Corrosion resistance evolution

Most metals (other than the alkali and alkaline-earth metals) are corrosion resistant when cathodically polarized to the potentials of hydrogen evolution, so that this reaction can be realized at many of them. It has thus been the subject of innumerable studies, and became the fundamental model in the development of current kinetic concepts for electrochemical reactions. Many of the principles... 

Titanium dioxide is a catalytically inactive but rather corrosion-resistant material. Ruthenium dioxide is one of the few oxides having metal-like conductivity. It is catalytically quite active toward oygen and chlorine evolution. However, its chemical stability is limited, and it dissolves anodically at potentials of 1.50 to 1.55 V (RHE) with appreciable rates. A layer of mixed titanium and ruthenium dioxides containing 1-2 mg/cm of the precious metal has entirely unique properties in terms of its activity and selectivity toward chlorine evolution and in terms of its stability. With a working current density in chlorine evolution of 20 to 50mA/cm, the service life of such anodes is several years (up to eight years). 

Graphite is offered moreover in flexible sheets (e.g. Sigraflex of the SGL-Carbon Group). This is primarily a sealing material, but it is suitable also as electrode or corrosion resistant current feeder (erosion in case of gas evolution is possible). 

Ceramic Materials An example of a sufficiently conductive metal oxide is magnetite Fe304, which has been used, for example, in the past as corrosion resistant anode material for industrial chlorine evolution (it can be smelted and casted at 1500 °C, but it is a very brittle material). 

Alloying to modify the overpotential of the metal surface for H2 evolution or O2 absorption can help control corrosion, although it is not always obvious whether these cathodic processes should be suppressed (i0 lowered) or stimulated to produce the desired corrosion resistance. In the case of titanium (see Section 16.6), for example, palladium was alloyed in to catalyze H2 evolution and to force the metal into a passive condition. 

A completely novel approach to technical electrolysis for anodic oxygen evolution from alkaline solution is the use of amorphous metals, i.e. chilled melts of nickel/cobalt mixtures whose crystallization is prevented by the addition of refractory metals like Ti, Zr, B, Mo, Hf, and P (46-51). For this type of material, enhanced catalytic activity in heterogeneous catalysis of gas-phase reactions has been observed (51). These amorphous metals are shown to be more corrosion resistant than the respective crystallized alloys, and the oxides being formed at their surfaces often exhibit a higher catalytic activity than those formed on ordered alloys, as shown by Kreysa (52-54). 

The main differences will occur with the design of baths suitable for aluminum and other water-sensitive metal salts. The evolution of HC1 will require materials which are more corrosion resistant, and the main difficulty will be in the development of plants which will allow the transfer of pieces in and out of the liquid under stricdy anhydrous conditions. 

At E > 1.0 V transpassive dissolution as QxCY2 is obtained in 0.5 M H2SO4, with a strong increase of the current density (Fig. 5). At E > 1.7 V oxygen evolution contributes to the large anodic current. These characteristic electrochemical properties indicate the importance of Cr as an alloying additive to obtain corrosion-resistant alloys, especially at negative potentials and in acidic solutions. 

In early attempts to oxidize hydrocarbons electrochemically, organic solvents and corrosion-resistant electrodes (PbO, C, Pt) were used to overcome low reactant solubility and anode dissolution at extreme potentials, -I-1.8 V and up to 4.5 V (326, 327). The primary anodic reaction was usually oxygen evolution or solvent decomposition. The electrode material, nonetheless, affected the product even at the small attainable yields. Thus, toluene oxidized to traces of aldehydes on PbO2 (333), while on Pt it yielded up to 19% benzaldehyde (326). The catalytic efifect of the anode, however, on rate and selectivity was not realized. 

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