Oxide-coated anodes

These anodes are used extensively in electrogalvanizing, tin electroplating, electrochemical production of copper foil for printed circuit boards, and electrowinning of copper and zinc [91-95]. The application of oxide-coated anodes to sodium sulfate electrolysis so far is small and is not a major driver of electrode development programs. However, environmental concerns associated with byproduct or waste sodium sulfate, along with possible imbalances in the demand for chlorine and caustic soda are enough to maintain interest in the technique. 

Mixed metal oxide coated anodes, also called dimensionally stable anodes (DSA), are based on electrode technology developed in the early 1960s for the production of chlorine and caustic soda. The mixed metal oxide films are thermally applied to a noble metal such as titanium, niobium, and tantalum as substrate materials and are available in a variety of sizes and shapes. These oxide coatings have excellent conductivity, are resistant to acidic environments, are chemically stable, and have relatively low consumption rates. Groundbed installation in soils usually specifies that the anode be prepackaged in a canister with carbonaceous backfill material. 

Many competitive programs to perfect a metallic anode for chlorine arose. In one, Dow Chemical concentrated on a coating based on cobalt oxide rather than precious metal oxides. This technology was patented (9,10) and developed to the semicommercial state, but the operating characteristics of the cobalt oxide coatings proved inferior to those of the platinum-group metal oxide. 

Cathodic Protection Systems. Metal anodes using either platinum [7440-06 ] metal or precious metal oxide coatings on titanium, niobium [7440-03-17, or tantalum [7440-25-7] substrates are extensively used for impressed current cathodic protection systems. A prime appHcation is the use of platinum-coated titanium anodes for protection of the hulls of marine vessels. The controUed feature of these systems has created an attractive alternative... 

Metal anodes using platinum and precious metal oxide coatings are also incorporated into a variety of designs of impressed current protection for pipeline and deep weU appHcations, as weU as for protection of condenser water boxes in power generating stations (see Pipelines Power generation). 

The second form consists of Pt metal but the iridium is present as iridium dioxide. Iridium metal may or may not be present, depending on the baking temperature (14). Titanium dioxide is present in amounts of only a few weight percent. The analysis of these coatings suggests that the platinum metal acts as a binder for the iridium oxide, which in turn acts as the electrocatalyst for chlorine discharge (14). In the case of thermally deposited platinum—iridium metal coatings, these may actually form an intermetallic. Both the electrocatalytic properties and wear rates are expected to differ for these two forms of platinum—iridium-coated anodes. 

Miscellaneous. Ruthenium dioxide-based thick-film resistors have been used as secondary thermometers below I K (92). Ruthenium dioxide-coated anodes ate the most widely used anode for chlorine production (93). Ruthenium(IV) oxide and other compounds ate used in the electronics industry as resistor material in apphcations where thick-film technology is used to print electrical circuits (94) (see Electronic materials). Ruthenium electroplate has similar properties to those of rhodium, but is much less expensive. Electrolytes used for mthenium electroplating (95) include [Ru2Clg(OH2)2N] Na2[Ru(N02)4(N0)0H] [13859-66-0] and (NH 2P uds(NO)] [13820-58-1], Several photocatalytic cycles that generate... 

The potential of the reaction is given as = (cathodic — anodic reaction) = 0.337 — (—0.440) = +0.777 V. The positive value of the standard cell potential indicates that the reaction is spontaneous as written (see Electrochemical processing). In other words, at thermodynamic equihbrium the concentration of copper ion in the solution is very small. The standard cell potentials are, of course, only guides to be used in practice, as rarely are conditions sufftciendy controlled to be called standard. Other factors may alter the driving force of the reaction, eg, cementation using aluminum metal is usually quite anomalous. Aluminum tends to form a relatively inert oxide coating that can reduce actual cell potential. 

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 ar and in fresh water is... 

Figure 19-1 shows the experimental setup with the position of the steel test pieces and the anodes. The anodes were oxide-coated titanium wires and polymer cable anodes (see Sections 7.2.3 and 7.2.4). The mixed-metal experimental details are given in Table 19-1. The experiments were carried out galvanostatically with reference electrodes equipped to measure the potential once a day. Thus, contamination of the concrete by the electrolytes of the reference electrodes was excluded. The potentials of the protected steel test pieces are shown in Table 19-1. The potentials of the anodes were between U(2u-cuso4 = -1-15 and -1.35 V. 

The impressed current method with metal oxide-coated niobium anodes is usually employed for internal protection (see Section 7.2.3). In smaller tanks, galvanic anodes of zinc can also be used. Potential control should be provided to avoid unacceptably negative potentials. Pure zinc electrodes serve as monitoring and control electrodes in exposed areas which have to be anodically cleaned in the course of operation. Ag-AgCl electrodes are used to check these reference electrodes. 

Plate anodes were used for corrosion protection in order to avoid damage due to erosion and cavitation. These consisted of enamelled steel bodies in which a metal oxide-coated titanium anode 1 dm in surface area was fitted. The enamel... 

Canister anodes consist of a spirally wound galvanised steel outer casing containing a carbonaceous based extender which surrounds the primary anode element which may be graphite, silicon iron, magnetite, platinised titanium, mixed metal oxide-coated titanium or platinised niobium, etc. 

The composition of the mixed metal oxide may well vary over wide limits depending on the environment in which the anode will operate, with the precious metal composition of the mixed metal oxide coating adjusted to favour either oxygen or chlorine evolution by varying the relative proportions of iridium and ruthenium. For chlorine production RuOj-rich coatings are preferred, whilst for oxygen evolution IrOj-rich coatings are utilised. ... 

The oxide coatings are porous and therefore the limitations on operating voltage for platinised titanium anodes apply as well to the oxide-coated titanium electrodes. It has been reported that breakdown of mixed metal oxide anodes may occur at 50-60 V in low-chloride concentration water but at only 10 V in chloride-rich environments . 

The most recently developed anode for the cathodic protection of steel in concrete is mixed metal oxide coated titanium mesh The anode mesh is made from commercially pure titanium sheet approximately 0-5-2mm thick depending upon the manufacturer, expanded to provide a diamond shaped mesh in the range of 35 x 75 to 100 x 200 mm. The mesh size selected is dictated by the required cathode current density and the mesh manufacturer. The anode mesh is supplied in strips which may be joined on site using spot welded connections to a titanium strip or niobium crimps, whilst electrical connections to the d.c. power source are made at selected locations in a suitably encapsulated or crimped connection. The mesh is then fitted to the concrete using non-metallic fixings. 

The active coating consists of a thermally deposited mixed metal oxide coating, the composition of which is considered proprietary information, although it is known that certain filler materials, e.g. Ta, may be added to the mixed metal oxide to reduce the precious metal content of the coating, and hence the cost of the anode. 

Table 15.3 Number of pores in anodic oxide coatings...

Anodic Oxidation Coatings on Aluminium, British Standard 1615 1972... 

Qualanod, Specifications for the Quality Sign for Anodic Oxidation Coatings on Wrought Aluminium for Architectural Purposes, Zurich (1983)... 

Hard Anodic Oxide Coatings on Aluminium for Engineering Purposes, British Standard 5599 1978... 

Method of specifying anodic oxidation coatings on aluminium and its alloys Specification for electroplated coatings of tin... 

Currem field characteristics measured wiih conjugated polymers sandwiched between an indium-tin oxide (ITO) anode and an aluminum cathode are usually hole dominated and are, consequently, appropriate for testing injection/lransport models for the case of unipolar current How. Data shown in Figure 12-1 refer to injection-limited currents recorded on typically 100 nm thick spin-coated films of derivatives of poly(y d/"fi-phenylenevinylene) (PPV) and a planarized poly(/ /" -pheny-leue) employing a Keilhley source measure unit. The polymers were ... 

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