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Structures and Properties of Ceramics

Introduction
Ceramics are groups of non-metallic inorganic solids formed between metallic (e.g. Mg, Al, Zr etc.) or semi-metallic (e.g. Si ) and non-metallic elements (e.g. O, C, N etc.). Ceramics may be fully crystalline (e.g. magnesia), fully amorphous (glasses) or partially crystalline where crystalline grains are cemented together by an amorphous matrix.

Familiar ceramics such as tableware are clay based, but for advanced engineering applications ceramics are often chemically synthesized (or use highly reformed natural materials). The group of engineering ceramics of most interest for SOFCs is electroceramics, e.g. alumina (Al2O3), and yttria-stabilisedzirconia (YSZ).

Bonding in Ceramics
Ionic Bonding is very common in ceramics containing mixtures of metallic and nonmetallic elements such as magnesia (MgO). Ionic bonding is nondirectional. Covalent Bonding is common in special ceramics such as silicon carbide (SiC). Covalent bonding is directional. Mixed Bonding consisting of ionic, covalent (and often molecular) bonding is the norm for ceramics.

Ceramic material are inorganic compounds consisting of metallic and non-metallic elements which are held together with ionic and/or covalent bonds

THE DEGREE OF IONIC CHARACTER


The degree of ionic character of a ceramic compound can be estimated approximately using the following formula: % Ionic Character = { 1 - exp[-0.25(XA-XB )2]} x 100 XA = Electronegativity of element A XB = Electronegativity of element B

Structure Of Ceramics
Number of Atoms per Unit Cell

When counting the number of lattice points belonging to each unit cell, we must recognize that lattice points may be shared more than one unit cell.

Simple Ionic Ceramic Structures


Factors which influence the crystal structures: (i) Electrical charges on the ions needed to be balanced. (ii) Relative sizes of ions: Radius Ratio = rc /ra COORDINATION NUMBERS (CN): the number of anion nearest neighbours for a cation is related to cation/anion radius ratio. (The most common CNs are 4, 6, and 8).

iii.Ions tend to be packed together as densely as possibly to lower the overall energy of the solid.

Properties of Ceramics

Most of the properties outlined below follow from the ionic and/or covalent bonding in ceramics.

1. Very high elastic modulii which are retained to elevated temperatures. 2. Very high melting points. 3. Chemically stable and resistant to decomposition or oxidation. 4. Good compressive strength.

5. Generally brittle: (a) dislocations in ceramics have narrow cores and hence require strong thermal activation to move; (b) only few slip systems are operative, either because of high resistance to motion of dislocations on a particular set of slip systems and/or because of the low symmetry of the material; (c) modes of slip which would cause ions of like charges to come closer are not favourable and (d) grain boundaries, pores, interface boundaries all act as good crack paths in ceramics, making ceramics very prone to brittleness. Ceramics and inorganic glasses are often sensitive to thermal shock, i.e., differential thermal expansion or contraction induced cracking.

6.

Usually ceramics are electrical insulators as all electrons are tied up in ionic/covalent bonds and thus are not available for conduction. However free electrons can be generated thermally and/or extrinsically and several ceramics acquire semi-conducting or even metallic properties. Defects in the ionic crystals can also result in ionic conduction which can be enhanced or combined with electronic conduction by doping.

7. Generally poor thermal conductors as heat is conducted by phonons alone, without help from free electrons. Insulating materials can be excellent thermal conductors when phononphonon interaction becomes favourable in the crystal structure, as for example in diamond and SiC. 8. Generally have low densities, since they tend to be comprised of atoms of low atomic numbers, but there are exceptions such as zirconia.

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