WO2014077957A1 - Electrolytic generation of manganese (iii) ions in strong sulfuric acid - Google Patents
Electrolytic generation of manganese (iii) ions in strong sulfuric acid Download PDFInfo
- Publication number
- WO2014077957A1 WO2014077957A1 PCT/US2013/061860 US2013061860W WO2014077957A1 WO 2014077957 A1 WO2014077957 A1 WO 2014077957A1 US 2013061860 W US2013061860 W US 2013061860W WO 2014077957 A1 WO2014077957 A1 WO 2014077957A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- manganese
- solution
- ions
- anode
- cathode
- Prior art date
Links
Classifications
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/042—Electrodes formed of a single material
- C25B11/043—Carbon, e.g. diamond or graphene
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
- C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
-
- 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
- C25B1/21—Manganese oxides
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
Definitions
- the present invention relates generally to a process of electrolytically generating manganese(III) ions in strong sulfuric acid using an improved anode.
- non-conductive substrates i.e. plastics
- Plastic moldings are relatively inexpensive to produce and metal plated plastic is used for many applications.
- metal plated plastics are used for decoration and for the fabrication of electronic devices.
- An example of a decorative use includes automobile parts such as trim.
- Examples of electronic uses include printed circuits, wherein metal plated in a selective pattern comprises the conductors of the printed circuit board, and metal plated plastics used for EMI shielding.
- ABS resins are the most commonly plated plastics for decorative purposes while phenolic and epoxy resins are the most commonly plated plastics for the fabrication of printed circuit boards.
- Plating on plastic surfaces is used in the production of a variety of consumer items.
- Plastic moldings are relatively inexpensive to produce and plated plastic is used for many applications, including automotive trim.
- ABS acrylonitrile/butadiene/styrene
- ABS/PC polycarbonate
- chromic acid is a recognized carcinogen and is increasingly regulated, insisting that wherever possible, the use of chromic acid is replaced with safer alternatives.
- the use of a chromic acid etchant also has well-known and serious drawbacks, including the toxicity of chromium compounds which makes their disposal difficult, chromic acid residues remaining on the polymer surface that inhibit electroless deposition, and the difficulty of rinsing chromic acid residues from the polymer surface following treatment.
- hot hexavalent chromium sulfuric acid solutions are naturally hazardous to workers. Burns and upper respiratory bleeding are common in workers routinely involved with these chrome etch solutions.
- Permanganate solutions are also described in U.S. Pat. No. 3,625,758 to Stahl et al., which is herein incorporated by reference in its entirety. Stahl suggests the suitability of either a chrome and sulfuric acid bath or a permanganate solution for preparing the surface.
- U.S. Pat. No. 4,948,630 to Courduvelis et al. which is herein incorporated by reference in its entirety, describes a hot alkaline permanganate solution that also contains a material, such as sodium hypochlorite, that has an oxidation potential higher than the oxidation potential of the permanganate solution and is capable of oxidizing manganate ions to permanganate ions.
- etching solutions have been suggested as a replacement for chromic acid in processes for preparing non-conductive substrates for metallization.
- none of these processes have proven satisfactory for various economic, performance and/or environmental reasons and thus none of these processes have achieved commercial success or been accepted by the industry as a suitable replacement for chromic acid etching.
- the stability of the etching solutions may also be poor, resulting in the formation of manganese dioxide sludge.
- the tendency for permanganate based solutions to form sludge and undergo self- decomposition has been noted by the inventors here.
- permanganate ions can react with hydrogen ions to produce manganese (II) ions and water according to the following reaction: 4Mn0 4 " + 12-H + ⁇ 4Mn 2+ + 6H 2 0 + 50 2 (1 )
- the manganese (II) ions formed by this reaction can then undergo further reaction with permanganate ions forming a sludge of manganese dioxide according to the following reaction:
- the present invention relates generally to an electrode suitable for the electrochemical oxidation of manganese (II) ions to manganese (III) ions in a strong sulfuric acid solution.
- the present invention relates generally to an electrolytic cell comprising:
- an electrolyte solution comprising manganese(III) ions in a solution of acid, which is preferably from 9 to 15 molar sulfuric acid;
- the present invention relates generally to a method of electrochemical oxidation of manganese (II) ions to manganese (III) ions comprising the steps of:
- an electrolyte comprising a solution of manganese (II) ions in a solution of acid, which is preferably from 9 to 15 molar sulfuric acid, in an electrolytic cell wherein the electrolytic cell comprises an anode and a cathode; and
- trivalent manganese can readily be produced by electrolysis at low current density of divalent manganese ions in strong sulfuric acid. More particularly, the inventors of the present invention have discovered that a solution of trivalent manganese ions in strongly acidic solution is capable of etching ABS.
- Trivalent manganese is unstable and is highly oxidizing (standard redox potential of 1.51 versus normal hydrogen electrode). In solution, it very rapidly disproportionates to manganese dioxide and divalent manganese via the following reaction:
- the present invention relates generally to a method of preparing a solution capable of etching a plastic substrate, the method comprising the steps of:
- an electrolyte comprising a solution of manganese (II) ions in a solution of acid in an electrolytic cell, wherein the electrolytic cell comprises an anode and a cathode;
- the plastic substrate comprises ABS or ABS/PC.
- the acid is sulfuric acid.
- the half life of the manganese (III) ions in 7M sulfuric acid is on of the order of 2 years.
- the half life of similar concentrations of manganese (III) ions in 7M phosphoric acid was around 12 days. It is suggested that the much higher stability of the manganese (III) ions in sulfuric acid is due to the formation of mangano-sulfate complexes and the higher concentration of available hydrogen ion concentration in the sulfuric acid solution.
- a further problem with the use of phosphoric acid is the limited solubility of manganese (III) phosphate.
- inorganic acids such as phosphoric acid
- sulfuric acid it is generally preferred to use sulfuric acid.
- the remarkable stability of manganese (III) ions in strong sulfuric acid provides the following advantages in use: 1) Because the Mn(III) ions are formed at a low current density, the power requirements for the process are typically very low.
- the etchant Because of the high stability of the Mn(III) ions in strong sulfuric acid, the etchant can be sold ready for use. In production, the etchant requires only a small regeneration cell at the side of the tank in order to maintain the Mn(III) content of the etch and prevent the build-up of Mn(II) ions.
- the acid is sulfuric acid.
- the concentration of sulfuric acid is preferably between about 9 and about 15 molar.
- the concentration of sulfuric acid is important in the process. Below a concentration of about 9 molar, the rate of etch becomes slow and above about 14 molar, the solubility of manganese ions in the solution becomes low. Additionally, very high concentrations of sulfuric acid tend to absorb moisture from the air and are hazardous to handle. Thus, in a most preferred embodiment, the concentration of sulfuric acid is between about 12 and 13 molar, which is dilute enough to allow the safe addition of water to the etch and strong enough to optimize the etch rate of the plastic.
- the concentration of manganese ions in solution should be as high as it is feasible to achieve.
- the manganese(II) ions are preferably selected from the group consisting of manganese sulfate, manganese carbonate and manganese hydroxide although other similar sources of manganese(II) ions known in the art would also be usable in the practice of the invention.
- the concentration of manganese(II) ions may be in the range of between about 0.005 molar and saturation.
- the electrolyte also comprises colloidal manganese dioxide. This may form to some extent as a natural result of disproportionation of manganese (III) in solution, or may be added deliberately.
- Manganese (III) ions can be conveniently generated by electrochemical means by the oxidation of manganese (II) ions. In addition, it is generally preferable that the electrolyte not contain any permanganate ions.
- the present invention comprises immersing the platable plastic in the metastable sulfate complex for a period of time to etch the surface of the platable plastic.
- the platable plastic is immersed in the solution at a temperature of between 30 and 80°C.
- the rate of etching increases with temperature and is slow below 50°C.
- the upper limit of temperature is determined by the nature of the plastic being etched. ABS begins to distort above 70°C, thus in a preferred embodiment the temperature of the electrolyte is maintained between about 50 and about 70°C, especially when etching ABS materials.
- the time period of the immersion of the plastic in the electrolyte is preferably between about 20 to about 30 minutes.
- Articles etched in this manner may be subsequently electroplated using conventional pretreatment for plated plastics or the etched surface of the plastic could be used to enhance the adhesion of paint, lacquers or other surface coatings.
- the inventors of the present invention have determined by means of cyclic voltammetry that at the concentration of manganese (II) ions used in the etch of this invention, the oxidation is diffusion , controlled so efficient agitation of the etch solution is necessary during the electrolytic oxidation process.
- II manganese
- the present invention relates generally to an electrolyte capable of etching a platable plastic, the electrolyte comprising a solution of manganese(III) in an acid solution.
- the acid solution is preferably sulfuric acid.
- the anodes and cathodes usable in the electrolytic cell described herein may comprise various materials.
- the cathode may comprise a material selected from the group consisting of platinum, platinized titanium, niobium, iridium oxide coated titanium, and lead.
- the cathode comprises platinum or platinized titanium.
- the cathode comprises lead.
- the anode may also comprise platinized titanium, platinum, iridium/tantalum oxide, niobium, or any other suitable material and is preferably platinum or platinized titanium.
- the inventors of the present invention have found that the anode may comprise vitreous carbon and that the use of vitreous carbon anodes provides a commercially suitable electrode.
- the inventors discovered that while the combination of manganese (III) ions and strong sulfuric acid (i.e., 9-15 molar) can etch ABS plastic, the etchant is also very aggressive towards the electrodes necessary to produce the manganese (III) ions.
- anodes having a titanium substrate may be rapidly degraded by the etchant.
- vitreous carbon and reticulated vitreous carbon were determined to be more robust and could produce manganese (HI) ions when an electrical current, preferably of between 0.1 and 0.4 A/dm (based on the nominal surface area), was applied.
- anodes made of vitreous carbon may be used as an electrode.
- vitreous carbon and reticulated vitreous carbon may not be cost- effective for use as the electrode in commercial applications, it was further determined that the anode may be manufactured from woven carbon fiber.
- Carbon fiber is manufactured from fibers of polyacrylonitrile (PAN). These fibers go through a process of oxidation at increasing temperatures followed by a carbonization step at a very higher temperature in an inert atmosphere. The carbon fibers are then woven into a sheet which is typically used in combination with various resin systems to produce high strength components. Carbon fiber sheets also have good electrical conductivity and the fibers typically have a turbostratic (i.e., disordered layer) structure. Without wishing to be bound by theory, the inventors of the present invention believe that it is this structure which makes the carbon fibers so effective as an electrode. The SP 2 hybridized carbon atoms in the lattice give good electrical conductivity while the SP 3 hybridized carbon atoms link the graphitic layers together, locking them in place and thus providing good chemical resistance.
- PAN polyacrylonitrile
- a preferred material for use in the electrodes of the invention comprises a woven carbon fiber containing at least 95% carbon and not impregnated with any resin.
- carbon fibers are typically sized with an epoxy resin and this may comprise up to 2% of the fiber weight.
- the epoxy sizing is rapidly removed by the high sulfuric acid content of the etch. This may cause an initial slight discoloration of the etch, but does not affect the performance.
- the anode appears to be resistant to the electrolyte and is effective at oxidizing manganese (II) ions to manganese (III).
- Anodes can be constructed by mounting the woven carbon fiber material in a suitable frame with a provision made for electrical contact. It is also possible to use carbon fiber as a cathode in the generation of manganese (III) ions, but it is more convenient to use lead, particularly as the cathode is much smaller than the anode if an undivided cell is used.
- the cathode can be immersed directly in the electrolyte and it is not necessary to have a divided cell (although the process would work with a divided cell arrangement, this would introduce unnecessary complexity and expense).
- the present invention also relates generally to an electrolytic cell comprising:
- anode in contact with the electrolyte solution, wherein the anode comprises a material selected from the group consisting of vitreous carbon, reticulated vitreous carbon, woven carbon fibers, and combinations of one or more of the foregoing.
- a solution of 0.08 molar of manganese(II) sulfate inl 2.5 molar sulfuric acid (500 ml) was heated to 70°C and a piece of platable grade ABS was immersed in the solution. Even after an hour immersed in this solution, there was no discernible etching of the test panel and upon rinsing, the surface was not "wetted" and would not support an unbroken film of water.
- Comparative Example 1 The solution of Comparative Example 1 was electrolyzed by immersing a platinized titanium anode of an area of 1 dm 2 and a platinized titanium cathode of surface area 0.01 dm 2 in the solution and applying a current of 200 mA for 5 hours.
- This solution was then heated to 70°C and a piece of platable grade ABS was immersed in the solution. After 10 minutes of immersion, the test piece was fully wetted and would support an unbroken film of water after rinsing. After 20 minutes of immersion, the sample was rinsed in water, dried and examined using a scanning electron microscope (SEM). This examination revealed that the test piece was substantially etched and many etch pits were visible.
- SEM scanning electron microscope
- a solution containing 12.5 M of sulfuric acid and 0.08 M manganese (II) sulfate was electrolyzed using a platinized titanium anode at a current density of 0.2 A/dm 2 .
- a platinized titanium cathode having an area of less than 1 % of the anode area was used in order to prevent cathodic reduction of the Mn(III) ions produced at the anode.
- the electrolysis was performed for long enough for sufficient coulombs to be passed to oxidize all of the manganese (II) ions to manganese (III).
- the resulting solution was a deep cherry purple/red color. There were no permanganate ions generated during this step. This was also confirmed by visible spectroscopy - the Mn(III) ions produced a completely different absorption spectrum from that of a solution of permanganate.
- test coupons of ABS were immersed in the solution for time periods of 20 and 30 minutes. Some of these test coupons were examined by SEM and some were processed in a normal plating on plastic pretreatment sequence (reduction in M-neutralize, predip, activate, accelerate, electroless nickel, copper plate to 25- 30 microns). These test coupons were then annealed and subjected to peel strength testing using an Instron machine.
- Cyclic voltammograms were obtained from a solution containing 12.5M sulfuric acid and 0.08M manganese sulfate using a platinum rotating disk electrode (RDE) having a surface area of 0.196 cm 2 at various rotation speeds.
- RDE platinum rotating disk electrode
- a model 263 A potentiostat and a silver/silver chloride reference electrode were used in conjunction with the RDE.
- the forward scan showed a peak at around 1 .6V vs. Ag/AgCl followed by a plateau up to around 1.75V followed by and increase in current.
- the reverse scan produced a similar plateau (at a slightly lower current and a peak around 1 .52V.
- the dependence of these results on the rate of electrode rotation indicates mass transport control is a primary factor in the mechanism.
- the plateau indicates the potential range over which Mn(III) ions are formed by electrochemical oxidation.
- a polentiostatic scan was performed at 1.7V. It was observed that the current initially dropped and then over a period of time increased. The current density at this potential varied between 0.15 and 0.4 A/dm 2 . Following this experiment, a galvanostatic measurement was taken at a constant current density of 0.3 A/dm 2 . Initially, the applied current density was achieved by a potential of about 1 .5V but as the experiment progressed, after about 2400 seconds, and increase in potential to about 1 .75V was observed.
- An electrode comprising graphite and having a nominal measured surface area of 1 dm 2 was immersed in 500 mL of a solution containing 0.08 M of manganese sulfate in 12.5 M sulfuric acid at a temperature of 65°C.
- the cathode in this cell was a piece of lead having a nominal measured surface area of 0.1 dm 2 .
- a current of 0.25 amps was applied to the cell, giving a nominal anode current density of 0.25 A dm 2 and a nominal cathode current density of 2.5 A/ dm 2 .
- An electrode comprising a titanium substrate coating with a mixed tantalum/iridium oxide coating (50% tantalum oxide, 50% iridium oxide) and having a nominal measured surface area of 1 dm 2 was immersed in 500 mL of a solution containing 0.08 M of manganese sulfate in 12.5 M sulfuric acid at a temperature of 65"C.
- the cathode in this cell was a piece of lead having a nominal measured surface are of 0. 1 dm " .
- a current of 0.25 amps was applied to the cell giving a nominal anode current density of 0.25 A/dm and a nominal cathode current density of 2.5 A/dm " .
- An electrode comprising a titanium substrate coated with platinum and having a nominal measured surface area of 1 dm 2 was immersed in 500 mL of a solution containing 0.08 M of manganese sulfate in 12.5 M sulfuric acid at a temperature of 65°C.
- the cathode in this cell was a piece of lead having a nominal measured surface area of 0.1 dm 2 .
- a current of 0.25 amps was applied to the cell giving a nominal anode current density of 0.25 A dm 2 and a nominal cathode current density of 2.5 A/dm 2 .
- An electrode comprising vitreous carbon and having a nominal measured surface area of 0.125 dm2 was immersed in 100 mL of a solution containing 0.08 M of manganese sulfate in 12.5 M sulfuric acid at a temperature of 65°C.
- the cathode in this cell was a piece of platinum wire having a nominal measured surface area of 0.0125 dm 2 .
- a current of 0.031 amps was applied to the cell giving a nominal anode current density of 0.25 A/dm 2 and a nominal cathode current density of 2.5 A/dm 2 . It was observed that manganese (III) was rapidly formed in the solution and the resulting solution was capable of etching ABS plastic and producing good adhesion upon subsequently electroplating the treated plastic.
- the electrode appeared unaffected by periods of extended electrolysis.
- An electrode comprising a piece of woven carbon fiber (Panex 35 50K Tow with epoxy sizing at 1.5%, available from the Zoltek Corporation) was mounted in a plastic frame constructed of polyvinylidenefluoride (PVDF).
- the electrode having a nominal measured area of 1 dm 2 , was immersed in 500 niL of a solution containing 0.08 M of manganese sulfate in 12.5 M sulfuric acid at a temperature of 65°C.
- the cathode in this cell was a piece of lead having a nominal measured surface area of 0.1 dm 2 .
- a current of 0.25 amps was applied to the cell, giving a nominal anode current density of 0.25 A/ dm 2 and a nominal cathode current density of 2.5 A/dm 2 .
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Chemically Coating (AREA)
- Electroplating Methods And Accessories (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020157015762A KR101950169B1 (en) | 2012-11-15 | 2013-09-26 | Electrolytic generation of manganese (ⅲ) ions in strong sulfuric acid |
CN201380059513.3A CN104838044B (en) | 2012-11-15 | 2013-09-26 | Electrolysis produces manganese (III) ion in strength sulfuric acid |
CA2889342A CA2889342C (en) | 2012-11-15 | 2013-09-26 | Electrolytic generation of manganese (iii) ions in strong sulfuric acid |
MX2015006178A MX2015006178A (en) | 2012-11-15 | 2013-09-26 | Electrolytic generation of manganese (iii) ions in strong sulfuric acid. |
EP13854930.8A EP2920341B1 (en) | 2012-11-15 | 2013-09-26 | Electrolytic generation of manganese (iii) ions in strong sulfuric acid |
PL13854930T PL2920341T3 (en) | 2012-11-15 | 2013-09-26 | Electrolytic generation of manganese (iii) ions in strong sulfuric acid |
JP2015543041A JP6060270B2 (en) | 2012-11-15 | 2013-09-26 | Electrolytic production of manganese (III) ions in concentrated sulfuric acid |
ES13854930T ES2704672T3 (en) | 2012-11-15 | 2013-09-26 | Electrolytic generation of manganese (III) ions in strong sulfuric acid |
KR1020177008782A KR20170039315A (en) | 2012-11-15 | 2013-09-26 | Electrolytic generation of manganese (ⅲ) ions in strong sulfuric acid |
BR112015011123-8A BR112015011123B1 (en) | 2012-11-15 | 2013-09-26 | METHOD OF ELECTROCHEMICAL OXIDATION FROM MANGANESE IONS (II) TO MANGANESE IONS (III) |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/677,798 | 2012-11-15 | ||
US13/677,798 US9752241B2 (en) | 2012-01-23 | 2012-11-15 | Electrolytic generation of manganese (III) ions in strong sulfuric acid using an improved anode |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014077957A1 true WO2014077957A1 (en) | 2014-05-22 |
Family
ID=50731593
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2013/061860 WO2014077957A1 (en) | 2012-11-15 | 2013-09-26 | Electrolytic generation of manganese (iii) ions in strong sulfuric acid |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP2920341B1 (en) |
JP (1) | JP6060270B2 (en) |
KR (2) | KR20170039315A (en) |
CN (1) | CN104838044B (en) |
BR (1) | BR112015011123B1 (en) |
CA (2) | CA2889342C (en) |
ES (1) | ES2704672T3 (en) |
MX (1) | MX2015006178A (en) |
PL (1) | PL2920341T3 (en) |
TR (1) | TR201900116T4 (en) |
TW (1) | TWI500582B (en) |
WO (1) | WO2014077957A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107078291A (en) * | 2014-08-28 | 2017-08-18 | 英克罗恩有限公司 | Crystalline transitional oxide particle and the continuation method for preparing the crystalline transitional oxide particle |
US11047052B2 (en) | 2014-07-10 | 2021-06-29 | Okuno Chemical Industries Co., Ltd. | Resin plating method |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2745071T3 (en) * | 2013-03-12 | 2020-02-27 | Macdermid Acumen Inc | Electrolytic generation of manganese (III) ions in strong sulfuric acid |
US10889905B2 (en) * | 2018-12-11 | 2021-01-12 | Rohm And Haas Electronic Materials Llc | Methods of generating manganese (III) ions in mixed aqueous acid solutions using ozone |
Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3625758A (en) | 1966-02-22 | 1971-12-07 | Photocircuits Corp | Base material and method for the manufacture of printed circuits |
US4042729A (en) | 1972-12-13 | 1977-08-16 | Kollmorgen Technologies Corporation | Process for the activation of resinous bodies for adherent metallization |
US4279705A (en) * | 1980-02-19 | 1981-07-21 | Kerr-Mcgee Corporation | Process for oxidizing a metal of variable valence by constant current electrolysis |
US4544450A (en) * | 1980-07-15 | 1985-10-01 | Anic S.P.A. | Electrochemical process for the synthesis of organic compounds |
US4610895A (en) | 1984-02-01 | 1986-09-09 | Shipley Company Inc. | Process for metallizing plastics |
US4948630A (en) | 1984-06-07 | 1990-08-14 | Enthone, Inc. | Three step process for treating plastics with alkaline permanganate solutions |
US5160600A (en) * | 1990-03-05 | 1992-11-03 | Patel Gordhanbai N | Chromic acid free etching of polymers for electroless plating |
US5213665A (en) * | 1988-02-29 | 1993-05-25 | Nippon Shokubai Kagaku Kogyo, Co., Ltd. | Process for producing 1-aminoanthraquinones |
US5648125A (en) | 1995-11-16 | 1997-07-15 | Cane; Frank N. | Electroless plating process for the manufacture of printed circuit boards |
EP0890566A1 (en) * | 1997-07-08 | 1999-01-13 | Ciba SC Holding AG | Oxidation process for the production of a chlorobenzaldehyde |
US20040074780A1 (en) * | 2002-10-18 | 2004-04-22 | Aker Kvaerner Canada Inc. | Mediated hydrohalic acid electrolysis |
US20050019958A1 (en) | 2000-10-16 | 2005-01-27 | Sui-Po Zhang | Ligand binding assays for vanilloid receptors |
US20080193847A1 (en) * | 2007-02-14 | 2008-08-14 | Tosoh Corporation | Electrolytic manganese dioxide, and method for its production and its application |
WO2009023628A2 (en) | 2007-08-10 | 2009-02-19 | Enthone Inc. | Chromium-free pickle for plastic surfaces |
US20090092757A1 (en) | 2006-04-18 | 2009-04-09 | Okuno Chemical Industries Co., Ltd. | Composition for etching treatment of resin molded article |
US20110189590A1 (en) * | 2010-01-29 | 2011-08-04 | Eveready Battery Company, Inc. | Method of Making an Electrochemical Cell with a Catalytic Electrode Including Manganese Dioxide |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3065155A (en) * | 1960-09-02 | 1962-11-20 | Manganese Chemicals Corp | Electrolytic manganese dioxide process |
IT1159931B (en) * | 1978-10-13 | 1987-03-04 | Oronzio De Nora Impianti | INDUSTRIAL PROCEDURE FOR THE PRODUCTION OF TITANIUM DIOXIDE FROM ILMENITE |
JPS58502027A (en) * | 1981-11-23 | 1983-11-24 | バロ−ス・コ−ポレ−ション | Peripherals adapted to monitor low data rate serial input/output interfaces |
JPS6447890A (en) * | 1987-08-13 | 1989-02-22 | Kenzo Yamaguchi | Electrolytic synthesis method |
US4936970A (en) * | 1988-11-14 | 1990-06-26 | Ebonex Technologies, Inc. | Redox reactions in an electrochemical cell including an electrode comprising Magneli phase titanium oxide |
JP2010121143A (en) * | 2008-11-17 | 2010-06-03 | Okuno Chem Ind Co Ltd | Post-processing agent of etching for resin-formed body, post-processing method using the same, and plating method for resin-formed body |
US10260000B2 (en) * | 2012-01-23 | 2019-04-16 | Macdermid Acumen, Inc. | Etching of plastic using acidic solutions containing trivalent manganese |
-
2013
- 2013-09-26 PL PL13854930T patent/PL2920341T3/en unknown
- 2013-09-26 WO PCT/US2013/061860 patent/WO2014077957A1/en active Application Filing
- 2013-09-26 ES ES13854930T patent/ES2704672T3/en active Active
- 2013-09-26 JP JP2015543041A patent/JP6060270B2/en active Active
- 2013-09-26 MX MX2015006178A patent/MX2015006178A/en unknown
- 2013-09-26 TR TR2019/00116T patent/TR201900116T4/en unknown
- 2013-09-26 BR BR112015011123-8A patent/BR112015011123B1/en active IP Right Grant
- 2013-09-26 KR KR1020177008782A patent/KR20170039315A/en not_active Application Discontinuation
- 2013-09-26 EP EP13854930.8A patent/EP2920341B1/en active Active
- 2013-09-26 CA CA2889342A patent/CA2889342C/en active Active
- 2013-09-26 CA CA3056665A patent/CA3056665A1/en not_active Abandoned
- 2013-09-26 CN CN201380059513.3A patent/CN104838044B/en active Active
- 2013-09-26 KR KR1020157015762A patent/KR101950169B1/en active IP Right Grant
- 2013-11-11 TW TW102140858A patent/TWI500582B/en active
Patent Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3625758A (en) | 1966-02-22 | 1971-12-07 | Photocircuits Corp | Base material and method for the manufacture of printed circuits |
US4042729A (en) | 1972-12-13 | 1977-08-16 | Kollmorgen Technologies Corporation | Process for the activation of resinous bodies for adherent metallization |
US4279705A (en) * | 1980-02-19 | 1981-07-21 | Kerr-Mcgee Corporation | Process for oxidizing a metal of variable valence by constant current electrolysis |
US4544450A (en) * | 1980-07-15 | 1985-10-01 | Anic S.P.A. | Electrochemical process for the synthesis of organic compounds |
US4610895A (en) | 1984-02-01 | 1986-09-09 | Shipley Company Inc. | Process for metallizing plastics |
US4948630A (en) | 1984-06-07 | 1990-08-14 | Enthone, Inc. | Three step process for treating plastics with alkaline permanganate solutions |
US5213665A (en) * | 1988-02-29 | 1993-05-25 | Nippon Shokubai Kagaku Kogyo, Co., Ltd. | Process for producing 1-aminoanthraquinones |
US5160600A (en) * | 1990-03-05 | 1992-11-03 | Patel Gordhanbai N | Chromic acid free etching of polymers for electroless plating |
US5648125A (en) | 1995-11-16 | 1997-07-15 | Cane; Frank N. | Electroless plating process for the manufacture of printed circuit boards |
EP0890566A1 (en) * | 1997-07-08 | 1999-01-13 | Ciba SC Holding AG | Oxidation process for the production of a chlorobenzaldehyde |
US20050019958A1 (en) | 2000-10-16 | 2005-01-27 | Sui-Po Zhang | Ligand binding assays for vanilloid receptors |
US20040074780A1 (en) * | 2002-10-18 | 2004-04-22 | Aker Kvaerner Canada Inc. | Mediated hydrohalic acid electrolysis |
US20090092757A1 (en) | 2006-04-18 | 2009-04-09 | Okuno Chemical Industries Co., Ltd. | Composition for etching treatment of resin molded article |
US20080193847A1 (en) * | 2007-02-14 | 2008-08-14 | Tosoh Corporation | Electrolytic manganese dioxide, and method for its production and its application |
WO2009023628A2 (en) | 2007-08-10 | 2009-02-19 | Enthone Inc. | Chromium-free pickle for plastic surfaces |
US20110140035A1 (en) * | 2007-08-10 | 2011-06-16 | Enthone Inc. | Chromium-free pickle for plastic surfaces |
US20110189590A1 (en) * | 2010-01-29 | 2011-08-04 | Eveready Battery Company, Inc. | Method of Making an Electrochemical Cell with a Catalytic Electrode Including Manganese Dioxide |
Non-Patent Citations (1)
Title |
---|
See also references of EP2920341A4 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11047052B2 (en) | 2014-07-10 | 2021-06-29 | Okuno Chemical Industries Co., Ltd. | Resin plating method |
CN107078291A (en) * | 2014-08-28 | 2017-08-18 | 英克罗恩有限公司 | Crystalline transitional oxide particle and the continuation method for preparing the crystalline transitional oxide particle |
Also Published As
Publication number | Publication date |
---|---|
TW201431793A (en) | 2014-08-16 |
PL2920341T3 (en) | 2019-05-31 |
KR20170039315A (en) | 2017-04-10 |
BR112015011123B1 (en) | 2021-08-03 |
CN104838044B (en) | 2017-12-05 |
JP2016504492A (en) | 2016-02-12 |
CN104838044A (en) | 2015-08-12 |
ES2704672T3 (en) | 2019-03-19 |
TR201900116T4 (en) | 2019-01-21 |
BR112015011123A2 (en) | 2017-07-11 |
EP2920341B1 (en) | 2018-11-14 |
CA2889342C (en) | 2019-11-12 |
EP2920341A4 (en) | 2016-04-27 |
KR101950169B1 (en) | 2019-02-20 |
EP2920341A1 (en) | 2015-09-23 |
CA2889342A1 (en) | 2014-05-22 |
KR20150082636A (en) | 2015-07-15 |
JP6060270B2 (en) | 2017-01-11 |
CA3056665A1 (en) | 2014-05-22 |
MX2015006178A (en) | 2015-11-06 |
TWI500582B (en) | 2015-09-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10221357B2 (en) | Etching of plastic using acidic solutions containing trivalent manganese | |
US10895016B2 (en) | Electrolytic generation of manganese (III) ions in strong sulfuric acid | |
EP2971260B1 (en) | Electrolytic generation of manganese (iii) ions in strong sulfuric acid | |
EP2920341B1 (en) | Electrolytic generation of manganese (iii) ions in strong sulfuric acid | |
US10246788B2 (en) | Electrolytic generation of manganese (III) ions in strong sulfuric acid using an improved anode |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13854930 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2889342 Country of ref document: CA |
|
ENP | Entry into the national phase |
Ref document number: 2015543041 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: MX/A/2015/006178 Country of ref document: MX |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112015011123 Country of ref document: BR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2013854930 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 20157015762 Country of ref document: KR Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 112015011123 Country of ref document: BR Kind code of ref document: A2 Effective date: 20150514 |