FUNDAMENTALS OF MATERIAL SCIENCE AND

ENGINEERING
BS CHEMICAL ENGINEERING 4
REPORTERS: Maurine Reolo

John Rhen Uy
TOPIC: Applications and Processing of
Ceramics, Chapter 13
Most Ceramic Materials fall into an applicationclassification scheme that includes the following
groups:
(1) Glasses
a. Glasses
b. Glass-Ceramics
(2) Clay products
a. Structural clay products
b. Whitewares
(3) Refractories
a. Fireclay
b. Silica
c. Basic
d. Special
(4) Abrasives
(5) Cements
(6) Advanced ceramics.
GLASSES
The glasses are a familiar group of
ceramics; containers, lenses, and fiberglass
represent typical applications. As already
mentioned, they are noncrystalline silicates
containing other oxides, notably CaO, Na2O, K2O,
and Al2O3, which influence the glass properties.
The two prime assets of these materials are
their optical transparency and the relative ease
with which they may be fabricated.
GLASS- CERAMICS
Most inorganic glasses can be made to
transform from a noncrystalline state to one that is
crystalline by the proper high-temperature heat
treatment. This process is called crystallization,
and the product is a fine-grained polycrystalline
material which is often called a glassceramic.
The formation of these small glass-ceramic grains
is, in a sense, a phase transformation, which
involves nucleation and growth stages.
A nucleating agent (e.g titanium dioxide) is
often added to the glass to promote crystallization.

Properties of GLASS-CERAMICS
(1) relatively high mechanical strengths;
(2) low coefficients of thermal expansion (to avoid
thermal shock);
(3) relatively high temperature capabilities;
(4) good dielectric properties (for electronic
packaging applications);
(5) good biological compatibility.
(6) Some glassceramics may be made optically
transparent; others are opaque.
Applications of GLASS-CERAMICS
Glassceramics are manufactured
commercially under the trade names of
Pyroceram, Corningware, Cercor,
and Vision.
The most common uses for these materials are
as ovenware, tableware, oven windows, and
rangetops primarily because of their strength
and excellent resistance to thermal shock. They
also serve as electrical insulators and as substrates
for printed circuit boards, and are used for
architectural cladding, and for heat exchangers and
regenerators.
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.
Classification of CLAY PRODUCTS
(1) Structural clay products include building
bricks, tiles, and sewer pipes applications
in which structural integrity is important.
(2) Whiteware ceramics become white after
the high-temperature firing. Included in this
group are porcelain, pottery, tableware,
china, and plumbing fixtures (sanitary ware).
In addition to clay, many of these products
also contain nonplastic ingredients, which
influence the changes that take place during

the drying and firing processes, and the

characteristics of the finished piece.
REFRACTORIES
Refractory ceramics are utilized in large
tonnages
Properties: the capacity to withstand high
temperatures without melting or
decomposing, the capacity to remain
unreactive and inert when exposed to
severe environments, and the ability to
provide thermal insulation.
Marketed in a variety of forms, most
common as bricks. Typical applications
include furnace linings for metal refining,
glass manufacturing, metallurgical heat
treatment, and power generation.
The performance of a refractory ceramic, to a
large degree, depends on its composition.
There are several classifications:
(1) Fireclay Refractories
The primary ingredients for the
fireclay refractories are high-purity 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.
(2) Silica Refractories
Sometimes termed as acid
refractories, these materials are well
known for their high-temperature loadbearing capacity, are commonly used in the
arched roofs of steel- and glass-making
furnaces; for these applications,
temperatures as high as 1650 degree
Celsius may be realized. The alumina
content should be held to a minimum,
normally to between 0.2 and 1.0 wt%.
(3) 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.
(4) Special Refractories
There are 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. These specialized refractories are
expensive.
Included in this group are alumina,
silica, magnesia, beryllia (BeO), zirconia
(ZrO2), and mullite (3Al2O32SiO2). Others
include carbide compounds, in addition to
carbon and graphite.
Silicon carbide (SiC) has been
used for electrical resistance heating
elements, as a crucible material, and in
internal furnace components. Carbon and
graphite are very refractory, but find limited
application because they are susceptible to
oxidation at temperatures in excess of
about.
ABRASIVES
Abrasive ceramics are used to wear, grind,
or cut away other material, which
necessarily is softer. The prime requisite for
this group of materials is hardness or wear
resistance; a high degree of toughness is
essential to ensure that the abrasive
particles do not easily fracture.
Diamonds, both natural and synthetic, are
utilized as abrasives; however, they are
relatively expensive. The more common
ceramic abrasives include silicon carbide,
tungsten carbide (WC), aluminum oxide (or
corundum), and silica sand.
Coated abrasives are those in which an
abrasive powder is coated on some type of
paper or cloth material; sandpaper is
probably the most familiar example. Wood,
metals, ceramics, and plastics are all
frequently ground and polished using this
form of abrasive.
CEMENT
Several familiar ceramic materials are
classified as inorganic cements: cement,
plaster of paris, and lime, which, as a group,
are produced in extremely large quantities.
The characteristic feature of these materials

is that when mixed with water, they form a

paste that subsequently sets and hardens.
The cementitious bond develops at room
temperature.
Portland Cement
Of cement group of materials, Portland
cement is consumed in the largest tonnages. It
is produced by grinding and intimately mixing
clay and lime-bearing 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. The
resulting clinker product is then ground into a
very fine powder to which is added a small
amount of gypsum (CaSO42H2O) to retard the
setting process. This product is portland
cement.
Several different constituents are found in
portland cement, the principal ones being
tricalcium silicate (3CaOSiO2) and
dicalcium silicate (2CaOSiO2). The setting
and hardening of this material result from
relatively complicated hydration reactions
that occur among the various cement
constituents and the water that is added.
It should be emphasized that the process by
which cement hardens is not one of drying
but, rather, of hydration in which water
actually participates in a chemical bonding
reaction.
Portland cement is termed a hydraulic
cement because its hardness develops by
chemical reactions with water. It is used
primarily in mortar and concrete to bind, into
a cohesive mass, aggregates of inert
particles (sand and/or gravel); these are
considered to be composite materials. Other
cement materials, such as lime, are
nonhydraulic; that is, compounds other
than water (e.g., CO2) are involved in the
hardening reaction.
ADVANCED CERAMICS
Although the traditional ceramics discussed
previously account for the bulk of the
production, the development of new and
what are termed advanced ceramics has
begun and will continue to establish a
prominent niche in our advanced
technologies. In particular, electrical,

magnetic, and optical properties and

property combinations unique to ceramics
have been exploited in a host of new
products.
Advanced ceramics are utilized in optical
fiber communications systems, in
microelectromechanical systems
(MEMS), as ball bearings, and in
applications that exploit the piezoelectric
behavior of a number of ceramic materials.
Optical Fibers
One new and advanced ceramic material
that is a critical component in our modern optical
communications systems. The optical fiber is made
of extremely high-purity silica, which must be free
of even minute levels of contaminants and other
defects that absorb, scatter, and attenuate a light
beam.
Ceramic Ball Bearings
A bearing consists of balls and races that
are in contact with and rub against one
another when in use.
Over the past decade or so silicon nitride
(Si3N4) balls have begun replacing steel
balls in a number of applications, since
several properties of Si3N4 make it a more
desirable material. In most instances races
are still made of steel, because its tensile
strength is superior to that of silicon nitride.
This combination of ceramic balls and steel
races is termed a hybrid bearing.
Some of the applications that employ these
hybrid bearings include inline skates,
bicycles, electric motors, machine tool
spindles, precision medical hand tools (e.g.,
high-speed dental drills and surgical saws),
and textile, food processing, and chemical
equipment.
Ceramic materials are inherently more
corrosion resistant than metal alloys;
because Si3N4 is an electrical insulator
(bearing steels are much more electrically
conductive), the ceramic bearings are
immune to arcing damage.
FABRICATION AND PROCESSING OF
CERAMICS
One chief concern in the application of
ceramic materials is the method of fabrication.
Since ceramic materials have relatively high
melting temperatures, casting them is normally

A classification scheme
for the ceramic-forming techniques

impractical. Furthermore, in most instances the

brittleness of these materials precludes
deformation. Some ceramic pieces are formed
from powders (or particulate collections) that
must ultimately be dried and fired. Glass
shapes are formed at elevated temperatures
from a fluid mass that becomes very viscous
upon cooling. Cements are shaped by placing
into forms a fluid paste that hardens and
assumes a permanent set by virtue of chemical
reactions.

Contrast of Specific Volume versusTemperature behavior of crystalline

and noncrystalline materials

Crystalline materials solidify at the melting

temperature, Tm. Characteristic of the noncrystalline
state is the glass transition temperature, Tg.
For glassy materials, volume decreases
continuously with temperature reduction; a slight
decrease in slope of the curve occurs at what is
called the glass transition temperature, or fictive
temperature, Tg. Below this temperature, the
material is considered to be a glass; above, it is first
a supercooled liquid, and finally a liquid.

GLASS PROPERTIES
Glassy, or noncrystalline, materials do not
solidify in the same sense as do those that are
crystalline. Upon cooling, a glass becomes more
and more viscous in a continuous manner with
decreasing temperature; there is no definite
temperature at which the liquid transforms to a solid
as with crystalline materials. In fact, one of the
distinctions between crystalline and noncrystalline
materials lies in the dependence of specific volume
(or volume per unit mass, the reciprocal of density)
on temperature.

Viscosity-Temperature Characteristics of the

Glass:
1. Melting point, the temperature at which the
viscosity is 10 Pa-s (100 P); the glass is
fluid enough to be considered a liquid.
2. Working point, the temperature at which
the viscosity is 10,000Pa-s (10^4 P); the
glass is easily deformed at this viscosity.
3. Softening point, the temperature at which
the viscosity is 4x10^6Pa-s (4 x 10^7 P), is
the maximum temperature at which a glass
piece may be handled without causing
significant dimensional alterations.
4. Annealing point, the temperature at which
the viscosity is 10^12Pa-s (10^13 P); at this
temperature, atomic diffusion is sufficiently
rapid that any residual stresses may be
removed within about 15 min.
5. Strain point, corresponds to the
temperature at which the viscosity becomes
3 x 10^13 Pa-s (3 x 10^14 P); 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.
Glass Forming
Most glass-forming operations are carried
out within the working range between the
working and softening temperatures. Of
course, the temperature at which each of
these points occurs depends on glass
composition.
Glass is produced by heating the raw
materials to an elevated temperature above
which melting occurs. Most commercial
glasses are of the silicasodalime variety.
For most applications, especially when
optical transparency is important, it is
essential that the glass product be
homogeneous and pore free.
Four different forming methods are used to
fabricate glass products:
1. Pressing - 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.
2. Blowing - 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.
3. Drawing - used to form long glass pieces
such as sheet, rod, tubing, and fibers, which
have a constant cross section. One process
by which sheet glass is formed is it may
also be fabricated by hot rolling.
4. Fiber Forming - 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.

Heat Treating Glasses

1. Annealing Heat Treatment - the glassware
is heated to the annealing point, then slowly

cooled to room temperature to reduce the

magnitude of thermal stresses. These
stresses are important in brittle ceramics,
especially glasses, since they may weaken
the material or, in extreme cases, lead to
fracture, which is termed thermal shock.
2. Glass Tempering - the strength of a glass
piece may be enhanced by intentionally
inducing compressive residual surface
stresses. This can be accomplished by a
heat treatment procedure called thermal
tempering.
FABRICATION AND PROCESSING OF CLAY
PRODUCTS
Clay Properties:
1. Hydroplasticity of Clay Minerals, when
water is added, they become very plastic.
2. Clays are Aluminosilicates, composed of
alumina (Al2O3) and silica (SiO2), that
contain chemically bound water.
Compositions of Clay Products
In addition to clay, many of these products
(in particular the whitewares) also contain some
nonplastic ingredients:
1. Quartz is used primarily as a filler material,
being inexpensive, relatively hard, and
chemically unreactive.
Flint - finely ground quartz
2. When mixed with clay, a flux forms a glass
that has a relatively low melting point. The
feldspars are some of the more common
fluxing agents; they are a group
of aluminosilicate materials that contain K+,
Na+ and Ca2+ ions.
Fabrication Techniques
Two common shaping techniques are utilized for
forming clay-based compositions:
1. 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.
2. Slip Casting - A slip is a suspension of clay
and/or other non-plastic materials in water.
When poured into a porous mold, 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), or it may be terminated when the

solid shell wall reaches the desired
thickness.
Drying
Liquid is removed from a ceramic piece. As
a clay-based ceramic body dries, it also
experiences some shrinkage. A body that has been
formed and dried but not fired is termed green
ceramic body.
Firing
After drying, a body is usually fired at a
high-temperature between 900 and 1400 C; the
firing temperature depends on the composition and
desired properties of the finished piece. During the
firing operation, the density is further increased and
the mechanical strength is enhanced.
Powder Pressing
Powder pressing, the ceramic analogue to
powder metallurgy, is used to fabricate both clay
and nonclay compositions, including electronic and
magnetic ceramics as well as some refractory brick
products. There are three basic powder-pressing
procedures:
1. Uniaxial Pressing, the powder is
compacted in a metal die by pressure that is
applied in a single direction.
2. Isostatic Pressing or Hydrostatic
Pressing, the powdered material is
contained in a rubber envelope and the
pressure is applied by a fluid.
3. Hot Pressing, the powder pressing and
heat treatment are performed
simultaneously the powder aggregate is

compacted at an elevated temperature. The

procedure is used for materials that do not
form a liquid phase except at very high and
impractical temperatures.
TAPE CASTING is an important ceramic fabrication
technique where thin sheets of a flexible tape are
produced by means of a casting process.
CEMENTATION is also considered to be a ceramic
fabrication process. The cement material, when
mixed with water, forms a paste that, after being
fashioned into a desired shape, subsequently
hardens as a result of complex chemical reactions