Structures and Properties of Ceramics

WHY STUDY Structures and Properties of Ceramics?

Some of the properties of ceramics may be explained by their
structures. For example: (a) The optical transparency of inorganic glass
materials is due, in part, to their noncrystallinity; (b) the hydroplasticity of
clays (i.e., development of plasticity upon the addition of water) is related to
interactions between water molecules and the clay structures; and (c) the
permanent magnetic and ferroelectric behaviors of some ceramic materials
are explained by their crystal structures.
The termceramic comes from the Greek word keramikos, which
means burnt stuff, indicating that desirable properties of these
materials are normally achieved through a high-temperature heat
treatment process called firing.
Ceramic materials
o inorganic and nonmetallic materials
o Most ceramics are compounds between metallic and nonmetallic
elements
o the interatomic bonds are either totally ionic, or predominantly ionic
but having some covalent character
Traditional Ceramics
-those for which the primary raw material is clay;
-products considered to be traditional ceramics are china, porcelain, bricks,
tiles, and,
in addition, glasses and high-temperature ceramics.
Ceramic Structures
Because ceramics are composed of at least two elements, and often
more, 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 electro
negativities of the atoms.
The properties of ceramic materials, like all materials, are dictated by
the types of atoms present, the types of bonding between the atoms, and
the way the atoms are packed together. The type of bonding and structure
helps determine what type of properties a material will have.

Ceramics usually have a combination of stronger

bonds called ionic (occurs between a metal and
nonmetal and involves the attraction of opposite charges
when electrons are transferred from the metal to the
nonmetal); and covalent (occurs between two nonmetals
and involves sharing of atoms). The strength of an ionic
bond depends on the size of the charge on each ion and
on the radius of each ion. The greater the number of
electrons being shared, is the greater the force of attraction, or the stronger
the covalent bond.

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. 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 chemical
formula of a compound indicates the ratio of cations to anions, or the
composition that achieves this charge balance (e.g. calcium fluoride, each
calcium ion has a +2 charge (Ca2+), and associated with each fluorine ion is a
single negative charge (F-). Thus, there must be twice as many F - as Ca2+
ions, which is reflected in the chemical formula CaF2.
The second criterion involves the sizes or ionic radii of the cations and
anions, rC and rA, respectively. Each cation prefers to have as many nearestneighbor anions as possible. The anions also desire a maximum number of
cation nearest neighbors. Stable ceramic crystal structures form when those
anions surrounding a cation are all in contact with that cation. The
coordination number (i.e., number of anion nearest neighbors for a cation) is
related to the
cationanion radius ratio. For a specific coordination number, there is a
critical or minimum rC/ rA ratio for which this cationanion contact is
established, this ratio may be determined from pure geometrical
considerations.
Ionic Radii for Several Cations and Anions
(for coordination number of 6)

The most common coordination numbers for ceramic materials are 4,

6, and 8. It should be noted that the relationships between coordination
number and cationanion radii ratios are based on geometrical
considerations and assuming hard sphere ions; therefore, these
relationships are only approximate, and there are exceptions.
These types of bonds result in high elastic modulus and hardness, high
melting points, low thermal expansion, and good chemical resistance. On the
other hand, ceramics are also hard and often brittle (unless the material is
toughened by reinforcements or other means), which leads to fracture.

In general, metals have weaker bonds than ceramics,

which allows the electrons to move freely between
atoms. Think of a box containing marbles surrounded by
water. The marbles can be pushed anywhere within the
box and the water will follow them, always surrounding
the marbles. This type of bond results in the property
called ductility, where the metal can be easily bent
without breaking, allowing it to be drawn into wire. The
free movement of electrons also explains why metals tend to be conductors
of electricity and heat.

Plastics or polymers of the organic type consist of long chains of

molecules which are either tangled or ordered at room temperature. Because

the forces (known as van der Waals) between the molecules are very weak,
polymers are very elastic (like a rubber band), can be easily melted, and
have low strength. Like ceramics, polymers have good chemical resistance,
electrical and thermal insulation properties. They are also brittle at low
temperatures.

AX-Type Crystal Structures

common ceramic materials with equal numbers of cations and anions

have this type of structure
Examples: sodium chloride(NaCl); cesium chloride(CsCl); zinc sulfide
(ZnS)

Am Xp -Type Crystal Structures

exists when the charges on the cations and anions are not the same
Examples: ZrO2 ; ThO2

Am Bn Xp Type Crystal Structures

Examples: Barium titanate (BaTiO3 )

Crystal Structures from the Close Packing of Anions

Ordinarily, the close-packed planes are composed of the large anions.
As these planes are stacked atop each other, small interstitial sites are
created between them in which the cations may reside.
These interstitial positions exist in two different types. Four atoms
(three in one plane, and a single one in the adjacent plane surround one
type; this is termed a tetrahedral position, since straight lines drawn from

the centers of the surrounding spheres form a four-sided tetrahedron. The

other site type in involves six ion spheres, three in each of the two planes.
Because an octahedron is produced by joining these six sphere centers, this
site is called an octahedral position. Thus, the coordination numbers for
cations filling tetrahedral and octahedral positions are 4 and 6, respectively.
Furthermore, for each of these anion spheres, one octahedral and two
tetrahedral positions will exist.
Ceramic crystal structures of this type depend on two factors: (1) the
stacking of the close-packed anion layers (both FCC and HCP arrangements
are possible, which correspond to ABCABC . . . and ABABAB . . . sequences,
respectively), and (2) the manner in which the interstitial sites are filled with
cations.

Ceramic Density Computations

Silicate Ceramics
Silicates are materials composed primarily of silicon and oxygen.
Rather than characterizing the crystal structures of these materials in terms
of unit cells, it is more convenient to use various arrangements of an SiO 44tetrahedron (Figure 12.9). 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. Often the silicates are not
considered to be ionic because there is a significant covalent character to
the interatomic SiO bonds which are directional and relatively strong.
Regardless of the character of the SiO bond, there is a 4
charge associated with every SiO4 tetrahedron, since each of the four
oxygen atoms requires an extra electron to achieve a stable electronic
structure. Various silicate structures arise from the different ways in which
the SiO4 units can be combined into one-, two-, and three-dimensional
arrangements.
Silica
Chemically, the most simple silicate material is silicon dioxide, or silica
(SiO2). Structurally, it is a three-dimensional network that is generated when
every corner oxygen atom in each tetrahedron is shared by adjacent
tetrahedra. Thus, the material is electrically neutral and all atoms have
stable electronic structures. Under these circumstances the ratio of Si to O
atoms is 1:2, as indicated by the chemical formula.
Silica Glasses
Silica can also be made to exist as a noncrystalline solid or glass,
having a high degree of atomic randomness, which is characteristic of the
liquid; such a material is called fused silica, or vitreous silica. As with
crystalline silica, the SiO4 tetrahedron is the basic unit; beyond this
structure, considerable disorder exists.
Other oxides (e.g., B2O3 and GeO2) may also form glassy structure;
these materials, as well as SiO2, are termed network formers.
The common inorganic glasses that are used for containers, windows,
and so on are silica glasses to which have been added other oxides such as
CaO and Na2O. These oxides do not form polyhedral networks. Rather, their

cations are incorporated within and modify the SiO4 network; for this reason,
these oxide additives are termed network modifiers.
Still other oxides, such as TiO2 and Al2O3, while not network formers,
substitute for silicon and become part of and stabilize the network; these are
called intermediates. From a practical perspective, the addition of these
modifiers and intermediates lowers the melting point and viscosity of a glass,
and makes it easier to form at lower temperatures.
The Silicates
For the various silicate minerals, one, two, or three of the corner
oxygen atoms of the SiO4 tetrahedra are shared by other tetrahedra to form
some rather complex structures. Some of these have formulas SiO 44-, Si2O76-,
Si3O96- , and so on; single-chain structures are also possible.
Positively charged cations such as Ca2 , Mg2 , and Al3 serve two roles.
First, they compensate the negative charges from the SiO4 units so that
charge neutrality is achieved; and second, these cations ionically bond the
SiO4 tetrahedra together.
Simple Silicates
Of these silicates, the most structurally simple ones involve isolated
tetrahedra. For example, forsterite (Mg2SiO4) has the equivalent of two Mg2
ions associated with each tetrahedron in such a way that every Mg2 ion has
6 oxygen-nearest neighbors. The Si2O6 ion is formed when two tetrahedra
share a common oxygen atom. Akermanite (Ca2MgSi2O7) is a mineral
having the equivalent of two Ca 2+ ions and one Mg2+ ion bonded to each
Si2O6 unit.7
Layered Silicates
Layered silicates (clay silicates) SiO4 tetrahedra connected together
to form 2-D plane (Si2
need cations to balance charge
Kaolinite clay alternates (Si2O5)2- layer with Al2(OH)4 2+ layer
-sheets loosely bound by van der waals forces
Can change the counterions
This changes layer spacing
The layers also allow absorption of water
Micas KAl3Si3O10(OH)2
Bentonite
used to seal wells
packaged dry
swells 2-3 fold in H2O
pump in to seal up well so no polluted ground water seeps in to
contaminate the water supply

Carbon
Carbon Forms
a. Carbon black
Amorphous
surface area ca. 1000 m2/g
b. Diamond
each carbon bonds to four other carbons, and these bonds are
totally covalent
Extremely hard
very low electrical conductivity (due to its crystal structure and
the strong inter-atomic covalent bonds)
unusually high thermal conductivity for a nonmetallic material
optically transparent in the visible and infrared regions of the
electromagnetic spectrum and has a high index of refraction
Relatively large diamond single crystals are used as gem stones.
Industrially, diamonds are utilized to grind or cut other softer
materials
diamond films
-Hard surface coat tools, medical devices, etc.
c. Graphite
polymorph of carbon
it has a crystal structure distinctly different from that of diamond
and is also more stable than diamond at ambient temperature
and pressure
layer structure
aromatic layers
weak van der Waals forces between layers
interplanar cleavage is facile, which gives rise to excellent
lubricative properties
high strength and good chemical stability at elevated
temperatures and in nonoxidizing atmospheres
high thermal conductivity
low coefficient of thermal expansion
high resistance to thermal shock
high adsorption of gases
good machinability

commonly used as heating elements for electric furnaces, as

electrodes for arc welding, in metallurgical crucibles, in casting
molds for metal alloys and ceramics, for high-temperature
refractories and insulations, in rocket nozzles, in chemical reactor
vessels, for electrical contacts, brushes and resistors, as
electrodes in batteries, and in air purification devices
d. Fullerenes

polymorphic form of carbon was discovered in 1985

exists in discrete molecular form and consists of a hollow
spherical cluster of sixty carbon atoms; a single molecule is
denoted by C60. Each molecule is composed of groups of carbon
atoms that are bonded to one another to form both hexagon and
pentagon geometrical configurations.
the molecular surface exhibits the symmetry of a soccer ball
The material composed of C60 molecules is known as
buckminsterfullerene, named in honor of R. Buckminster Fuller,
who invented the geodesic dome; each C60 is simply a molecular
replica of such a dome
The term fullerene is used to denote the class of materials that
are composed of this type of molecule
In the solid state, the C60 units form a crystalline structure and
pack together in a face-centered cubic array, this material is
electrically insulating, with proper impurity additions, it can be
made highly conductive and semi conductive

e. Carbon Nanotube
Its structure consists of a single sheet of graphite, rolled into a
tube, both ends of which are capped with C60 fullerene
hemispheres
The nano prefix denotes that tube diameters are on the order of
a nanometer
Each nanotube is a single molecule composed of millions of
atoms; the length of this molecule is much greater (on the order
of thousands of times greater) than its diameter.
Multiple-walled carbon nanotubes consisting of concentric
cylinders have also been found to exist. These nanotubes are
extremely strong and stiff, and relatively ductile
For single-walled nanotubes, tensile strengths range between 50
and 200 GPa (approximately an order of magnitude greater than
for carbon fibers); this is the strongest known material
Elastic modulus values are on the order of one tetrapascal [TPa
(1 TPa 103 GPa)], with fracture strains between about 5% and
20%
have relatively low densities
has been termed the ultimate fiber and is extremely promising
as a reinforcement in composite materials
Depending on the orientation of the hexagonal units in the
graphene plane (i.e., tube wall) with the tube axis, the nanotube
may behave electrically as either a metal or a semiconductor
Imperfections in Ceramics

Atomic Point Defects

Atomic defects involving host atoms may exist in ceramic compounds
defect structure is often used to designate the types and
concentrations of atomic defects in ceramics; Because the atoms exist
as charged ions, when defect structures are considered, conditions of
electroneutrality must be maintained
Electroneutrality is the state that exists when there are equal numbers
of positive and negative charges from the ions. As a consequence,
defects in ceramics do not occur alone.
Frenkel defect involves a cationvacancy and a cationinterstitial pair
Schottky defect is a cation vacancyanion vacancy pair

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.

Impurities in Ceramics
Impurity atoms can form solid solutions in ceramic materials much as
they do in metals. Solid solutions of both substitutional and interstitial types
are possible. For an interstitial, the ionic radius of the impurity must be
relatively small in comparison to the anion. Since there are both anions and
cations, a substitutional impurity will substitute for the host ion to which it
is most similar in an electrical sense: if the impurity atom normally forms a
cation in a ceramic material, it most probably will substitute for a host cation.
For example, in sodium chloride, impurity Ca2 and O2 ions would most likely
substitute for Na and Cl ions, respectively.
Diffusion in Ionic Materials
For ionic compounds, the phenomenon of diffusion is more complicated
than for metals inasmuch as it is necessary to consider the diffusive motion
of two types of ions that have opposite charges. Diffusion in these materials
usually occurs by a vacancy. Also, in order to maintain charge neutrality in an
ionic material, the following may be said about vacancies: (1) ion vacancies
occur in pairs [as with Schottky defects], (2) they form in nonstoichiometric
compounds, and (3) they are created by substitutional impurity ions having
different charge states than the host ions. In any event, associated with the
diffusive motion of a single ion is a transference of electrical charge. In order
to maintain localized charge neutrality in the vicinity of this moving ion, it is
necessary that another species having an equal and opposite charge
accompany the ions diffusive motion. Possible charged species include
another vacancy, an impurity atom, or an electronic carrier [i.e., a free
electron or hole]. It follows that the rate of diffusion of these electrically

charged couples is limited by the diffusion rate of the slowest moving

species.
When an external electric field is applied across an ionic solid, the
electrically charged ions migrate (i.e., diffuse) in response to forces that are
brought to bear on them. This ionic motion gives rise to an electric current.
Furthermore, the electrical conductivity is a function of the diffusion
coefficient. Consequently, much of the diffusion data for ionic solids come
from electrical conductivity measurements.
Ceramic Phase Diagrams
Phase diagram is a graphical representation of the physical states of a
substance under different conditions of temperature and pressure. A typical
phase diagram has pressure on the y-axis and temperature on the x-axis. As
we cross the lines or curves on the phase diagram, a phase change occurs.
In addition, two states of the substance coexist in equilibrium on the lines or
curves.
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 are especially useful in assessing the hightemperature performance of ceramic materials.

The Al2O3 Cr2O3 System

-consisting of single
liquid and single
solid phase regions
separated by a twophase
solidliquid
region
-The Al2O3Cr2O3
solid solution is a
substitutional one
in
which
Al3
substitutes for Cr3 ,
and vice versa
-It exists for all
compositions below
the melting point of
Al2O3 inasmuch as both aluminum and chromium ions have
the same charge as well as similar radii
-Al2O3 and Cr2O3 have the same crystal structure.

The MgO Al2O3 System

-There exists an
intermediate
phase,
a
compound called
spinel, which has
the
chemical
formula MgAl2O4
(or MgOAl2O3).
-Thus, spinel is

nonstoichiometric for other than the 50 mol% Al2O350 mol% MgO

composition
-there is limited solubility of Al2O3 in MgO below about 1400 C
(2550 F) at the left-hand extremity of Figure, which is due primarily
to the differences in charge and radii of the Mg2 and Al3 ions
-is virtually insoluble in Al2O3, as evidenced by a lack of a terminal solid
solution on the right-hand side of the phase diagram. Also, two eutectics are
found, one on either side of the spinel phase field, and stoichiometric spinel
melts congruently at about 2100 C (3800 F)
The ZrO2 CaO System
- ZrO2 phases having three
different crystal structures
exist in this systemnamely,
tetragonal, monoclinic, and
cubic

The SiO2Al2 O3 System

Commercially, the silicaalumina system is an important one

since the principal constituents of many ceramic refractories are
these two materials. The polymorphic form of silica that is stable at
these temperatures is termed cristobalite, the unit cell for which is
shown in Figure. Silica and alumina are not mutually soluble in one
another, which is evidenced by the absence of terminal solid
solutions at both extremities of the phase diagram.

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.
Brittle Fracture of Ceramics
Brittle fracture is fracture that involves little or no plastic, or
permanent, deformation. Many nonmetals lack ductility and normally are
subject to brittle fracture; examples are chalk, rock, brick, and - under
normal conditions of use - glass.
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 measure of a ceramic materials ability to resist fracture
when a crack is present is specified in terms of fracture
toughness. The plane strain fracture toughness KIc:

Fractography of Ceramics
It is sometimes necessary to
acquire information regarding
the cause of a ceramic fracture
so that measures may be taken
to reduce the likelihood of future
incidents. A failure analysis
normally
focuses
on
determination of the location,
type, and source of the crackinitiating flaw. A fractographic
study is normally a part of such
an analysis, which involves
examining the path of crack
propagation
as
well
as
microscopic features of the
fracture surface.

Stress-Strain Behavior
Flexural Strength is defined as a material's ability to resist deformation
under load
Elastic Behavior
The elastic stressstrain behavior for ceramic materials using flexure
tests is similar to the tensile test results for metals: a linear
relationship exists between stress and strain.
MECHANISMS OF PLASTIC DEFORMATION
At room temperature most ceramic materials suffer fracture before the
onset of plastic deformation. Plastic deformation is different for crystalline
and noncrystalline ceramics.
Crystalline materials do show plastic deformation. However, due to the
rigid structure of these materials, there are very few available slip
systems for dislocations to move, and so they deform very slowly. With the
non-crystalline (glassy) materials, viscous flow is the dominant source of
plastic deformation, and is also very slow. It is therefore neglected in many
applications of ceramic materials.
To overcome the brittle behavior, ceramic material development has
introduced the class of ceramic matrix composite materials, in which ceramic
fibers are embedded and with specific coatings are forming fiber bridges
across any crack. This mechanism substantially increases the fracture
toughness of such ceramics. The ceramic disc brakes are, for example using
a ceramic matrix composite material manufactured with a specific process.
Miscellaneous Mechanical Considerations

Many ceramic bodies contain residual porosity, which is deleterious to

both their moduli of elasticity and fracture strengths. In addition to their
inherent brittleness, ceramic materials are distinctively hard. Also, since
these materials are frequently utilized at elevated temperatures and under
applied loads, creep characteristics are important.
APPLICATIONS AND PROCESSING OF CERAMICS
A. GLASSES
Glasses are a familiar group of ceramics, which are widely used in
containers, lenses, fiberglasses and other miscellaneous items. They are
noncrystalline silicates containing other oxides such as CaO and Na 2O. The
two prime aspects of a glass are its optical transparency and its easy
fabrication process.
GLASS-CERAMICS
Inorganic glasses can be made to transform noncrystalline states
to one that is crystallized by controlled high temperature treatment. This
process is called crystallization, and the product is a fine-grained
polycrystalline material called glass-ceramics. Basically, the whole
transformation of the glass-ceramic is a phase transformation, which
involves nucleation and growth stages.
A nucleating agent (usually titanium dioxide) is utilized to trigger
and fasten the crystallization rate. In addition, this agent adds opacity and
authenticity to the glass-ceramics which is why they are not optically
transparent. Glass-ceramic materials have been designed to have the
following characteristics: relatively high mechanical strengths; low
coefficients of thermal expansion (to avoid thermal shock); relatively high
temperature capabilities; good dielectric properties (for electronic packaging
applications); and good biological compatibility.

B. CLAY PRODUCTS
One of the most widely used ceramic raw materials is clay. This
inexpensive ingredient, found naturally in great abundance, often is used as
mined without any upgrading of quality. Another reason for its popularity lies
in the ease with which clay products may be formed; when mixed in the
proper proportions, clay and water form a plastic mass that is very amenable
to shaping. The formed piece is dried to remove some of the moisture, after

which it is fired at an elevated temperature to improve its mechanical

strength.
Two broad classifications: a) Structural clay products - include building
bricks, tiles, and sewer pipesapplications in which structural integrity is
important; b) Whitewares - become white after the high-temperature firing.
Included in this group are porcelain, pottery, tableware, china, and plumbing
fixtures (sanitary ware).

C. REFRACTORIES
The salient properties of these materials include the capacity to
withstand high temperatures without melting or decomposing, and the
capacity to remain unreactive and inert when exposed to severe
environments. In addition, the ability to provide thermal insulation is often an
important consideration. Refractory materials are marketed in a variety of
forms, but bricks are the most common. Typical applications include furnace
linings for metal refining, glass manufacturing, metallurgical heat treatment,
and power generation.
Porosity is one microstructural variable that must be controlled to
produce a suitable refractory brick. Strength, load-bearing capacity, and
resistance to attack by corrosive materials all increase with porosity
reduction
FIRECLAY REFRACTORIES
The primary ingredients for the fireclay refractories are highpurity fireclays, alumina and silica mixtures usually containing between 25
and 45 wt% alumina. Fireclay bricks are used principally in furnace
construction, to confine hot atmospheres, and to thermally insulate
structural members from excessive temperatures.
SILICA REFRACTORIES
The prime ingredient for silica refractories, sometimes termed
acid refractories, is silica. These materials, well known for their hightemperature load-bearing capacity, are commonly used in the arched roofs
of steel- and glass-making furnaces. These refractory materials are also
resistant to slags that are rich in silica (called acid slags) and are often used

as containment vessels for them. On the other hand, they are readily
attacked by slags composed of a high proportion of CaO and/or MgO (basic
slags), and contact with these oxide materials should be avoided.
BASIC REFRACTORIES
The refractories that are rich in periclase, or magnesia (MgO), are
termed basic; they may also contain calcium, chromium, and iron
compounds. The presence of silica is deleterious to their high-temperature
performance. Basic refractories are especially resistant to attack by slags
containing high concentrations of MgO and CaO, and find extensive use in
some steel-making open hearth furnaces.
SPECIAL REFRACTORIES
There are yet other ceramic materials that are used for rather
specialized refractory applications. Some of these are relatively high-purity
oxide materials, many of which may be produced with very little porosity. As
would be expected, these specialized refractories are relatively expensive.
D. ABRASIVES
Abrasive ceramics are used to wear, grind, or cut away other material, which
necessarily is softer. Therefore, the prime requisite for this group of materials
is hardness or wear resistance; in addition, a high degree of toughness is
essential to ensure that the abrasive particles do not easily fracture.
Furthermore, high temperatures may be produced from abrasive frictional
forces, so some refractoriness is also desirable. Abrasives are used in several
formsbonded to grinding wheels, as coated abrasives, and as loose grains.
E. CEMENTS
The characteristic feature of these materials is that when mixed with
water, they form a paste that subsequently sets and hardens. This trait is
especially useful in that solid and rigid structures having just about any
shape may be expeditiously formed. Also, some of these materials act as a
bonding phase that chemically binds particulate aggregates into a single
cohesive structure. Under these circumstances, the role of the cement is
similar to that of the glassy bonding phase that forms when clay products
and some refractory bricks are fired. One important difference, however, is
that the cementitious bond develops at room temperature.

Of this group of materials, portland cement is consumed in the largest

tonnages. It is produced by grinding and intimately mixing clay and limebearing minerals in the proper proportions, and then heating the mixture to
about in a rotary kiln; this process, sometimes called calcination, produces
physical and chemical changes in the raw materials.

FABRICATION AND PROCESSING

A. GLASS FORMING
On the viscosity scale several specific points that are important in the
fabrication and processing of glasses are labeled:
1. The melting point corresponds to the temperature at which the viscosity is
10 Pa-s (100 P); the glass is fluid enough to be considered a liquid.
2. The working point represents the temperature at which the viscosity is 10 3
Pa-s; the glass is easily deformed at this viscosity.
3. The softening point, the temperature at which the viscosity is 4 X 10 6 Pa-s,
is the maximum temperature at which a glass piece may be handled without
causing significant dimensional alterations.
4. The annealing point is the temperature at which the viscosity is 10 12Pa-s;
at this temperature, atomic diffusion is sufficiently rapid that any residual
stresses may be removed within about 15 min.
5. The strain point corresponds to the temperature at which the viscosity
becomes 3X1013Pa-s; for temperatures below the strain point, fracture will
occur before the onset of plastic deformation. The glass transition
temperature will be above the strain point.
PRESSING
Pressing is used in the fabrication of relatively thick-walled
pieces such as plates and dishes. The glass piece is formed by pressure
application in a graphite-coated cast iron mold having the desired shape; the
mold is ordinarily heated to ensure an even surface.
BLOWING
Although some glass blowing is done by hand, especially for art
objects, the process has been completely automated for the production of

glass jars, bottles, and light bulbs. From a raw gob of glass, a parison, or
temporary shape, is formed by mechanical pressing in a mold. This piece is
inserted into a finishing or blow mold and forced to conform to the mold
contours by the pressure created from a blast of air.
DRAWING
Drawing is used to form long glass pieces such as sheet, rod,
tubing, and fibers, which have a constant cross section. Flatness and the
surface finish may be improved significantly by floating the sheet on a bath
of molten tin at an elevated temperature; the piece is slowly cooled and
subsequently heat treated by annealing.
FIBER FORMING
Continuous glass fibers are formed in a rather sophisticated
drawing operation. The molten glass is contained in a platinum heating
chamber. Fibers are formed by drawing the molten glass through many small
orifices at the chamber base. The glass viscosity, which is critical, is
controlled by chamber and orifice temperatures.

B. CLAY PRODUCTS FORMING

The clay minerals play two very important roles in ceramic bodies.
First, when water is added, they become very plastic, a condition termed
hydroplasticity. In addition, clay fuses or melts over a range of temperatures;
thus, a dense and strong ceramic piece may be produced during firing
without complete melting such that the desired shape is maintained.
HYDROPLASTIC FORMING
Clay minerals, when mixed with water, become highly plastic and
pliable and may be molded without cracking; however, they have extremely
low yield strengths. The consistency (waterclay ratio) of the hydroplastic
mass must give yield strength sufficient to permit a formed ware to maintain
its shape during handling and drying. The most common hydroplastic
forming technique is extrusion, in which a stiff plastic ceramic mass is forced
through a die orifice having the desired cross-sectional geometry.
SLIP CASTING

A slip is a suspension of clay and/or other nonplastic materials in

water.When poured into a porous mold (commonly made of plastic of paris),
water from the slip is absorbed into the mold, leaving behind a solid layer on
the mold wall the thickness of which depends on the time. This process may
be continued until the entire mold cavity becomes solid (solid casting). The
solid is then removed by separating the molds, leaving the product.
POWDER PRESSING
Used to fabricate both clay and nonclay compositions , including
magnetic and electronic ceramics as well as refractories.
Three (3) processes:

Uniaxial - the powder is compacted in a metal die by pressure that is

applied in a single direction. The formed piece takes on the
configuration of die and platens through which the pressure is applied
Isostatic - the powdered material is contained in a rubber envelope and
the pressure is applied by a fluid, isostatically (i.e., it has the same
magnitude in all directions)
Hot pressing - the powder pressing and heat treatment are performed
simultaneouslythe powder aggregate is compacted at an elevated
temperature

C. DRYING
As a clay-based ceramic body dries, it also experiences some
shrinkage. In the early stages of drying the clay particles are virtually
surrounded by and separated from one another by a thin film of water. As
drying progresses and water is removed, the interparticle separation
decreases, which is manifested as shrinkage.
Shrinkage factors:

Body thickness Thickness and shrinkage is directly proportional

Water content of formed body Water content and shrinkage is
directly proportional
Clay particle sizes Particle size and shrinkage is inversely
proportional

D. FIRING
After drying, a body is usually fired at a temperature between
900 and 1400C; the firing temperature depends on the composition and
desired properties of the finished piece. During the firing operation, the
density is further increased (with an attendant decrease in porosity) and the
mechanical strength is enhanced. The degree of vitrification, of course,
controls the room-temperature properties of the ceramic ware; strength,
durability, and density are all enhanced as it increases.