CA2244158A1 - Method of applying conductive coating - Google Patents
Method of applying conductive coating Download PDFInfo
- Publication number
- CA2244158A1 CA2244158A1 CA002244158A CA2244158A CA2244158A1 CA 2244158 A1 CA2244158 A1 CA 2244158A1 CA 002244158 A CA002244158 A CA 002244158A CA 2244158 A CA2244158 A CA 2244158A CA 2244158 A1 CA2244158 A1 CA 2244158A1
- Authority
- CA
- Canada
- Prior art keywords
- coating
- substrate
- applying
- titanium suboxide
- laser
- 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.)
- Abandoned
Links
Classifications
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
- C23C4/11—Oxides
-
- 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
Abstract
A titanium suboxide of the formula TiOx where x is 1.55 to 1.95, is applied to a substrate by a thermal process to form a coating of the same composition.
The thermal process may be plasma spraying, and the formed article may be an electrode of enhanced corrosion resistance and electrical conductivity.
The thermal process may be plasma spraying, and the formed article may be an electrode of enhanced corrosion resistance and electrical conductivity.
Description
CA 022441~8 1998-07-21 METHOD QF APPLYING
COi\lDUCTlVE COATING
.~
The invention relates to a method for the formation of a corrosion resistant electrically conductive coating on a substrate. The substrate may be an electrode, for say an electrochemical cell.
It has been realised that titanium suboxides are useful as coatings. It is also known that a layer of such a ,I,aLe,ial may be formed on a substrate by flame spraying or plasma spraying, see e.g. GB-A-1438462; US-A-5225382; and G8-A-159506~. In these disclosures mixtures which are precursors for titanium suboxide are plasma sprayed on to a substrate under conditions selected to form the suboxide. Typically the suboxides are of the formula TiOx, where x is between 1.95 and 1.99, see e.g. GB-A-1438462 and lJS
5225382. While such suboxides are corrosion resistant, their electrical conductivity is not acceptable.
US-A-4252629 discloses a corrosion resistant carrier consisting of sintered TiOx where x is 0.25 to 1.5 having a coating of manganese dioxide. The carrier can be made by plasma spraying the titanium oxide under argon.
EP-A-00475g5 discloses that bulk titanium suboxide of the formula TiOx where x is 1.55 to 1.95 has corrosion resistance and electrical conductivity. The disclosure teaches that the material may be formed into shapes by pressing or extrusion.
CA 022441~8 1998-07-21 W O 97/27344 PCTtGB97/00202 It has now been discovered that if a m~Lerial of known stoichiometry is appiied to a substrate one can obtain a coating of predetermined composition and which has a particularly enhanced corrosion resistance and electrical conductivity.
According to the invention in one aspect there is provided a method of forming acorrosion resistant electrically conductive coating on a substrate, com~ ,ing forming a predetermined titanium suboxide of the forrrlula TiOx where x is 1.5~ to 1.95 and then applying that ~I,aLenal on to the substrate to form a coating of the same substantially stoichiometry on the substrate.
The ~l~ lial may be applied by any suitable sFF'iG; ~ion technique which will not affect the sloichio.,lel~y of the ,-,dlerial. Such techniques include plasma spraying and laser coating. De-gun coating in which the material is melted and then projected by delondliu,~
and other thermal coating techniques may also be considered.
Because the starting Illd~ lial is of a known :,: hio~ L,y having desired properties one can obtain directly a coating of the desired stoichiometry and hence the desiredcombination of properties, e.g. electrical conductivity, co., osion resistance etc. It is possible to apply a mixture of the suboxides or just a single one. Most preferably the plasma spraying of the defined titanium suboxide is carried out under conditions which preclude the risk that the stoicl,;o~,lelly will be affected. To this end the applicalion for example may be carried out under vacuum or under a shield of a suitable inert gas, e.g. v argon.
CA 022441~8 1998-07-21 It is advantageous to pretreat the surface of the substrate to enhance the adhesion of the applied coating. The pretreatment may be mec;hani~al, chemical or ele.,l,uchemical, e.g.
sand/grit blasting, deposition, laser ablation, etching, stove codlil 19, or the iike.
~) The method may include the variation of adding minor properties of a dopant to the ,I,dLeridl to be applied. Examples include electrocatalysts and other stabilisers, e.g. Pt, Ir, Ta, Nb, Ru, V; and the like, and oxides, e.g. tin oxide and mixtures thereof. These may influence conductivity, adhesion, CGr. osion resisLa"ce properties. Typically the composition will be in particulate form, e.g. a powder. Such additions may be made as a subsequent treatment, e.g. a further coating of an electrocatalyst may be applied by electroplating, thennal stove-coating, or the like to influence the electrochemical properties of the end product.
The application equipment, e.g. plasma gun, may be of known type with appropriate additional ~LIacllments to ensure an inert gas blanket, e.g. as described in GB-A-2281488.
The laser will be adapted to melt the powder en route to the substrate, but is particularly efficacious since it can be operated in a more co,..~ Iete vacuum or purer inert gas atmosphere. In addition it is possible to clean the surface of the substrate to be coated by a laser surface ablation technique wherein a second laser process can deliver a high energy pulse (typically 35MW over 20 nS) to blast away surface oxides and other conldllli, la-.L:, from the substrate immediately prior to the arrival of the molten powder.
CA 022441~8 1998-07-21 The coated item can be used as an eiectrode (either anode or cathode) in low current density applications directly, or where necessary for high current density with the ~FP'i- on of a suitable electrocatalyst as noted above. The surface may also be electroplated with, for instance, lead or zinc metals to assist electrical connectivity to or adhesion of active materials in a battery. The electrode may be used in electrochemical cells, metal winning, chlorine cells, effluent treatment; and the like.
The method allows coatings to be applied up to thicknesses well in excess of those required for corrosion resistance alone, whilst ~"ai"Ldi~-ing good conductivities. The coating thickness may range from about 50 to about 1000xS0~3mm. For very high corrosion resistances a typical coating would be either of the order of 200-500x103mm where x is about 1.75 to 1.8, or a thinner coating of about 100-200 x10 3 of a stoichiometry where x is about 1.85 to 1.9. For less arduous duty, high conductivity coatings of about 100-200x10~3mm and a stoichiometry of x = 1.75-1.8 are preferred. A
coating of the invention will have conductivity of the order of 10 to 100 S/cm. In even less arduous corrosion duty, dopants can be added which further increase the conductivity.
In order that the invention may be well understood it will now be described with reference to the following examples which are given by way of illu:,L,dlion only.
EXAMPLE I
Test electrodes for electrowinning of zinc were prepared in the following manner Two sheets of commercial grade aluminium 2 mm thick and 230 x 80 mm width and breadth, were lightly filed around all edges to remove sharp edges and burrs, and then grit blasted. The items were then plasma sprayed using a Metco gun equipped with a CA 022441~8 1998-07-21 Shroud as described in GB-A-2281488 which was controlled by a robot which ensured an even coating over the entire surface and edges. The gun was fed with a pre-prepared powder of whose ~i- h;a.~etry had been measured by X-ray diffraction as being as of composition TiOx where x = 1.72. The conductivity was found to be ~0S/cm. The coating was found to be 120 microns thick with a bulk density of 3.84 gm/cc. Subsequently adiusl"~enb were made to the argon and hydrogen flowrates and pressures and a stoichiometry of TiOx where x = 1.76 was obtained and a bulk density of 4.03 gm/cc obtained. (It is generally accepted that if the bulk density is within 5% of the theoretical full density then no interconnected porosity is present).
The coated anode was further treated with an electrocatalytic coating based on mixed oxides of tantalum and iridium. During bhe stove coating one of the test electrodes lost a high proportion of its coating due to the thermal expansion difference between the ceramic and metallic components and was discarded. However the other survived temperature cycling to about 400~C through 30 coats. This anode was used in a test cell as an anode in the electrodeposition of zinc from a solution of 50 gmAitres Zn2+ and 180--200 gm/litre H2SO4 with traces of fluoride (- 10 mgAitre) Mn2+ (5-8 mg/litre) and other conld",il,ant ",ale,ia;s found in a commercial zinc electrowinning stream performing sucGessfully at a current density of 450A/m2 for over 1000 hours of operation. It was notable in this test that although the electrode potential did rise from an initially low (and preferred) level in the long term the anode had a potenbal of about 250mV lower than the Pb/Ag anode ,-,aterial more conventionally used and that any MnO2 which formed on the anode fell off of its own accord from time to time or could be assisted by occasional ullldsol1ic treatment.
CA 022441~8 1998-07-21 Token pieces of titanium metal were coated by the process of Example 1. Because of the smaller difference between the expansion coefficients of the metai and the coating, they were stove coated with electrocatalysts without any spalling of the coating layer. ",~
Solid pieces and expanded metai meshes of aluminium and of titanium were coated with conductive ceramic by the method of Example I and then electrocoated at modest temperatures with lead dioxide7 platinum metal, and antimony/tin oxide coatings.
EXAMPLE IV
Conductive ceramic coatings were applied using the method of Example I to test pieces made of steel, brass, copper, lead and KEVL~R (which is not metallic).
COi\lDUCTlVE COATING
.~
The invention relates to a method for the formation of a corrosion resistant electrically conductive coating on a substrate. The substrate may be an electrode, for say an electrochemical cell.
It has been realised that titanium suboxides are useful as coatings. It is also known that a layer of such a ,I,aLe,ial may be formed on a substrate by flame spraying or plasma spraying, see e.g. GB-A-1438462; US-A-5225382; and G8-A-159506~. In these disclosures mixtures which are precursors for titanium suboxide are plasma sprayed on to a substrate under conditions selected to form the suboxide. Typically the suboxides are of the formula TiOx, where x is between 1.95 and 1.99, see e.g. GB-A-1438462 and lJS
5225382. While such suboxides are corrosion resistant, their electrical conductivity is not acceptable.
US-A-4252629 discloses a corrosion resistant carrier consisting of sintered TiOx where x is 0.25 to 1.5 having a coating of manganese dioxide. The carrier can be made by plasma spraying the titanium oxide under argon.
EP-A-00475g5 discloses that bulk titanium suboxide of the formula TiOx where x is 1.55 to 1.95 has corrosion resistance and electrical conductivity. The disclosure teaches that the material may be formed into shapes by pressing or extrusion.
CA 022441~8 1998-07-21 W O 97/27344 PCTtGB97/00202 It has now been discovered that if a m~Lerial of known stoichiometry is appiied to a substrate one can obtain a coating of predetermined composition and which has a particularly enhanced corrosion resistance and electrical conductivity.
According to the invention in one aspect there is provided a method of forming acorrosion resistant electrically conductive coating on a substrate, com~ ,ing forming a predetermined titanium suboxide of the forrrlula TiOx where x is 1.5~ to 1.95 and then applying that ~I,aLenal on to the substrate to form a coating of the same substantially stoichiometry on the substrate.
The ~l~ lial may be applied by any suitable sFF'iG; ~ion technique which will not affect the sloichio.,lel~y of the ,-,dlerial. Such techniques include plasma spraying and laser coating. De-gun coating in which the material is melted and then projected by delondliu,~
and other thermal coating techniques may also be considered.
Because the starting Illd~ lial is of a known :,: hio~ L,y having desired properties one can obtain directly a coating of the desired stoichiometry and hence the desiredcombination of properties, e.g. electrical conductivity, co., osion resistance etc. It is possible to apply a mixture of the suboxides or just a single one. Most preferably the plasma spraying of the defined titanium suboxide is carried out under conditions which preclude the risk that the stoicl,;o~,lelly will be affected. To this end the applicalion for example may be carried out under vacuum or under a shield of a suitable inert gas, e.g. v argon.
CA 022441~8 1998-07-21 It is advantageous to pretreat the surface of the substrate to enhance the adhesion of the applied coating. The pretreatment may be mec;hani~al, chemical or ele.,l,uchemical, e.g.
sand/grit blasting, deposition, laser ablation, etching, stove codlil 19, or the iike.
~) The method may include the variation of adding minor properties of a dopant to the ,I,dLeridl to be applied. Examples include electrocatalysts and other stabilisers, e.g. Pt, Ir, Ta, Nb, Ru, V; and the like, and oxides, e.g. tin oxide and mixtures thereof. These may influence conductivity, adhesion, CGr. osion resisLa"ce properties. Typically the composition will be in particulate form, e.g. a powder. Such additions may be made as a subsequent treatment, e.g. a further coating of an electrocatalyst may be applied by electroplating, thennal stove-coating, or the like to influence the electrochemical properties of the end product.
The application equipment, e.g. plasma gun, may be of known type with appropriate additional ~LIacllments to ensure an inert gas blanket, e.g. as described in GB-A-2281488.
The laser will be adapted to melt the powder en route to the substrate, but is particularly efficacious since it can be operated in a more co,..~ Iete vacuum or purer inert gas atmosphere. In addition it is possible to clean the surface of the substrate to be coated by a laser surface ablation technique wherein a second laser process can deliver a high energy pulse (typically 35MW over 20 nS) to blast away surface oxides and other conldllli, la-.L:, from the substrate immediately prior to the arrival of the molten powder.
CA 022441~8 1998-07-21 The coated item can be used as an eiectrode (either anode or cathode) in low current density applications directly, or where necessary for high current density with the ~FP'i- on of a suitable electrocatalyst as noted above. The surface may also be electroplated with, for instance, lead or zinc metals to assist electrical connectivity to or adhesion of active materials in a battery. The electrode may be used in electrochemical cells, metal winning, chlorine cells, effluent treatment; and the like.
The method allows coatings to be applied up to thicknesses well in excess of those required for corrosion resistance alone, whilst ~"ai"Ldi~-ing good conductivities. The coating thickness may range from about 50 to about 1000xS0~3mm. For very high corrosion resistances a typical coating would be either of the order of 200-500x103mm where x is about 1.75 to 1.8, or a thinner coating of about 100-200 x10 3 of a stoichiometry where x is about 1.85 to 1.9. For less arduous duty, high conductivity coatings of about 100-200x10~3mm and a stoichiometry of x = 1.75-1.8 are preferred. A
coating of the invention will have conductivity of the order of 10 to 100 S/cm. In even less arduous corrosion duty, dopants can be added which further increase the conductivity.
In order that the invention may be well understood it will now be described with reference to the following examples which are given by way of illu:,L,dlion only.
EXAMPLE I
Test electrodes for electrowinning of zinc were prepared in the following manner Two sheets of commercial grade aluminium 2 mm thick and 230 x 80 mm width and breadth, were lightly filed around all edges to remove sharp edges and burrs, and then grit blasted. The items were then plasma sprayed using a Metco gun equipped with a CA 022441~8 1998-07-21 Shroud as described in GB-A-2281488 which was controlled by a robot which ensured an even coating over the entire surface and edges. The gun was fed with a pre-prepared powder of whose ~i- h;a.~etry had been measured by X-ray diffraction as being as of composition TiOx where x = 1.72. The conductivity was found to be ~0S/cm. The coating was found to be 120 microns thick with a bulk density of 3.84 gm/cc. Subsequently adiusl"~enb were made to the argon and hydrogen flowrates and pressures and a stoichiometry of TiOx where x = 1.76 was obtained and a bulk density of 4.03 gm/cc obtained. (It is generally accepted that if the bulk density is within 5% of the theoretical full density then no interconnected porosity is present).
The coated anode was further treated with an electrocatalytic coating based on mixed oxides of tantalum and iridium. During bhe stove coating one of the test electrodes lost a high proportion of its coating due to the thermal expansion difference between the ceramic and metallic components and was discarded. However the other survived temperature cycling to about 400~C through 30 coats. This anode was used in a test cell as an anode in the electrodeposition of zinc from a solution of 50 gmAitres Zn2+ and 180--200 gm/litre H2SO4 with traces of fluoride (- 10 mgAitre) Mn2+ (5-8 mg/litre) and other conld",il,ant ",ale,ia;s found in a commercial zinc electrowinning stream performing sucGessfully at a current density of 450A/m2 for over 1000 hours of operation. It was notable in this test that although the electrode potential did rise from an initially low (and preferred) level in the long term the anode had a potenbal of about 250mV lower than the Pb/Ag anode ,-,aterial more conventionally used and that any MnO2 which formed on the anode fell off of its own accord from time to time or could be assisted by occasional ullldsol1ic treatment.
CA 022441~8 1998-07-21 Token pieces of titanium metal were coated by the process of Example 1. Because of the smaller difference between the expansion coefficients of the metai and the coating, they were stove coated with electrocatalysts without any spalling of the coating layer. ",~
Solid pieces and expanded metai meshes of aluminium and of titanium were coated with conductive ceramic by the method of Example I and then electrocoated at modest temperatures with lead dioxide7 platinum metal, and antimony/tin oxide coatings.
EXAMPLE IV
Conductive ceramic coatings were applied using the method of Example I to test pieces made of steel, brass, copper, lead and KEVL~R (which is not metallic).
Claims (14)
1. A method of forming a corrosion resistant electrically conductive coating on a substrate, comprising forming a predetermined titanium suboxide of the formula TiOx where x is 1.55 to 1.95 and then applying that material on to the substrate to form a coating of substantially the same stoichiometry on the substrate.
2. A method according to Claim 1, wherein the material is applied by plasma spraying.
3. A method according to Claim 1, wherein the material is applied by laser coating.
4. A method according to Claim 1, wherein the material is applied by a de-gun coating technique.
5. A method according to Claim 1, 2, 3, or 4, including adding a dopant to the titanium suboxide and applying that doped composition on to the substrate.
6. A method according to Claim 5, wherein the dopant is an electrocatalyst and/or other stabilizer.
7. A method according to any preceding Claim, wherein the coating is applied to a thickness of the order of 50-1000x10-3 mm.
8. A method according to any preceding Claim, including the preliminary step of treating the surface of the substrate by mechanical, laser, chemical or electrochemical treatment before the composition is applied thereon.
9. A method according to Claim 8, wherein the pretreatment is blasting, chemical or deposition; stove coating; or the like.
10. A method according to any preceding Claim, wherein the application of the material is carried out under vacuum.
11. A method according to Claim 10, wherein the application of the material is carried out in an atmosphere comprising a gas selected to exclude ingredients which will affect the titanium suboxide.
12. A method according to Claim 11, wherein the gas is argon.
13. A method according to any preceding Claim, including the subsequent step of applying an electrocatalytic material, whereby the surface is further coated with an electrocatalyst including precious metals, mixtures thereof and their oxides and mixtures thereof, lead dioxide, doped tin oxide and the like.
14. A method according to any preceding Claim, wherein the substrate comprises an electrode for an electrochemical cell.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9601236.4 | 1996-01-22 | ||
| GBGB9601236.4A GB9601236D0 (en) | 1996-01-22 | 1996-01-22 | Conductive coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2244158A1 true CA2244158A1 (en) | 1997-07-31 |
Family
ID=10787366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002244158A Abandoned CA2244158A1 (en) | 1996-01-22 | 1997-01-22 | Method of applying conductive coating |
Country Status (5)
| Country | Link |
|---|---|
| CN (1) | CN1212025A (en) |
| AU (1) | AU1451497A (en) |
| CA (1) | CA2244158A1 (en) |
| GB (2) | GB9601236D0 (en) |
| WO (1) | WO1997027344A1 (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6517962B1 (en) | 1999-08-23 | 2003-02-11 | Ballard Power Systems Inc. | Fuel cell anode structures for voltage reversal tolerance |
| DE10000979C1 (en) * | 1999-10-01 | 2001-05-10 | Daimler Chrysler Ag | Coating powder used in plasma spraying, high speed flame spraying and detonation spraying of components of engines is based on a titanium sub-oxide |
| US6524750B1 (en) | 2000-06-17 | 2003-02-25 | Eveready Battery Company, Inc. | Doped titanium oxide additives |
| US7993773B2 (en) | 2002-08-09 | 2011-08-09 | Infinite Power Solutions, Inc. | Electrochemical apparatus with barrier layer protected substrate |
| US20070264564A1 (en) | 2006-03-16 | 2007-11-15 | Infinite Power Solutions, Inc. | Thin film battery on an integrated circuit or circuit board and method thereof |
| ITRM20020622A1 (en) * | 2002-12-13 | 2004-06-14 | Ct Sviluppo Materiali Spa | PROCEDURE FOR PLASMA THERMAL SPRAYING OF DRY SEMICONDUCTIVE OXIDE-BASED COATINGS. |
| FI118159B (en) * | 2005-10-21 | 2007-07-31 | Outotec Oyj | Method for forming an electrocatalytic surface of an electrode and electrode |
| US7608358B2 (en) | 2006-08-25 | 2009-10-27 | Bdf Ip Holdings Ltd. | Fuel cell anode structure for voltage reversal tolerance |
| TWI441937B (en) | 2007-12-21 | 2014-06-21 | Infinite Power Solutions Inc | Method for sputter targets for electrolyte films |
| US8518581B2 (en) | 2008-01-11 | 2013-08-27 | Inifinite Power Solutions, Inc. | Thin film encapsulation for thin film batteries and other devices |
| US8906523B2 (en) | 2008-08-11 | 2014-12-09 | Infinite Power Solutions, Inc. | Energy device with integral collector surface for electromagnetic energy harvesting and method thereof |
| US8599572B2 (en) | 2009-09-01 | 2013-12-03 | Infinite Power Solutions, Inc. | Printed circuit board with integrated thin film battery |
| US20130017471A1 (en) * | 2009-12-22 | 2013-01-17 | Ford Motor Company | Fuel cell with selectively conducting anode component |
| CN102947976B (en) | 2010-06-07 | 2018-03-16 | 萨普拉斯特研究有限责任公司 | Chargeable, highdensity electrochemical apparatus |
| FI2823079T3 (en) | 2012-02-23 | 2023-05-04 | Treadstone Tech Inc | Corrosion resistant and electrically conductive surface of metal |
| ITMI20120873A1 (en) * | 2012-05-21 | 2013-11-22 | Industrie De Nora Spa | ELECTRODE FOR EVOLUTION OF GASEOUS PRODUCTS AND METHOD FOR ITS ACHIEVEMENT |
| CN104241655A (en) * | 2014-07-04 | 2014-12-24 | 超威电源有限公司 | Conductive ceramic battery grid |
| CN105297073A (en) * | 2015-10-30 | 2016-02-03 | 昆明理工大学 | Preparation method of copper-based titanium black electrode plate |
| CN105776429B (en) * | 2016-03-15 | 2019-08-09 | 中国矿业大学(北京) | With active tubular ring Asia oxidation titanium film electrode of electrochemical oxidation and preparation method thereof |
| WO2019176956A1 (en) * | 2018-03-12 | 2019-09-19 | 三菱マテリアル株式会社 | Titanium base material, method for producing titanium base material, electrode for water electrolysis, and water electrolysis device |
| CN109457270A (en) * | 2018-12-29 | 2019-03-12 | 西安泰金工业电化学技术有限公司 | A kind of preparation method of ti-based coating Ni―Ti anode |
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|---|---|---|---|---|
| US3330707A (en) * | 1963-10-07 | 1967-07-11 | Varian Associates | Method for reducing electron multipactor on a dielectric window surface |
| DE2300422C3 (en) * | 1973-01-05 | 1981-10-15 | Hoechst Ag, 6000 Frankfurt | Method of making an electrode |
| GB1464375A (en) * | 1974-05-22 | 1977-02-09 | Ass Eng Ltd | Abrading devices |
| US3962488A (en) * | 1974-08-09 | 1976-06-08 | Ppg Industries, Inc. | Electrically conductive coating |
| GB1595061A (en) * | 1976-11-22 | 1981-08-05 | Atomic Energy Authority Uk | Electrically conductive layers produced by plasma spraying |
| DE2714605A1 (en) * | 1977-04-01 | 1978-10-05 | Sigri Elektrographit Gmbh | Lead di:oxide electrode having sub:oxide-coated titanium support - used in fuel and galvanic cells, for electrochemical reactions and for anticorrosion purposes |
| US4194022A (en) * | 1977-07-25 | 1980-03-18 | Ppg Industries, Inc. | Transparent, colorless, electrically conductive coating |
| US4422917A (en) * | 1980-09-10 | 1983-12-27 | Imi Marston Limited | Electrode material, electrode and electrochemical cell |
| DE3046757C2 (en) * | 1980-12-12 | 1985-09-12 | W.C. Heraeus Gmbh, 6450 Hanau | Gravure cylinder |
| US4395432A (en) * | 1981-12-16 | 1983-07-26 | Westinghouse Electric Corp. | β-Alumina coating |
| JPS59230773A (en) * | 1983-06-14 | 1984-12-25 | Kyocera Corp | Thermal head |
| JPS60251291A (en) * | 1984-05-29 | 1985-12-11 | Ishifuku Kinzoku Kogyo Kk | Anode for electrolyzing diluted chloride solution |
| DE3513892A1 (en) * | 1985-04-17 | 1986-10-23 | Plasmainvent AG, Zug | CR (DOWN ARROW) 2 (DOWN ARROW) O (DOWN ARROW) 3 (DOWN ARROW) PROTECTIVE LAYER AND METHOD FOR PRODUCING THE SAME |
| US5538612A (en) * | 1987-12-09 | 1996-07-23 | Ngk Spark Plug Co., Ltd. | Oxygen sensor element |
| US4861680A (en) * | 1988-02-11 | 1989-08-29 | Southwall Technologies | Bronze-grey glazing film and window made therefrom |
| JPH0774470B2 (en) * | 1990-03-20 | 1995-08-09 | ダイソー株式会社 | Manufacturing method of anode for oxygen generation |
| DE4421007A1 (en) * | 1994-06-18 | 1995-12-21 | Philips Patentverwaltung | Electronic component and method for its production |
| US5521029A (en) * | 1995-02-22 | 1996-05-28 | At&T Corp. | Current collecting elements |
-
1996
- 1996-01-22 GB GBGB9601236.4A patent/GB9601236D0/en active Pending
-
1997
- 1997-01-22 CN CN97192455A patent/CN1212025A/en active Pending
- 1997-01-22 CA CA002244158A patent/CA2244158A1/en not_active Abandoned
- 1997-01-22 WO PCT/GB1997/000202 patent/WO1997027344A1/en active Application Filing
- 1997-01-22 GB GB9701229A patent/GB2309230A/en not_active Withdrawn
- 1997-01-22 AU AU14514/97A patent/AU1451497A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| GB9601236D0 (en) | 1996-03-20 |
| GB2309230A (en) | 1997-07-23 |
| CN1212025A (en) | 1999-03-24 |
| WO1997027344A1 (en) | 1997-07-31 |
| AU1451497A (en) | 1997-08-20 |
| GB9701229D0 (en) | 1997-03-12 |
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