US3234110A - Electrode and method of making same - Google Patents

Electrode and method of making same Download PDF

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Publication number
US3234110A
US3234110A US362180A US36218064A US3234110A US 3234110 A US3234110 A US 3234110A US 362180 A US362180 A US 362180A US 36218064 A US36218064 A US 36218064A US 3234110 A US3234110 A US 3234110A
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core
titanium
barrier layer
electrode
noble metal
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Beer Henri Bernard
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AMALGAMATED CURACAO PATENTS CO
AMALGAMATED CURACAO PATENTS Co NV
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AMALGAMATED CURACAO PATENTS CO
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    • 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
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals using reducing agents
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
    • C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
    • C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
    • C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
    • C23F13/12—Electrodes characterised by the material
    • C23F13/14—Material for sacrificial anodes
    • 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
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • 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
    • 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
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F2213/00—Aspects of inhibiting corrosion of metals by anodic or cathodic protection
    • C23F2213/30—Anodic or cathodic protection specially adapted for a specific object
    • C23F2213/31—Immersed structures, e.g. submarine structures

Definitions

  • the present invention relates to' an electrode having a base or core oftitanium or titanium with small amounts of alloying metals therein,.which core is covered with a barrier layer of titanium oxide and coated with a noble metal coating, and to a method of producing such an electrode.
  • an electrode particularly suitable for use as an anode which has such a core or base of titanium, either substantially pure titanium or titanium with small amounts of alloying metals therein, and a coating of a noble met-a1, such as platinum, iridium, rodium, or alloys of these metals.
  • a noble met-a1 such as platinum, iridium, rodium, or alloys of these metals.
  • the core of titanium is treated so as to remove any oxide coating therefrom and the noble metal-coating is formed thereon. Since such coatings are at best slightlyporous, there are places in the'coating at which the titanium core is exposed. At these pores there is formed a barrier layer of titanium oxide. This barrier layer is for-med by placing the electrode in an electrolyte and electrolytically forming the barrier layer.
  • the barrier layer can be formed by a chemical and/ or a thermal treatment which makes a more stable and chemically inert barrier layer than forming the barrier layer electrolytically.
  • ionic current flow can take place through the noble metal coating and electronic current flow will take place" from the noble metal coating to the titanium core.
  • the barrier layer over theutitanium core which is exposed through the pores in the noble metal coating will prevent ionic current flow directly to the titanium core, and will thereby prevent a chemical attack by the electrolyte, which is usually quite corrosive on the titanium of the core.
  • the noble metal coating is chemically resistant so that the titanium core is protected from chemical attack where it is coated by the noble metal.
  • the titanium or titanium alloy core of such an electrode can be'entirely covered with a barrier layer of titanium oxide, and thereafter coated with a noble metal coatinggand it will still act as an electrode, particularly as an anode in electrolytic processes suchas, for example, brine electrolysis, and as an anode in cathodic protection methods.
  • a barrier layer of titanium oxide between the noble metal coating and the titanium core or base does not. interfere with the electronic flow of current from the noble metal coating to the titanium base, while at the places where the noble metal coating is imperfectly formed or has pores in it, the barrier layer prevents ionic flow of current from the electrolyte to the titanium base.
  • an electrode having a core of aluminum whichhas been oxidized in air or has been intentionally provided with a layer of oxide for example by anodizing, and which has been coatedwith a noble metal offers a high resistance to the passage of electric current from the noble metal coating to the aluminum core.
  • the electrode according to the invention is particularly valuable in that if, during use, the noble metal coating should be damaged, for example by peeling off, 'there will be a barrier layer already formed beneath the noble metal coating which will immediately resist attack by the electrolyte, and the electrode will accordingly be preserved and itslife extended.
  • his a further'object of the present invention to provide a method of making an electrode particularly suitable for use as an anode by forming a barrier layer of titanium oxide on such a core or base, and then coating a noble have vanadium or aluminum therein in an amount up to 4% by weight, or it can have zirconium therein up to 10% by weight.
  • a noble have vanadium or aluminum therein in an amount up to 4% by weight, or it can have zirconium therein up to 10% by weight.
  • These percentages of metals other than titan- ..ium will not inhibit the film forming characteristic of the titanium. Accordingly, where reference is made to a core or base of titanium in this specification, it -is to be under 'stood'th'at such a core or base includes a base of substantially pure titanium aswell as a base of titanium and an alloying metal as herein described.
  • barrier layer as used to describe the oxide layer formed on the titanium core of the electrode of the present invention, is meant a layer of oxide which resists attack by the electrolyte in which the electrode is used, and at-the same time prevents passage'of current directly from the electrolyte to the titanium core but permits passage of current from the noble metal coating to the core.
  • the voltage which is impressed on the core must be below the breakdown, voltage for titanium in the electrolyte in'question. Otherwise, if the breakdown voltage for titanium in the particular electrolyte is exceeded, the form of oxide which will be produced is not that which produces a barrier layer, but rather is one which, when itis coated with a conducting-metal, will not permit electronic current conduction therethrough from a noble metal coating to the titanium core at the normal operating voltages of the electrodes during their use in electrolysis.
  • the breakdown voltage will vary depending on the particular elec trolyte in which the barrier layer is being formed on the titanium core, and in fact the breakdown voltage will. be further dependent on the metal of the core, should it be, for example, an alloy of titanium. For this reason,
  • thevoltages at which the barrier layer is formed can vary from example to example.
  • the voltage utilized will amount to to 60% of the breakdown voltage depending on the concentration and temperature of the electrolyte.
  • the method of making the electrodes according tothe invention comprises at least partially immersing a core of'titanium in an electrolyte, impressing a voltage on said core, which voltage is below the breakdown-voltage for titanium in said electrolyte, but :sufiicient 'to form a barrier layer of titanium oxide on the portion of the core which is immersed in the electrolyte, painting a solution of at least one salt of a noble metal taken from.
  • the thus treated specimens 1, 3,v 5 and 6 were then used as anodes in theelectrolysis of 30% brine solutions at a temperature of 60 C; and a current density of 1500 amperes per square meter, at an applied voltage of 2.8. volts.
  • Specimens 2 and 4 were used as anodes in-a similar chloride alkali electrolysis with excellent results.
  • rhodium compound for example rhodiumchloride
  • Specimens 13-18 were :each'coated twice: with a paint f l I whichcontaine'd 10% by weight platinum chloride, 20%
  • vender an ethereal oil (lavender) and the remainder an or v ganic diluent, for example acetone and isopropyl alcohol.
  • Ionic resistance Intensity in Ionic resistance in 1 ohms rmcroamperes in ohms microamperes in ohms 4 36,000 111 57 70,250 1% NaCLQ 20" 0. 001-0. 005 6 100,000 37, 500 5% N aCl 0. 001-0. 005 6 25,000 240 52, 700 1% NaCl 0. (101-0005 4 45, 000 89 S0 50, 000 1% H450 0. 001-0. 005 4 100,000 40 100 40, 000 10% H2304. 0. 001-0. 005 4 115,000 35 130 80, 800 10% NaOH 0. 001-0.
  • a platinum salt for example platinum tetraiodide
  • solvent for. exampleethanol. After each coating the -water, and proved very satisfactory.
  • Example 19 A plate of substantially pure titanium was partly coated with platinum, and was at least partially immersed as an anode in an electrolyte which was an aqueous solution having 5% NaCl at a temperature of 70 C. so that at least part of the platinum coated portion of the electrode was in the electrolyte. A voltage of 4 volts was applied to the electrode to form a barrier layer on the uncoated portions of the electrode which were immersed in the electrolyte. Immediately after the application of the voltage, the current intensity was 1,000,000 microamperes and the ionic resistance was 4 ohms.
  • a barrier layer was formed on the uncoated parts of the electrode-which had a resistance as measured
  • a plate of titanium metal is thoroughly degreased by rinsing it with e.g. petrol or carbon tetrachloride. The plate is dried and placed as anode between two graphite cathodes in a solution of 95 parts by volume of concentrated phosphoric acid (98% or more) and 5 parts by volume of concentrated nitric acid. The voltage between the titanium anode and the graphite cathodes is gradually raised to 100 volts, a barrier layer of titanium oxide forming which also after the termination of the electrolysis remains of excellent quality.
  • the plate When from the color it appears that the entire plate is covered by the mixture, the plate is dried and the whole is heated in an open flame to a temperature of at most 700 C. A rhodium coating of about 2 microns will form.
  • the electrode thus manufactured is found to be very satisfactory when used as anode for carrying out electro lyses of all kinds of electrolytes, more particularly also of baths containing chloride, with the exception only of electrolyses evolving fluorine.
  • the allowable current density is 70 amperes per square decimeter or higher.
  • an electrode in which there is a barrier layer completely covering the titanium of the base, so that where there are pores or breaks in the noble metal coating on the electrode, the titanium of the base is protected by the barrier layer. Should the coating peel or otherwise be removed, all that is exposed is the barrier layer, the titanium of the core being protected from attack by the electrolyte in which the electrode is immersed.
  • this type of electrode it is possible with this type of electrode to provide the electrode with a fresh coating of noble metal a substantially unlimited number of times, if desired.
  • the barrier layer remains intact once it has been formed, so that it is not necessary to pickle the electrode before applying a new noble metal coating, as has heretofore been done with this type of electrode.
  • a further advantage of the electrodes according to the invention is that the adherence of the coating of noble metal is enhanced because the surface of the oxide barrier layer is rougher than the surface of the bare titanium metal.
  • An electrode comprising a core of a metal taken from the group consisting of 'titanium and an alloy of titanium and small amounts of alloying metals, a high ionic resistance, low electronic resistance barrier layer of titanium oxide covering at least a part of said core, and a noble metal coating over said barrier layer, the noble metal being selected from the group consisting of platnium, rhodium, iridium, and alloys thereof, said barrier layer being electrolytically deposited on said core by impressing thereon a voltage below the breakdown voltage of the metal of the core in the electrolyte used for the formation of the barrier layer.
  • An electrode comprising a core of a metal taken from the group consisting of titanium and an alloy of titanium and small amounts of alloying metals, a high ionic resistance, low electronic resistance barrier layer of titanium oxide covering at least part of said core, and a noble metal coating over said barrier layer, the noble metal being selected from the group consisting of platinum, rhodium, iridium, and alloys thereof, said barrier layer being electrolytically deposited on said core by im pressing thereon a voltage below the breakdown voltage of the metal of the core in the electrolyte used for the formation of the barrier layer, and the noble metal coating being deposited on the barrier layer by painting onto the barrier layer a solution containing a compound of the noble metal and evaporating the solvent.
  • An electrode comprising a core of a metal taken from the group consisting of titanium and an alloy of titanium and small amounts of alloying metals, a barrier layer of titanium oxide covering at least a part of said core, and a noble metal coating over said barrier layer, the noble metal being selected from the group consisting of platinum, rhodium, iridium, and alloys thereof, said barrier layer having an electronic resistance in the range of about 0.001 to 0.005 ohm and an ionic resistance of at least about 35,000 ohms which is formed by immersing the core in .a sodium chloride electrolyte for about 15 minutes with an impressed voltage of about 4 volts.
  • a method of making an electrode comprising the steps of immersing at least a part of a core of a metal taken from the group consisting of titanium and an alloy of titanium and small amounts of alloying metals in an electrolyte as an anode, impressing a voltage on said core, which voltage is below the breakdown voltage for titanium in said electrolyte, to thereby form a high ionic resistance, low electronic resistance barrier layer of titanium oxide on the immersed part of said core, and then coating over said barrier layer a noble metal taken from the group consisting of platinum, rhodium, iridium, and alloys thereof.
  • a method of making an electrode comprising the steps of immersing at least a part of a core of a metal taken from the group consisting of titanium and an alloy 7 t of titaniumand small amounts of alloying metals in an electrolyte as an anode, impressing a voltage .on said core,
  • a method as claimed in claim 6 in which the painted core is heated in air for evaporating and. burning the solvent, and then is heated in a reducing atmosphere for reducing thecornpound of the noble metal while leaving the barrier layer unaifected.
  • a method of making an electrode comprising the steps of partly coating a core of a metal taken'fromthe group consisting of titanium and an alloy of titaniumand small amounts of alloying metals with a noble metal,

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
US362180A 1959-02-06 1964-04-23 Electrode and method of making same Expired - Lifetime US3234110A (en)

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BE (1) BE587237A (US07608600-20091027-C00054.png)
CH (1) CH398512A (US07608600-20091027-C00054.png)
DE (1) DE1115721B (US07608600-20091027-C00054.png)
DK (1) DK98880C (US07608600-20091027-C00054.png)
FR (1) FR1311108A (US07608600-20091027-C00054.png)
GB (1) GB925080A (US07608600-20091027-C00054.png)
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US3497426A (en) * 1964-07-02 1970-02-24 Nippon Carbide Kogyo Kk Manufacture of electrode
US3497425A (en) * 1964-07-20 1970-02-24 Imp Metal Ind Kynoch Ltd Electrodes and methods of making same
US3751296A (en) * 1967-02-10 1973-08-07 Chemnor Ag Electrode and coating therefor
US3786680A (en) * 1972-11-01 1974-01-22 D Clark Voltage sensing system
US3878072A (en) * 1973-11-01 1975-04-15 Hooker Chemicals Plastics Corp Electrolytic method for the manufacture of chlorates
US3884777A (en) * 1974-01-02 1975-05-20 Hooker Chemicals Plastics Corp Electrolytic process for manufacturing chlorine dioxide, hydrogen peroxide, chlorine, alkali metal hydroxide and hydrogen
US3897320A (en) * 1973-11-01 1975-07-29 Hooker Chemicals Plastics Corp Electrolytic manufacture of chlorates, using a plurality of electrolytic cells
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US4005003A (en) * 1975-04-15 1977-01-25 Olin Corporation Multi-component metal electrode
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US4696731A (en) * 1986-12-16 1987-09-29 The Standard Oil Company Amorphous metal-based composite oxygen anodes
US4702813A (en) * 1986-12-16 1987-10-27 The Standard Oil Company Multi-layered amorphous metal-based oxygen anodes
US4705610A (en) * 1985-06-24 1987-11-10 The Standard Oil Company Anodes containing iridium based amorphous metal alloys and use thereof as halogen electrodes
US4781803A (en) * 1985-02-26 1988-11-01 The Standard Oil Company Electrolytic processes employing platinum based amorphous metal alloy oxygen anodes
US4797182A (en) * 1986-04-17 1989-01-10 Eltech Systems Corporation Electrode with a platinum metal catalyst in surface film and its use
US5004626A (en) * 1986-10-27 1991-04-02 Huron Technologies, Inc. Anodes and method of making
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
US5328584A (en) * 1992-06-19 1994-07-12 Water Regeneration Systems, Inc. Passive circulation in electrolytic fluid treatment systems
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WO2002038833A1 (en) * 2000-11-13 2002-05-16 Akzo Nobel N.V. Gas diffusion electrode
US20020110726A1 (en) * 2000-11-13 2002-08-15 Bernd Busse Electrode
US6527939B1 (en) 1999-06-28 2003-03-04 Eltech Systems Corporation Method of producing copper foil with an anode having multiple coating layers
US20030168348A1 (en) * 2001-03-14 2003-09-11 Yasuhito Kondo Method and apparatus for generating ozone by electrolysis
US20040211676A1 (en) * 2001-07-16 2004-10-28 Miox Corporation Electrolytic cell for surface and point of use disinfection
US20040226873A1 (en) * 2001-07-16 2004-11-18 Miox Corporation Gas drive electrolytic cell
US20050131509A1 (en) * 2003-12-16 2005-06-16 Liliana Atanassoska Coatings for implantable electrodes
DE102004015633A1 (de) * 2004-03-31 2005-10-20 Studiengesellschaft Kohle Mbh Verfahren zur Herstellung von Beschichtungen aus Iridiumoxiden
US20060037869A1 (en) * 2004-08-19 2006-02-23 Miox Corporation Scented electrolysis product
US20060137973A1 (en) * 2004-11-24 2006-06-29 Miox Corporation Device and method for instrument steralization
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GB925080A (en) 1963-05-01
FR1311108A (fr) 1962-12-07
DK98880C (da) 1964-06-01
NL235848A (US07608600-20091027-C00054.png)
BE587237A (nl) 1960-05-30
NL122179C (US07608600-20091027-C00054.png) 1966-12-15
CH398512A (de) 1966-03-15

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