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  • 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
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  • 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
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  • C23C18/04—Pretreatment of the material to be coated
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  • 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
  • C23C18/02—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 thermal decomposition
  • C23C18/08—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 thermal decomposition characterised by the deposition of metallic material
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  • 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
  • C23C18/02—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 thermal decomposition
  • C23C18/12—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 thermal decomposition characterised by the deposition of inorganic material other than metallic material
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  • 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
  • C23C18/02—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 thermal decomposition
  • C23C18/12—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 thermal decomposition characterised by the deposition of inorganic material other than metallic material
  • C23C18/1204—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 thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
  • C23C18/1208—Oxides, e.g. ceramics
  • C23C18/1216—Metal oxides
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  • 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
  • C23C18/02—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 thermal decomposition
  • C23C18/12—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 thermal decomposition characterised by the deposition of inorganic material other than metallic material
  • C23C18/1225—Deposition of multilayers of inorganic material
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  • 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
  • C23C18/02—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 thermal decomposition
  • C23C18/12—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 thermal decomposition characterised by the deposition of inorganic material other than metallic material
  • C23C18/1229—Composition of the substrate
  • C23C18/1241—Metallic substrates
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  • 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
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  • 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
  • C23C18/02—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 thermal decomposition
  • C23C18/12—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 thermal decomposition characterised by the deposition of inorganic material other than metallic material
  • C23C18/125—Process of deposition of the inorganic material
  • C23C18/1275—Process of deposition of the inorganic material performed under inert atmosphere
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  • 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
  • C23C18/02—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 thermal decomposition
  • C23C18/12—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 thermal decomposition characterised by the deposition of inorganic material other than metallic material
  • C23C18/125—Process of deposition of the inorganic material
  • C23C18/1279—Process of deposition of the inorganic material performed under reactive atmosphere, e.g. oxidising or reducing atmospheres
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  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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  • C25B1/00—Electrolytic production of inorganic compounds or non-metals
  • C25B1/01—Products
  • C25B1/14—Alkali metal compounds

Definitions

• the invention relates to a method for forming a coating of metal oxides comprising at least one precious metal of group VIII of the periodic table of elements possibly associated with titanium and / or zirconium, on an electroconductive substrate.
• the invention also relates to an activated cathode obtained from the electroconductive substrate coated according to the method of the invention.
• the invention also relates to the use of said activated cathode, in particular for the electrolysis of aqueous solutions of alkali metal chlorides and particularly for the preparation of chlorine and sodium hydroxide as well as for the preparation of sodium chlorate.
• chlorine and sodium hydroxide as well as sodium chlorate
• electrolytic cells each of which comprises a plurality of steel cathodes and a plurality of titanium anodes coated with a mixture of titanium oxides. and ruthenium.
• electrolytic solution consisting of about 200 to 300 g / l of sodium chloride.
• sodium chlorate they generally contain 50 to 250 g / l of sodium chloride.
• overvoltage is meant the difference between the thermodynamic potential of the redox couple concerned (H2O / H2) with respect to a reference cathode and the potential actually measured in the medium concerned, with respect to the same reference electrode.
• overvoltage we use the term overvoltage to designate the absolute value of the cathode overvoltage.
• a cathode whose substrate is a plate of titanium, zirconium, niobium or alloy consisting essentially of a combination of these metals and on which is applied a layer of metal oxide, essentially consisting of an oxide of one or a plurality of metals selected from ruthenium, rhodium, palladium, osmium, iridium and platinum and optionally an oxide of one or more metals selected from calcium, magnesium, strontium, barium, zinc, chromium, molybdenum, tungsten, selenium and tellurium.
• US Pat. No. 4,100,049 describes a cathode comprising a substrate of iron, nickel, cobalt or an alloy of these metals and a coating of palladium oxide and zirconium oxide.
• the intermediate and superficial layers can be constituted by the oxide of the only metal concerned or by a mixed oxide of the metal in question and the second metal in a small proportion.
• an activated cathode constituted by an electroconductive substrate, either titanium or nickel, coated with an intermediate layer of titanium-based oxides and a precious metal of the group VIII of the Periodic Table of Elements and an outer layer of metal oxides comprising titanium, zirconium and a precious metal of group VIII of the Periodic Table of Elements; said coating being obtained by thermal decomposition of a solution of chloride or oxychloride of these metals in ethanol or isopropanol.
• the Applicant has found that by judiciously choosing organometallic compounds and their solvents, it obtained coatings of the aforementioned metal oxides having a very good adhesion to substrates made of steel or iron.
• the subject of the invention is therefore a process for forming a coating of metal oxides comprising at least one precious metal of group VIII of the periodic table of elements possibly associated with titanium and / or zirconium, on an electroconductive substrate, said method consisting in applying to said substrate a solution comprising at least one organometallic compound and then converting said (or said) organometallic compound (s) into metal oxide (s) by means of a heat treatment; said method being characterized in that the electroconductive substrate is of steel or iron and in that the only solution applied to said substrate is a non-aqueous solution of metallic acetylacetonate or a mixture of dissolved metal acetylacetonates ( ) in a solvent (s) specifically solubilizing each metal acetylacetonate, the solvent (s)
• precious metal of Group VIII of the Periodic Table of Elements is currently ruthenium, rhodium, palladium, osmium, iridium or platinum.
• ruthenium or iridium and especially ruthenium will be used.
• alcohols which can be used according to the present invention, mention may be made of ethanol and isopropanol.
• ketones used according to the present invention include acetone, methyl ethyl ketone.
• chloromethanes that may be used according to the present invention, mention may be made of methylene chloride or chloroform.
• the solution which is applied to the electroconductive substrate is a solution of an acetylacetonate of a metal selected from the group: Ru, Rh, Pd, Os, Ir, Pt, Ti and Zr or a mixture of acetylacetonates of two or more of the metals included in this group.
• a metal selected from the group: Ru, Rh, Pd, Os, Ir, Pt, Ti and Zr or a mixture of acetylacetonates of two or more of the metals included in this group.
• said solution contains only a metal acetylacetonate, it can be obtained by dissolving this metal acetylacetonate in its specific solvent, or in a solvent mixture containing the specific solvent.
• the solution can be advantageously carried out with stirring, at room temperature, or at a slightly higher temperature to improve the dissolution of metal acetylacetonates.
• concentrated solutions of metal acetylacetonates will preferably be used and, to prepare said solutions, it is for the person skilled in the art to take into account the solubility of the various metal acetylacetonates in the solvents (or mixture of solvents). usable according to the present invention.
• an ethanolic solution of ruthenium acetylacetonate (0.25 mole / liter) will be used, and an acetone solution of titanyl acetylacetonate (CsH7O2) 2 TiO 3 at 0, 8 mole / liter.
• a preferred method of forming a metal oxide coating according to the present invention is, in a first step, to pretreat the steel or iron substrate to impart roughness characteristics to the surface and then, in a second step depositing on said pretreated substrate the solution containing the metal acetylacetonate (s) prepared as indicated above; then to dry and calcine the substrate thus coated.
• This second step - impregnation / drying / calcination - can be advantageously repeated one or more times to obtain the coating.
• this second step is repeated until a desired metal mass is obtained.
• this step is repeated between 2 and 6 times.
• the pretreatment generally consists of subjecting the substrate to sandblasting, followed optionally by acid washing, or to etching with an aqueous solution of oxalic acid, hydrofluoric acid, a mixture of hydrofluoric acid and nitric acid, a mixture of hydrofluoric acid and glycerol, a mixture of hydrofluoric acid, nitric acid and glycerol or a mixture of hydrofluoric acid, nitric acid and hydrogen peroxide, followed by one or more washing (s) with degassed demineralised water.
• the substrate may be in the form of a solid plate, perforated plate, expanded metal or cathode basket made from the expanded or perforated metal.
• the solution can be deposited on the pretreated substrate using various techniques such as sol-gel, spraying or coating.
• the pretreated substrate is coated with the solution, for example with the aid of a brush.
• the substrate thus coated is then dried in air and / or in an oven at a temperature at most equal to
• the substrate is calcined under air or under inert gas enriched with oxygen at a temperature of at least 300 ° C and preferably between 400 ° C and 600 ° C for a period of 10 minutes to 2 hours.
• This method of operation makes it possible to convert the acetylacetonate (s) metal (s) into a coating of metal oxide (s) uniform and adherent on the substrate steel or iron.
• the solution can be deposited on one of the pretreated substrate faces as well as on both sides.
• the weight of precious metal deposited, expressed in g / m 2 relative to the geometrical surface of the substrate is at least equal to 2 g / m 2 , generally between 2 and 20 g / m 2 and preferably between 5 and 10 g / m 2 .
• the subject of the invention is also an so-called activated cathode obtained from an electroconductive substrate coated according to the invention.
• the cathode of the present invention is particularly suitable for the electrolysis of aqueous solutions of alkali metal chlorides and especially aqueous solutions of NaCl.
• the use of the cathode of the present invention in combination with an anode makes it possible to electrolytically synthesize the chlorine and hydroxide of an alkali metal.
• the use of the cathode of the present invention in combination with an anode makes it possible to electrolytically synthesize the chlorate of an alkali metal.
• DSA Dissionally Stable Anode
• anodes consist of a titanium substrate coated with a layer of titanium oxide and ruthenium.
• the ruthenium / titanium molar ratio in this layer is advantageously between 0.4 and 2.4.
• the cathode of the present invention has the advantage of having a low overvoltage and of being a cheap substrate.
• the coating solution is prepared by dissolving 0.653 g of ruthenium acetylacetonate, 0.329 g of titanyl acetylacetonate and 0.178 g of zirconium acetylacetonate in 10 ml of ethanol + 10 ml of acetone + 10 ml. chloroform to obtain a molar distribution 45 Ru / 45 Ti / 10 Zr.
• the support consists of a solid iron plate (3.5 x 2.5 cm) on which is welded a steel rod; the total surface is 33 cm 2 .
• the substrate is sandblasted with Corundum and then rinsed with acetone.
• the support is then completely coated with the solution, placed in an oven at 120 ° C. for 15 minutes and then in an oven at 450 ° C. for 15 minutes. This gives a coating of 2.4 g / m 2 .
• This procedure is repeated 3 times (4 layers in total) so as to obtain a coating having a mass of 7.9 g / m 2 , ie an equivalent weight of 3.3 g (Ru) / m 2 .
• the last heat treatment of the support is 30 minutes at 450 ° C.
• the steel rod Prior to the electrochemical evaluation, the steel rod is masked with Teflon tape to delineate a well-defined surface.
• the coated support is then placed in an electrochemical cell containing 200 ml of 1 M sodium hydroxide at room temperature and will be tested cathode.
• a counter electrode consisting of a titanium anode coated with RuO 2 -TiO 2 and a saturated Calomel reference electrode (ECS) extended with a capillary containing a saturated solution of KCl is used.
• the electrodes are connected to the terminals of a potentiostat (Solartron).
• the activity of the cathode is measured from the polarization curves (from the drop potential up to -1, 3 or -1.4 V / ECS at a rate of I mV / s).
• An activation step is then carried out by applying a current of an intensity equal to 2 amperes to the cathode for 1 hour, and a new polarization curve is then drawn to evaluate the changes in the electrochemical performances of the cathode. This activation step is repeated until a stable polarization curve is obtained, that is to say identical to the curve preceding the last activation (generally 3 or 4 times).
• Table (1) below shows the evolution of the cathode potential for a current density of 1, 6 kA / m 2 as a function of the number of activation steps.
• the voltage gain is the difference between the potential of the activated cathode and the potential of the bare iron cathode for the same current density (here 1, 6 kA / m 2 ).
• the solution is prepared by dissolving 0.500 g of ruthenium acetylacetonate and 0.329 g of titanyl acetylacetonate in 10 ml of ethanol + 10 ml of acetone so as to obtain an equimolar Ru / Ti solution.
• the support consists of a solid iron plate (3.5 x 2.5 cm) on which is welded a steel rod; the total surface is 33 cm 2 .
• the support is sandblasted with Corundum and then rinsed with acetone.
• the support is then completely coated with the solution, placed in an oven at 120 ° C. for 15 minutes and then in an oven at 450 ° C. for 15 minutes. This gives a coating of 2.2 g / m 2 .
• This procedure is repeated 3 times (4 layers in total) so as to obtain a coating having a mass of 9.8 g / m 2 , ie an equivalent mass of 4.6 g (Ru) / m 2 .
• the last heat treatment is 30 minutes at 450 ° C.
• the solution is prepared by dissolving 0.500 g of ruthenium acetylacetonate in 10 ml of ethanol + 10 ml of acetone.
• the support consists of a solid iron plate (3.5 x 2.5 cm) on which is welded a steel rod; the total surface is 33 cm 2 .
• the substrate is sandblasted with Corundum and then rinsed with acetone.
• the support is then completely coated with the solution, placed in an oven at 120 ° C. for 15 minutes and then in an oven at 450 ° C. for 15 minutes. This gives a coating of 1.9 g / m 2 .
• This procedure is repeated twice (3 layers in total) so as to obtain a coating having a mass of 3.8 g / m 2 , ie an equivalent mass of 2.9 g (Ru) / m 2 .
• the last heat treatment is timed at 450 ° C.
• the solution is prepared by dissolving 0.500 g of ruthenium acetylacetonate in 10 ml of ethanol.
• the support consists of a solid steel plate (3.5 x 2.5 cm) on which - is welded a steel rod; the total surface is 33 cm 2 .
• the substrate is sandblasted with Corundum and then rinsed with acetone.
• the support is then completely coated with the solution, placed in an oven at 120 ° C. for 15 minutes and then in an oven at 450 ° C. for 15 minutes. This gives a coating of 2.1 g / m 2 . This procedure is repeated 3 times (4 layers in total) so as to obtain a coating having a mass of 7.6 g / 2 , ie an equivalent mass of 5.8 g (Ru) / m 2 .
• the last heat treatment is 30 minutes at 450 ° C.
• Cathode for chlorine-soda electrolysis pilot diaphragm An activated cathode of 72 cm 2 was prepared for a laboratory pilot of electrolysis chlorine-soda diaphragm.
• the substrate consists of a steel mesh, used on industrial cells.
• the desired coating is of equimolar composition in Ru and Ti, it is prepared according to the procedure described in Example 2, it is deposited on both sides of the support material.
• the coating weight is 13.7 g / m 2 , ie 6.5 g (Ru) / m 2 , deposited in 4 layers. No electrochemical characterization is made on this cathode before its mounting on the pilot cell because of its size.
• the activated cathode is mounted in an electrolysis cell pilot diaphragm chlor-soda ® Polyramix using a diaphragm and operating continuously 24h / 24h, 7days / 7.
• a racking and feeding game keeps the concentration of the different products in the electrolysis cell constant.
• the operating conditions are as follows: 2.5 kA / m 2 , 85 ° C., sodium hydroxide concentration in the cathode liquor between 120 g / l and 140 g / l, expanded titanium anode coated Ru0 2 -TiO ⁇ .
• An uncoated iron cathode from the same industrial support is installed in an equivalent cell, operating with the same operating conditions.
• Graph (1) shows the evolution of the potential of these two cathodes over 120 days of operation. In this graph: ⁇ denotes activated cathode and denotes bare steel cathode.
• the gain in voltage, obtained by difference of the two potentials, is of the order of 180 mV over the period 20 days - 120 days of operation.
• EXAMPLE 6 Use of an Activated Cathode for Sodium Chlorate Electrolysis
• a 200 cm 2 (5 cm ⁇ 40 cm) activated cathode is prepared for a sodium chlorate electrolysis pilot.
• An iron support is coated on these two faces with an equimolar deposit of Ru and Ti according to the procedure described in Example 2, except that the final heat treatment is 1 hour at 450 ° C.
• the deposit mass is 10.3 g / m 2 , 4.9 g (Ru) / m 2 .
• This cathode is then placed in a pilot cell of sodium chlorate electrolysis.
• the anode consists of an expanded titanium support coated RuO2-TiO 2 .
• a racking and feeding game keeps the concentration of the different products in the electrolysis cell constant.
• a substrate consisting of a solid nickel plate and a substrate consisting of a solid iron plate are coated with an equimolar RuO 2 -TiO 2 deposit according to the procedure described in Example 2 by repeating the cycle "coating / drying / calcination "until a deposit of 9 - 10 g / m 2 is obtained, ie 4.3 to 4.7 g (Ru) / m 2 .
• the last heat treatment is 30 minutes at 450 ° C. 3 layers are necessary for the iron support, 6 layers for the nickel support: the deposit is less adherent on nickel than on iron; these cathodes are then evaluated electrochemically according to the procedure described in Example 1.
• Graph (2) shows the polarization curves after stabilization of each of these cathodes.
• An equimolar coating solution Ru / Ti is prepared by dissolving 5.18 g of RuCl 3 , 1.5H 2 O and 3.1 ml of TiOCI 2 , 2HCl (124.5 g (Ti) / l) in 10 ml of absolute ethanol. The solution is stirred to allow the products to dissolve.
• a first support consists of a solid iron plate (3.5 x 2.5 cm) on which is welded a steel rod; the total surface is 33 cm 2 .
• the substrate is sandblasted with Corundum and then rinsed with acetone.
• a second support consists of a solid nickel plate (3.5 x 2.5 cm) on which is welded a nickel rod; the total surface is 33 cm 2 .
• the substrate is sandblasted with Corundum and then rinsed with acetone.
• Each support is then completely coated with the solution, placed in an oven at 120 ° C for 15 minutes, and then in an oven at 450 ° C for 15 minutes.
• the last heat treatment is 30 minutes at 450 ° C.
• Table (5) shows the evolution of the mass of the deposit as a function of the number of cycles "coating / drying / calcination" for each of the two supports.

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• Inorganic Chemistry (AREA)
• Electrochemistry (AREA)
• Ceramic Engineering (AREA)
• Electrodes For Compound Or Non-Metal Manufacture (AREA)
• Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
• Chemically Coating (AREA)
• Oxygen, Ozone, And Oxides In General (AREA)

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• 2003
  • 2003-03-28 FR FR0303867A patent/FR2852973B1/fr not_active Expired - Fee Related
• 2004
  • 2004-03-25 MX MXPA05010353A patent/MXPA05010353A/es active IP Right Grant
  • 2004-03-25 UA UAA200510604A patent/UA80610C2/uk unknown
  • 2004-03-25 ES ES04742353T patent/ES2270380T3/es not_active Expired - Lifetime
  • 2004-03-25 WO PCT/FR2004/000746 patent/WO2004087992A2/fr not_active Ceased
  • 2004-03-25 AT AT04742353T patent/ATE330043T1/de not_active IP Right Cessation
  • 2004-03-25 DE DE602004001230T patent/DE602004001230T2/de not_active Expired - Lifetime
  • 2004-03-25 CN CN2004800147636A patent/CN1795291B/zh not_active Expired - Fee Related
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  • 2004-03-25 JP JP2006505751A patent/JP4532471B2/ja not_active Expired - Fee Related
  • 2004-03-25 US US10/550,646 patent/US7790233B2/en not_active Expired - Fee Related
  • 2004-03-25 BR BRPI0408905-7A patent/BRPI0408905A/pt not_active Application Discontinuation
  • 2004-03-25 PL PL04742353T patent/PL1608795T3/pl unknown
  • 2004-03-25 EP EP04742353A patent/EP1608795B1/de not_active Expired - Lifetime
• 2005
  • 2005-09-27 ZA ZA200507825A patent/ZA200507825B/en unknown

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