US3878083A - Anode for oxygen evolution - Google Patents

Anode for oxygen evolution Download PDF

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Publication number
US3878083A
US3878083A US361022A US36102273A US3878083A US 3878083 A US3878083 A US 3878083A US 361022 A US361022 A US 361022A US 36102273 A US36102273 A US 36102273A US 3878083 A US3878083 A US 3878083A
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US
United States
Prior art keywords
metal
electrode
base
oxide
coating
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Expired - Lifetime
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US361022A
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English (en)
Inventor
Nora Oronzio De
Giuseppe Bianchi
Antonio Nidola
Giovanni Trisoglio
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ELECTRODE Corp A DE CORP
Electronor Corp
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Electronor Corp
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Priority to US546112*A priority Critical patent/US3926751A/en
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Publication of US3878083A publication Critical patent/US3878083A/en
Assigned to ELECTRODE CORPORATION, A DE CORP. reassignment ELECTRODE CORPORATION, A DE CORP. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: DIAMOND SHAMROCK TECHNOLOGIES, S.A.
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • 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
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/061—Metal or alloy
    • 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

Definitions

  • These dimensionally stable electrodes usually have a film forming valve metal base such as titanium, tantalum, zirconium, aluminum, niobium and tungsten, which has the capacity to conduct current in the cathodic direction and to resist the passage of current in the anodic direction and are sufficiently resistant to the electrolyte and conditions used within an electrolytic cell, for example, in the production of chlorine and caustic soda, to be used as electrodes in electrolytic processes.
  • a film forming valve metal base such as titanium, tantalum, zirconium, aluminum, niobium and tungsten
  • Electrode coatings must have the capacity to continue to conduct current to the electrolyte over long periods of time without becoming passivated, and in chlorine production, must have the capacity to catalyze the formation of chlorine molecules from the chloride ions at an anode. They must be electroconductive and electrocatalytic and must adhere firmly to the valve metal base over long periods of time under cell operating conditions.
  • the commercially available coatings contain. a catalytic metal or oxide from the platinum group metals, i.e., platinum, palladium, iridium, ruthenium, rhodium, osmium and a binding or protective agent such as titanium, dioxide, tantalum pentoxide and other valve metal oxides in sufficient amount to protect the platinum group metal or oxide from being removed from the electrode in the electrolysis process and to bind the platinum group metal or oxide to the electrode base.
  • the binding and protective metal oxide is usually in excess of the platinum group metal or oxide. Anodes of this nature have been described in British Pat. No. 1,231,280.
  • novel electrodes of the invention are comprised of an electroconductive base provided with a coating over at least a portion of its outer surface of a mixed material of tantalum oxide and iridium oxide.
  • the coating may be as little as 5% of the outer surface of the electrode but preferably covers 50 to of the active face of the electrode.
  • the preferred ratio of tantalum to iridium calculated in percent of metal is 1:1 to 0.34:1.
  • the electrode base may be made of any electroconductive material such as iron, nickel, lead, copper, etc. or alloys thereof but is preferably a valve metal such as tungsten, titanium, tantalum, niobium, aluminum or zirconium or alloys of two or more of said metals.
  • the valve metals bases may be provided with an intermediate layer such as an oxide of the valve metal or a coating of another metal such as platinum group metals.
  • the base may be a valve metal and at least either one metal having a low hydrogen overvoltage such as alloy of titanium with iron, cobalt, nickel, palladium, vandadium or molybdenum, or mixtures of two or more of said metals; or one metal suitable to form with titanium a protective oxide film even in acid solution such as an alloy of titanium with niobium, tantalum, zirconium or mixtures of two or more of said metals.
  • one metal having a low hydrogen overvoltage such as alloy of titanium with iron, cobalt, nickel, palladium, vandadium or molybdenum, or mixtures of two or more of said metals
  • one metal suitable to form with titanium a protective oxide film even in acid solution such as an alloy of titanium with niobium, tantalum, zirconium or mixtures of two or more of said metals.
  • the electroconductive base is an alloy of a valve metal with a platinum group metal which has an improved corrosion resistance to acid electrolytes encountered in the use of the electrodes such as 5 to 15% sulfuric acid or 1 to 5% hydrochloric acid.
  • a particularly useful alloy is titanium containing 0.1 to 0.20% by weight of palladium. This corrosion resistance of the support of the coating prevents chipping off of the coating even if the anode is immersed for a few hours in an acid electrolyte without anodic polarization.
  • the coating containing tantalum oxide and iridium oxide can be doped with an oxide of a metal with a valence of less than +4 to increase the catalytic activity for oxygen evolution without adversely effecting the mechanical properties of the coatings.
  • the semiconductivity of the Ta O -IrO- system is of the n type and that the addition of the doping metal oxide reverses the type of conductivity from n-type to p-type which improves the anodic process by producing electronic holes.
  • the doping metal oxide may be present in the coating in amounts ranging from 0.5 to 5.0% preferably 1.5 to 3.0% by weight of the said system calculated as metal.
  • suitable doping metal oxides are alkaline earth metals such as calcium, magnesium, barium and members of Groups VIII, VI B and VII B of the periodic Table such as cobalt, iron and nickel, chromium, molybdenum, manganese, etc.
  • the increase in the catalytic activity of the doped coatings is shown by the lower anode potential of doped anodes as compared to undoped anodes after 8,000 hours of operation of the anodes under identical working conditions.
  • the doping seems to have no adverse effect on the mechanical properties of the coatings as there is no coating loss in either instance even after 8,000 hours operation.
  • the electrodes of the invention are particularly useful for electrolytic processes such as cathodic protection, electroflotation, organic electrosynthesis such as hydrodimerization of acrylonitrile and most particularly the electrowinning of metals.
  • the said electrodes have a high electrocatalytic activity and a very low passivation rate of a few millivolts per month at a current density of 1.2 to 2.0 KA per m and a negligible weight loss if kept under anodic polarization.
  • the novel method of the invention for the preparation of the electrodes of the invention comprises applying to an electroconductive electrode base a solution of a thermally decomposible compound of tantalum and a thermally decomposible compound ofiridium, drying the coated electrode base by evaporation of the solvent and then heating the dried electrode base in the presence of an oxygen containing gas such as to form the desired electrode.
  • the heating step is preferably effected at temperatures of 350 to 600C, the optinum temperature being 500 to 550C. At temperatures below 350C, the oxidation is not completed or requires too long heating time and at temperatures above 600C, the electrode base is likely to be subjected to distortions and/or destruction by the high temperatures.
  • the preliminary drying step is preferably effected by gentle heating in air to evaporate the solvent and codeposit the metal compounds.
  • any convenient procedure may be used to remove the solvent such as standing under reduced pressure.
  • the coating is applied in multiple coats with short periods of intermediate heating such as 500 to 550C for 5 to minutes with a longer final heating after the last coat such as 500 to 550C for 45 minutes to l 1% hours.
  • the electrodes of this invention are particularly useful for electrowinning process used in the production of various metals because they do not add impurities to the bath which deposit on the cathode, .with the metals being won, and thereby contaminate the refined metal, as do anodes of for example lead containing antimony and bismuth which give impure cathode refined metals. Moreover, their resistance to the acid solutions and oxygen evolution and their excellent anode potential makes them desirable for this use.
  • EXAMPLE I 24 Titanium plates 10 mm by 10 mm were etched in boiling 20% hydrochoric acid for 60 minutes and were then thoroughly washed with water. The plates were then coated with an aqueous solution of the compositions of Table I in 12 to 15 coats. After the application of each coat, the plates were dried and then heated for 10 minutes at 450C to 600C in an oven with forced air circulation and then allowed to air cool. After the last coat, the plates were heated in the oven at the same temperature for 1 hour and were then air cooled. The values of Table I are calculated as weight of free metal. The tantalum chloride was used as a solution in 20% hydrochloric acid.
  • the anode potential for each anode was then determined by electrolysis of 10% by weight sulfuric acid at 60C and a current density of 1.2 KA/m
  • the initial anode potential (against NHE) and the anode potential after 3,000 and 6,000 hours was determined and the coating loss' was then determined. The values are reported in Table II.
  • NHE Anode potential in Volts after coating loss initial 600 h i000 h 1200 h in mg/cm anode potential and the anode potential after 600, 1,000 or 1,200 hours are reported in Table IV. The final loss of the coating was determined at the end of 5 the test.
  • compositions in mg of Sample No. free metal plates were then coated with the compositions of Table V.
  • the compositions were applied in 15 to 20 coats 2 and the Ta O -RuO coated electrodes are only slightly improved and the TiO -lrO coated electrodes are no better.
  • EXAMPLE II For comparative purposes, electrodes were prepared as follows. Titanium plates 10 mm by 10 mm were The results of Table 11 show that the electrodes of the invention have high electrocatalytic activity and a very low passivation rate and that the weight loss of the coating is negligible when within the limits of the invention. It should be noted that the ratio of Ta to lr for samples F to F is about 034. Optimum values are obtained in the heating range of 500550C.
  • EXAMPLE IV To demonstrate the improved corrosion resistance of a titanium palladium alloy, 10 plates made of titanium containing 0.15% by weight of palladium (10 X 10 mm) were sand-blasted and then etched in refluxing 20% hydrochloric acid for 60 minutes. The plates were then coated with the compositions of Table V using the procedure of Example 111. The anode potential was determined for each electrode by electrolysis of 10% sulfuric acid at 60C and a current density of 1.2 KA/m The initial anode potential and the value after 1,000 and 2,000 hours and the coating weight loss after 2,000 hours was determined. Moreover, the current was halted for minutes in each 24 hour period without removing the electrode from the acid bath. The results are reported in Table V11.
  • EXAMPLE V 10 titanium plates X 20 mm) were etched in refluxing 20% hydrochloric acid for 60 minutes and after being thoroughly washed with water, the plates were coated with an aqueous solution containing 2.01 mg (as free metal) of TaCl 3.2 mg (as free metal) oflrC1 and 0.0394 ml of hydrochloric acid. The solution was applied in 12 coats-with intermediate heating and cooling and a final heating as described in Example I.
  • the coated titanium plates were used as anodes in cells for the recovery of zinc from an aqueous electrolyte containing 100 g/liter of Zn S0 (as free metal), 10% sulfuric acid and 10 to 50 ppm of glue.
  • the cathode was a pure aluminum sheet with a smooth surface and the electrolyte gap was 10 mm.
  • the current density was 500 A/m and the electrolyte temperature was 35C.
  • the anode potential, loss of coating, zinc thickness on the cathode and the morphology of the zinc deposit are reported in Table V111 The cathodic current efficiency was found to be 92-95% in all cases and the purity of the zinc deposit was 99.9999%.
  • EXAMPLE V1 Using the procedure of Example V, five titanium plates (20 X 20 cm) were coated with the composition of Example V. The coated plates were used as anodes in ace for recovery of copper from an aqueous electrolyte containing 100 g/liter (as free metal) of CuSO and 10 g/liter of sulfuric acid and the cathode was a smooth steel plate. The electrolyte gap was 15 mm and the bath temperature was C. The current density was 500 A/m The anode potential, loss of coating and copper thickness and morphology of the copper deposit are reported in Table 1X.
  • lrCl 3.2 do. do. lr 1(1 CaCl2.6HgO 0.26 do. do. Ca HCl 0.0362 mls.
  • An electrode comprising an electroconductive base provided with a coating over at least a portion of its outer surface of a mixed material of tantalum oxide
  • EXAMPLE V111 Using the procedure of Example V11, 20 X 20mm titanium coupons were coated with the composition of Table X11 with the same heatings.
  • iridium oxide in which the ratio of tantalum to iridium calculated as metal is 1:1 to 0.34 to l.
  • the electrode of claim 1 wherein the said base is an alloy of a valve metal and at least one of the platinum group metals.
  • valve metal is titanium
  • the electrode of claim 1 wherein the said base is an alloy containing at least two valve metals and at least 0.34 to l.
  • An electrode comprising an electroconductive base provided with a coating over at least a portion of its outer surface of a mixed material of tantalum oxide and iridium oxide, in which the ratio of the tantalum to the iridium calculated as metal is 1:1 to 0.34 to 1, said coating further contains 0.1 to 5.0% by weight of an oxide of a metal selected from the group consisting of alkaline earth metals, cobalt, iron, nickel, chromium, molybdenum and manganese.
  • An electrode of claim 9 wherein the metal is selected from the group consisting of cobalt and an alkaline earth metal.

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  • 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)
US361022A 1972-05-18 1973-05-17 Anode for oxygen evolution Expired - Lifetime US3878083A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US546112*A US3926751A (en) 1972-05-18 1975-01-31 Method of electrowinning metals

Applications Claiming Priority (1)

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IT24526/72A IT959730B (it) 1972-05-18 1972-05-18 Anodo per sviluppo di ossigeno

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US (1) US3878083A (enrdf_load_stackoverflow)
CA (1) CA989773A (enrdf_load_stackoverflow)
FR (1) FR2185014B1 (enrdf_load_stackoverflow)
GB (1) GB1399576A (enrdf_load_stackoverflow)
IT (1) IT959730B (enrdf_load_stackoverflow)
ZA (1) ZA732977B (enrdf_load_stackoverflow)

Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3926751A (en) * 1972-05-18 1975-12-16 Electronor Corp Method of electrowinning metals
US4003817A (en) * 1967-12-14 1977-01-18 Diamond Shamrock Technologies, S.A. Valve metal electrode with valve metal oxide semi-conductive coating having a chlorine discharge in said coating
US4032427A (en) * 1975-11-03 1977-06-28 Olin Corporation Porous anode separator
US4072585A (en) * 1974-09-23 1978-02-07 Diamond Shamrock Technologies S.A. Valve metal electrode with valve metal oxide semi-conductive coating having a chlorine discharge catalyst in said coating
US4072586A (en) * 1975-12-10 1978-02-07 Diamond Shamrock Technologies S.A. Manganese dioxide electrodes
US4107025A (en) * 1977-11-09 1978-08-15 Noranda Mines Limited Stable electrode for electrochemical applications
FR2408665A1 (fr) * 1977-11-09 1979-06-08 Noranda Mines Ltd Electrode stable pour applications electrochimiques
US4173518A (en) * 1974-10-23 1979-11-06 Sumitomo Aluminum Smelting Company, Limited Electrodes for aluminum reduction cells
US4185142A (en) * 1978-08-09 1980-01-22 Diamond Shamrock Corporation Oxygen electrode rejuvenation methods
DE3020260A1 (de) * 1979-05-29 1980-12-11 Diamond Shamrock Corp Verfahren zur herstellung von chromsaeure unter verwendung von zweiraum- und dreiraum-zellen
US4263112A (en) * 1980-06-20 1981-04-21 Frosch Robert A Cell and method for electrolysis of water and anode therefor
US4285799A (en) * 1978-03-28 1981-08-25 Diamond Shamrock Technologies, S.A. Electrodes for electrolytic processes, especially metal electrowinning
US4306950A (en) * 1979-10-15 1981-12-22 Westinghouse Electric Corp. Process for forming sulfuric acid
US4468416A (en) * 1981-05-19 1984-08-28 Permelec Electrode Ltd. Electrolytic electrodes having high durability and process for the production of same
US4543174A (en) * 1983-02-16 1985-09-24 Eltech Systems Corporation Method of making a catalytic lead-based oxygen evolving anode
US4797182A (en) * 1986-04-17 1989-01-10 Eltech Systems Corporation Electrode with a platinum metal catalyst in surface film and its use
US5098546A (en) * 1989-12-22 1992-03-24 Tdk Corporation Oxygen-generating electrode
US5314601A (en) * 1989-06-30 1994-05-24 Eltech Systems Corporation Electrodes of improved service life
US5324407A (en) * 1989-06-30 1994-06-28 Eltech Systems Corporation Substrate of improved plasma sprayed surface morphology and its use as an electrode in an electrolytic cell
US5545262A (en) * 1989-06-30 1996-08-13 Eltech Systems Corporation Method of preparing a metal substrate of improved surface morphology
EP1162288A1 (en) * 2000-06-09 2001-12-12 De Nora Elettrodi S.P.A. Electrode characterized by highly adhering superficial catalytic layer
US6527939B1 (en) 1999-06-28 2003-03-04 Eltech Systems Corporation Method of producing copper foil with an anode having multiple coating layers
US20030085199A1 (en) * 2001-11-08 2003-05-08 Korea Atomic Energy Research Institute & Technology Winners Co., Ltd. Method for manufacturing catalytic oxide anode using high temperature sintering
US6589405B2 (en) 2000-05-15 2003-07-08 Oleh Weres Multilayer oxide coated valve metal electrode for water purification
RU2216609C2 (ru) * 2001-04-23 2003-11-20 Общество с ограниченной ответственностью "Эмеральд" Способ изготовления малоизнашиваемых анодов
US20040045834A1 (en) * 2002-04-18 2004-03-11 Bayer Aktiengesellschaft Process for the utilization of vanadium bound in chromium ore as vanadium(V) oxide by electrolysis
US20040182551A1 (en) * 2003-03-17 2004-09-23 Cooligy, Inc. Boiling temperature design in pumped microchannel cooling loops
US20040234378A1 (en) * 2003-01-31 2004-11-25 James Lovette Method and apparatus for low-cost electrokinetic pump manufacturing
US20050044352A1 (en) * 2001-08-30 2005-02-24 Riverhead Networks, Inc. Protecting against spoofed DNS messages
US20070080071A1 (en) * 2005-10-12 2007-04-12 All My Relations, Inc. Internal combustion apparatus and method utilizing electrolysis cell
US20070201204A1 (en) * 2006-02-16 2007-08-30 Girish Upadhya Liquid cooling loops for server applications
US20090288856A1 (en) * 2008-05-24 2009-11-26 Phelps Dodge Corporation Multi-coated electrode and method of making
US20100096260A1 (en) * 2008-10-16 2010-04-22 Finnchem Usa Inc Water chlorinator having dual functioning electrodes
US8580091B2 (en) 2010-10-08 2013-11-12 Water Star, Inc. Multi-layer mixed metal oxide electrode and method for making same
WO2014165912A1 (en) * 2013-04-10 2014-10-16 Murdoch University Coated composite anodes
WO2016112976A1 (en) 2015-01-15 2016-07-21 Abb Technology Ltd Ionomer coated electrode
CN105803482A (zh) * 2016-03-17 2016-07-27 同济大学 一种电解水制氢用电解池的集电极材料的改性方法及用途
CN114774998A (zh) * 2022-04-08 2022-07-22 西安泰金工业电化学技术有限公司 一种低贵金属Ir-Ta复合氧化物涂层阳极的制备方法
US11668017B2 (en) 2018-07-30 2023-06-06 Water Star, Inc. Current reversal tolerant multilayer material, method of making the same, use as an electrode, and use in electrochemical processes

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CA1232227A (en) * 1982-02-18 1988-02-02 Christopher Vance Manufacturing electrode by immersing substrate in aluminium halide and other metal solution and electroplating
DE102004015633A1 (de) * 2004-03-31 2005-10-20 Studiengesellschaft Kohle Mbh Verfahren zur Herstellung von Beschichtungen aus Iridiumoxiden
DK3271091T3 (da) 2015-03-19 2019-08-26 Elie Elgressy Nedbrydning af brændstofkomponenter og opløsningsmidler i grundvand og kontamineret jord
CN111686727B (zh) * 2020-05-25 2022-10-04 中国科学院广州能源研究所 一种负载型析氧催化剂及水电解器膜电极的制备方法

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US3711385A (en) * 1970-09-25 1973-01-16 Chemnor Corp Electrode having platinum metal oxide coating thereon,and method of use thereof
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US3751296A (en) * 1967-02-10 1973-08-07 Chemnor Ag Electrode and coating therefor
US3616446A (en) * 1969-03-28 1971-10-26 Ppg Industries Inc Method of coating an electrode
US3711385A (en) * 1970-09-25 1973-01-16 Chemnor Corp Electrode having platinum metal oxide coating thereon,and method of use thereof

Cited By (51)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4003817A (en) * 1967-12-14 1977-01-18 Diamond Shamrock Technologies, S.A. Valve metal electrode with valve metal oxide semi-conductive coating having a chlorine discharge in said coating
US3926751A (en) * 1972-05-18 1975-12-16 Electronor Corp Method of electrowinning metals
US4072585A (en) * 1974-09-23 1978-02-07 Diamond Shamrock Technologies S.A. Valve metal electrode with valve metal oxide semi-conductive coating having a chlorine discharge catalyst in said coating
US4173518A (en) * 1974-10-23 1979-11-06 Sumitomo Aluminum Smelting Company, Limited Electrodes for aluminum reduction cells
US4032427A (en) * 1975-11-03 1977-06-28 Olin Corporation Porous anode separator
US4072586A (en) * 1975-12-10 1978-02-07 Diamond Shamrock Technologies S.A. Manganese dioxide electrodes
US4107025A (en) * 1977-11-09 1978-08-15 Noranda Mines Limited Stable electrode for electrochemical applications
FR2408665A1 (fr) * 1977-11-09 1979-06-08 Noranda Mines Ltd Electrode stable pour applications electrochimiques
US4285799A (en) * 1978-03-28 1981-08-25 Diamond Shamrock Technologies, S.A. Electrodes for electrolytic processes, especially metal electrowinning
US4185142A (en) * 1978-08-09 1980-01-22 Diamond Shamrock Corporation Oxygen electrode rejuvenation methods
DE3020260A1 (de) * 1979-05-29 1980-12-11 Diamond Shamrock Corp Verfahren zur herstellung von chromsaeure unter verwendung von zweiraum- und dreiraum-zellen
US4306950A (en) * 1979-10-15 1981-12-22 Westinghouse Electric Corp. Process for forming sulfuric acid
US4263112A (en) * 1980-06-20 1981-04-21 Frosch Robert A Cell and method for electrolysis of water and anode therefor
US4468416A (en) * 1981-05-19 1984-08-28 Permelec Electrode Ltd. Electrolytic electrodes having high durability and process for the production of same
US4469581A (en) * 1981-05-19 1984-09-04 Permelec Electrode Ltd. Electrolytic electrode having high durability
US4543174A (en) * 1983-02-16 1985-09-24 Eltech Systems Corporation Method of making a catalytic lead-based oxygen evolving anode
US4797182A (en) * 1986-04-17 1989-01-10 Eltech Systems Corporation Electrode with a platinum metal catalyst in surface film and its use
US6071570A (en) * 1989-06-30 2000-06-06 Eltech Systems Corporation Electrodes of improved service life
US5314601A (en) * 1989-06-30 1994-05-24 Eltech Systems Corporation Electrodes of improved service life
US5324407A (en) * 1989-06-30 1994-06-28 Eltech Systems Corporation Substrate of improved plasma sprayed surface morphology and its use as an electrode in an electrolytic cell
US5435896A (en) * 1989-06-30 1995-07-25 Eltech Systems Corporation Cell having electrodes of improved service life
US5545262A (en) * 1989-06-30 1996-08-13 Eltech Systems Corporation Method of preparing a metal substrate of improved surface morphology
US5578176A (en) * 1989-06-30 1996-11-26 Eltech Systems Corporation Method of preparing electrodes of improved service life
US5672394A (en) * 1989-06-30 1997-09-30 Eltech Systems Corporation Electrodes of improved service life
US5098546A (en) * 1989-12-22 1992-03-24 Tdk Corporation Oxygen-generating electrode
US6527939B1 (en) 1999-06-28 2003-03-04 Eltech Systems Corporation Method of producing copper foil with an anode having multiple coating layers
US6589405B2 (en) 2000-05-15 2003-07-08 Oleh Weres Multilayer oxide coated valve metal electrode for water purification
EP1162288A1 (en) * 2000-06-09 2001-12-12 De Nora Elettrodi S.P.A. Electrode characterized by highly adhering superficial catalytic layer
RU2216609C2 (ru) * 2001-04-23 2003-11-20 Общество с ограниченной ответственностью "Эмеральд" Способ изготовления малоизнашиваемых анодов
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FR2185014A1 (enrdf_load_stackoverflow) 1973-12-28
GB1399576A (en) 1975-07-02
IT959730B (it) 1973-11-10
FR2185014B1 (enrdf_load_stackoverflow) 1977-12-30
ZA732977B (en) 1974-12-24
CA989773A (en) 1976-05-25

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