GB2283983A - Controlling the nitrate content of ammoniacal etching agent by electrolytic regeneration of used agent and recycling - Google Patents
Controlling the nitrate content of ammoniacal etching agent by electrolytic regeneration of used agent and recycling Download PDFInfo
- Publication number
- GB2283983A GB2283983A GB9422669A GB9422669A GB2283983A GB 2283983 A GB2283983 A GB 2283983A GB 9422669 A GB9422669 A GB 9422669A GB 9422669 A GB9422669 A GB 9422669A GB 2283983 A GB2283983 A GB 2283983A
- Authority
- GB
- United Kingdom
- Prior art keywords
- accordance
- etching
- added
- agent
- nitrate
- 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
Links
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
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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)
- Electrolytic Production Of Metals (AREA)
- ing And Chemical Polishing (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Description
[PATGLINN94.A121 2283983 PROCESS FOR THE ACCELERATED ETCHING AND REFINING
or METALS IN AMMONIACAL ETCHING SYSTEMS
BACKGROUND OF THE-INVENTION
Etching systems that operate with ammoniacal etching reagents are particularly suitable f or the regeneration of the etching reagent in recycling processes in which at the same time the etched metal is ref ined metallically in electrolysis cells.
In terms of commercial application, it is of great importance that the etching speed as well as refining speed of the metal in the electrolysis cell be accelerated.
It is also important that to the extent possible the substances that result from etching or regeneration or refining of the metal do not bring about any excessive enrichment. Interference from secondary reactions should be avoided to the extent possible.
SUMMARY OF THE INVENTION
Task of the invention is to outline a process which reaches this ideal goal as closely as possible.
In this regard, the invention is attributed special 25 significance in that it utilizes in a positive fashion the interference of secondary phenomena f ound in traditional systems with electrolysis cellsY i.e. the occurrence of oxygen and, as a secondary reaction, the oxidation of ammonium ions to nitrate.
Patent DE 42 18 843 Al, for example, describes a process which proposes the removal of nitrate from the etching reagent through reaction with a reducing agent.
EPATGURN94A121 It completely disregarded the accelerating effect of the etching process by the nitrate, which no longer applies when removed from the etching reagent, not even with a residual concentration between 10 and 40 g/1.
D9TAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
In accordance with the invention, the nitrate that occurs on the electrodes of the electrolysis cell in the etching reagent is enriched to a value of at least 50 to 200 g/1. This makes it possible to achieve a significant acceleration of the etching process.
In order to prevent an excessive nitrate concentration, it is recommended to add reducing agents as soon as values rises too much.
As a particularly effective reducing agent, formaldehyde is recommended, which is a proven product in the electroplating area.
But an increased nitrate concentration in conjunction with reducing agents, added in accordance with the invention, also improves the refining of metals in the electrolysis cell, since for example for copper, the necessary reduction from copper II to copper I - required for the metallic refining of copper - is accelerated. Etching with high nitrate content as proposed in accordance with the invention also offers the advantage that it is very suitable for use in certain acceleration additions, e.g. on the basis of compounds that contain vanadium. 30 In accordance with the invention, the addition of accelerators containing selenium or cobalt is also proposed. Since the recommended processes do not bring about any substances that affect the etching process, the advantages are obvious.
EPATGUMN94X21 Examples of etching solutions in accordance with the invention with trades of vanadium as accelerator are:
Solution 1:
Solution 2:
- 20 g Cull - 220 9 S0411 - 100 g N0311 0.5 - 5 g Cl/1 1 - 20 mg V/1 120 g Cull 120 220 g SO 411 - 100 g N0311 g Cl/1 0.5 - 20 g PO 4/1 1 - 20 mg V/1 0.5 - In addition, solutions 1 and 2 contain ammonia for setting the alcalic pH value.
It is known that the etching speed is a function of temperature and pH value. For the examples of the etching solutions in accordance with the invention, optimum temperatures were 350C to 600C with a pH value of 8.1 to 8.8 and a nitrate concentration of 70-80 g/1.
The addition of reducing agents to avoid excessive nitrate concentrations is not critical. In most cases. a weekly analysis and addition are sufficient.
obviously. it is also possible to foresee an on-going addition, e.g. with dosing pumps, because the nitrate formation of the refined copper amount corresponds proportionately to the current balance of the electrolysis cell and can therefore easily be calculated in advance.
EPATGUNN94A123 Especially in the continuous additional dosage of reducing agents. it is recommended to do this in the area of the electrolysis -cell. e.g. at the intake,, so that a better result is obtained, e. g. in the conversion form copper II to copper I.
Claims (7)
1 CLAIM:
[PATGUNN94.AI23 CLAIMS 1. Process f or the accelerated etching with ammoniacal 2 etching reagents and subsequent regeneration of the etching reagent whereby the etched metal is refined in an 4 electrolysis cell and whereby the nitrate that occurs in the etching reagent during electrolysis is enriched up to 6 a concentration of at least 50 to 200 g/1.
2. Process in accordance with Claim 1 whereby the addition of reducing agents prevents the nitrate concentration from increasing excessively beyond an optimum operating point.
2
3. Process in accordance with Claim 2, whereby 2 formaldehyde is added as a reducing agent.
4. Process in accordance with one or several of the 2 preceding claims whereby an accelerator containing vanadium is also added to the etching reagent.
5. Process in accordance with one or several of the preceding claims whereby an accelerator containing selenium is added.
2
6. Process in accordance with one or several of the preceding claims whereby an accelerator containing cobalt is added.
7. Process in accordance with one or several of the preceding claims whereby the reducing agent is added in the area of the electrolysis cell.
2
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4339320A DE4339320A1 (en) | 1993-11-18 | 1993-11-18 | Process for accelerated etching and deposition of metals in ammoniacal etching systems |
Publications (3)
Publication Number | Publication Date |
---|---|
GB9422669D0 GB9422669D0 (en) | 1995-01-04 |
GB2283983A true GB2283983A (en) | 1995-05-24 |
GB2283983B GB2283983B (en) | 1997-07-02 |
Family
ID=6502857
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB9422669A Expired - Fee Related GB2283983B (en) | 1993-11-18 | 1994-11-10 | Process for the accelerated etching and refining of metals in ammoniacal etching systems |
Country Status (7)
Country | Link |
---|---|
JP (1) | JPH07197300A (en) |
CN (1) | CN1107902A (en) |
DE (1) | DE4339320A1 (en) |
FR (1) | FR2712607B1 (en) |
GB (1) | GB2283983B (en) |
HK (1) | HK1001095A1 (en) |
IT (1) | IT1276359B1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110042425A (en) * | 2019-04-23 | 2019-07-23 | 博罗县华盈科技有限公司 | A kind of heavy process for copper of alkaline etching waste liquid for producing direct electrowinning |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3783113A (en) * | 1971-10-12 | 1974-01-01 | Shipley Co | Electrolytic regeneration of spent etchant |
EP0448870A1 (en) * | 1990-03-21 | 1991-10-02 | Macdermid Incorporated | System and process for etching with, and regenerating, alkaline ammoniacal etchant solution |
WO1992001086A1 (en) * | 1990-07-05 | 1992-01-23 | Elo-Chem Ätztechnik Gmbh | Etching solution |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1294804A (en) * | 1970-07-24 | 1972-11-01 | Shipley Co | Etchant for cupreous metals |
DE2216269A1 (en) * | 1972-04-05 | 1973-10-18 | Hoellmueller Maschbau H | METHOD OF ETCHING COPPER AND COPPER ALLOYS |
DE3305319A1 (en) * | 1983-02-16 | 1984-08-16 | Siemens AG, 1000 Berlin und 8000 München | Electrolytic full regeneration process for an ammoniacal etching solution |
DE4218843C2 (en) * | 1991-11-09 | 1994-04-28 | Hoellmueller Maschbau H | Process for the regeneration of an ammoniacal etchant and device for carrying out this process |
WO1993009267A1 (en) * | 1991-11-09 | 1993-05-13 | Hans Höllmüller Maschinenbau GmbH & Co. | Process for regenerating an ammoniacal etching agent and device for implementing it |
-
1993
- 1993-11-18 DE DE4339320A patent/DE4339320A1/en not_active Ceased
-
1994
- 1994-11-10 GB GB9422669A patent/GB2283983B/en not_active Expired - Fee Related
- 1994-11-17 JP JP6283829A patent/JPH07197300A/en active Pending
- 1994-11-17 FR FR9413991A patent/FR2712607B1/en not_active Expired - Fee Related
- 1994-11-17 IT IT94BO000512A patent/IT1276359B1/en active IP Right Grant
- 1994-11-17 CN CN94120116.3A patent/CN1107902A/en active Pending
-
1997
- 1997-12-31 HK HK97102708A patent/HK1001095A1/en not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3783113A (en) * | 1971-10-12 | 1974-01-01 | Shipley Co | Electrolytic regeneration of spent etchant |
EP0448870A1 (en) * | 1990-03-21 | 1991-10-02 | Macdermid Incorporated | System and process for etching with, and regenerating, alkaline ammoniacal etchant solution |
WO1992001086A1 (en) * | 1990-07-05 | 1992-01-23 | Elo-Chem Ätztechnik Gmbh | Etching solution |
Also Published As
Publication number | Publication date |
---|---|
FR2712607A1 (en) | 1995-05-24 |
ITBO940512A0 (en) | 1994-11-17 |
DE4339320A1 (en) | 1995-05-24 |
HK1001095A1 (en) | 1998-05-22 |
CN1107902A (en) | 1995-09-06 |
ITBO940512A1 (en) | 1996-05-17 |
GB9422669D0 (en) | 1995-01-04 |
JPH07197300A (en) | 1995-08-01 |
FR2712607B1 (en) | 1997-06-20 |
GB2283983B (en) | 1997-07-02 |
IT1276359B1 (en) | 1997-10-30 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19981110 |