EP2920341B1 - 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
- 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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- EP
- European Patent Office
- Prior art keywords
- manganese
- solution
- ions
- anode
- iii
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims description 88
- -1 manganese (iii) ions Chemical class 0.000 title claims description 55
- 239000000243 solution Substances 0.000 claims description 81
- 239000004033 plastic Substances 0.000 claims description 47
- 229920003023 plastic Polymers 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 25
- 239000004917 carbon fiber Substances 0.000 claims description 25
- 238000005530 etching Methods 0.000 claims description 25
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 20
- 239000003792 electrolyte Substances 0.000 claims description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 18
- 229910052719 titanium Inorganic materials 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 12
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 9
- 239000008151 electrolyte solution Substances 0.000 claims description 9
- 229940099596 manganese sulfate Drugs 0.000 claims description 9
- 239000011702 manganese sulphate Substances 0.000 claims description 9
- 235000007079 manganese sulphate Nutrition 0.000 claims description 9
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 5
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 5
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 4
- 238000006056 electrooxidation reaction Methods 0.000 claims description 4
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000008569 process Effects 0.000 description 16
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 15
- 239000000758 substrate Substances 0.000 description 15
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 13
- 238000012360 testing method Methods 0.000 description 9
- 238000005868 electrolysis reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000009713 electroplating Methods 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 229910001437 manganese ion Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920006942 ABS/PC Polymers 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 241000167854 Bourreria succulenta Species 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 235000019693 cherries Nutrition 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- JAWGVVJVYSANRY-UHFFFAOYSA-N cobalt(3+) Chemical compound [Co+3] JAWGVVJVYSANRY-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 2
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 2
- 238000010137 moulding (plastic) Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- JOJPFQVZNUNZBO-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+2].[Mn+2].[Mn+2].[Mn+2].[Mn+2].[Mn+2] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+2].[Mn+2].[Mn+2].[Mn+2].[Mn+2].[Mn+2] JOJPFQVZNUNZBO-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 229910000471 manganese heptoxide Inorganic materials 0.000 description 1
- BECVLEVEVXAFSH-UHFFFAOYSA-K manganese(3+);phosphate Chemical compound [Mn+3].[O-]P([O-])([O-])=O BECVLEVEVXAFSH-UHFFFAOYSA-K 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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 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)
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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 (en) | 2012-11-15 | 2013-09-26 | Electrolytic generation of manganese (iii) ions in strong sulfuric acid |
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EP2920341A1 EP2920341A1 (en) | 2015-09-23 |
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EP (1) | EP2920341B1 (zh) |
JP (1) | JP6060270B2 (zh) |
KR (2) | KR101950169B1 (zh) |
CN (1) | CN104838044B (zh) |
BR (1) | BR112015011123B1 (zh) |
CA (2) | CA3056665A1 (zh) |
ES (1) | ES2704672T3 (zh) |
MX (1) | MX2015006178A (zh) |
PL (1) | PL2920341T3 (zh) |
TR (1) | TR201900116T4 (zh) |
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PL2971260T3 (pl) * | 2013-03-12 | 2020-03-31 | Macdermid Acumen, Inc. | Elektrolityczne wytwarzanie jonów manganu (iii) w mocnym kwasie siarkowym |
EP3168326B2 (en) | 2014-07-10 | 2023-09-20 | Okuno Chemical Industries Co., Ltd. | Resin plating method |
CN107078291A (zh) * | 2014-08-28 | 2017-08-18 | 英克罗恩有限公司 | 结晶过渡氧化物颗粒及制备该结晶过渡氧化物颗粒的连续方法 |
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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US3065155A (en) * | 1960-09-02 | 1962-11-20 | Manganese Chemicals Corp | Electrolytic manganese dioxide process |
AT310285B (de) | 1966-02-22 | 1973-09-25 | Photocircuits Corp | Verfahren zur Herstellung eines Schichtkörpers für gedruckte Schaltungen |
US4042729A (en) | 1972-12-13 | 1977-08-16 | Kollmorgen Technologies Corporation | Process for the activation of resinous bodies for adherent metallization |
IT1159931B (it) * | 1978-10-13 | 1987-03-04 | Oronzio De Nora Impianti | Procedimento industriale per la produzione di biossido di titanio da ilmenite |
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IT1132194B (it) * | 1980-07-15 | 1986-06-25 | Anic Spa | Processo elettrochimico per la sintesi di composti organici |
JPS58502027A (ja) * | 1981-11-23 | 1983-11-24 | バロ−ス・コ−ポレ−ション | 低デ−タ転送率の直列入出力インタ−フェイスをモニタするようにされた周辺装置 |
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JPS6447890A (en) * | 1987-08-13 | 1989-02-22 | Kenzo Yamaguchi | Electrolytic synthesis method |
US5213665A (en) * | 1988-02-29 | 1993-05-25 | Nippon Shokubai Kagaku Kogyo, Co., Ltd. | Process for producing 1-aminoanthraquinones |
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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 |
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JP2010121143A (ja) * | 2008-11-17 | 2010-06-03 | Okuno Chem Ind Co Ltd | 樹脂成形体に対するエッチングの後処理剤、該後処理剤を用いる後処理方法、及び樹脂成形体に対するめっき方法 |
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US10260000B2 (en) * | 2012-01-23 | 2019-04-16 | Macdermid Acumen, Inc. | Etching of plastic using acidic solutions containing trivalent manganese |
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KR20170039315A (ko) | 2017-04-10 |
KR20150082636A (ko) | 2015-07-15 |
WO2014077957A1 (en) | 2014-05-22 |
ES2704672T3 (es) | 2019-03-19 |
TWI500582B (zh) | 2015-09-21 |
JP2016504492A (ja) | 2016-02-12 |
KR101950169B1 (ko) | 2019-02-20 |
CA2889342A1 (en) | 2014-05-22 |
EP2920341A1 (en) | 2015-09-23 |
CA2889342C (en) | 2019-11-12 |
BR112015011123A2 (pt) | 2017-07-11 |
EP2920341A4 (en) | 2016-04-27 |
MX2015006178A (es) | 2015-11-06 |
JP6060270B2 (ja) | 2017-01-11 |
CN104838044B (zh) | 2017-12-05 |
TW201431793A (zh) | 2014-08-16 |
BR112015011123B1 (pt) | 2021-08-03 |
PL2920341T3 (pl) | 2019-05-31 |
TR201900116T4 (tr) | 2019-01-21 |
CN104838044A (zh) | 2015-08-12 |
CA3056665A1 (en) | 2014-05-22 |
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