Atoms in ceramics

The diffusion of impurity atoms in ceramic fuel is important in connection with the diffusion of fission products, but few systematic studies with particular attention to the effect of nonstoichiometry have been reported. 

We reviewed some of the fundamentals that underlie all aspects of materials science. Knowing the electron configuration of an atom allows us to understand some of the properties of materials that contain that atom. It also helps us to determine the type of bonding that occurs between different atoms. In ceramics the bonding is important because it is not straightforward. It often involves ionic and covalent contributions and sometimes also a metallic component. 

Ultimately, the surface energy is used to produce a cohesive body during sintering. As such, surface energy, which is also referred to as surface tension, y, is obviously very important in ceramic powder processing. Surface tension causes liquids to fonn spherical drops, and allows solids to preferentially adsorb atoms to lower tire free energy of tire system. Also, surface tension creates pressure differences and chemical potential differences across curved surfaces tlrat cause matter to move. 

Microscopists in every technical field use the microscope to characterize, compare, and identify a wide variety of substances, eg, protozoa, bacteria, vimses, and plant and animal tissue, as well as minerals, building materials, ceramics, metals, abrasives, pigments, foods, dmgs, explosives, fibers, hairs, and even single atoms. In addition, microscopists help to solve production and process problems, control quaUty, and handle trouble-shooting problems and customer complaints. Microscopists also do basic research in instmmentation, new techniques, specimen preparation, and appHcations of microscopy. The areas of appHcation include forensic trace evidence, contamination analysis, art conservation and authentication, and asbestos control, among others. 

The ultimate covalent ceramic is diamond, widely used where wear resistance or very great strength are needed the diamond stylus of a pick-up, or the diamond anvils of an ultra-high pressure press. Its structure, shown in Fig. 16.3(a), shows the 4 coordinated arrangement of the atoms within the cubic unit cell each atom is at the centre of a tetrahedron with its four bonds directed to the four corners of the tetrahedron. It is not a close-packed structure (atoms in close-packed structures have 12, not four, neighbours) so its density is low. 

There apparently exists a critical amount of liquid phase for the optimization of grain/interface boundary sliding during superplastic deformation. The optimum amount of liquid phase may depend upon the precise material composition and the precise nature of a grain boundary or interface, such as local chemistry (which determines the chemical interactions between atoms in the liquid phase and atoms in its neighboring grains) and misorientation. The existence of an equilibrium thickness of intergranular liquid phase in ceramics has been discussed [14]. This area of detailed study in metal alloys has not been addressed. 

The key to the superconducting properties of these ceramics seems to be the presence of planes of copper and oxygen atoms bonded to one another. The significance of the other atoms in the lattice seems to be to provide a stmctural framework for the copper and oxygen atoms. Thus, in the superconducting compound YBa2Cu30, the substitution of other rare earths for yttrium resrrlts in little change in the properties of the material. 

Most metals and ceramics have elastic elongation of less than 2%. Stretching in these materials involves the movement of atoms. In contrast, polymers can be easily elongated because the applied stress promotes linear formation of the polymer backbone. 

Silicon exists in nature only in the most thermodynamically stable form in a oxygen-containing atmosphere. Each silicon atom is surrounded by four oxygen atoms in tetrahedral symmetry. Mankind has used the special stability of such compounds to prepare glass, chinaware, ceramics, and building materials like concrete, etc. Silicates today are still one of the most important materials. 

The amount and positions (atomic locations) of oxygen atoms in the superconductors are highly critical and determine the properties of the superconductor. The oxygen vacancies (or deficiency) can be ordered in these materials. Neutron-diffraction experiments were required to determine the population parameters and the atomic positions of oxygen in these structures. The superconducting transition temperature in these "ceramic" oxides is a critical balance between the oxygen content and a proper mix of Cu2+ and Cus+ ions generated in the anneal or post-heat treatment. 

In earlier literature reports, x-ray data of a-based ceramics, the /3-like phase observed in certain silica minerals was explained by a structural model based on disordered Q -tridymite. However, others have suggested that the structure of the stabilized jS-cristobalite-like ceramics is closer to that of a-cristobalite than that of Q -tridymite, based on the 29Si nuclear magnetic resonance (NMR) chemical shifts (Perrota et al 1989). Therefore, in the absence of ED data it is impossible to determine the microstructure of the stabilized jS-cristobalite-like phase. ED and HRTEM have provided details of the ceramic microstructure and NMR has provided information about the environments of silicon atoms in the structure. Infrared spectroscopy views the structure on a molecular level. 

Atoms in the free surface of solids (with no neighbors) have a higher free energy than those in the interior and surface energy can be estimated from the number of surface bonds (Cottrell 1971). We have discussed non-stoichiometric ceramic oxides like titania, FeO and UO2 earlier where matter is transported by the vacancy mechanism. Segregation of impurities at surfaces or interfaces is also important, with equilibrium and non-equilibrium conditions deciding the type of defect complexes that can occur. Simple oxides like MgO can have simple anion or cation vacancies when surface and Mg + are removed from the surface,... 

The nebulization was also employed to generate composite powders for specific applications, such as in ceramics, by hydrolyzing with water vapor droplets containing Al(5ec-OBu) and silicon methoxide in the atomic ratio Al/Si = 3. This ratio of alkoxides was chosen in order to produce mullite, which was achieved by calcination of the resulting amorphous particles at rather high temperatures (up to I400 C) (52). In another approach a mixed Al-Mg-Si ethoxide was first synthesized, and then nebulized and hydrolyzed as usual (77). Depending on the experimental conditions, the powders calcined at 500 C exhibited structures of pure cordierite, or mixed with forsterite. In all of these described cases the nebulization yielded spherical but polydisperse particles. 

Figure 2.27 Schematic representation of surface and bulk atoms in a condensed phase. From W. D. Kingery, H. K. Bowen, and D. R. Uhhnann, Introduction to Ceramics. Copyright 1976 by John Wiley Sons, Inc. This material is used by permission of John Wiley Sons, Inc.

Close packing, which is described in more detail in Section 11.2.1.2, gives not only the densest packing of spheres but also represents the arrangement of lowest energy when an array of like charges is confined to a fixed volume. This rule not only applies separately to the cations and the anions in ceramics, it also applies to the arrangement of the atoms in a metal. One consequence is that the same cation lattices are found in both metals and in ceramic materials (O Keeffe and Hyde 1985). 

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