Zinc oxide activated sintering

The measures of solid state reactivity to be described include experiments on solid-gas, solid-liquid, and solid-solid chemical reaction, solid-solid structural transitions, and hot pressing-sintering in the solid state. These conditions are achieved in catalytic activity measurements of rutile and zinc oxide, in studies of the dissolution of silicon nitride and rutile, the reaction of lead oxide and zirconia to form lead zirconate, the monoclinic to tetragonal transformation in zirconia, the theta-to-alpha transformation in alumina, and the hot pressing of aluminum nitride and aluminum oxide. 

Two methods are available for the preparation of the powder (Smith, 1969). In one, zinc oxide is ignited at 900 to 1000 °C for 12 to 24 hours until activity is reduced to the desired level. This oxide powder is yellow, presumably because zinc is in excess of that required for stoichiometry. Alternatively, a blend of zinc oxide and magnesium oxide in the ratio of 9 1 is heated for 8 to 12 hours to form a sintered mass. This mass is ground and reheated for another 8 to 12 hours. The powder is white. Altogether the powder is similar to that used in zinc phosphate cements. 

To dissociate molecules in an adsorbed layer of oxide, a spillover (photospillover) phenomenon can be used with prior activation of the surface of zinc oxide by particles (clusters) of Pt, Pd, Ni, etc. In the course of adsorption of molecular gases (especially H2, O2) or more complex molecules these particles emit (generate) active particles on the surface of substrate [12], which are capable, as we have already noted, to affect considerably the impurity conductivity even at minor concentrations. Thus, the semiconductor oxide activated by cluster particles of transition metals plays a double role of both activator and analyzer (sensor). The latter conclusion is proved by a large number of papers discussed in detail in review [13]. The papers cited maintain that the particles formed during the process of activation are fairly active as to their influence on the electrical properties of sensors made of semiconductor oxides in the form of thin sintered films. 

The nickel-based systems include the flowing systems nickel—iron (Ni/Fe), nickel—cadmium (NiCd), nickel—metal hydrides (NiMH), nickel—hydrogen (Ni/ H2), and nickel—zinc (Ni/Zn). All nickel systems are based on the use of a nickel oxide active material (undergoing one valence change from charge to discharge or vice versa). The electrodes can be pocket type, sintered type, fibrous type, foam type, pasted type, or plastic roll-bonded type. All systems use an alkaline electrolyte, KOH. 

The existence of other deep surface levels, for example Tamm levels (discussed in the preceding section), on the surface of zinc oxide is placed in doubt by an experiment of Bevan and Anderson (32) on sintered zinc oxide. They observed that the activation energy of the conduction electrons (of the order of an electron volt when the sample is subjected to high oxygen pressure) decreases to a few hundredths of an electron volt if the measurements are taken at low pressure (less than 10 mm.) and high temperature (the order of 600°C). Surface traps other than those asso-... 

This evidently does not apply to sintered zinc oxide, since at low temperature its conductivity shows an activation energy of a few hundredths of an electron volt, the same as is shown by the Hall coefficient (26), independent of the previous treatment of the sample. This, then, indicates that the grains of sintered zinc oxide are actually fused, rather than merely touching. 

The modern methanol synthesis catalyst consists of copper, zinc oxide, and alumina. Copper metal is seen as the catalytically active phase, and ZnO as the promoter. It is well known that the interaction between the two components is essential for achieving a high activity, but the nature of the promoting effect is still a matter of debate. Loss of activity is caused by sintering of the Cu crystallites, and, if the feed gas contains impurities such as chlorine and sulfur, by poisoning. 

The solids used are either large surface solids, like silica, alumina, active charcoal, 4-5 A. molecular sieves, or small surface solids like sintered silica, quartz wool and powdered zinc oxide. 

The main functions of a carrier or support are usually to lend mechanical strength, increase stability to sintering and provide a larger active surface area than would otherwise be available. There is evidence that, in many instances, compound or complex formation takes place between the catalyst and the support, with a consequent effect on the catalytic properties. The most commonly used support materials are silica, alumina, silica-alumina, titania, silicon carbide, diatomaceous earths, magnesia, zinc oxide, iron oxide and activated carbon. 

DoUimore and Tonge [15] ascribed the deceleratory decomposition of zinc formate in air (0 < nr < 0.3) to an initial instantaneous and extensive nucleation of reactant crystalhte surfaces with product zinc oxide and the operation of a contracting sphere mechanism. For 0.3 < nr < 0.8 the reaction rate is almost constant, probably as a result of reactant cracking. for both processes is 67 kJ mol". During the course of reaction the yields of hydrogen and carbon monoxide increased, while that of carbon dioxide decreased. This was attributed to a decrease in the catalytic activity of the product oxide, possibly as a result of sintering. The formation of higher molecular mass products was mentioned. 

Pure iron(iii) oxide performs rather poorly as a WGS catalyst, due to rapid catalyst deactivation by sintering. Traditional iron catalysts typically consist of iron(iii) oxide (80-90% by mass), chromium(iii) oxide (8-10% by mass) and small amounts of other stabilisers and promoters such as copper(ii) oxide, aluminium oxide, alkali metals, zinc oxide and magnesium oxide. The small fraction of chromium(iii) oxide acts to prevent catalyst sintering, and also promotes the catalytic activity of iron. Catalyst deactivation is typically caused by poisons in the feedstock gases and by deposition of solids on the catalyst surface. 

On the other hand, while chlorides accumulate near the top of the catalyst, they are more mobile and can be detected in significant concentrations, up to 0.05%, at all levels in a deactivated bed. Although reasonable hves of at least two years can often be achieved in the presence of chloride there is more rapid movement of the peak in temperature profile, and the concentration of carbon monoxide in the outlet gas increases more rapidly. Surface chlorides, which are formed by reaction with zinc oxide, are mobile and sinter the catalyst surface. Chlorides are also soluble in condensed steam and can be washed down onto lower, more active catalyst layers. 

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