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WO1989006639A1 - Procede et appareil de regeneration de solutions d'attaque au permanganate alkalin - Google Patents

Procede et appareil de regeneration de solutions d'attaque au permanganate alkalin Download PDF

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Publication number
WO1989006639A1
WO1989006639A1 PCT/US1989/000169 US8900169W WO8906639A1 WO 1989006639 A1 WO1989006639 A1 WO 1989006639A1 US 8900169 W US8900169 W US 8900169W WO 8906639 A1 WO8906639 A1 WO 8906639A1
Authority
WO
WIPO (PCT)
Prior art keywords
permanganate
solution
anode
anions
cathode
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.)
Ceased
Application number
PCT/US1989/000169
Other languages
English (en)
Inventor
John Fakler
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.)
Circuit Chemistry Corp
Original Assignee
Circuit Chemistry Corp
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 Circuit Chemistry Corp filed Critical Circuit Chemistry Corp
Publication of WO1989006639A1 publication Critical patent/WO1989006639A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/36—Regeneration of waste pickling liquors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Complex oxides containing manganese and at least one other metal element
    • C01G45/1207—Permanganates ([MnO4)-] or manganates ([MnO4)2-]
    • C01G45/1214—Permanganates ([MnO4)-] or manganates ([MnO4)2-] containing alkali metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/28—Per-compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0011—Working of insulating substrates or insulating layers
    • H05K3/0055—After-treatment, e.g. cleaning or desmearing of holes

Definitions

  • compositions for chemically polishing stainless steel are aqueous solutions containing alkali metal hydroxides, and alkali metal permanganate. Typical solutions contain 3.9% NaOH, 3.2% KMn0 4 and 9.6% Na 2 C0 3 .
  • U.S. Patent No. 3,489,625 discloses acid pickling of carbon steel, followed by treatment with an alkaline permanganate solution.
  • U.S. Patent No. 3,506,397 discloses the treatment of ABS plastic with a composition containing phosphoric acid and sodium permanganate.
  • U.S. Patent No. 3,833,414 discloses a method for removing aluminized coatings from metal by treating the metal with a mixed acid solution followed by treatment with an alkaline permanganate solution and then a second treatment in mixed acid.
  • the alkaline permanganate solution contains 8-11% NaOH, 8-11% Na 2 C0 3 , and 4-6% KMn0 4 .
  • U.S. Patent No. 4,294,651 discloses the etching of a semiconductor substrate with a composition containing a fluorine compound, an oxidizing agent such as KMn0 4 , and an alkali metal hydroxide.
  • the solution contains 7-38 of a fluorine compound, 2.5-7% KMn0 4 , and 1-10% KOH.
  • U.S. Patent No. 4,430,154 discloses a method for removing an adhesive medium from printed circuit boards without corroding the base material by treating the board with an alkaline permanganate solution.
  • the alkaline permanganate solution contains 5% KMn0 4 and 5% NaOH.
  • U.S. Patent No. 3,625,758 discloses permanganate as an oxidizing agent used in the manufacturing of printed circuit boards. No specific examples regarding the composition of the permanganate solution are provided.
  • U.S. Patent Nos. 4,042,729; 4,054,693? and 4,073,740 relate to treating resinous surfaces with a solution of manganate and permanganate where the molar ratio of manganate to permanganate is up to 1-1.2, and the pH of the solution is 11-13.
  • U.S. Patent No. 4,425,380 discloses a process for removing resin smear (desmear) from an interior wall of a hole in a resinous substrate.
  • the process involves contacting the substrate with an alkaline permanganate solution having a pH of 11-13, at an elevated temperature.
  • the permanganate used is any metal salt which is stable and soluble in water to lOg/1.
  • the upper practical limit of solubility for the permanganate salt is set at 60g/l.
  • U.S. Patent No. 4,592,929 discloses a process for the metalization of plastic using an oxidizing solution as a pretreatment.
  • solution contains 4% KMn0 4 , 3% NaOH, and 0.05% surfactant.
  • 4,698,124 discloses a method for regenerating spent permanganate ions in alkaline permanganate solutions by adding a combination of inorganic oxidizing agents to oxidize Mn0 4 ⁇ 2 to Mn0 4 -1 .
  • the preferred embodiment contains a mixture of inorganic peroxydisulfate and inorganic hypochlorite.
  • the present invention overcomes the deficiencies of the prior art in that electrochemical oxidation can be utilized to oxidize non-permanganate manganese species in permanganate etching solutions, thereby eliminating the necessity of replenishing or replacing the bath.
  • This regeneration technique makes permanganate etching solutions much more practical and economical to operate, and does not contaminate the solution with potentially harmful by-products from the regeneration process or with extrinsic oxidizing agents.
  • FIG. 1 illustrates a perspective view of apparatus for performing the method of the invention.
  • the permanganate solution used according to the invention contains alkali metal hydroxide in an amount of about 0.1%-9.0% by weight. It also contains 1.0% by weight, or more, of a soluble, stable permanganate salt such as sodium, potassium permanganate, or a like alkali metal salt.
  • the preferred solution has a pH of 13 or above and contains Mn0 4 ions.
  • the Mn0 4 ""1 anions to the sum of the Mn0 4 -1 and Mn0 4 ⁇ 2 anions is about 1/0.65. It will be apparent in view of this disclosure that the configuration and composition of the anode cathode pair can be of any like structure for the success of the electrochemical regeneration of permanganate.
  • the cell voltage is a function of the relative cathode surface area, the extent of electrode shielding, the distance between the electrodes, the conductivity of the electrode materials, or the presence of a membrane around an electrode.
  • the above solution was then recirculated through an anode cathode pair for electrochemical oxidation with an anode-cathode potential of 4.0 volts DC.
  • the anode was stainless steel wire mesh in the shape of a cylinder, and the cathode was a solid copper rod.
  • the anode surface area was approximately 30 times greater than the cathode surface area.
  • FIG. 1 illustrates a perspective view of a manganate regenerator 10. It contains an anode 11, anode connector bars 12 and 14, and a cathode 16 in a tank 18, which has an inlet 20, an outlet 22 and a cover 24 with vent holes 26a-26n. Holes 28, 30 and 32 in the cover 24 accommodate anode connector bars 14 and 12 and the cathode 16, respectively, by sliding over the upper ends of the anode connector bars 14 and 12 and the cathode. The wires from the DC source 28, of course, would be connected to the anode connector bars 14 and 12 and the cathode 16 after the cover 24 is fitted over the anode connector bars 14 and 12 and the cathode 16.
  • the anode 11 can be a 316 stainless steel screen about 26" high and 9" in diameter, and the cathode 16 can be copper, 26" high and 1 1/4" in diameter.
  • a DC current source 28 can supply 0-8 volts at 1-100 amps by way of example and for purposes of illustration only and is not to be construed as limiting of the present invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

Le procédé et l'appareil décrits servent à régénérer les espèces de manganèse sans permanganate contenues dans des solutions d'attaque au permanganate de cartes de circuits imprimés. Ledit appareil comprend un réservoir (18), une anode (11), une cathode (16) et un organe redresseur (28). On régénère la solution d'attaque en plaçant la solution en contact avec la paire d'anode et de cathode (11, 16) à un potentiel tel que les espèces de manganèse sans permanganate sont oxydées et transformées en permanganate au niveau de l'anode (11), pendant que celle-ci se trouve dans la solution.
PCT/US1989/000169 1988-01-19 1989-01-13 Procede et appareil de regeneration de solutions d'attaque au permanganate alkalin Ceased WO1989006639A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US14496388A 1988-01-19 1988-01-19
US144,963 1988-01-19

Publications (1)

Publication Number Publication Date
WO1989006639A1 true WO1989006639A1 (fr) 1989-07-27

Family

ID=22510972

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1989/000169 Ceased WO1989006639A1 (fr) 1988-01-19 1989-01-13 Procede et appareil de regeneration de solutions d'attaque au permanganate alkalin

Country Status (1)

Country Link
WO (1) WO1989006639A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5660712A (en) * 1995-06-07 1997-08-26 Carus, Iii; Paul Electrolytic production of potassium permanganate using a cationic membrane in an electrolytic cell
CN110438506A (zh) * 2019-07-08 2019-11-12 深圳市裕展精密科技有限公司 退镀液的再生制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1281085A (en) * 1917-06-14 1918-10-08 Armour Fertilizing Works Process of making permanganates.
US2908620A (en) * 1957-01-09 1959-10-13 Carus Chemical Company Production of potassium permanganate
US3470044A (en) * 1965-04-28 1969-09-30 Fmc Corp Electrolytic regeneration of spent ammonium persulfate etchants
US3843504A (en) * 1972-08-16 1974-10-22 Western Electric Co Method of continuously regenerating and recycling a spent etching solution
US3986941A (en) * 1974-07-12 1976-10-19 Nippon Chemical Industrial Co., Ltd. Process for the production of alkali permanganate
US4698124A (en) * 1985-05-31 1987-10-06 Morton Thiokol, Inc. Method of regenerating permanganate etch bath

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1281085A (en) * 1917-06-14 1918-10-08 Armour Fertilizing Works Process of making permanganates.
US2908620A (en) * 1957-01-09 1959-10-13 Carus Chemical Company Production of potassium permanganate
US3470044A (en) * 1965-04-28 1969-09-30 Fmc Corp Electrolytic regeneration of spent ammonium persulfate etchants
US3843504A (en) * 1972-08-16 1974-10-22 Western Electric Co Method of continuously regenerating and recycling a spent etching solution
US3986941A (en) * 1974-07-12 1976-10-19 Nippon Chemical Industrial Co., Ltd. Process for the production of alkali permanganate
US4698124A (en) * 1985-05-31 1987-10-06 Morton Thiokol, Inc. Method of regenerating permanganate etch bath

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5660712A (en) * 1995-06-07 1997-08-26 Carus, Iii; Paul Electrolytic production of potassium permanganate using a cationic membrane in an electrolytic cell
CN110438506A (zh) * 2019-07-08 2019-11-12 深圳市裕展精密科技有限公司 退镀液的再生制备方法

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