Ceramic Structures

As discussed in the introduction, ceramics and related materials cover a wide range of objects.
Ceramics are a little more complex than metallic structures, which is why metals were covered
first. A ceramic has traditionally been defined as “an inorganic, nonmetallic solid that is prepared
from powdered materials and is fabricated into products through the application of heat. Most
ceramics are made up of two or more elements. This is called a compound. For example, alumina
(Al2O3) is a compound made up of aluminum atoms and oxygen atoms.

The two most common chemical bonds for ceramic materials are covalent and ionic. The
bonding of atoms together is much stronger in covalent and ionic bonding than in metallic. This
is why ceramics generally have the following properties: high hardness, high compressive
strength, and chemical inertness. This strong bonding also accounts for the less attractive
properties of ceramics, such as low ductility and low tensile strength. The absence of free
electrons is responsible for making most ceramics poor conductors of electricity and heat.

However, it should be noted that the crystal structures of ceramics are many and varied and this
results in a very wide range of properties. For example, while ceramics are perceived as
electrical and thermal insulators, ceramic oxide (initially based on Y-Ba-Cu-O) is the basis for
high temperature superconductivity. Diamond and silicon carbide have a higher thermal
conductivity than aluminum or copper. Control of the microstructure can overcome inherent
stiffness to allow the production of ceramic springs, and ceramic composites which have been
produced with a fracture toughness about half that of steel. Also, the atomic structures are often
of low symmetry that gives some ceramics interesting electromechanical properties like
piezoelectricity, which is used in sensors and transducers.

The structure of most ceramics varies from relatively simple to very complex. The
microstructure can be entirely glassy (glasses only); entirely crystalline; or a combination of
crystalline and glassy. In the latter case, the glassy phase usually surrounds small crystals,
bonding them together. The main compositional classes of engineering ceramics are the oxides,
nitrides and carbides.

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 SiO2-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.