Ceramic Structures (continued)

Ceramic Glass
Ceramics with an entirely glassy structure have certain properties that are quite different from those of metals. Recall that when metal in the liquid state is cooled, a crystalline solid precipitates when the melting freezing point is reached. However, with a glassy material, as the liquid is cooled it becomes more and more viscous. There is no sharp melting or freezing point. It goes from liquid to a soft plastic solid and finally becomes hard and brittle. Because of this unique property, it can be blown into shapes, in addition to being cast, rolled, drawn and otherwise processed like a metal.

Glassy behavior is related to the atomic structure of the material. If pure silica (SiO₂) is fused together, a glass called vitreous silica is formed on cooling. The basic unit structure of this glass is the silica tetrahedron, which is composed of a single silicon atom surrounded by four equidistant oxygen atoms. The silicon atoms occupy the openings (interstitials) between the oxygen atoms and share four valence electrons with the oxygen atoms through covalent bonding. The silica atom has four valence electrons and each of the oxygen atoms has two valence electrons so the silica tetrahedron has four extra valence electrons to share with adjacent tetrahedral. The silicate structures can link together by sharing the atoms in two corners of the SiO₂ tetrahedrons, forming chain or ring structures. A network of silica tetrahedral chains form, and at high temperatures these chains easily slide past each other. As the melt cools, thermal vibrational energy decreases and the chains can not move as easily so the structure becomes more rigid. Silica is the most important constituent of glass, but other oxides are added to change certain physical characteristics or to lower the melting point.

Ceramic Crystalline or Partially Crystalline Material
Most ceramics usually contain both metallic and nonmetallic elements with ionic or covalent bonds. Therefore, the structure the metallic atoms, the structure of the nonmetallic atoms, and the balance of charges produced by the valence electrons must be considered. As with metals, the unit cell is used in describing the atomic structure of ceramics. The cubic and the hexagonal cells are most common. Additionally, the difference in radii between the metallic and nonmetallic ions plays an important role in the arrangement of the unit cell.

In metals, the regular arrangement of atoms into densely packed planes led to the occurrence of slip under stress, which gives metal their characteristic ductility. In ceramics, brittle fracture rather than slip is common because both the arrangement of the atoms and the type of bonding is different. The fracture or cleavage planes of ceramics are the result of planes of regularly arranged atoms.

The building criteria for the crystal structure are:

• maintain neutrality
• charge balance dictates chemical formula
• achieve closest packing

A few of the different types of ceramic materials outside of the glass family are described below.

Silicate Ceramics
As mentioned previously, the silica structure is the basic structure for many ceramics, as well as glass. It has an internal arrangement consisting of pyramid (tetrahedral or four-sided) units. Four large oxygen (0) atoms surround each smaller silicon (Si) atom. When silica tetrahedrons share three corner atoms, they produce layered silicates (talc, kaolinite clay, mica). Clay is the basic raw material for many building products such as brick and tile. When silica tetrahedrons share four comer atoms, they produce framework silicates (quartz, tridymite). Quartz is formed when the tetrahedra in this material are arranged in a regular, orderly fashion. If silica in the molten state is cooled very slowly it crystallizes at the freezing point. But if molten silica is cooled more rapidly, the resulting solid is a disorderly arrangement which is glass.

Cement
Cement (Portland cement) is one of the main ingredients of concrete. There are a number of different grades of cement but a typical Portland cement will contain 19 to 25% SiO₂ , 5 to 9% Al₂O₃, 60 to 64% CaO and 2 to 4% FeO. Cements are prepared by grinding the clays and limestone in proper proportion, firing in a kiln, and regrinding. When water is added, the minerals either decompose or combine with water, and a new phase grows throughout the mass. The reaction is solution, recrystallization, and precipitation of a silicate structure. It is usually important to control the amount of water to prevent an excess that would not be part of the structure and would weaken it. The heat of hydration (heat of reaction in the adsorption of water) in setting of the cement can be large and can cause damage in large structures.

Nitride Ceramics
Nitrides combine the superior hardness of ceramics with high thermal and mechanical stability, making them suitable for applications as cutting tools, wear-resistant parts and structural components at high temperatures. TiN has a cubic structure which is perhaps the simplest and best known of structure types. Cations and anions both lie at the nodes of separate fcc lattices. The structure is unchanged if the Ti and N atoms (lattices) are interchanged.

Ferroelectric Ceramics
Depending on the crystal structure, in some crystal lattices, the centers of the positive and negative charges do not coincide even without the application of external electric field. In this case, it is said that there exists spontaneous polarization in the crystal. When the polarization of the dielectric can be altered by an electric field, it is called ferroelectric. A typical ceramic ferroelectric is barium titanate, BaTiO₃. Ferroelectric materials, especially polycrystalline ceramics, are very promising for varieties of application fields such as piezoelectric/electrostrictive transducers, and electrooptic.

Phase Diagram
The phase diagram is important in understanding the formation and control of the microstructure of the microstructure of polyphase ceramics, just as it is with polyphase metallic materials. Also, nonequilibrium structures are even more prevalent in ceramics because the more complex crystal structures are more difficult to nucleate and to grow from the melt.

Imperfections in Ceramics
Imperfections in ceramic crystals include point defects and impurities like in metals. However, in ceramics defect formation is strongly affected by the condition of charge neutrality because the creation of areas of unbalanced charges requires an expenditure of a large amount of energy. In ionic crystals, charge neutrality often results in defects that come as pairs of ions with opposite charge or several nearby point defects in which the sum of all charges is zero. Charge neutral defects include the Frenkel and Schottky defects. A Frenkel-defect occurs when a host atom moves into a nearby interstitial position to create a vacancy-interstitial pair of cations. A Schottky-defect is a pair of nearby cation and anion vacancies. Schottky defect occurs when a host atom leaves its position and moves to the surface creating a vacancy-vacancy pair.

Sometimes, the composition may alter slightly to arrive at a more balanced atomic charge. Solids such as SiO₂, which have a well-defined chemical formula, are called stoichiometric compounds. When the composition of a solid deviates from the standard chemical formula, the resulting solid is said to be nonstoichiometric. Nonstoichiometry and the existence of point defects in a solid are often closely related. Anion vacancies are the source of the nonstoichiometry in SiO_2-x,

Introduction of impurity atoms in the lattice is likely in conditions where the charge is maintained. This is the case of electronegative impurities that substitute a lattice anion or electropositive substitutional impurities. This is more likely for similar ionic radii since this minimizes the energy required for lattice distortion. Defects will appear if the charge of the impurities is not balanced.