JP5932028B2 - 酸素発生用陽極 - Google Patents
酸素発生用陽極 Download PDFInfo
- Publication number
- JP5932028B2 JP5932028B2 JP2014516365A JP2014516365A JP5932028B2 JP 5932028 B2 JP5932028 B2 JP 5932028B2 JP 2014516365 A JP2014516365 A JP 2014516365A JP 2014516365 A JP2014516365 A JP 2014516365A JP 5932028 B2 JP5932028 B2 JP 5932028B2
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- Prior art keywords
- electrode
- valve metal
- oxide
- electrode according
- titanium
- Prior art date
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims description 21
- 229910052760 oxygen Inorganic materials 0.000 title claims description 21
- 239000001301 oxygen Substances 0.000 title claims description 21
- 239000000243 solution Substances 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 22
- 229910052719 titanium Inorganic materials 0.000 claims description 22
- 239000010936 titanium Substances 0.000 claims description 22
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 14
- 229910052741 iridium Inorganic materials 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 12
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052715 tantalum Inorganic materials 0.000 claims description 11
- 229910052718 tin Inorganic materials 0.000 claims description 11
- 239000011241 protective layer Substances 0.000 claims description 10
- 229910052787 antimony Inorganic materials 0.000 claims description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052797 bismuth Inorganic materials 0.000 claims description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 238000004070 electrodeposition Methods 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910001069 Ti alloy Inorganic materials 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 238000000354 decomposition reaction Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910000457 iridium oxide Inorganic materials 0.000 description 5
- 230000001680 brushing effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000005363 electrowinning Methods 0.000 description 3
- -1 fluoride ions Chemical class 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000013081 microcrystal Substances 0.000 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 description 3
- 229910001936 tantalum oxide Inorganic materials 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000010285 flame spraying Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- ODNHQUQWHMGWGT-UHFFFAOYSA-N iridium;oxotin Chemical compound [Ir].[Sn]=O ODNHQUQWHMGWGT-UHFFFAOYSA-N 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 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
- C25B11/051—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
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Metals (AREA)
- Vending Machines For Individual Products (AREA)
- Measuring Oxygen Concentration In Cells (AREA)
- Inert Electrodes (AREA)
Description
200×200×3mmの大きさのグレード1のチタンシートを、超音波浴中でアセトンを用いて10分間脱脂し、最初に、表面粗Rzの値が40〜45μmとなるまでコランダムグリットでサンドブラストし、次に570℃で2時間アニールし、次に27重量%H2SO4中85℃の温度で105分間エッチングして、得られた重量減が180〜250g/m2の間となることを確認した。
200×200×3mmの大きさのグレード1のチタンシートをあらかじめ処理し、上記実施例のように80:20のモル比のチタンおよびタンタルの酸化物を主成分とする保護層を設けた。
200×200×3mmの大きさのグレード1のチタンシートをあらかじめ処理し、上記実施例のように80:20のモル比のチタンおよびタンタルの酸化物を主成分とする保護層を設けた。
200×200×3mmの大きさのグレード1のチタンシートをあらかじめ処理し、上記実施例のように80:20のモル比のチタンおよびタンタルの酸化物を主成分とする保護層を設けた。
上記実施例および比較例の電極から20mm×60mmの大きさのクーポンを得て、当技術分野において周知のルギン管および白金プローブにより、150g/lのH2SO4水溶液中50℃の温度で測定することによって、酸素発生下での陽極電位測定を行った。表1に示されるデータ(SEP)は、PbAg基準電極に対する300A/m2の電流密度における電位差値を表している。さらに表1は、X線回折(XRD)技術によって検出した微結晶の平均サイズ、および150g/lのH2SO4水溶液中、60A/m2の電流密度、50℃の温度における加速寿命試験で測定された寿命を示している。
前表の加速持続期間試験を、フッ化カリウム(1mg/lまたは5mg/lのF−)またはMnCl2(20g/lのMn++)を加えて、同じ電極から得られた同等のクーポンで同じ条件で繰り返し、その結果を表2に示しており、本発明による電極サンプルが予想よりも高い許容度を示している。
Claims (8)
- 電解プロセスにおける酸素発生に好適な電極であって、バルブ金属基材と、外部触媒層と、前記基材と前記触媒層との間に介在するバルブ金属酸化物からなる保護層とを含み、前記触媒層が、イリジウムと、スズと、ビスマス、アンチモン、タンタル、およびニオブからなる群から選択される少なくとも1種類のドーピング元素Mとの混合酸化物を含み、前記混合酸化物の平均微結晶サイズが5nm未満であり、モル比Ir:(Ir+Sn)が0.25〜0.55の範囲であり、モル比M:(Ir+Sn+M)が0.02〜0.15の範囲である、電極。
- 前記ドーピング元素Mがビスマスおよびアンチモンの間から選択され、前記モル比M:(Ir+Sn+M)が0.05〜0.12の範囲である、請求項1に記載の電極。
- 前記モル比Ir:(Ir+Sn)が0.40〜0.50の範囲である、請求項1または2に記載の電極。
- 前記混合酸化物の平均微結晶サイズが4nm未満である、請求項1〜3のいずれか一項に記載の電極。
- 前記保護層の前記バルブ金属酸化物が、チタンまたはタンタルの少なくとも1種類の酸化物を含む、請求項1〜4のいずれか一項に記載の電極。
- 前記バルブ金属基材が、チタンまたはチタン合金中実シート、穴あきシート、または発泡シート、あるいはメッシュである、請求項1〜5のいずれか一項に記載の電極。
- 請求項1〜6のいずれか一項に記載の電極の製造方法であって、イリジウム、スズ、および前記少なくとも1種類のドーピング元素Mの前駆体を含有する溶液を、バルブ金属基材に塗布するステップと、続いて、空気中480〜530℃の温度で熱処理することによって前記溶液を分解させるステップとを含む、方法。
- 請求項1〜6のいずれか一項に記載の電極の表面上で酸素を陽極で発生させるステップを含む、水溶液からの金属の陰極電着方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ITMI2011A001132 | 2011-06-22 | ||
IT001132A ITMI20111132A1 (it) | 2011-06-22 | 2011-06-22 | Anodo per evoluzione di ossigeno |
PCT/EP2012/062088 WO2012175673A1 (en) | 2011-06-22 | 2012-06-22 | Anode for oxygen evolution |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2014517158A JP2014517158A (ja) | 2014-07-17 |
JP5932028B2 true JP5932028B2 (ja) | 2016-06-08 |
Family
ID=44515177
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2014516365A Active JP5932028B2 (ja) | 2011-06-22 | 2012-06-22 | 酸素発生用陽極 |
Country Status (21)
Country | Link |
---|---|
US (1) | US11001935B2 (ja) |
EP (1) | EP2723918B1 (ja) |
JP (1) | JP5932028B2 (ja) |
KR (1) | KR101894706B1 (ja) |
CN (1) | CN103597124B (ja) |
AP (1) | AP2013007339A0 (ja) |
AR (1) | AR086725A1 (ja) |
AU (1) | AU2012274018B2 (ja) |
BR (1) | BR112013029743B1 (ja) |
CA (1) | CA2835233C (ja) |
CL (1) | CL2013003326A1 (ja) |
EA (1) | EA024916B1 (ja) |
ES (1) | ES2558179T3 (ja) |
IN (1) | IN2014DN00250A (ja) |
IT (1) | ITMI20111132A1 (ja) |
MX (1) | MX350803B (ja) |
PE (1) | PE20140885A1 (ja) |
PL (1) | PL2723918T3 (ja) |
TW (1) | TWI550136B (ja) |
WO (1) | WO2012175673A1 (ja) |
ZA (1) | ZA201308554B (ja) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ITMI20130991A1 (it) * | 2013-06-17 | 2014-12-18 | Industrie De Nora Spa | Sistema per la misurazione di correnti presenti sugli elettrodi in celle elettrolitiche interconnesse. |
WO2015029367A1 (ja) * | 2013-08-30 | 2015-03-05 | Jx日鉱日石エネルギー株式会社 | 電気化学還元装置 |
CN107075702B (zh) * | 2014-10-21 | 2020-05-05 | 懿华水处理技术有限责任公司 | 具有双层涂层的电极、其使用和制备方法 |
EP3314041B1 (en) * | 2015-06-23 | 2019-05-08 | Industrie De Nora S.P.A. | Electrode for electrolytic processes |
WO2017091858A1 (en) * | 2015-11-30 | 2017-06-08 | Newsouth Innovations Pty Limited | Method for improving catalytic activity |
CN106676618A (zh) * | 2017-03-22 | 2017-05-17 | 苏州市汉宜化学有限公司 | 一种改良的枪色电镀网状阳极 |
KR102403412B1 (ko) * | 2019-09-06 | 2022-05-31 | 한국재료연구원 | 입체 나노시트 구조를 갖는 촉매를 포함하는 수전해전극, 그 제조방법 및 그를 포함하는 수전해장치 |
CN112921354B (zh) * | 2021-01-25 | 2022-07-01 | 深圳市飞猫电器有限公司 | 一种阳极及其制备方法和应用、臭氧发生系统和食品净化器 |
CN114272920B (zh) * | 2021-11-22 | 2023-10-03 | 广东省科学院资源利用与稀土开发研究所 | 一种有机污染物降解用复合氧化物涂层电极及其制备方法 |
CN114645295B (zh) * | 2022-03-31 | 2023-06-02 | 华南理工大学 | 一种用于电解水的阳极催化剂的制备方法 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0774470B2 (ja) * | 1990-03-20 | 1995-08-09 | ダイソー株式会社 | 酸素発生用陽極の製法 |
JP3212327B2 (ja) * | 1991-08-30 | 2001-09-25 | ペルメレック電極株式会社 | 電解用電極 |
NL9101753A (nl) * | 1991-10-21 | 1993-05-17 | Magneto Chemie Bv | Anodes met verlengde levensduur en werkwijzen voor hun vervaardiging. |
JP3231556B2 (ja) * | 1994-07-29 | 2001-11-26 | ペルメレック電極株式会社 | ジスルフィド化合物の電解還元方法 |
JP3507278B2 (ja) * | 1997-06-03 | 2004-03-15 | ペルメレック電極株式会社 | 電気めっき方法 |
IT1294749B1 (it) * | 1997-09-17 | 1999-04-12 | Nora De | Anodo per evoluzione di ossigeno in elettroliti contenenti manganese e fluoruri |
IT1302581B1 (it) * | 1998-10-01 | 2000-09-29 | Nora De | Anodo con migliorato rivestimento per la reazione di evoluzione diossigeno in elettroliti contenenti manganese. |
ITMI20021128A1 (it) * | 2002-05-24 | 2003-11-24 | De Nora Elettrodi Spa | Elettrodo per sviluppo di gas e metodo per il suo ottenimento |
ITMI20031543A1 (it) | 2003-07-28 | 2005-01-29 | De Nora Elettrodi Spa | Elettrodo per processi elettrochimici e metodo per il suo ottenimento |
ITMI20041006A1 (it) * | 2004-05-20 | 2004-08-20 | De Nora Elettrodi Spa | Anodo per sviluppo ossigeno |
JP4961825B2 (ja) * | 2006-05-09 | 2012-06-27 | アタカ大機株式会社 | 電気化学反応用陽極 |
JP4972991B2 (ja) * | 2006-05-09 | 2012-07-11 | アタカ大機株式会社 | 酸素発生用電極 |
CN1995464A (zh) * | 2006-11-28 | 2007-07-11 | 北京科技大学 | 一种纳米晶铱系氧化物涂层电极制备方法 |
IT1391767B1 (it) * | 2008-11-12 | 2012-01-27 | Industrie De Nora Spa | Elettrodo per cella elettrolitica |
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2011
- 2011-06-22 IT IT001132A patent/ITMI20111132A1/it unknown
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2012
- 2012-04-27 TW TW101115023A patent/TWI550136B/zh active
- 2012-06-22 AU AU2012274018A patent/AU2012274018B2/en active Active
- 2012-06-22 WO PCT/EP2012/062088 patent/WO2012175673A1/en active Application Filing
- 2012-06-22 ES ES12731378.1T patent/ES2558179T3/es active Active
- 2012-06-22 KR KR1020137031371A patent/KR101894706B1/ko active IP Right Grant
- 2012-06-22 CN CN201280029073.2A patent/CN103597124B/zh active Active
- 2012-06-22 MX MX2013013412A patent/MX350803B/es active IP Right Grant
- 2012-06-22 US US14/116,882 patent/US11001935B2/en active Active
- 2012-06-22 CA CA2835233A patent/CA2835233C/en active Active
- 2012-06-22 PL PL12731378T patent/PL2723918T3/pl unknown
- 2012-06-22 AR ARP120102246A patent/AR086725A1/es active IP Right Grant
- 2012-06-22 EP EP12731378.1A patent/EP2723918B1/en active Active
- 2012-06-22 EA EA201301175A patent/EA024916B1/ru not_active IP Right Cessation
- 2012-06-22 IN IN250DEN2014 patent/IN2014DN00250A/en unknown
- 2012-06-22 PE PE2013002521A patent/PE20140885A1/es active IP Right Grant
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AU2012274018B2 (en) | 2017-03-09 |
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EA024916B1 (ru) | 2016-11-30 |
AR086725A1 (es) | 2014-01-15 |
BR112013029743A2 (pt) | 2017-01-17 |
US11001935B2 (en) | 2021-05-11 |
KR101894706B1 (ko) | 2018-10-24 |
ES2558179T3 (es) | 2016-02-02 |
ITMI20111132A1 (it) | 2012-12-23 |
CL2013003326A1 (es) | 2014-05-09 |
EA201301175A1 (ru) | 2014-04-30 |
WO2012175673A1 (en) | 2012-12-27 |
TW201300576A (zh) | 2013-01-01 |
CN103597124B (zh) | 2016-08-17 |
MX350803B (es) | 2017-09-25 |
PE20140885A1 (es) | 2014-08-22 |
EP2723918B1 (en) | 2015-12-09 |
CA2835233C (en) | 2019-11-12 |
MX2013013412A (es) | 2013-12-12 |
EP2723918A1 (en) | 2014-04-30 |
KR20140021673A (ko) | 2014-02-20 |
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