EP2971260B1 - Electrolytic generation of manganese (iii) ions in strong sulfuric acid - Google Patents

Electrolytic generation of manganese (iii) ions in strong sulfuric acid Download PDF

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Publication number
EP2971260B1
EP2971260B1 EP14779082.8A EP14779082A EP2971260B1 EP 2971260 B1 EP2971260 B1 EP 2971260B1 EP 14779082 A EP14779082 A EP 14779082A EP 2971260 B1 EP2971260 B1 EP 2971260B1
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Prior art keywords
manganese
ions
solution
iii
acid
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EP14779082.8A
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German (de)
English (en)
French (fr)
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EP2971260A1 (en
EP2971260A4 (en
Inventor
Trevor Pearson
Terence Clarke
Roshan V. CHAPANERI
Craig Robinson
Alison Hyslop
Amrik Singh
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MacDermid Acumen Inc
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MacDermid Acumen Inc
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Priority claimed from US13/795,382 external-priority patent/US9534306B2/en
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Priority to SI201431343T priority Critical patent/SI2971260T1/sl
Priority to PL14779082T priority patent/PL2971260T3/pl
Publication of EP2971260A1 publication Critical patent/EP2971260A1/en
Publication of EP2971260A4 publication Critical patent/EP2971260A4/en
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Publication of EP2971260B1 publication Critical patent/EP2971260B1/en
Priority to HRP20191626 priority patent/HRP20191626T1/hr
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    • 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
    • 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
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • 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
    • 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
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics

Definitions

  • the present invention relates generally to an improved process for etching platable plastics such as ABS and ABS/PC.
  • 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, requiring 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.
  • 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 75°C to 93°C (165°F to 200°F).
  • permanganate based solutions to form sludge and undergo self-decomposition has been investigated by the inventors here.
  • permanganate ions can react with hydrogen ions to produce manganese (II) 4MnO 4 - + 12H + ⁇ 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)
  • the present invention relates generally to an electrolytic cell comprising:
  • the present invention relates generally to electrodes that are suitable for the electrochemical oxidation of manganese(II) ions to manganese(III) ions in a strong acid solution.
  • the present invention relates generally to a method of electrochemical oxidation of manganese(II) ions to manganese(III) ions comprising the steps of:
  • trivalent manganese can readily be produced by electrolysis at low current density of divalent manganese ions in a strong acid solution, preferably a strong sulfuric acid solution, most preferably an at least 8M sulfuric acid solution. More particularly, the inventors of the present invention have discovered that a solution of trivalent manganese ions in a 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)
  • a method of preparing a solution capable of etching a plastic substrate 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.
  • sulfuric acid is used.
  • the acid is sulfuric acid.
  • the concentration of sulfuric acid is at least 8 molar, 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 up to 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 inventors have found that it is possible to increase the amount of manganese that can be dissolved in the bath by replacing a portion of the sulfuric acid with another acid in which the manganese ions may be more soluble.
  • acids which may be suitable are limited. For example, hydrochloric acid would produce chlorine at the anodes and nitric acid would produce nitric oxides at the cathode. Perchloric and periodic acids would be expected to generate permanganate ions which would decompose to manganese dioxide. Organic acids would generally be rapidly oxidized by the manganese(III) ions. Thus, acids which would have both the necessary stability to oxidation and the ability to increase the solubility of manganese ions in the bath are methane sulfonic acid and methane disulfonic acid.
  • methane sulfonic acid is the preferred additional acid and sulfuric acid is the preferred primary acid.
  • the present invention also relates generally to an electrolyte for etching ABS and ABS/PC plastics comprising sulfuric acid in combination with either methane sulfonic acid or methane disulfonic acid in order to obtain better solubility of manganese ions in the bath, wherein the electrolyte contains at least 8M of sulfuric acid and contains about 0M to about 6M of methane sulfonic acid or methane disulfonic acid, preferably from about 1M to about 6M methane sulfonic acid.
  • the present invention relates generally to an electrolytic cell comprising:
  • the present invention also relates generally to a method of electrochemical oxidation of manganese(II) ions to manganese(III) ions comprising the steps of:
  • the platable plastic may be immersed in the metastable complex for a period of time to etch the surface of the platable plastic.
  • the platable plastic is immersed in the metastable complex 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 10 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 may be used to enhance the adhesion of paint, lacquers or other surface coatings.
  • the concentration of manganese(II) ions used in the etch of this invention can be determined by means of cyclic voltammetry.
  • the oxidation is diffusion controlled so efficient agitation of the etch solution is necessary during the electrolytic oxidation process.
  • the anode and cathode 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, boron doped diamond, or any other suitable material.
  • the inventors discovered that while the combination of manganese(III) ions and strong sulfuric acid (i.e., 8-15 molar) can etch ABS plastic, the etchant is also very aggressive towards the electrodes necessary to produce the manganese(III) ions. In particular, 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 were capable of producing manganese(III) ions when an electrical current, preferably of between 0.1 and 0.4 A/dm 2 (based on the nominal surface area), was applied.
  • the anode may also 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, it is believed that it is this structure which makes the carbon fibers 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.
  • 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 current density which can be applied in the electrolytic cell is limited in part by the oxygen overpotential on the anode material chosen.
  • the potential of the anode is sufficiently high to liberate oxygen.
  • the conversion efficiency of manganese(II) ions to manganese(III) ions falls and thus any further increase in current density is wasted.
  • operating the anodes at the higher overpotential required to produce the higher current density tends to produce manganese dioxide at the anode surface rather than manganese(III) ions.
  • lead anodes can be effectively used in the electrolytic cell described herein.
  • Lead becomes passive in strong sulfuric acid due to the formation of a layer of lead sulfate on the surface which has very limited solubility in sulfuric acid. This renders the anode passive until a very high overpotential (More than 2V versus a standard hydrogen electrode) is reached. At potentials above this level, a mixture of oxygen and lead dioxide is produced. While, it would be expected that such a high operating potential would favor oxygen production and the formation of permanganate ions instead of manganese(III) ions, experiments using a lead anode produced only manganese(III) ions and no permanganate.
  • the inventors of the present invention have discovered that monitoring the rate of oxidation is necessary when lead anodes are used because of the very high efficiency of these anodes for the oxidation of manganese(II) ions. Thus, if the rate of oxidation is not monitored and controlled, too high a proportion of the manganese(II) ions are oxidized, leaving a very low concentration of manganese(II). In the absence of manganese (II) ions, the anode begins to oxidize manganese (III) ions to manganese(IV), which rapidly forms insoluble manganese dioxide.
  • the anodes may comprise lead or a suitable lead alloy, and the type of alloy chosen can affect the efficiency of conversion. Pure lead or lead containing a small percentage of tin are particularly effective and produce conversion efficiencies of approximately 70%. It was also discovered that with a reasonable degree of agitation, surprisingly high current densities can be applied and still maintain this conversion rate.
  • the electrolysis process is preferably interrupted when the manganese(III) ions have reached a suitable working concentration which may be between 0.01 and 0.04M based on a total manganese content of 0.08M, such that there remains in solution an effective amount of manganese(II) ions such that the bath is stable and does not precipitate excessive amounts of manganese dioxide.
  • Preferred electrode materials include, for example, pure lead, lead antimony containing about 4% antimony, lead tin anodes containing up to 5% tin and lead/tin/calcium anodes.
  • 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.
  • 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 2 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 an 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 .
  • a solution was formulated comprising 10.5M sulfuric acid and 2M methane sulfonic acid. At a temperature of 68-70°C, it was possible to dissolve 0.16M of manganous sulfate with ease, whereas in the comparative case of dissolving manganous sulfate in a solution of 12.5M sulfuric acid, it was only possible to dissolve 0.08M.
  • the formulated solution was electrolyzed to produce a manganese(III) concentration of 0.015M manganese(III) ions, which gave a comparable etch rate to that obtained from a solution of 12.5M sulfuric acid having a manganese(III) concentration of 0.015M.
  • Electrolysis was continued in the bath of Example 4 until the manganese(III) content reached 0.04M and another panel was etched. An enhanced etch rate was obtained at this higher concentration of manganese(III) ions (approximately 25% higher than that obtained at a concentration of 0.015M).
  • 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 .
  • An anode consisting of lead having an effective surface area (i.e., not counting the back of the electrode) of 0.4 dm 2 was immersed in a beaker containing 2 liters of a solution comprising 0.08M of manganese sulfate in 12.5M sulfuric acid at a temperature of 68-70°C.
  • the other electrode in the cell consisted of a lead cathode having a surface area of approximately 0.04 dm 2 .
  • the solution was stirred using a magnetic stirrer to obtain moderate agitation over the surface of the electrolyte.
  • a current density of 0.4 A/dm 2 was applied to the anode and the rate of manganese(III) was determined versus electrolysis time.
  • the amount of manganese(III) was determined by diluting a sample of the bath with phosphoric acid to prevent disproportionation of the manganese(III) and titrating with a solution of ferrous ammonium sulfate using diphenylamine dissolved in acid as an indicator.
  • the experiment was repeated using a current density of 0.8 A/dm 2 and 1.6 A/dm 2 .
  • the oxidation did not appear to be mass transport limited at a current density of 1.6 A/dm 2 as the conversion efficiency was the same as that obtained at 0.4 A/dm 2 (70%).
  • a further experiment was conducted at 3.2 A/dm 2 and it was found that the conversion efficiency had fallen to 42% and the rate of manganese(III) generation was only about 10% higher than that obtained at 1.6 A/dm 2 . This indicates that under the agitation conditions used in the experiment, the overall limiting current density for manganese generation was about 1.6 A/dm 2 . This corresponds to a conversion rate approximately four times higher than that which can be achieved from a platinized titanium anode.
  • the slower etch rate of the manganese based etch of the invention as compared with the etch rate obtained from a chromic acid etch has demonstrated a need to provide a pretreatment step to produce higher adhesion values and enable shorter etch times.
  • the aim of the pretreatment step is to condition the surface of the plastic to be etched so that it is etched more rapidly and evenly, leading to shorter etch times and better adhesion.
  • Propylene carbonate is a relatively safe solvent having good water solubility, low toxicity and low flammability (flash point is 135°C) and is ideal from a health and safety point of view.
  • Gamma butyrolactone also works but is more toxic and in some countries is a controlled drug due to its recreational use.
  • the concentration of propylene carbonate is between about 100 and about 500 mL/L and the concentration of the organic acid is between about 100 and about 500 mL/L.
  • the operating temperature is typically between about 20° and 70°C and the immersion time is between about 2 and about 10 minutes.
  • the present invention also relates generally to a pretreatment composition for the platable plastic substrate comprising Gamma butyrolactone or propylene carbonate in combination with an organic hydroxy acid such as lactic acid, glycolic acid or gluconic acid.
  • a test coupon composed of an ABS/PC blend consisting of 45% polycarbonate was immersed in a solution containing 150 mL/L of propylene carbonates for the times and temperature shown in Table 1. Following this, the panel was rinsed and etched in a solution containing 12.5M sulfuric acid and 0.08M manganese, where 0.015M of the manganese ions had been electrolytically oxidized to manganese(III). The etching was carried out for 30 minutes at a temperature of 68-70°C.
  • the adhesion values are quite variable and it was noted that spots and pitting were observed on the plated parts. The copper coating was also pitted.
EP14779082.8A 2013-03-12 2014-03-07 Electrolytic generation of manganese (iii) ions in strong sulfuric acid Active EP2971260B1 (en)

Priority Applications (3)

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SI201431343T SI2971260T1 (sl) 2013-03-12 2014-03-07 Elektrolitsko tvorjenje manganovih (III) ionov v močni žveplovi kislini
PL14779082T PL2971260T3 (pl) 2013-03-12 2014-03-07 Elektrolityczne wytwarzanie jonów manganu (iii) w mocnym kwasie siarkowym
HRP20191626 HRP20191626T1 (hr) 2013-03-12 2019-09-10 Elektrolitsko stvaranje manganovih (iii) iona u snažnoj sumpornoj kiselini

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US13/795,382 US9534306B2 (en) 2012-01-23 2013-03-12 Electrolytic generation of manganese (III) ions in strong sulfuric acid
PCT/US2014/021618 WO2014164272A1 (en) 2013-03-12 2014-03-07 Electrolytic generation of manganese (iii) ions in strong sulfuric acid

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CN105209667B (zh) 2017-12-05
LT2971260T (lt) 2019-09-25
HUE045344T2 (hu) 2019-12-30
KR101749947B1 (ko) 2017-06-22
BR112015021067B1 (pt) 2021-06-08
JP6167222B2 (ja) 2017-07-19
ES2745071T3 (es) 2020-02-27
CN105209667A (zh) 2015-12-30
KR20150126935A (ko) 2015-11-13
EP2971260A1 (en) 2016-01-20
DK2971260T3 (da) 2019-09-23
PL2971260T3 (pl) 2020-03-31
AU2014249521B2 (en) 2018-03-01
AU2014249521A1 (en) 2015-08-27
EP2971260A4 (en) 2017-04-19
WO2014164272A1 (en) 2014-10-09
CA2955467C (en) 2021-03-16
TWI489007B (zh) 2015-06-21
CA2955467A1 (en) 2014-10-09
SI2971260T1 (sl) 2019-12-31
MX2015012584A (es) 2016-01-14
CA2901589C (en) 2019-01-22
TW201500593A (zh) 2015-01-01
PT2971260T (pt) 2019-09-27
BR112015021067A2 (pt) 2017-07-18
CA2901589A1 (en) 2014-10-09
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