Solid oxides ionicity/covalency

Recent developments in the synthesis, structures, and properties of ionic/covalent ternary nitrides are reviewed. A description, including synthetic conditions, is given of preparative methods reported in the literature. Solid state synthetic reactions from binary nitrides as well as novel synthetic approaches such as amide synthesis and ammonolysis of ternary oxides are described. Examples of common structure types as well as electronic and magnetic properties are discussed. 

Very large molecules behave like small pieces of solid. Oxidic colloidal particles are basically strongly cross-linked inorganic polymers. Such compounds can best be made using colloidal methods, such as the sol-gel technique for covalent or ionic metal oxides. These methods will be discussed in Chapters 6 and 8. 

The word ceramics is derived from the Greek keramos, meaning solid materials obtained from the firing of clays. According to a broader modern definition, ceramics are either crystalline or amorphous solid materials involving only ionic, covalent, or iono-covalent chemical bonds between metallic and nonmetallic elements. Well-known examples are silica and silicates, alumina, magnesia, calcia, titania, and zirconia. Despite the fact that, historically, oxides and silicates have been of prominent importance among ceramic materials, modern ceramics also include borides, carbides, silicides, nitrides, phosphides, and sulfides. 

Actually, minerals which are transparent transmit light much like glass. These minerals are essentially solids with ionic or covalent bond such as oxides, carbonates, silicates (e.g., calcite, quartz), or native element (e.g., diamond). Minerals which are translucent transmit light on thin edges or in thin section. By contrast, opaque minerals do not transmit light even in thin section and comprise solids with metallic or partially metallic bond characterized by a free electron cloud (i.e., Fermi gas) such as native element (e.g., Cu, Ag, Au), most iron and copper bearing sulfides (e.g., CuS, FeS ), and several transition metal oxides (e.g., Fe, ,. FeTiOj, FeCrp J. As a general rule, all minerals with a metalhc luster are commonly opaque. 

The classification of surfaces considered above was introduced for ionic or semiionic metal oxides. In covalent solids, the creation of a surface requires cutting covalent bonds, which means that dangling bonds would be present at the surface. The saturation of dangling bonds by chemisorption is important, for example, in sihcates. When a surface is cut out from the bulk, unstable Si-0 radicals at the surface react readily with water to give a fully hydroxylated surface with hydrophilic character [568]. 

The idea of point defects in crystals goes back to Frenkel, who in 1926 proposed the existence of point defects to explain the observed values of ionic conductivity in crystalline solids. In a crystal of composition MX such as a monovalent metal halide or a divalent metal oxide or sulfide, volume ionic conductivity occurs by motion of positive or negative ions in the lattice under the influence of an electric field. If the crystal were perfect, imperfections, such as vacant lattice sites or interstitial atoms, would need to be created for ionic conductivity to occur. A great deal of energy is required to dislodge an ion from its normal lattice position and thus the current in perfect crystals would be very, very small under normal voltages. To get around this difficulty, Frenkel proposed that point defects existed in the lattice prior to the application of the electric field. This, of course, has been substantiated by subsequent work and the concept of point defects in all classes of solids, metals, ionic crystals, covalent crystals, semiconductors, etc., is an important part of the physics and chemistry of crystalline solids, not only with respect to ionic conductivity but also with respect to diffusion, radiation damage, creep, and many other properties. 

When an element has more than one oxidation state the lower halides tend to be ionic whilst the higher ones are covalent—the anhydrous chlorides of lead are a good example, for whilst leadfll) chloride, PbCl2, is a white non-volatile solid, soluble in water without hydrolysis, leadflV) chloride, PbC, is a liquid at room temperature (p. 200) and is immediately hydrolysed. This change of bonding with oxidation state follows from the rules given on p.49... 

Apart from the three broad categories of student conceptions discussed above, students displayed several inappropriate conceptions relating to the stractural properties of substances. For example, 14% of students suggested that Mg + ions were present in magnesium ribbon. A second example involved the chemical reaction between copper(II) oxide powder and dilute sulphuric acid. In this instance, 25% of students suggested that Cu + ions were present only in aqueous solution but not in the solid and liquid states. This view was rather unexpected because students had earlier been introdnced to ionic and covalent compounds. It is likely that students had merely rote-learned the general rale without sufficient understanding that ionic solids are formed between metallic and non-metallic elements. 

Based on the concept of mixed-framework lattices, we have reported a novel class of hybrid solids that were discovered via salt-inclusion synthesis [4—7]. These new compounds exhibit composite frameworks of covalent and ionic lattices made of transition-metal oxides and alkali and alkaline-earth metal halides, respectively [4]. It has been demonstrated that the covalent frameworks can be tailored by changing the size and concentration of the incorporated salt. The interaction at the interface of these two chemically dissimilar lattices varies depending upon the relative strength of covalent vs. ionic interaction of the corresponding components. In some cases, the weak interaction facilitates an easy... 

In addition to ionic solids, covalent molecules containing halogen atoms (primarily F and Cl) can function as "oxidizers" in pyrotechnic compositions, especially with active metal fuels. Examples of this are the use of hexachloroethane (C with zinc... 

After a survey of the basic theory and some experimental aspects of photoelectron spectroscopy which are relevant to actinide solids, two systems are illustrated elemental actinide metals, in which the Mott transition between plutonium and americium is evidenced in a photographic way by photoemission, and strongly ionic oxides, in which the 5f localized behaviour is clearly seen, and indications of f-p or d-p covalent mixing are investigated. 

Polar framework compounds. These are compounds where no individual molecules exist, and range from ionic compounds like sodium chloride, through part-ionic, part-covalent compounds like aluminum oxide, to polar covalent framework solids like silicon dioxide. 

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