vorzugsweise jeweils vor Beginn der Elektrolyse aus ca. 95% Ergänzungslösung und 5% Ätzlösung. Dies ist wegen des Dichte-Unterschieds (1,05 g/ml bei der Ergänzungslösung und 1,2 g/ml bei der Ätzlösung mit ca. 150 g Cu++/1) notwendig, um eine Wanderung von Ätzlösung in den Anodenraum 3 zu vermeiden, d.h. eine direkte Kupferzementation an der Al-Platte zu verhindern. Die Ergänzungslösung im Anodenraum 3 wird von Zeit zu Zeit durch Filtrieren vom Al(OH)3-Schlamm abgetrennt und wieder als Anodenflüssigkeit verwendet. Das abgeschiedene Al(OH)3 kann verworfen werden.In this way, the liquid in the
Claims (5)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2917597 | 1979-04-30 | ||
DE19792917597 DE2917597A1 (en) | 1979-04-30 | 1979-04-30 | METHOD FOR REGENERATING AMMONIACAL ETCH SOLUTIONS FOR ETCHING METALLIC COPPER |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0018592A1 true EP0018592A1 (en) | 1980-11-12 |
Family
ID=6069704
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP80102194A Withdrawn EP0018592A1 (en) | 1979-04-30 | 1980-04-23 | Process for the regeneration of ammoniacal etching solutions for etching metallic copper |
Country Status (4)
Country | Link |
---|---|
US (1) | US4280887A (en) |
EP (1) | EP0018592A1 (en) |
JP (1) | JPS55148772A (en) |
DE (1) | DE2917597A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0393270A1 (en) * | 1989-04-21 | 1990-10-24 | Ming-Hsing Lee | Process for etching copper with ammoniacal etchant solution and reconditioning the used etchant solution |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3031567A1 (en) * | 1980-08-21 | 1982-04-29 | Elochem Ätztechnik GmbH, 7758 Meersburg | METHOD FOR REGENERATING AN AMMONIA ACAL SOLUTION |
US4525254A (en) * | 1982-10-07 | 1985-06-25 | Gosudarstvenny Nauchno-Issledovatelsky I Proektny Institut Po Obogascheniju Rud Tsvetnykh Metallov "Kazmekhanobr" | Process and apparatus for purifying effluents and liquors |
US4655895A (en) * | 1982-10-07 | 1987-04-07 | Gosudarstvenny Nauchno-Issledovatelsky I Proektny Institut Po Obogascheniju Rud Tsvetnykh Metallov "Kazmekhanobr" | Apparatus for purifying effluents and liquids |
DE3324450A1 (en) * | 1983-07-07 | 1985-01-17 | ELO-CHEM Ätztechnik GmbH, 7758 Meersburg | AMMONIUM SULFATE-CONTAINING ETCH SOLUTION AND METHOD FOR REGENERATING THE ETCH SOLUTION |
US4490224A (en) * | 1984-04-16 | 1984-12-25 | Lancy International, Inc. | Process for reconditioning a used ammoniacal copper etching solution containing copper solute |
JPH01190907A (en) * | 1988-01-25 | 1989-08-01 | Nissan Motor Co Ltd | Remolten chilled camshaft |
US5348629A (en) * | 1989-11-17 | 1994-09-20 | Khudenko Boris M | Method and apparatus for electrolytic processing of materials |
US5133873A (en) * | 1991-02-22 | 1992-07-28 | Miles Inc. | Process for removal of copper ions from aqueous effluent |
US5417818A (en) * | 1993-11-24 | 1995-05-23 | Elo-Chem Atztechnik Gmbh | Process for the accelerated etching and refining of metals in ammoniacal etching systems |
AU3115295A (en) * | 1994-07-19 | 1996-02-16 | Hoogovens Staal Bv | Process for electrochemically dissolving a metal such as zinc or tin |
US5524780A (en) * | 1995-01-31 | 1996-06-11 | Applied Electroless Concepts Inc. | Control of regeneration of ammoniacal copper etchant |
US5626736A (en) | 1996-01-19 | 1997-05-06 | Shipley Company, L.L.C. | Electroplating process |
US6086779A (en) * | 1999-03-01 | 2000-07-11 | Mcgean-Rohco, Inc. | Copper etching compositions and method for etching copper |
US6869519B2 (en) * | 2001-09-27 | 2005-03-22 | National Institute Of Advanced Industrial Science And Technology | Electrolytic process for the production of metallic copper and apparatus therefor |
US20050082172A1 (en) * | 2003-10-21 | 2005-04-21 | Applied Materials, Inc. | Copper replenishment for copper plating with insoluble anode |
CN100378014C (en) * | 2005-02-03 | 2008-04-02 | 黄伟君 | Sewage treating and resource recovering system |
US20060193750A1 (en) * | 2005-02-28 | 2006-08-31 | Medis El Ltd. | Electrochemical detection of explosives in air |
CN113200635B (en) * | 2021-06-17 | 2022-05-10 | 徐鸿顺 | Circuit board etching wastewater treatment device and method |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2072986A5 (en) * | 1969-12-09 | 1971-09-24 | Didier Werke Ag | |
US3761369A (en) * | 1971-10-18 | 1973-09-25 | Electrodies Inc | Process for the electrolytic reclamation of spent etching fluids |
AT313671B (en) * | 1971-03-08 | 1974-02-25 | Hoellmueller Maschbau H | Process for regenerating etching solutions for copper and copper alloys, regeneration system for carrying out this process and measuring and control device for this regeneration system |
GB1416637A (en) * | 1972-09-09 | 1975-12-03 | Loewe Opta Gmbh | Treatment of used copper etching solutions |
AT326973B (en) * | 1973-03-03 | 1976-01-12 | Hoellmueller Maschbau H | METHOD AND DEVICE FOR PURIFYING COPPER-CONTAINING AMMONIA SOLUTIONS |
DE2651675A1 (en) * | 1976-01-09 | 1977-07-14 | C Paul Pesek | ARRANGEMENT FOR THE CONTINUOUS RECOVERY OF ETCHED MATERIAL AND ETCHED MATERIAL |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
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NL6603696A (en) * | 1965-04-28 | 1966-10-31 | ||
US4035269A (en) * | 1971-04-23 | 1977-07-12 | Snam Progetti, S.P.A. | Process for the galvanic purification of the waste waters |
US3766036A (en) * | 1972-03-06 | 1973-10-16 | Occidental Petroleum Corp | Process for the removal of ionic metallic impurities from water |
US4152229A (en) * | 1978-04-19 | 1979-05-01 | London Laboratories Limited | Apparatus and method for removal of soluble metal ions from aqueous effluent |
-
1979
- 1979-04-30 DE DE19792917597 patent/DE2917597A1/en not_active Withdrawn
-
1980
- 1980-04-21 US US06/142,007 patent/US4280887A/en not_active Expired - Lifetime
- 1980-04-23 EP EP80102194A patent/EP0018592A1/en not_active Withdrawn
- 1980-04-28 JP JP5704180A patent/JPS55148772A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2072986A5 (en) * | 1969-12-09 | 1971-09-24 | Didier Werke Ag | |
AT313671B (en) * | 1971-03-08 | 1974-02-25 | Hoellmueller Maschbau H | Process for regenerating etching solutions for copper and copper alloys, regeneration system for carrying out this process and measuring and control device for this regeneration system |
US3761369A (en) * | 1971-10-18 | 1973-09-25 | Electrodies Inc | Process for the electrolytic reclamation of spent etching fluids |
GB1416637A (en) * | 1972-09-09 | 1975-12-03 | Loewe Opta Gmbh | Treatment of used copper etching solutions |
AT326973B (en) * | 1973-03-03 | 1976-01-12 | Hoellmueller Maschbau H | METHOD AND DEVICE FOR PURIFYING COPPER-CONTAINING AMMONIA SOLUTIONS |
DE2651675A1 (en) * | 1976-01-09 | 1977-07-14 | C Paul Pesek | ARRANGEMENT FOR THE CONTINUOUS RECOVERY OF ETCHED MATERIAL AND ETCHED MATERIAL |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0393270A1 (en) * | 1989-04-21 | 1990-10-24 | Ming-Hsing Lee | Process for etching copper with ammoniacal etchant solution and reconditioning the used etchant solution |
Also Published As
Publication number | Publication date |
---|---|
DE2917597A1 (en) | 1980-11-13 |
US4280887A (en) | 1981-07-28 |
JPS55148772A (en) | 1980-11-19 |
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