Reference: Fundamentals of Materials Science and

Engineering by Calister
Ceramic Crystal Structures
 Ceramics are composed of at least
two elements, and often more,
and their crystal structures are
generally more complex than
those for metals.
 The atomic bonding in these
materials ranges from purely ionic
to totally covalent; many ceramics
exhibit a combination of these
two bonding types, the degree of
ionic character being dependent
on the electronegativities of the
atoms.
Factors that Determne the Crystal
Structure
 Maintenance of Charge Neutrality - all the cation
positive charges must be balanced by an equal number
of anion negative charges.

 Metalic calcium
atom donates 2 F-
electrons to 2 CaF2= Ca2+ + anions
flourine atoms F-
creating the
ceramic compound
calcium flouride.
Factors that Determine the Crystal
Structure
 Sizes or ionic radii of
the cations and anions,
rC and rA
Factors that Determine the Crystal
Structure
AX-TYPE CRYSTAL STRUCTURES
 Rock Salt Structure - the most common AX crystal
structure. Some of the common ceramic materials that
form with this crystal structure are NaCl, MgO, MnS,
LiF, and FeO.
AX-TYPE CRYSTAL STRUCTURES
 Cesium Chloride Structure
AX-TYPE CRYSTAL STRUCTURES
 Zinc Blende Structure - A third AX structure is one
in which the coordination number is 4; that is, all ions
are tetrahedrally coordinated. This is called the zinc
blende, or sphalerite structure, after the mineralogical
term for zinc sulfide (ZnS).
AmXp-TYPE CRYSTAL STRUCTURES
 An example for which a common crystal structure AX2
would be found in fluorite (CaF2).
AmBnXp-TYPE CRYSTAL STRUCTURES
 Ceramic compounds to having more than one type of
cation. Barium titanate (BaTiO3), having both Ba2+
and Ti4+ cations, falls into this classification.
Ceramic Cystal Structures
DENSITY COMPUTATIONS IN
CERAMICS
SILICATE CERAMICS
 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.
CARBON
 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.
 Diamond
 Graphite
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).
Each carbon bonds to four other carbons, and these
bonds are totally covalent.
Graphite
 Graphite has a crystal structure (Figure 3.17) 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.
Graphite
POLYMORPHISM AND ALLOTROPY
 Some metals, as well as nonmetals, may have more
than one crystal structure, a phenomenon known as
polymorphism. When found in elemental solids, the
condition is often termed allotropy. The prevailing
crystal structure depends on both the temperature and
the external pressure. One familiar example is found
in carbon as discussed in the previous section: graphite
is the stable polymorph at ambient conditions,
whereas diamond is formed at extremely high
pressures.