EP2920341B1 - Génération électrolytique d'ions de manganèse (iii) dans l'acide sulfurique fort - Google Patents

Génération électrolytique d'ions de manganèse (iii) dans l'acide sulfurique fort Download PDF

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Publication number
EP2920341B1
EP2920341B1 EP13854930.8A EP13854930A EP2920341B1 EP 2920341 B1 EP2920341 B1 EP 2920341B1 EP 13854930 A EP13854930 A EP 13854930A EP 2920341 B1 EP2920341 B1 EP 2920341B1
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Prior art keywords
manganese
solution
ions
anode
iii
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German (de)
English (en)
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EP2920341A4 (fr
EP2920341A1 (fr
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Trevor Pearson
Terence Clarke
Roshan V. CHAPANERI
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MacDermid Acumen Inc
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MacDermid Acumen Inc
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Priority claimed from US13/677,798 external-priority patent/US9752241B2/en
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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. Thus, it is very desirable that safer alternatives to acidic chromium etching solutions be developed.
  • Permanganate solutions are also described in U.S. Pat. No. 3,625,758 to Stahl et al. 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. 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.
  • 5,648,125 to Cane describes the use of an alkaline permanganate solution comprising potassium permanganate and sodium hydroxide, wherein the permanganate solution is maintained at an elevated temperature, i.e., between about 74°C and 93°C (165°F and 200°F).
  • U.S. Pat. No. 4,042,729 to Polichette et al describes an etching solution that comprises water, permanganate ion, and manganate ion, wherein the molar ratio of manganate ion to permanganate ion is controlled and the pH of the solution is maintained at 11-13.
  • 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.
  • permanganate ions can react with hydrogen ions to produce manganese (II) ions and water according to the following reaction: 4MnO 4 - + 12-H + ⁇ 4Mn 2+ + 6H 2 O + 5O 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: 2MnO 4 - + 2H 2 O + 3Mn 2+ ⁇ 5MnO 2 + 4H + (2)
  • Attempts to etch ABS without the use of chromic acid have include the use of electrochemically generated silver (II) or cobalt (III).
  • Certain metals can be anodically oxidized to oxidation states which are highly oxidizing.
  • manganese (II) can be oxidized to permanganate (manganese VI)
  • cobalt can be oxidized from cobalt (II) to cobalt (III)
  • silver can be oxidized from silver (I) to silver (II).
  • 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 provides an electrolytic cell according to claim 1, comprising:
  • the present invention also provides a method according to claim 10 of electrochemical oxidation of manganese (II) ions to manganese (III) ions comprising the steps of:
  • the present invention also provides a method according to claim 28 of etching a plastic part.
  • 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: 2Mn 3+ + 2H 2 O ⁇ MnO 2 + Mn 2+ + 4H+ (3)
  • the trivalent manganese ion becomes meta-stable and forms a cherry purple/red colored sulfate complex.
  • the inventors have found that this sulfate complex is a suitable medium for the etching of ABS and has many advantages over chromium-free etches previously described.
  • Also disclosed herein is a method of preparing a solution capable of etching a plastic substrate, the method comprising the steps of:
  • 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.
  • other inorganic acids such as phosphoric acid can be usable in the compositions of the present invention, it is generally preferred to use sulfuric acid.
  • 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.
  • the electrolyte 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.
  • 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 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.
  • vitreous carbon anodes provides a commercially suitable electrode.
  • anodes having a titanium substrate may be rapidly degraded by the etchant.
  • 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.
  • anode area which is large in comparison to the area of the cathode.
  • the area ratio of anode to cathode is at least about 10:1.
  • the present invention relates generally to an electrolytic cell comprising:
  • a solution of 0.08 molar of manganese(II) sulfate in 12.5 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.
  • the etching solution prepared as described above in Example 3 was heated to 65-70°C on a magnetic stirrer/hotplate and 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 263A 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 potentiostatic 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 .
  • 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 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 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 .
  • 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 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 .

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Chemically Coating (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Claims (31)

  1. Cellule électrolytique, comprenant :
    une solution d'électrolyte comportant des ions de manganèse(III) dans une solution d'acide ;
    une cathode en contact avec la solution d'électrolyte ; et
    une anode en contact avec la solution d'électrolyte, dans lequel l'anode comporte une matière sélectionnée dans le groupe consistant en carbone vitreux, carbone vitreux réticulé, fibres de carbone tressées et des combinaisons de l'un ou de plusieurs des éléments cités précédemment.
  2. Cellule électrolytique selon la revendication 1, dans lequel l'anode comporte du carbone vitreux.
  3. Cellule électrolytique selon la revendication 1, dans lequel l'anode comprend des fibres de carbone tressées.
  4. Cellule électrolytique selon la revendication 3, dans lequel les fibres de carbone tressées ont une structure turbostratique.
  5. Cellule électrolytique selon la revendication 3, dans lequel les fibres de carbone tressées comprennent au moins 95 % de carbone.
  6. Cellule électrolytique selon la revendication 1, dans lequel la solution d'acide comprend une solution d'acide sulfurique.
  7. Cellule électrolytique selon la revendication 6, dans lequel la solution d'acide comprend une solution d'acide sulfurique ayant un rapport molaire de 9:15.
  8. Cellule électrolytique selon la revendication 1, dans lequel la cathode comprend une matière sélectionnée dans le groupe consistant en platine, titane platiné, oxyde d'indium/de tantale, niobium et plomb.
  9. Cellule électrolytique selon la revendication 8, dans lequel la cathode comprend du plomb
  10. Procédé d'oxydation électrochimique d'ions de manganèse (II) vers des ions de manganèse (III), comprenant les étapes consistant à :
    fournir un électrolyte comportant une solution d'ions de manganèse (II) dans une solution d'acide sulfurique ou une solution d'acide phosphorique dans une cellule électrolytique, dans lequel la cellule électrolytique comporte une anode et une cathode, et dans lequel l'anode comporte une matière sélectionnée dans le groupe consistant en carbone vitreux, carbone vitreux réticulé et fibres de carbone tressées ;
    appliquer un courant entre l'anode et la cathode, dans lequel la densité du courant anodique se situe entre 0,1 et 0,4 A/dm2 ; et
    oxyder l'électrolyte pour former des ions de manganèse (III), dans lequel les ions de manganèse (III) forment un complexe métastable.
  11. Procédé selon la revendication 10, dans lequel la solution d'acide comprend de l'acide sulfurique.
  12. Procédé selon la revendication 10, dans lequel la solution d'acide comprend une solution d'acide sulfurique ayant un rapport molaire de 9 :15.
  13. Procédé selon la revendication 12, dans lequel l'acide sulfurique a une concentration ayant un rapport molaire de 12:13.
  14. Procédé selon la revendication 10, comprenant en outre l'étape consistant à mettre en contact du plastique apte au plaquage et le complexe métastable pendant une certaine période de temps, pour mordancer le plastique apte au placage.
  15. Procédé selon la revendication 10, dans lequel les ions de manganèse (II) proviennent d'un composé sélectionné dans le groupe consistant en sulfate de manganèse, carbonate de manganèse et hydroxyde de manganèse.
  16. Procédé selon la revendication 14, dans lequel le plastique apte au plaquage comprend de l'acrylonitrile-butadiène-styrène ou de l'acrylonitrile-butadiène-styrène/polycarbonate.
  17. Procédé selon la revendication 10, dans lequel la solution comprend en outre du dioxyde de manganèse colloïdal, ou dans lequel la concentration des ions de manganèse (II) dans l'électrolyte se situe entre environ un rapport molaire de 0,005 et la saturation.
  18. Procédé selon la revendication 10, dans lequel la cathode comprend une matière sélectionnée dans le groupe consistant en platine, titane platiné, oxyde d'indium/de tantale, niobium et plomb.
  19. Procédé selon la revendication 18, dans lequel la cathode comprend du plomb ou dans lequel la cathode comprend du titane platiné ou du platine.
  20. Procédé selon la revendication 10, dans lequel l'anode comprend du carbone vitreux.
  21. Procédé selon la revendication 10, dans lequel l'anode comprend des fibres de carbone tressées.
  22. Procédé selon la revendication 21, dans lequel les fibres de carbone tressées ont une structure turbostratique.
  23. Procédé selon la revendication 21, dans lequel les fibres de carbone tressées sont constituées de fibres de polyacrylonitrile.
  24. Procédé selon la revendication 21, dans lequel les fibres de carbone tressées comprennent au moins 95 % de carbone et sont imprégnées de résine à moins de 2 %, en fonction du poids des fibres de carbone.
  25. Procédé selon la revendication 10, dans lequel une région de l'anode est plus étendue qu'une région de la cathode.
  26. Procédé selon la revendication 10, dans lequel la température de l'électrolyte est maintenue entre 30 °C et environ 90 °C.
  27. Procédé selon la revendication 10, dans lequel l'électrolyte ne contient pas de permanganate.
  28. Procédé pour mordancer une pièce en plastique, dans lequel ledit procédé comprend la mise en contact de la pièce en plastique avec une solution comportant des ions de manganèse (III) et de l'acide,
    dans lequel le manganèse (III) est généré dans la solution par oxydation électrolytique du manganèse (II), et dans lequel l'oxydation électrolytique a lieu à hauteur d'une anode dans la solution et ladite anode comprend du carbone vitreux, du carbone vitreux réticulé ou des fibres de carbone tressées.
  29. Procédé selon la revendication 28, dans lequel l'acide comprend de l'acide sulfurique.
  30. Procédé selon la revendication 29, dans lequel l'acide comprend de l'acide sulfurique ayant un rapport molaire de 9:15.
  31. Procédé selon l'une quelconque des revendications 28 à 30, dans lequel la pièce en plastique comprend de l'acrylonitrile-butadiène-styrène (ABS).
EP13854930.8A 2012-11-15 2013-09-26 Génération électrolytique d'ions de manganèse (iii) dans l'acide sulfurique fort Active EP2920341B1 (fr)

Priority Applications (1)

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PL13854930T PL2920341T3 (pl) 2012-11-15 2013-09-26 Elektrolityczne generowanie jonów manganu (III) w silnym kwasie siarkowym

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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
PCT/US2013/061860 WO2014077957A1 (fr) 2012-11-15 2013-09-26 Génération électrolytique d'ions de manganèse (iii) dans l'acide sulfurique fort à l'aide d'une anode améliorée

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CA (2) CA3056665A1 (fr)
ES (1) ES2704672T3 (fr)
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PL (1) PL2920341T3 (fr)
TR (1) TR201900116T4 (fr)
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CN110344033A (zh) 2014-07-10 2019-10-18 奥野制药工业株式会社 树脂镀敷方法以及树脂镀敷用蚀刻浴的管理方法
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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

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WO2014077957A1 (fr) 2014-05-22
TWI500582B (zh) 2015-09-21
CN104838044B (zh) 2017-12-05
CA2889342A1 (fr) 2014-05-22
CN104838044A (zh) 2015-08-12
KR20170039315A (ko) 2017-04-10
CA2889342C (fr) 2019-11-12
TW201431793A (zh) 2014-08-16
KR101950169B1 (ko) 2019-02-20
JP2016504492A (ja) 2016-02-12
TR201900116T4 (tr) 2019-01-21
PL2920341T3 (pl) 2019-05-31
KR20150082636A (ko) 2015-07-15
BR112015011123A2 (pt) 2017-07-11
MX2015006178A (es) 2015-11-06
EP2920341A4 (fr) 2016-04-27
BR112015011123B1 (pt) 2021-08-03
JP6060270B2 (ja) 2017-01-11
EP2920341A1 (fr) 2015-09-23
CA3056665A1 (fr) 2014-05-22
ES2704672T3 (es) 2019-03-19

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