Chapter 12- Ceramics

 Crystal structures
For those ceramic materials for which the atomic bonding is predominantly ionic, the crystal
structures may be thought of as being composed of electrically charged ions instead of atoms. The
metallic ions, or cations, are positively charged, because they have given up their valence electrons to the
nonmetallic ions, or anions, which are negatively charged.

Table 12.1 Ionic Radii for Several Cations

and Anions (for a Coordination Number of
6).

Figure 12.1 Stable and unstable anion–cation coordination

configurations. Red circles represent anions; blue circles denote
cations.

- Cations go in lattice sites based on

o Size
Two characteristics of the component ions in crystalline ceramic materials
influence the crystal structure: the magnitude of the electrical charge on each of the
component ions, and the relative sizes of the cations and anions. With regard to the first
characteristic, the crystal must be electrically neutral; that is, all the cation positive
charges must be balanced by an equal number of anion negative charges.
The size of an ion will depend on several factors. One of these is coordination
number: ionic radius tends to increase as the number of nearest-neighbor ions of opposite
charge increases. Ionic radii given in Table 12.1 are for a coordination number of 6.
Therefore, the radius will be greater for a coordination number of 8 and less when the
coordination number is 4.
o Stoichiometry
The ratio of cations to anions is not altered by the formation of either a Frenkel or
a Schottky defect. If no other defects are present, the material is said to be stoichiometric.
Stoichiometry may be defined as a state for ionic compounds wherein there is the exact
ratio of cations to anions as predicted by the chemical formula. For example, NaCl is
stoichiometric if the ratio of Na+ ions to Cl- ions is exactly 1:1. A ceramic compound is
nonstoichiometric if there is any deviation from this exact ratio.

o Charge balance
 The second criterion involves the sizes or ionic radii of the cations and anions, rc
and rA, respectively. Because the metallic elements give up electrons when ionized,
cations are ordinarily smaller than anions, and, consequently, the ratio rc/rA is less than
unity. Each cation prefers to have as many nearest-neighbor anions as possible. The
anions also desire a maximum number of cation nearest neighbors.
In addition, the charge on an ion will influence its radius. For example, from
Table 12.1, the radii for Fe2+ and Fe3+ are 0.077 and 0.069 nm, respectively, which values
may be contrasted to the radius of an iron atom—viz. 0.124 nm. When an electron is
removed from an atom or ion, the remaining valence electrons become more tightly
bound to the nucleus, which results in a decrease in ionic radius. Conversely, ionic size
increases when electrons are added to an atom or ion.

o Bond hybridization
Stable ceramic crystal structures form when those anions surrounding a cation
are all in contact with that cation, as illustrated in Figure 12.1. The coordination number
(i.e., number of anion nearest neighbors for a cation) is related to the cation–anion radius
ratio. For a specific coordination number, there is a critical or minimum ratio for which
this cation–anion contact is established (Figure 12.1); this ratio may be determined from
pure geometrical considerations.

 Silicates
Silicates are materials composed primarily of silicon and oxygen, the two most abundant
elements in the earth’s crust; consequently, the bulk of soils, rocks, clays, and sand come under the
silicate classification. Rather than characterizing the crystal structures of these materials in terms of unit
cells, it is more convenient to use various arrangements of an SiO44- tetrahedron (Figure 12.2). Each atom
of silicon is bonded to four oxygen atoms, which are situated at the corners of the tetrahedron; the silicon
atom is positioned at the center. Since this is the basic unit of the silicates, it is often treated as a
negatively charged entity.

Figure 12.2 A silicon–oxygen (SiO44-) tetrahedron. Figure 12.3. A Five silicate ion structures formed
from SiO44- tetrahedra.

- Built up SiO44-
Of these silicates, the most structurally simple ones involve isolated tetrahedra (Figure
12.3a). For example, forsterite (Mg2SiO4) has the equivalent of two Mg2+ ions associated with
each tetrahedron in such a way that every Mg2+ ion has six oxygen nearest neighbors.

- Layered Silicates
A two-dimensional sheet or layered structure can also be produced by the sharing of three
oxygen ions in each of the tetrahedra (Figure 12.4); for this structure the repeating unit formula
 may be represented by (Si2O5)2-. The net negative charge is associated with the unbonded oxygen
atoms projecting out of the plane of the page. Electroneutrality is ordinarily established by a
second planar sheet structure having an excess of cations, which bond to these unbonded oxygen
atoms from the Si2O5 sheet. Such materials are called the sheet or layered silicates, and their
basic structure is characteristic of the clays and other minerals.

Figure 12.4. Schematic representation of the two-dimensional

silicate sheet structure having a repeat unit formula of (Si 2O5)2-.
 Carbon forms
Carbon is an element that exists in various polymorphic forms, as well as in the amorphous state.
This group of materials does not really fall within any one of the traditional metal, ceramic, polymer
classification schemes.

Figure 12.5. A unit cell for the Figure 12.6. The structure of Figure 12.7. The structure of a C60
diamond cubic crystal structure. graphite. molecule.

- Diamond
Diamond is a metastable carbon polymorph at room temperature and atmospheric
pressure. Its crystal structure is a variant of the zinc blende, in which carbon atoms occupy all
positions (both Zn and S), as indicated in the unit cell shown in Figure 12.5 (and also on the front
cover of the book).Thus, each carbon bonds to four other carbons, and these bonds are totally
covalent. This is appropriately called the diamond cubic crystal structure, which is also found for
other Group IVA elements in the periodic table [e.g., germanium, silicon, and gray tin, below
13°C].

- Graphite
Another polymorph of carbon is graphite; it has a crystal structure [Figure 12.6] distinctly
different from that of diamond and is also more stable than diamond at ambient temperature and
pressure. The graphite structure is composed of layers of hexagonally arranged carbon atoms;
within the layers, each carbon atom is bonded to three coplanar neighbor atoms by strong
 covalent bonds. The fourth bonding electron participates in a weak van der Waals type of bond
between the layers. As a consequence of these weak interplanar bonds, interplanar cleavage is
facile, which gives rise to the excellent lubricative properties of graphite. Also, the electrical
conductivity is relatively high in crystallographic directions parallel to the hexagonal sheets

- Fullerenes
Another polymorphic form of carbon was discovered in 1985. It exists in discrete
molecular form and consists of a hollow spherical cluster of sixty carbon atoms; a single
molecule is denoted by Each molecule is composed of groups of carbon atoms that are bonded to
one another to form both hexagon (six-carbon atom) and pentagon (five-carbon atom)
geometrical configurations. One such molecule, shown in Figure 12.7, is found to consist of 20
hexagons and 12 pentagons, which are arrayed such that no two pentagons share a common side;
the molecular surface thus exhibits the symmetry of a soccer ball.

 Lattice imperfections
Atomic defects involving host atoms may exist in ceramic compounds. As with metals, both
vacancies and interstitials are possible; however, since ceramic materials contain ions of at least two
kinds, defects for each ion type may occur. For example, in NaCl, Na interstitials and vacancies and Cl
interstitials and vacancies may exist. It is highly improbable that there would be appreciable
concentrations of anion interstitials. The anion is relatively large, and to fit into a small interstitial
position, substantial strains on the surrounding ions must be introduced.

Figure 12.8. Schematic diagram showing Frenkel and Schottky defect in ionic solids.

- Frenkel defect – cation displaced into interstitial site

Defects in ceramics do not occur alone. One such type of defect involves a cation–
vacancy and a cation–interstitial pair. This is called a Frenkel defect (Figure 12.8). It might be
thought of as being formed by a cation leaving its normal position and moving into an interstitial
site. There is no change in charge because the cation maintains the same positive charge as an
interstitial.

- Schottky defect – missing cation/ anion pair

Another type of defect found in AX materials is a cation vacancy–anion vacancy pair
known as a Schottky defect, also schematically diagrammed in Figure 12.8.This defect might be
thought of as being created by removing one cation and one anion from the interior of the crystal
and then placing them both at an external surface. Since both cations and anions have the same
charge, and since for every anion vacancy there exists a cation vacancy, the charge neutrality of
the crystal is maintained.
  Phase diagrams
Phase diagrams have been experimentally determined for a large number of ceramic systems. For
binary or two-component phase diagrams, it is frequently the case that the two components are
compounds that share a common element, often oxygen. These diagrams may have configurations similar
to metal–metal systems, and they are interpreted in the same way. Phase diagrams for the Al2O3-
Cr2O3,MgO-Al2O3, ZrO2-CaO, and SiO2-Al2O3 systems are shown in the figures below.

Figure 12.9. The aluminum oxide– chromium oxide Figure 12.10. The magnesium oxide– aluminum
phase diagram. oxide phase diagram; ss denotes solid solution.
Figure 12.9. The aluminum oxide– Figure 12.10. The magnesium oxide– aluminum oxide
chromium oxide phase diagram. phase diagram; ss denotes solid solution.

Figure 12.11. A portion of the zirconia–calcia Figure 12.12. The silica–alumina phase diagram.
phase diagram; ss denotes solid solution.
  Mechanical properties
Ceramic materials are somewhat limited in applicability by their mechanical properties, which in
many respects are inferior to those of metals. The principal drawback is a disposition to catastrophic
fracture in a brittle manner with very little energy absorption.
At room temperature, both crystalline and noncrystalline ceramics almost always fracture before
any plastic deformation can occur in response to an applied tensile load. The brittle fracture process
consists of the formation and propagation of cracks through the cross section of material in a direction
perpendicular to the applied load. Crack growth in crystalline ceramics may be either transgranular (i.e.,
through the grains) or intergranular (i.e., along grain boundaries); for transgranular fracture, cracks
propagate along specific crystallographic (or cleavage) planes, planes of high atomic density.