Conductivity fluorites

While past efforts were focused on expanding the electrolytic domain of oxygen ion conducting fluorite-t5q)e ceramics, more recently one has begim to introduce enhanced electronic conduction in fluorite matrices. Extrinsic elec-... 

The (heavily) semi-conducting fluorite-type Mg2Sn is one of the rare bone fide examples of 5p6 tin(— IV). The lowest/ (116) close to 2 eVcorresponds to / 5 eV. 

That is why in the current chapter we will confine ourselves to the ionic transfer discussion of fluorine-conductive fluorites and tysonites from a slightly different standpoint we wiU try to observe an influence of various doping types on the structure features and the defect structure of nonstoichiometric fluorine-containing phases. 

Fig. 7.32 Wagnei Hebb analysis for determination of the n and p conductivity in Y-doped conducting fluorites with the aid of the cell N2,Pt YSZ or YST adr,Pt (left current voltage curve for Tho.9Yo.101.95 (YST), right electronic and ionic pautial conductivities for Zro.9Yo.1O1.95 (YSZ)). Prom Ref. [608].

The isomorphous diiodides of Ce, Pr and Gd stand apart from all the other, salt-like, dihalides. These three, like LaH, are notable for their metallic lustre and very high conductivities and are best formulated as (Ln ,2I",e", the electron being in a delocalized conduction band. Besides the dihalides, other reduced species have been obtained such as LnsCln (Ln = Sm, Gd, Ho). They have fluorite-related structures (p. 118) in which the anionic sublattice is partially rearranged to accommodate additional anions. 

Ceria is another type of mixed conducting oxide which has been shown already to induce electrochemical promotion.71 Ceria is a catalyst support of increasing technological importance.73 Due to its nonstoichiometry and significant oxygen storage capacity it is also often used as a promoting additive on other supports (e.g. y-A Cb) in automobile exhaust catalysts.79 It is a fluorite type oxide with predominant n-type semiconductivity. The contribution of its ionic conductivity has been estimated to be 1-3% at 350°C.71... 

Other refractory oxides that can be deposited by CVD have excellent thermal stability and oxidation resistance. Some, like alumina and yttria, are also good barriers to oxygen diffusion providing that they are free of pores and cracks. Many however are not, such as zirconia, hafnia, thoria, and ceria. These oxides have a fluorite structure, which is a simple open cubic structure and is particularly susceptible to oxygen diffusion through ionic conductivity. The diffusion rate of oxygen in these materials can be considerable. 

The correlation of phosphate precipitation with decrease of conductivity (Wilson Kent, 1968), increase in pH (Kent Wilson, 1969) and hardness (Wilson et al, 1972) is shown in Figure 6.16. These results demonstrate the relationship between the development of physical properties and the underlying chemical changes, but there are no sharp changes at the gel point. Evidence from infrared spectroscopy (Wilson Mesley, 1968) and electron probe microanalysis (Kent, Fletcher Wilson, 1970 Wilson et al, 1972) indicates that the main reaction product is an amorphous aluminophosphate. Also formed in the matrix were fluorite (CaF ) and sodium acid phosphates. 

Yahiro, H. Eguchi, Y. Eguchi, K. Arai, H. 1988. Oxygen ion conductivity of the ceria samarium oxide system with fluorite structure. I. Appl. Electrochem. 18 527-531. 

Four solid oxide electrolyte systems have been studied in detail and used as oxygen sensors. These are based on the oxides zirconia, thoria, ceria and bismuth oxide. In all of these oxides a high oxide ion conductivity could be obtained by the dissolution of aliovalent cations, accompanied by the introduction of oxide ion vacancies. The addition of CaO or Y2O3 to zirconia not only increases the electrical conductivity, but also stabilizes the fluorite structure, which is unstable with respect to the tetragonal structure at temperatures below 1660 K. The tetragonal structure transforms to the low temperature monoclinic structure below about 1400 K and it is because of this transformation that the pure oxide is mechanically unstable, and usually shatters on cooling. The addition of CaO stabilizes the fluorite structure at all temperatures, and because this removes the mechanical instability the material is described as stabilized zirconia (Figure 7.2). 

A number of oxides with the fluorite structure are used in solid-state electrochemical systems. They have formulas A02 xCaO or A02 xM203, where A is typically Zr, Hf, and Th, and M is usually La, Sm, Y, Yb, or Sc. Calcia-stabilized zirconia, ZrC)2.xCaO, typifies the group. The technological importance of these materials lies in the fact that they are fast ion conductors for oxygen ions at moderate temperatures and are stable to high temperatures. This property is enhanced by the fact that there is negligible cation diffusion or electronic conductivity in these materials, which makes them ideal for use in a diverse variety of batteries and sensors. 

The first data about nonbarrier iron accumulation by external layers of tree trunk bark were received by us on Ermakovskii fluorite-beryllium deposit in Zabaikalye. Detailed research of chemical element (CE) distribution in cross-sections of trees trunks and in their other parts and species of plants were conducted here for... 

Floatability of bastnaesite found in barite-fluorite ores is extremely poor using either fatty acid flotation or sodium oleate. Research work conducted on an ore from Central Asia showed that the floatability of bastnaesite improved significantly after barite preflotation [5]. The flotation of bastnaesite from a carbonatite ore improved with the use of oleic acid modified with phosphate ester. The flotation of bastnaesite from deposits ofpegmatitic origin can be successfully accomplished with several types of collectors, including tall oil modified with secondary amine, and tall oil modified with petroleum sulphonate-encompassing group. 

The maximum conductivity of fluorite-structured oxygen ion conductors is not only a function of dopant concentration, but also of dopant radius [9], For stabilized zirconia, the conductivity increases as the radius becomes close to that of Zr4 (rvm = 0.084 nm). The best value is reached for Sc3+ (rvlll = 0.087 nm) with a conductivity of 0.1 Scnr1 at 800°C for (ScjC o. ZrO o. ). For the sake of comparison,... 

Anion conduction, particularly oxide and fluoride ion conduction, is found in materials with the fluorite structure. Examples are Cap2 and Zr02 which, when doped with aliovalent impurities. Fig. 2.2, schemes 2 and 4, are F and 0 ion conductors, respectively, at high temperature. The 3 polymorph of 61303 has a fluorite-related structure with a large number of oxide vacancies. It has the highest oxide ion conductivity found to date at high temperatures, > 660 °C. 

The most well-studied and useful materials to date are those with fluorite-related structures, especially ones based on ZrOj, ThOj, CeOj and Bi203 (Steele, 1989). To achieve high oxide ion conductivity in ZrOj, CeOj and ThOj, aliovalent dopants are required that lead to creation of oxide vacancies. Fig. 2.2, scheme 4. The dopants are usually alkaline earth or trivalent rare earth oxides. 

Some pyrochlore, A2B2O7, phases are moderately good oxide ion conductors. The pyrochlore structure may be regarded as a fluorite derivative in which g of the oxygens are missing but since the oxygen sublattice, ideally, is fully ordered, it is necessary to introduce defects to achieve high conductivity. 

The F -ion conductor first discovered by Faraday represents a more complex order-disorder transition to fast ionic conduction. At all temperatures, PbF2 is reported to have the fluorite structure in which the F ions occupy all the tetrahedral sites of a face-centred-cubic Pb -ion array however, the site potential of the Pb ions is asymmetric, and a measurement of the charge density with increasing temperature indicates that the F ions spend an increasing percentage of the time at the... 

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