Layered structure oxides

The electrode potential of aluminium would lead us to expect attack by water. The inertness to water is due to the formation of an unreactive layer of oxide on the metal surface. In the presence of mercury, aluminium readily forms an amalgam (destroying the original surface) which is. therefore, rapidly attacked by water. Since mercury can be readily displaced from its soluble salts by aluminium, contact with such salts must be avoided if rapid corrosion and weakening of aluminium structures is to be prevented. 

Ancient iron structures sometimes show no sign of corrosion or at most, very little. The clean atmosphere of past centuries may be responsible in that it allowed a very thin adherent layer of oxide to develop on the surface [22], This layer very often protects against even today s increasingly aggressive industrial pollutants Very often the conditions of the initial corrosion are the ones that determine the lifespan of metals [23], A well-known example is the sacred pillar of Kutub in Delhi, which was hand forged from large iron blooms in 410 a.d. In the pure dry air, the pillar remains free of rust traces but shows pitting corrosion of the iron... 

The major artifacts contributing to uncertainties in PDCE results stem from effects caused by bombardment of nonideal specimens, particularly thick specimens. The ideal thick specimen would be a homogeneous, smooth electrical conductor that does not change during bombardment. Except for rather simple, well-defined layered structures (e.g., surface oxide layers), specimens having compositional variations with depth yield spectra whose analyses can have large inaccuracies. 

Feitknecht has examined the corrosion products of zinc in sodium chloride solutions in detail. The compound on the inactive areas was found to be mainly zinc oxide. When the concentration of sodium chloride was greater than 0-1 M, basic zinc chlorides were found on the corroded parts. At lower concentrations a loose powdery form of a crystalline zinc hydroxide appeared. A close examination of the corroded areas revealed craters which appeared to contain alternate layers and concentric rings of basic chlorides and hydroxides. Two basic zinc chlorides were identified, namely 6Zn(OH)2 -ZnClj and 4Zn(OH)2 ZnCl. These basic salts, and the crystalline zinc hydroxides, were found to have layer structures similar in general to the layer structure attributed to the basic zinc carbonate which forms dense adherent films and appears to play such an important role in the corrosion resistance of zinc against the atmosphere. The presence of different reaction products in the actual corroded areas leads to the view that, in addition to action between the major anodic and cathodic areas as a whole, there is also a local interaction between smaller anodic and cathodic elements. 

In 1929 Pfeil" published a most interesting account of the way layered structures form and the manner in which they influence oxidation rates. From detailed studies of the growth and composition of scales he was able to show clearly how the formation of barrier layers reduced scale formation by hindering outward diffusion of iron through the scale. Naturally, this work had to be largely based on the study of scales of sufficient thickness so that the mechanism of the early stages of oxidation could not be studied in this way. Pfeil analysed the outer, middle and inner layers of scales formed... 

Figure 8. Schematic drawing of the layered manganese oxides. The structure consists of a stacking of empty and Mn(III, IV)-filled layers of edge-sharing octahedra.

The crystal structure of the mineral chalcophanite, ZnMn307-3H20 (see Fig. II), was one of the first layer structures of manganese oxides that has been determined. 

Gartner, G., Jamiel, P., and Lydtin, H., Plasma-Activated Metalorganic CVD of Illb Oxides/Tungsten Layer Structures, Proc. of 11th Int. Conf on CVD, (K. Spear and G. Cullen, eds.), pp. 589-595, Electrochem. Soc., Pennington, NJ 08534 (1990)... 

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