US3882002A - Anode for electrolytic processes - Google Patents
Anode for electrolytic processes Download PDFInfo
- Publication number
- US3882002A US3882002A US494110A US49411074A US3882002A US 3882002 A US3882002 A US 3882002A US 494110 A US494110 A US 494110A US 49411074 A US49411074 A US 49411074A US 3882002 A US3882002 A US 3882002A
- Authority
- US
- United States
- Prior art keywords
- oxide
- anode
- tin oxide
- coating
- noble metal
- 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.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—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
- the present invention relates to improved electrodes particularly adapted for use as anodes in electrochemical process involving the electrolysis of brines.
- the electrical conductivity of the noble metals is substantially higher and the chlorine overvoltage substantially lower than that of graphite.
- the dimensional stability of the noble metals and noble metal oxides represents a substantial improvement over graphite.
- the use of noble metals as a major material of construction in anodes results in an economic disadvantage due to the excessively high cost of such materials.
- This invention provides a novel electrode. especially suited for use as an anode in chlor-alkali cells; the novel electrode comprising a valve metal substrate having a protective coating of conductive tin oxide on the surface thereof and an outer. thin layer of a noble metal or noble metal oxide. Electrodes of this type exhibit a high degree of durability in addition to the relatively low overvoltage characteristics of a noble metal or noble metal oxide. making them wellsuited for use as anodes in the electrolytic production of chorine.
- the preferred substrate materials of the anodes of the invention are the valve metals. such as titanium. tantalum. niobium or zirconium. especially titanium. However. where suitably thick intermediate layers of tin oxide are employed. other more conductive metals may be considered for use as substrates.
- the tin oxide coating which may range in coating weight from about 0.l grams per square meter to lOO grams per square meter or more. depending on the degree of protection desired. prevents contact of the substrate and the electrolyte, thus preventing or minimizing corrosion or surface oxidation and the attendant deterioration or passivation of the substrate. At the same time.
- the outer layer provides the advantageous catalytic properties of the noble metals or noble metal oxides.
- the protective layer of conductive tin oxide permits the use ofa relatively thin layer of the noble metal or noble metal oxide and a consequent savings resulting from a minimal use of the precious metal.
- the layer of noble metal or noble metal oxide will have a coating weight in the range of about 0.] grams per square meter to about 20 grams per square meter or higher and preferably about 3 to [0 grams per square meter in thickness.
- the disadvantage of pores or pinholes in the noble metal layer common in extremely thin layers is obviated by the presence of the intermediate layer of conductive tin oxide. Pores or pinholes in the noble metal layer.
- the intermediate layer of tin oxide will continue to provide a catalytically active surface in those exposed areas.
- the catalytic character istics of tin oxide although not as high as the noble metals or noble metal oxides. is quite substantially higher than the valve metal oxide. Thus. the overall deterioration of the catalytic properties of the anode is more gradual and maintenance problems are accordingly lessened.
- the intermediate layer of tin oxide provides an increase in surface area of the anode with a consequent improvement in overvoltage. It has further been found that the adhesion of the noble metal or noble metal oxide to the substrate is increased by the presence of the intermediate layer of tin oxide and the problem of spalling of the surface layer is thereby reduced.
- valve metal substrate which forms the inner or base component of the electrode is an electroconductive metal having sufficient mechanical strength to serve as a support for the coating and having a high degree of chemical resistivity, especially to the anodic environment of electrolytic cells.
- Typical valve metals include. for example. Ti. Ta. Nb. Zr. and alloys thereof.
- the valve metals are well known for their tendency to form an inert oxide film upon exposure to an anodic environment.
- the preferred valve metal. based on cost and availability as well as electrical and chemical properties is titanium.
- the conductivity ofthe substrate may be improved. if desired. by providing a central core of a highly conductive metal such as copper. in such an arrangement. the core must be electrically connected to and completely protected by the valve metal substrate.
- Tin oxide can be readily formed as an adherent coat ing on a valve metal substrate, in a manner described hereinafter. to provide a protective. electrically conductive layer which is especially resistant to chemical attack in anodic environments. Pure tin oxide however has a relatively high electrical resistivity in comparison to metals and exhibits undesireble change in electrical resistivity as a function of temperature. It is well known that the electrical stability oftin oxide coatings may be substantially improved and the electrical resistivity lowered through the introduction of a minor proportion of a suitable inorganic material (commonly referred to as a dopant). A variety of materials. especially various metal oxides and other metal compounds and mixtures thereof.
- fluorine compounds especially the metal salts of fluorine. such as sodium fluoride. potassium fluoride. lithium fluoride. berylium fluoride. aluminum fluoride. lead fluoride. chromium fluoride. calcium fluoride. and other metal fluorides. hydrazine. phenylhydrazine; phosphorus compounds such as phosphorus chloride.
- the conductive tin oxide coatings of this invention comprise tin oxide. preferably containing a minor amount of a suitable dopant.
- the preferred dopant is an antimony compound which may be added to the tin oxide coating composition either as an oxide or as a compound such as SbCl which may form the oxide when heated in an oxidizing atmosphere. Although the exact form of the antimony in the final coating is not certain.
- compositions of this invention comprise mixtures of tin oxide and a minor amount of antimony oxide. the later being present preferably in an amount of between about 0.1 and 20 weight percent (calculated on the basis of total weight of SnO and Sb- O
- Conductive tin oxide coatings may be adherently formed on the surface of the valve metal substrate by various methods known in the art. Typically such coatings may be formed by first chemically cleaning the substrate. for example. by degreasing and etching the surface in a suitable acid, e.g.. oxalic acid. then applying a solution of appropriate thermally decomposable salts.
- the salts that may be employed include. in general. any thermally decomposable inorganic or organic salt or ester of tin and dopant. e.g.. antimony. including for example their chlorides. alkoxides, alkoxy halides. resinates. amines and the like.
- Typical salts include for example. stannic chloride. dibutyltin dichloride. tin tetraethoxide. antimony trichloride. antimony pentachloride and the like.
- Suitable solvents include for example. ethyl alcohol. propyl alcohol. butyl alcohol. pentyl alcohol. amyl alcohol. toluene. benzene and other organic solvents as well as water.
- the solution of thermally decomposable salts containing for example. a salt of tin and a salt of antimony. or other dopant. in the desired proportions. may be applied to the cleaned surface of the valve metal substrate by painting. brushing. dipping. rolling. spraying or other method.
- the coating is then dried by heating for example at about to 200 C for several minutes to evaporate the solvent. and then heating at a higher temperature. e.g.. 250 to 800 C in oxidizing atmosphere to convert the tin and antimony compounds'to their respective oxides.
- the procedure may be repeated as many times as necessary to achieve a desired coating weight or thickness.
- the final coating weight of this conductive tin oxide coating may vary considerably. but is preferably in the range of about 3 to about 30 grams per square meter.
- a small amount. such as up to 3 percent by weight of a chlorine discharge catalyst such as at least one of the difluorides of manganese. iron. cobalt or nickel may by included in the tin oxide coating to lower the overpotential required for chlorine gas liberation in a chlor-alkali cell.
- the chorine discharge catalyst may be added to the tin oxide coating by suspending a fine particulate preformed sinter of tin dioxide and the catalyst in the solution of thermally decomposable salts.
- Such chlorine discharge catalysts in the tin oxide coating is not essential to the anodes of this invention but may be employed if desired in a known manner such as disclosed in US. Pat. No. 3.627.699.
- the outer coating of the anode comprises a noble metal or noble metal oxide such as platinum. iridium. rhodium. palladium ruthenium or somium or mixtures or alloys of these metals or the oxides or mixtures of the oxides of these metals.
- a noble metal or noble metal oxide such as platinum. iridium. rhodium. palladium ruthenium or somium or mixtures or alloys of these metals or the oxides or mixtures of the oxides of these metals.
- An outer coating of a noble metal may be applied by known methods such as electroplating. chemical deposition from a platinum coating solution. spraying. or other methods.
- the outer coating of the anode comprises a noble metal oxide.
- Noble metal oxide coating may be applied by first depositing the noble metal in the metallic state and then oxidizing the noble metal coating. for example. by galvanic oxidation or chemical oxidation by means of an oxidant such as an oxidizing salt melt. or by heating to an elevated temperature. e.g.. 300 to 600 C or higher in an oxidizing atmosphere such as air oxygen. at atmospheric or superatmospheric pressures to convert the noble metal coating to a coating of the corresponding noble metal oxide.
- Other suitable methods include. for example. electrophoretic deposition of the noble metal oxide; or application of a dispersion of the noble metal oxide in a carrier. such as alcohol. by spraying. brushing. rolling. dipping.
- a preferred method for the formation of the noble metal oxide coating involves coating the conductive tin oxide surface with a solution of a noble metal compound. evaporating the solvent and converting the coating of noble metal compound to the oxide by chemical or electrochemical reaction.
- the conductive tin oxide surface may be coated with a solution of a thermally decomposable salt of a noble metal. such as a solution of a noble metal halide in an alcohol. evaporation of the solvent.
- EXAMPLE I lA Preparation of conductive tin oxide coating A strip of titanium plate was prepared by immersion in hot oxalic acid for several hours to etch the surface. then washed and dried. The titanium was then coated with a composition of tin oxide doped with antimony oxide. following the procedure of Example 4 of US. Pat. No. 3.627.699. in the following manner:
- Tin dioxide was prepared by dissolving metallic tin (84 parts) in concentrated nitric acid and heating until tin dioxide was precipitated.
- Antimony trioxide (l8 parts) was boiled in concentrated nitric acid until evolution of nitrogen oxides ceased. then thoroughly mixed with the precipitated tin oxide.
- the mixture was further treated with hot nitric acid. then washed free of acid and air dried at about 200C.
- About 3 percent by weight of manganese difluoride was added and mixed with the dried mixed oxides.
- the mixture was then compressed into pellets. heated in air at about 800 C for 24 hours. then crushed and reduced to a particle size of less than 60 microns.
- the crushed mixed oxide composition was again pelletized and heated as before and then crushed and ball-milled to a particle size of less than 5 mcirons.
- An antimony trichloride-alkoxy-tin solution was prepared by boiling at reflux conditions for 24 hours a mixture of l5 parts of stannic chloride and 55 parts of namyl alcohol then dissolving therein 2. l 3 parts of antimony trichloride.
- a suspension of 0.17 parts of the mixed oxide composition in 3.6 parts ofthe antimony trichloride-alkoxytin solution was prepared and painted on to the cleaned titanium surface and the coating was oven-dried at 150 C.
- Two additional coats of the same composition were similarly applied and dried after which the coated strip was heated in air at 450 C for about 15 minutes to convert the coating substantially to oxides of tin and antimony with manganese fluoride.
- the coating operation. including the final heating at 450 C was repeated three times to increase the thickness of the coating.
- the theoretical composition of the conductive coating thus prepared. was 85.6 percent SnO 13.7 percent antimony oxides (calculated as Sb O and 0.7 percent MnF
- the coating weight of the finished coating was 2L2 grams per square meter. lB. Preparation of RuO. Coating The conductive tin oxide coated titanium was further coated in the following manner:
- Example 2 a minor proportion of a chlorine discharge agent.
- manganese difluoride was incorporated in the conductive tin oxide coating.
- An anode may also be prepared in accordance with this invention. following the procedure of Example I except that no chlorine discharge agent is added.
- EXAMPLE ll Chlorine Cell Test The anode. prepared as described in Example [8. was installed and tested as an anode in a chlorine cell having a steel cathode separated from the anode by a cationic membrane. The anode compartment was supplied with preheated brine having a composition of about 310 g/l NaCl and pH of about 4.5. The anolyte was maintained at about C. The test was conducted at a constant current density of 310 malcm (2.0 ASl). The anode exhibited a potential of 1. l9 volts (v. a saturated calomel electrode) which potential remained stable during an extended test period.
- anode composed of a titanium substrate leaving a coating of ruthenium oxide directly on the surface thereof was installed and tested under identical conditions.
- the anode exhibited a potential of [.26 volts (v. a saturated calomel electrode).
- anodes such as the anode of Example IB. where the outer coating of noble metal oxide is deposited on the surface of a layer of conductive tin oxide rather than directly on the surface of the valve metal substrate.
- EXAMPLE 111 An anode prepared in accordance with Example 18. that is. an anode consisting of a titanium substrate. an outer coating of ruthenium oxide. and an intermediate layer of conductive tin oxide, was tested in comparison with an anode prepared in accordance with Example IA. that is. an anode consisting of a titanium substrate and a coating of conductive tin oxide.
- the anodes were installed and tested under identical conditions in a chlorine cell having a steel cathode. separated from the anode by a cationic membrane.
- the anode compartment was supplied with preheated brine having a concentration of about 310 grams of NaCl per liter and a pH of about 4.5.
- the anolyte was maintained at about 95 C and the test was conducted at a constant current density of 310 ma/cm (2.0 A81).
- the anode of Example 1B exhibited an initial potential of about 1.20 volts (v. a saturated calomel electrode), the potential remaining essentially constant over a 127 hour test period.
- the anode of Example 1A exhibited an initial potential of about 1.52 volts (v. a saturated calomel electrode), the potential rising to 1.76 volts over the 128 hour test period.
- EXAMPLE IV A sample of titanium mesh was coated with a layer of conductive tin oxide following the procedure of Example IA.
- Example II A sample of titanium mesh coated with conductive tin oxide as described in Example IVA was further coated with an outer layer of ruthenium dioxide following the procedure of Example 18.
- the mesh anodes prepared as described in A and B above. were installed and tested as anodes in chlorine cells wherein the electrode gap between the anode and a steel cathode was 1/8 inch. and the anode and cathode were separated by a cationic membrane.
- the cells were operated with anolyte concentrations ranging from 250 to 310 grams NaCl/liter at a pH of 4.5. and temperatures ranging from 80 to 90 C.
- the tests were conducted at a constant current density of 310 ma/cm (2.0 A5]
- Anode plates (5 inches X 6 inches) prepared in accordance with the procedures of Examples 1A and 18.
- the electrolyte composition ranged from 400 to 550 grams of NaClQ and to grams NaCl and 1.0 to 1.5 grams sodium dichromate per liter and a pH of about 6.7.
- Example 1A having an outer coating of conductive tin oxide, exhibited an initial potential of 4.0 volts. The potential rose gradually to 5.4 volts during the first 40 hours of operation and the anode failed completely in less than two days of operation. Under identical conditions the anode of Example 15 exhibited a lower initial potential (3.50 volts) and excellent stability. rising to about 4.05 volts over an operating time of 91 days.
- An electrolytic anode comprising a valve metal substrate. a coating thereon of conductive tin oxide. and an outer coating of at least one of a noble metal or noble metal oxide.
- an electrolytic anode comprising a mixture of tin oxide and between about 0.1 and about 20 percent by weight of antimony oxide. based on the total weight of said mixture when calculated as Sn0 and Sb- O 7.
- a method of electrolyzing aqueous alkali metal chloride solutions wherein chlorine is liberated at the anode the improvement which comprises using as said anode, a composite structure comprising a valve metal substrate. a coating of conductive tin oxide on the surface thereof. and an outer coating. on the surface of the conductive tin oxide. of at least one of a noble metal or noble metal oxide.
- anode comprises a titanium substrate, a coating thereon of conductive tin oxide. and an outer coating of ruthenium oxide.
- the conductive tin oxide comprises a mixture of tin oxide and between about 0.1 and 20 percent by weight of antimony oxide. based on the total weight of the mixture when calculated as SnO and Sb O
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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)
- Chemically Coating (AREA)
Abstract
Description
Claims (9)
Priority Applications (17)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US494110A US3882002A (en) | 1974-08-02 | 1974-08-02 | Anode for electrolytic processes |
AR259713A AR205045A1 (en) | 1974-08-02 | 1975-01-01 | ELECTROLYTIC ANODE |
US05/553,860 US3986942A (en) | 1974-08-02 | 1975-02-27 | Electrolytic process and apparatus |
US05/564,529 US3951766A (en) | 1974-08-02 | 1975-04-02 | Electrolytic cell and method of using same |
US05/574,806 US3956083A (en) | 1974-08-02 | 1975-05-05 | Electrochemical anode and process using the anode |
US05/574,478 US3943042A (en) | 1974-08-02 | 1975-05-05 | Anode for electrolytic processes |
US05/574,805 US3940323A (en) | 1974-08-02 | 1975-05-05 | Anode for electrolytic processes |
CA230,660A CA1058563A (en) | 1974-08-02 | 1975-07-03 | Anode for electrolytic processes |
GB29900/75A GB1485884A (en) | 1974-08-02 | 1975-07-16 | Anode for electrolytic cells |
DE19752532553 DE2532553A1 (en) | 1974-08-02 | 1975-07-21 | ANODE FOR ELECTROLYTIC PROCEDURES |
NL7508764A NL7508764A (en) | 1974-08-02 | 1975-07-23 | ELECTROLYSIS ANODE AND METHOD FOR ELECTROLYZING Aqueous ALKALINE METAL CHLORIDE SOLUTIONS. |
BR7504830*A BR7504830A (en) | 1974-08-02 | 1975-07-28 | ELECTROLYTIC ANODES AND PERFECTING IN THE ELECTROLYSIS PROCESS OF AQUEOUS METAL CHLORIDE SOLUTIONS |
FR7523984A FR2280718A1 (en) | 1974-08-02 | 1975-07-31 | ANODE FOR ELECTROLYTIC PROCESSES |
BE158853A BE832010A (en) | 1974-08-02 | 1975-07-31 | ANODE FOR ELECTROLYTIC PROCESSES |
IT25973/75A IT1040223B (en) | 1974-08-02 | 1975-07-31 | ANODE FOR ELECTROLYTIC PROCESSES |
SE7508697A SE7508697L (en) | 1974-08-02 | 1975-07-31 | ELECTROLYSIS ANOD |
JP50094673A JPS592753B2 (en) | 1974-08-02 | 1975-08-02 | How to get the job done |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US494110A US3882002A (en) | 1974-08-02 | 1974-08-02 | Anode for electrolytic processes |
Related Child Applications (5)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/553,860 Continuation-In-Part US3986942A (en) | 1974-08-02 | 1975-02-27 | Electrolytic process and apparatus |
US05/564,529 Continuation-In-Part US3951766A (en) | 1974-08-02 | 1975-04-02 | Electrolytic cell and method of using same |
US05/574,805 Continuation-In-Part US3940323A (en) | 1974-08-02 | 1975-05-05 | Anode for electrolytic processes |
US05/574,806 Continuation-In-Part US3956083A (en) | 1974-08-02 | 1975-05-05 | Electrochemical anode and process using the anode |
US05/574,478 Continuation-In-Part US3943042A (en) | 1974-08-02 | 1975-05-05 | Anode for electrolytic processes |
Publications (1)
Publication Number | Publication Date |
---|---|
US3882002A true US3882002A (en) | 1975-05-06 |
Family
ID=23963089
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US494110A Expired - Lifetime US3882002A (en) | 1974-08-02 | 1974-08-02 | Anode for electrolytic processes |
Country Status (12)
Country | Link |
---|---|
US (1) | US3882002A (en) |
JP (1) | JPS592753B2 (en) |
AR (1) | AR205045A1 (en) |
BE (1) | BE832010A (en) |
BR (1) | BR7504830A (en) |
CA (1) | CA1058563A (en) |
DE (1) | DE2532553A1 (en) |
FR (1) | FR2280718A1 (en) |
GB (1) | GB1485884A (en) |
IT (1) | IT1040223B (en) |
NL (1) | NL7508764A (en) |
SE (1) | SE7508697L (en) |
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3940323A (en) * | 1974-08-02 | 1976-02-24 | Hooker Chemicals & Plastics Corporation | Anode for electrolytic processes |
US3943042A (en) * | 1974-08-02 | 1976-03-09 | Hooker Chemicals & Plastics Corporation | Anode for electrolytic processes |
US3956083A (en) * | 1974-08-02 | 1976-05-11 | Hooker Chemicals & Plastics Corporation | Electrochemical anode and process using the anode |
US3986942A (en) * | 1974-08-02 | 1976-10-19 | Hooker Chemicals & Plastics Corporation | Electrolytic process and apparatus |
US4028215A (en) * | 1975-12-29 | 1977-06-07 | Diamond Shamrock Corporation | Manganese dioxide electrode |
JPS5544514A (en) * | 1978-09-22 | 1980-03-28 | Permelec Electrode Ltd | Electrode for electrolysis and production thereof |
US4223049A (en) * | 1978-05-23 | 1980-09-16 | Research Triangle Institute | Superficially mixed metal oxide electrodes |
US4233148A (en) * | 1979-10-01 | 1980-11-11 | Great Lakes Carbon Corporation | Electrode composition |
US4378406A (en) * | 1979-03-28 | 1983-03-29 | University Of Florida | Thin platinum films on tin oxide substrates |
US4584084A (en) * | 1984-03-02 | 1986-04-22 | Permelec Electrode Ltd. | Durable electrode for electrolysis and process for production thereof |
US4585540A (en) * | 1984-09-13 | 1986-04-29 | Eltech Systems Corporation | Composite catalytic material particularly for electrolysis electrodes and method of manufacture |
FR2599050A1 (en) * | 1986-05-22 | 1987-11-27 | Permelec Electrode Ltd | SUSTAINABLE ELECTRODES FOR ELECTROLYSIS WITH ANODE OXYGEN RELEASE AND PROCESS THEREOF |
US5232576A (en) * | 1990-09-04 | 1993-08-03 | Permelec Electrode Ltd. | Anode for chromium plating and processes for producing and using the same |
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 |
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 |
US20070261968A1 (en) * | 2005-01-27 | 2007-11-15 | Carlson Richard C | High efficiency hypochlorite anode coating |
WO2007148085A3 (en) * | 2006-06-19 | 2008-02-28 | Clarizon Ltd | Electrode, method of manufacture and use thereof |
US20100044219A1 (en) * | 2003-05-07 | 2010-02-25 | Eltech Systems Corporation | Smooth Surface Morphology Chlorate Anode Coating |
EP2447395A2 (en) | 2010-10-28 | 2012-05-02 | Bayer MaterialScience AG | Electrode for producing chlorine through electrolysis |
US8580091B2 (en) | 2010-10-08 | 2013-11-12 | Water Star, Inc. | Multi-layer mixed metal oxide electrode and method for making same |
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 |
CN116573728A (en) * | 2023-06-05 | 2023-08-11 | 江阴米尔克电解设备有限公司 | Titanium anode plate for water treatment and preparation method thereof |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS586786B2 (en) * | 1976-03-15 | 1983-02-07 | ダイヤモンド・シヤムロツク・コ−ポレ−シヨン | Improved electrode manufacturing method |
JPS53153736U (en) * | 1977-05-11 | 1978-12-04 | ||
JPS5597486A (en) * | 1979-01-21 | 1980-07-24 | Tdk Corp | Electrode for electrolysis and its manufacture |
CA1175883A (en) * | 1980-06-30 | 1984-10-09 | Joseph W. Mitchell | Electrolytic printing electrode |
JPS60184691A (en) * | 1984-03-02 | 1985-09-20 | Permelec Electrode Ltd | Durable electrode and its manufacture |
JPS61196056A (en) * | 1985-02-26 | 1986-08-30 | 篠田 和殷 | Roof snow falling apparatus |
JPS6233965A (en) * | 1985-04-09 | 1987-02-13 | 高口 博行 | Apparatus for conveying and removing snow |
JPH0240690Y2 (en) * | 1985-07-04 | 1990-10-30 | ||
JPH0312115Y2 (en) * | 1986-01-17 | 1991-03-22 | ||
JPS6311778A (en) * | 1986-07-01 | 1988-01-19 | 山口 肇 | Snow removing apparatus |
CN102464382B (en) * | 2010-11-05 | 2013-10-23 | 同济大学 | High oxygen evolution potential and electrode preparation method for treating fluorine containing organic waste water |
CN102689948B (en) * | 2011-03-24 | 2013-11-13 | 同济大学 | SnO2 electrode for treating fluorine-containing organic pollutants |
JP7037937B2 (en) * | 2014-07-17 | 2022-03-17 | インドゥストリエ・デ・ノラ・ソチエタ・ペル・アツィオーニ | Chlorine dioxide catalyst or electrode catalyst generation |
Citations (5)
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US3627669A (en) * | 1968-12-13 | 1971-12-14 | Ici Ltd | Electrodes for electrochemical cells |
US3711385A (en) * | 1970-09-25 | 1973-01-16 | Chemnor Corp | Electrode having platinum metal oxide coating thereon,and method of use thereof |
US3775284A (en) * | 1970-03-23 | 1973-11-27 | J Bennett | Non-passivating barrier layer electrodes |
US3776834A (en) * | 1972-05-30 | 1973-12-04 | Leary K O | Partial replacement of ruthenium with tin in electrode coatings |
US3810770A (en) * | 1967-12-14 | 1974-05-14 | G Bianchi | Titanium or tantalum base electrodes with applied titanium or tantalum oxide face activated with noble metals or noble metal oxides |
Family Cites Families (1)
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GB1244650A (en) * | 1968-10-18 | 1971-09-02 | Ici Ltd | Electrodes for electrochemical processes |
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1974
- 1974-08-02 US US494110A patent/US3882002A/en not_active Expired - Lifetime
-
1975
- 1975-01-01 AR AR259713A patent/AR205045A1/en active
- 1975-07-03 CA CA230,660A patent/CA1058563A/en not_active Expired
- 1975-07-16 GB GB29900/75A patent/GB1485884A/en not_active Expired
- 1975-07-21 DE DE19752532553 patent/DE2532553A1/en not_active Withdrawn
- 1975-07-23 NL NL7508764A patent/NL7508764A/en unknown
- 1975-07-28 BR BR7504830*A patent/BR7504830A/en unknown
- 1975-07-31 IT IT25973/75A patent/IT1040223B/en active
- 1975-07-31 BE BE158853A patent/BE832010A/en unknown
- 1975-07-31 SE SE7508697A patent/SE7508697L/en unknown
- 1975-07-31 FR FR7523984A patent/FR2280718A1/en active Granted
- 1975-08-02 JP JP50094673A patent/JPS592753B2/en not_active Expired
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Cited By (37)
Publication number | Priority date | Publication date | Assignee | Title |
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US3940323A (en) * | 1974-08-02 | 1976-02-24 | Hooker Chemicals & Plastics Corporation | Anode for electrolytic processes |
US3943042A (en) * | 1974-08-02 | 1976-03-09 | Hooker Chemicals & Plastics Corporation | Anode for electrolytic processes |
US3956083A (en) * | 1974-08-02 | 1976-05-11 | Hooker Chemicals & Plastics Corporation | Electrochemical anode and process using the anode |
US3986942A (en) * | 1974-08-02 | 1976-10-19 | Hooker Chemicals & Plastics Corporation | Electrolytic process and apparatus |
US4028215A (en) * | 1975-12-29 | 1977-06-07 | Diamond Shamrock Corporation | Manganese dioxide electrode |
US4223049A (en) * | 1978-05-23 | 1980-09-16 | Research Triangle Institute | Superficially mixed metal oxide electrodes |
JPS5544514A (en) * | 1978-09-22 | 1980-03-28 | Permelec Electrode Ltd | Electrode for electrolysis and production thereof |
JPS5639716B2 (en) * | 1978-09-22 | 1981-09-16 | ||
US4378406A (en) * | 1979-03-28 | 1983-03-29 | University Of Florida | Thin platinum films on tin oxide substrates |
US4233148A (en) * | 1979-10-01 | 1980-11-11 | Great Lakes Carbon Corporation | Electrode composition |
WO1981000865A1 (en) * | 1979-10-01 | 1981-04-02 | Great Lakes Carbon Corp | Electrode composition |
US4584084A (en) * | 1984-03-02 | 1986-04-22 | Permelec Electrode Ltd. | Durable electrode for electrolysis and process for production thereof |
US4585540A (en) * | 1984-09-13 | 1986-04-29 | Eltech Systems Corporation | Composite catalytic material particularly for electrolysis electrodes and method of manufacture |
FR2599050A1 (en) * | 1986-05-22 | 1987-11-27 | Permelec Electrode Ltd | SUSTAINABLE ELECTRODES FOR ELECTROLYSIS WITH ANODE OXYGEN RELEASE AND PROCESS THEREOF |
US4941953A (en) * | 1986-05-22 | 1990-07-17 | Permelec Electrode Ltd. | Durable electrodes having a plated tinor tin oxide intermediate layer for electrolysis and process for producing the same |
US5435896A (en) * | 1989-06-30 | 1995-07-25 | Eltech Systems Corporation | Cell having 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 |
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 |
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 |
US5232576A (en) * | 1990-09-04 | 1993-08-03 | Permelec Electrode Ltd. | Anode for chromium plating and processes for producing and using the same |
EP0576402B1 (en) * | 1992-06-25 | 1997-03-05 | Eltech Systems Corporation | Electrodes of improved service life |
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 |
US8142898B2 (en) | 2003-05-07 | 2012-03-27 | De Nora Tech, Inc. | Smooth surface morphology chlorate anode coating |
US20100044219A1 (en) * | 2003-05-07 | 2010-02-25 | Eltech Systems Corporation | Smooth Surface Morphology Chlorate Anode Coating |
US20070261968A1 (en) * | 2005-01-27 | 2007-11-15 | Carlson Richard C | High efficiency hypochlorite anode coating |
WO2007148085A3 (en) * | 2006-06-19 | 2008-02-28 | Clarizon Ltd | Electrode, method of manufacture and use thereof |
US7985327B2 (en) * | 2006-06-19 | 2011-07-26 | Clarizon Limited | Electrode, method of manufacture and use thereof |
US20100065420A1 (en) * | 2006-06-19 | 2010-03-18 | Clarizon Limited | Electrode, method of manufacture and use thereof |
US8580091B2 (en) | 2010-10-08 | 2013-11-12 | Water Star, Inc. | Multi-layer mixed metal oxide electrode and method for making same |
EP2447395A2 (en) | 2010-10-28 | 2012-05-02 | Bayer MaterialScience AG | Electrode for producing chlorine through electrolysis |
DE102010043085A1 (en) | 2010-10-28 | 2012-05-03 | Bayer Materialscience Aktiengesellschaft | Electrode for electrolytic chlorine production |
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 |
CN116573728A (en) * | 2023-06-05 | 2023-08-11 | 江阴米尔克电解设备有限公司 | Titanium anode plate for water treatment and preparation method thereof |
CN116573728B (en) * | 2023-06-05 | 2024-04-16 | 江阴米尔克电解设备有限公司 | Preparation method of titanium anode plate for water treatment |
Also Published As
Publication number | Publication date |
---|---|
AR205045A1 (en) | 1976-03-31 |
NL7508764A (en) | 1976-02-04 |
JPS5140381A (en) | 1976-04-05 |
DE2532553A1 (en) | 1976-02-19 |
GB1485884A (en) | 1977-09-14 |
CA1058563A (en) | 1979-07-17 |
SE7508697L (en) | 1976-02-03 |
FR2280718B1 (en) | 1978-10-13 |
FR2280718A1 (en) | 1976-02-27 |
BE832010A (en) | 1976-02-02 |
IT1040223B (en) | 1979-12-20 |
JPS592753B2 (en) | 1984-01-20 |
BR7504830A (en) | 1976-08-03 |
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