Metal Oxide-Coated Valve Metals

Good results are obtained with oxide-coated valve metals as anode materials. These electrically conducting ceramic coatings of p-conducting spinel-ferrite (e.g., cobalt, nickel and lithium ferrites) have very low consumption rates. Lithium ferrite has proved particularly effective because it possesses excellent adhesion on titanium and niobium [26]. In addition, doping the perovskite structure with monovalent lithium ions provides good electrical conductivity for anodic reactions. Anodes produced in this way are distributed under the trade name Lida [27]. The consumption rate in seawater is given as 10 g A a and in fresh water is 

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Commercial metal anodes for the chlorine industry came about after the late 1960s when a series of worldwide patents were awarded (6—8). These were based not on the use of the platinum-group metals (qv) themselves, but on coatings comprised of platinum-group metal oxides or a mixture of these oxides with valve metal oxides, such as titanium oxide (see Platinum-GROUP metals, compounds Titanium compounds). In the case of chlor-alkaH production, the platinum-group metal oxides that proved most appropriate for use as coatings on anodes were those of mthenium and iridium. 

Iridium Oxide. Iridium dioxide [12030 9-8] coatings, typically used in combination with valve metal oxides, are quite similar in stmcture to those of mthenium dioxide coatings. X-ray diffraction shows the mtile crystal stmcture of the iridium dioxide scanning electron micrographs show the micro-cracked surface typical of these thermally prepared oxide coatings. 

It is a valve metal and when made anodic in a chloride-containing solution it forms an anodic oxide film of TiOj (rutile form), that thickens with an increase in voltage up to 8-12 V, when localised film breakdown occurs with subsequent pitting. The TiOj film has a high electrical resistivity, and this coupled with the fact that breakdown can occur at the e.m.f. s produced by the transformer rectifiers used in cathodic protection makes it unsuitable for use as an anode material. Nevertheless, it forms a most valuable substrate for platinum, which may be applied to titanium in the form of a thin coating. The composite anode is characterised by the fact that the titanium exposed at discontinuities is protected by the anodically formed dielectric Ti02 film. Platinised titanium therefore provides an economical method of utilising the inertness and electronic conductivity of platinum on a relatively inexpensive, yet inert substrate. 

Titanium as a carrier metal Titanium (or a similar metal such as tantalum, etc.) cannot work directly as anode because a semiconducting oxide layer inhibits any electron transport in anodic direction ( valve metal ). But coated with an electrocatalytic layer, for example, of platinum or of metal oxides (see below), it is an interesting carrier metal due to the excellent corrosion stability in aqueous media, caused by the self-healing passivation layer (e.g. stability against chlorine in the large scale industrial application of Dimension Stable Anodes DSA , see below). 

The DSA-type anodes are inert , coated anodes made of a valve metal (titanium, niobium, or tantalum) base coated with an electrochemically active coating. The active coating is made either of noble metals or of mixed metal oxides. Noble metals in active coatings are usually platinum or platinum alloys. Mixed metal-oxide coatings contain active oxides and inert oxides the active components are usually ruthenium dioxide (R.UO2) and iridium dioxide (IrC>2) and the inert components are mostly titanium dioxide (TiC>2) and other oxides such as tantalum... 

The dimensionally stable anode in this system is composed of an electrically conductive substrate of titanium, having a coating of a defect solid solution containing mixed crystals of precious metal oxides. These substitutional solid solutions are both electrically conductive, electrocatalytic, and dimensionally stable. Within the aforementioned solid-solution host structures the valve metals include titanium, tantalum, niobium, and... 

As stated in the introduction, Ta coating may be used as substrate in the preparation of DSA oxygen electrodes it consists of a thin and porous layer of Iridium oxide, which acts as catalyst, obtained by thermal oxidation of an iridium compound on a valve metal. The lifetime of the anode in water electrolysis in extreme conditions of polarization (anodic current = 50 A/m ), acid concentration (30% m/m) and temperature (T = 80°C) is sensitive to the corrosion resistance of the valve metal This is shown on table I [24], which standardized life time (lifetime reported for the mass surface density of the catalyst Ir02) for some varieties of titanium base alloys and a tantalum coating as substrate ... 

The colloidal particles are often deposited on metallic electrodes in the form of adsorbed coatings. Rubber and graphite coatings can be formed in this way, using solvent mixtures (water-acetone) as the dispersion media. The advantage of this method is that additives can firmly be codeposited with, for example, rubber latex. Thermionic emitters for radio valves are produced in a similar manner. The colloidal suspensions of alkaline earth carbonates are deposited electrophoretically on the electrode and are later converted to oxides by using an ignition process. 

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