Sintering energy facts

The conclusion regarding the fact that constant current conductivity involves not all microcrystals of the sample is proved by results of measurements of electric conductivity in sintered ZnO films in case of alternating current (Fig. 2.10). The availability of barrier-free ohmic pathways is proved by a low value of initial resistivity in sintered samples ( 1 - 5 kOhm) in addition to exponential dependence of electric conductivity plotted as a function of inverse temperature having activation energy 0.03 - 0.5 eV, which coincides with ionization energy of shallow dope levels. The same value is obtained from measurements of the temperature dependence of the Hall constant [46]. 

It should be noted that the results for the formic acid decomposition donor reaction have no bearing for ammonia synthesis. On the contrary, if that synthesis is indeed governed by nitrogen chemisorption forming a nitride anion, it should behave like an acceptor reaction. Consistent with this view, the apparent activation energy is increased from 10 kcal/mole for the simply promoted catalyst (iron on alumina) to 13-15 kcal/mole by addition of K20. Despite the fact that it retards the reaction, potassium is added to stabilize industrial synthesis catalysts. It has been shown that potassium addition stabilizes the disorder equilibrium of alumina and thus retards its self-diffusion. This, in turn, increases the resistance of the iron/alumina catalyst system to sintering and loss of active surface during use. 

The fact that in the case of the bicrystal in Figure 54 the effective thickness calculated from the low-frequency semicircle is very much greater than expected from the width of the boundary, while the activation energy is almost equal to that of the bulk, points towards a frequently overlooked complication, namely to current-constriction effects. Such constriction effects occur287 when the crystal grains are not ideally sintered together, if pores or second phases are included, and interrupt the lateral conductivity of boundaries, as is the case for inhomogeneous electrode contacts. 

The formation of an amorphous solid was first reported in 1935 [132,133]. These authors used the route of depositing warm water vapor on a cold substrate, which freezes in excess free energy by the rapid change in temperature. At substrate temperatures above 160K, the deposit was found to be crystalline ice I, whereas below this temperature, an amorphous solid was obtained. These deposits are referred to as ASW, which is a microporous material that can adsorb gases [134, 135]. In fact, ASW also condenses on interstellar dust particles and is likely the most abundant form of solid water in the universe. Therefore, studies on ASW bear an astrophysical relevance [134, 136]. The microporosity can be reduced greatly by sintering the sample to no more than 120 K. 

In all the models discussed so far, the support surface was assumed to be flat. In fact, very many case studies, particularly of supported metals, have used flat, low-surface-area substrates. However, Wynblatt and Ahn [36] have demonstrated that surface curvature does affect the surface free energy, the growth of particles (sintering) via particle migration and interparticle transport. Therefore, the sintering process of practical supported catalysts which frequently use high-surface-area, porous supports must be significantly more complex than described by the simple models. 

---