Chemistry in

Everyday
Life
(Advance Materials)

Submitted by:
Jane Francis Mallapre
Jocelle D. Mella
Jhenevie Lubiano
IV-Diamond

Submitted to:
Ma. Clara Hitta

Ceramics
Ceramics can be defined as heat-resistant, nonmetallic, inorganic solids that
are (generally) made up of compounds formed from metallic and nonmetallic
elements. Although different types of ceramics can have very different
properties, in general ceramics are corrosion-resistant and hard, but brittle.
Most ceramics are also good insulators and can withstand high
temperatures. These properties have led to their use in virtually every aspect
of modern life.
The two main categories of ceramics are traditional and advanced.
Traditional ceramics include objects made of clay and cements that have
been hardened by heating at high temperatures. Traditional ceramics are
used in dishes, crockery, flowerpots, and roof and wall tiles. Advanced
ceramics include carbides, such as silicon carbide, SiC; oxides, such as
aluminum oxide, Al2O3; nitrides, such as silicon nitride, Si3N4; and many
other materials, including the mixed oxide ceramics that can act as
superconductors. Advanced ceramics require modern processing techniques,
and the development of these techniques has led to advances in medicine
and engineering.
Glass is sometimes considered a type of ceramic. However, glasses and
ceramics differ in that ceramics have a crystalline structure while glasses
contain impurities that prevent crystallization. The structure of glasses is
amorphous, like that of liquids. Ceramics tend to have high, well-defined
melting points, while glasses tend to soften over a range of temperatures
before becoming liquids. In addition, most ceramics are opaque to visible
light, and glasses tend to be translucent. Glass ceramics have a structure
that consists of many tiny crystalline regions within a non crystalline matrix.
This structure gives them some properties of ceramics and some of glasses.
In general, glass ceramics expand less when heated than most glasses,
making them useful in windows, for wood stoves, or as radiant glass-ceramic
cook top surfaces.

Composition
Some ceramics are composed of only two elements. For example, alumina is
aluminum oxide, Al2O3; zirconia is zirconium oxide, ZrO2; and quartz is
silicon dioxide, SiO2. Other ceramic materials, including many minerals, have
complex and even variable compositions. For example, the ceramic mineral
feldspar, one of the components of granite, has the formula KAlSi3O8.
The chemical bonds in ceramics can be covalent, ionic, or polar covalent,
depending on the chemical composition of the ceramic. When the
components of the ceramic are a metal and a nonmetal, the bonding is
primarily ionic; examples are magnesium oxide (magnesia), MgO, and
barium titanate, BaTiO3. In ceramics composed of a metalloid and a
nonmetal, bonding is primarily covalent; examples are boron nitride, BN, and
silicon carbide, SiC. Most ceramics have a highly crystalline structure, in

which a three-dimensional unit, called a unit cell, is repeated throughout the

material. For example, magnesium oxide crystallizes in the rock salt
structure. In this structure, Mg2+ ions alternate with O2 ions along each
perpendicular axis.

Manufacture of Traditional Ceramics

Traditional ceramics are made from natural materials such as clay that have
been hardened by heating at high temperatures (driving out water and
allowing strong chemical bonds to form between the flakes of clay). In fact,
the word "ceramic" comes from the Greek keramos, whose original meaning
was "burnt earth." When artists make ceramic works of art, they first mold
clay, often mixed with other raw materials, into the desired shape. Special
ovens called kilns are used to "fire" (heat) the shaped object until it hardens.
Clay consists of a large number of very tiny flat plates, stacked together but
separated by thin layers of water. The water allows the plates to cling
together, but also acts as a lubricant, allowing the plates to slide past one
another. As a result, clay is easily molded into shapes. High temperatures
drive out water and allow bonds to form between plates, holding them in
place and promoting the formation of a hard solid. Binders such as bone ash
are sometimes added to the clay to promote strong bond formation, which
makes the ceramic resistant to breakage. The common clay used to make
flowerpots and roof tiles is usually red-orange because of the presence of
iron oxides. White ceramics are made from rarer (and thus more expensive)
white clays, primarily kaolin.
The oldest known ceramics made by humans are figurines found in the
former Czechoslovakia that are thought to date from around 27 000 b.c.e. It
was determined that the figurines were made by mixing clay with bone,
animal fat, earth, and bone ash (the ash that results when animal bones are
heated to a high temperature), molding the mixture into a desired shape,
and heating it in a domed pit. The manufacture of functional objects such as
pots, dishes, and storage vessels, was developed in ancient Greece and
Egypt during the period 9000 to 6000 b.c.e.
An important advance was the development of white porcelain. Porcelain is a
hard, tough ceramic that is less brittle than the ceramics that preceded it. Its
strength allows it to be fashioned into beautiful vessels with walls so thin
they can even be translucent. It is made from kaolin mixed with china stone,
and the mixture is heated to a very high temperature (1,300C, or 2,372F).
Porcelain was developed in China around c.e. 600 during the T'ang dynasty
and was perfected during the Ming dynasty, famous for its blue and white
porcelain. The porcelain process was introduced to the Arab world in the
ninth century; later Arabs brought porcelain to Spain, from where the process
spread throughout Europe.

Bone china has a composition similar to that of porcelain, but at least 50

percent of the material is finely powdered bone ash. Like porcelain, bone
china is strong and can be formed into dishes with very thin, translucent
walls. Stoneware is a dense, hard, gray or tan ceramic that is less expensive
than bone china and porcelain, but it is not as strong. As a result, stoneware
dishes are usually thicker and heavier than bone china or porcelain dishes.

Manufacture of Advanced Ceramics

The preparation of an advanced ceramic material usually begins with a finely
divided powder that is mixed with an organic binder to help the powder
consolidate, so that it can be molded into the desired shape. Before it is
fired, the ceramic body is called "green." The green body is first heated at a
low temperature in order to decompose or oxidize the binder. It is then
heated to a high temperature until it is "sintered," or hardened, into a dense,
strong ceramic. At this time, individual particles of the original powder fuse
together as chemical bonds form between them. During sintering the
ceramic may shrink by as much as 10 to 40 percent. Because shrinkage is
not uniform, additional machining of the ceramic may be required in order to
obtain a precise shape.
Sol-gel technology allows better mixing of the ceramic components at the
molecular level, and hence yields more homogeneous ceramics, because the
ions are mixed while in solution. In the sol-gel process, a solution of an
organometallic compound is hydrolyzed to produce a "sol," a colloidal
suspension of a solid in a liquid. Typically the solution is a metal alkoxide
such as tetramethoxysilane in an alcohol solvent. The sol forms when the
individual formula units polymerize (link together to form chains and
networks). The sol can then be spread into a thin film, precipitated into tiny
uniform spheres called microspheres, or further processed to form a gel
inside a mold that will yield a final ceramic object in the desired shape. The
many crosslinks between the formula units result in a ceramic that is less
brittle than typical ceramics.
Although the sol-gel process is very expensive, it has many advantages,
including low temperature requirements; the ceramist's ability to control
porosity and to form films, spheres, and other structures that are difficult to
form in molds; and the attainment of specialized ceramic compositions and
high product purity.
Porous ceramics are made by the sol-gel process. These ceramics have
spongelike structures, with many porelike lacunae, or openings, that can
make up from 25 to 70 percent of the volume. The pore size can be large, or
as small as 50 nanometers (2 106 inches) in diameter. Because of the
large number of pores, porous ceramics have enormous surface areas (up to
500 square meters, or 5,382 square feet, per gram of ceramic), and so can
make excellent catalysts. For example, zirconium oxide is a ceramic oxygen
sensor that monitors the air-to-fuel ratio in the exhaust systems of
automobiles.

Aerogels are solid foams prepared by removing the liquid from the gel during
a sol-gel process at high temperatures and low pressures. Because aerogels
are good insulators, have very low densities, and do not melt at high
temperatures, they are attractive for use in spacecraft.

Properties and Uses

For centuries ceramics were used by those who had little knowledge of their
structure. Today, understanding of the structure and properties of ceramics is
making it possible to design and engineer new kinds of ceramics.
Most ceramics are hard, chemically inert, refractory (can withstand very high
heat without deformation), and poor conductors of heat and electricity.
Ceramics also have low densities. These properties make ceramics attractive
for many applications. Ceramics are used as refractories in furnaces and as
durable building materials (in the form of bricks, tiles, cinder blocks, and
other hard, strong solids). They are also used as common electrical and
thermal insulators in the manufacture of spark plugs, telephone poles,
electronic devices, and the nose cones of spacecraft. However, ceramics also
tend to be brittle. A major difficulty with the use of ceramics is their
tendency to acquire tiny cracks that slowly become larger until the material
falls apart. To prevent ceramic materials from cracking, they are often
applied as coatings on inexpensive materials that are resistant to cracks. For
example, engine parts are sometimes coated with ceramics to reduce heat
transfer.
Composite materials that contain ceramic fibers embedded in polymer
matrices possess many of the properties of ceramics; these materials have
low densities and are resistant to corrosion, yet are tough and flexible rather
than brittle. They are used in tennis rackets, bicycles, and automobiles.
Ceramic composites may also be made from two distinct ceramic materials
that exist as two separate ceramic phases in the composite material. Cracks
generated in one phase will not be transferred to the other. As a result, the
resistance of the composite material to cracking is considerable. Composite
ceramics made from diborides and/or carbides of zirconium and hafnium
mixed with silicon carbide are used to create the nose cones of spacecraft.
Break-resistant cookware (with outstanding thermal shock resistance) is also
made from ceramic composites.
Although most ceramics are thermal and electrical insulators, some, such as
cubic boron nitride, are good conductors of heat, and others, such as
rhenium oxide, conduct electricity as well as metals. Indium tin oxide is a
transparent ceramic that conducts electricity and is used to make liquid
crystal calculator displays. Some ceramics are semiconductors, with
conductivities that become enhanced as the temperature increases. For
example, silicon carbide, SiC, is used as a semiconductor material in high
temperature applications.

High temperature superconductors are ceramic materials consisting of

complex ionic oxides that become superconducting when cooled by liquid
nitrogen. That is, they lose all resistance to electrical current. One example is
the material YBa2Cu3O7x , which crystallizes to form "sheets" of copper
and oxygen atoms that can carry electrical current in the planes of the
sheets.
Some ceramics, such as barium ferrite or nickel zinc ferrites, are magnetic
materials that provide stronger magnetic fields, weigh less, and cost less
than metal magnets. They are made by heating powdered ferrite in a
magnetic field under high pressure until it hardens. Ceramic magnets are
brittle, but are often used in computers and microwave devices.
The properties of piezoelectric ceramics are modified when voltage is applied
to them, making them useful as sensors and buzzers. For example, lead
zirconium titanate is a piezoelectric ceramic used to provide "muscle action"
in robot limbs in response to electrical signals.
Some ceramics are transparent to light of specific frequencies. These optical
ceramics are used as windows for infrared and ultraviolet sensors and in
radar installations. However, optical ceramics are not as widely used as glass
materials in applications in which visible light must be transmitted. An
electro-optic ceramic such as lead lanthanum zirconate titanate is a material
whose ability to transmit light is altered by an applied voltage. These electrooptic materials are used in color filters and protective goggles, as well as in
memory-storage devices.
Still other ceramics are important in medicine. For example, they are used to
fabricate artificial bones and to crown damaged teeth. The fact that many
ceramics can be easily sterilized and are chemically inert makes ceramic
microspheres made of these materials useful as biosensors. Drugs and other
chemicals can be carried within microsphere pores to desired sites in the
body.

Ceramics are:

Lighter, stiffer and corrosion resistant. They are brittle because of

strong directional bonds. So they shatter rather than deform.

The electrons in ceramics are tightly held because of covalent bonds.

There are no mobile electrons to conduct current. Therefore ceramics
are good insulators.

Ceramics are prone to cracking because their low thermal conductivity

makes them vulnerable for sudden temperature changes. Some
ceramic alloys like sialon are hard, strong and light - a rare
combination. Such alloys can withstand temperatures up to 1300oC.

Ceramics are of the following types:

a) Silicate - Bricks, tiles, terracotta, dinnerware

b) Non-silicate - oxide and non-oxide ceramics

(i) Oxide ceramics - Al2O3, MgO, Be2O3 (beryllia)
(ii) Non-oxide ceramics - SiC, Si3 N4, BN, B4C.

12.4 Ceramics
Ceramics are inorganic, nonmetallic, solid materials. They can be crystalline
or noncrystalline. Noncrystalline ceramics include glass and a few other
materials with amorphous structures. Ceramics can possess a covalent
network structure, ionic bonding, or some combination of the two. They are
normally hard and brittle and are stable to very high temperatures. Familiar
examples of ceramic materials are pottery, china, cement, roof tiles,
refractory bricks used in furnaces, and the insulators in spark plugs.
Ceramic materials come in a variety of chemical forms,
including silicates (silica, SiO2, with metal oxides), oxides (oxygen and
metals), carbides (carbon and metals), nitrides (nitrogen and metals),
and aluminates (alumina, Al2O3, with metal oxides). Although most ceramic
materials contain metal ions, some do not. Table 12.4 lists a few ceramic
materials and contrasts their properties with those of metals.

Ceramics are highly resistant to heat, corrosion, and wear, do not readily
deform under stress, and are less dense than the metals used for hightemperature applications. Some ceramics used in aircraft, missiles, and
spacecraft weigh only 40 percent as much as the metal components they
replace (Figure 12.24). In spite of these many advantages, the use of
ceramics as engineering materials has been limited because of their
extremely brittle nature. Whereas a metal component might suffer a dent
when struck, a ceramic part typically shatters because the bonding prevents
the atoms from sliding over one another. Ceramic components are also
difficult to manufacture free of defects. Indeed, high fabrication costs and
uncertain component reliability are barriers that must be overcome before
ceramics are more widely used to replace metals and other structural
materials. Attention has therefore focused in recent years on the processing
of ceramic materials, as well as on the formation of composite ceramic
materials and the development of thin ceramic coatings on conventional
materials.
Processing of Ceramics
Ceramic parts often develop random, undetectable microcracks and voids
(hollow spaces) during processing. These defects are more susceptible to
stress than the rest of the ceramic; thus, they are generally the origin of
cracking and fractures. To "toughen" a ceramicto increase its resistance to
fracturescientists frequently produce very pure uniform particles of the
ceramic material that are less than a m (106 m) in diameter. These are
then sintered(heated at high temperature under pressure so that the
individual particles bond together) to form the desired object.
The sol-gel process is an important method of forming extremely fine
particles of uniform size. A typical sol-gel procedure begins with a metal
alkoxide. An alkoxide contains organic groups bonded to a metal atom
through oxygen atoms. Alkoxides are produced when the metal reacts with
an alcohol, which is an organic compound containing an OH group bonded to
carbon. To illustrate this process, we will use titanium as the metal and
ethanol, CH3CH2OH, as the alcohol:

[12.6]
The alkoxide product, Ti(OCH2CH3)4, is dissolved in an appropriate alcohol
solvent. Water is then added, and it reacts with the alkoxide to form Ti OH
groups and to regenerate ethanol:

[12.7]
If you examine Equations 12.6 and 12.7, you might wonder why the reaction
with ethanol is used, since the ethanol is simply regenerated. The reason is
that the direct reaction of Ti(s) with H2O(l) leads to a complex mixture of
titanium oxides and titanium hydroxides. The intermediate formation of

Ti(OC2H5)4(s) ensures that a uniform suspension of Ti(OH)4 will be formed.

The Ti(OH)4 is present at this stage as a sol, a suspension of extremely small
particles. The acidity or basicity of the sol is adjusted to cause water to be
split out from between two of the Ti OH bonds:

[12.8]
This is another example of a condensation reaction, a reaction that involves
the splitting out of a small molecule, such as H2O, from between two
reactants. In the above reaction, condensation also occurs at some of the
other OH groups bonded to the central titanium atom, producing a threedimensional network. The resultant material, called a gel, is a suspension of
extremely small particles with the consistency of gelatin. When this material
is heated carefully at 200C to 500C, all the liquid is removed, and the gel is
converted to a finely divided metal oxide powder with particles in the range
of 0.003 to 0.1 m in diameter. Figure 12.25 shows SiO2 particles, formed
with remarkably uniform, spherical shapes by a precipitation process similar
to the sol-gel process.
To form a ceramic object with a complex three-dimensional shape, the finely
divided ceramic powder, possibly mixed with other powders, is compacted
under pressure and then sintered at high temperature. The temperatures
required are about 1650C for alumina, 1700C for zirconium oxide, and
2050C for silicon carbide. During sintering the ceramic particles coalesce
without actually melting (compare the sintering temperatures with the
melting points listed in Table 12.4).
Ceramic Composites
Ceramic objects are much tougher when they are formed from a complex
mixture of two or more materials. Such a mixture is called a composite. The
most effective composites are formed by addition of ceramic fibers to a
ceramic material. Thus, the composite consists of a ceramic matrix
containing embedded fibers of a ceramic material, which may or may not be
of the same chemical composition as the matrix. Figure 12.26 shows an
electron micrograph of a ceramic composite. Notice how the fibers are
embedded throughout the host ceramic material.
By definition, a fiber has a length at least 100 times its diameter. Fibers
typically have great strength with respect to loads applied along the long
axis. When they are embedded in a matrix, they strengthen it by resisting
deformations that exert a stress on the fiber along its long axis.
The formation of ceramic fibers is illustrated by the case of silicon carbide,
SiC, or carborundum. The first step in the production of SiC fibers is the
synthesis of a polymer, polydimethylsilane:

When this polymer is heated to about 400C, it converts to a material that

has alternating carbon and silicon atoms along the chain:

Fibers formed from this polymer are then heated slowly to about 1200C in a
nitrogen atmosphere to drive off all the hydrogen and all carbon atoms other
than those that directly link the silicon atoms. The final product is a ceramic
material of composition SiC, in the form of fibers ranging in diameter from 10
to 15 m. By similar procedures, beginning with an appropriate organic
polymer, ceramic fibers of other compositions such as boron nitride, BN, can
be fabricated. When the ceramic fibers are added to a ceramic material
processed as described above, the resulting product has a much higher
resistance to catastrophic crack failure.
Applications of Ceramics
Ceramics, particularly new ceramic composites, are widely used in the
cutting-tool industry. For example, alumina reinforced with silicon carbide
whiskers (extremely fine fibers) is used to cut and machine cast iron and
harder nickel-based alloys. Ceramic materials are also used in grinding
wheels and as abrasives because of their exceptional hardness (Table 12.4).
Silicon carbide is the most widely used abrasive.
Ceramic materials play an important role in the electronics industry.
Semiconductor integrated circuits are typically mounted on a ceramic
substrate, usually alumina (Figure 12.27). Some ceramics, notably quartz
(crystalline SiO2), are piezoelectric, which means that they generate an
electrical potential when subjected to mechanical stress. This property
enables us to use piezoelectric materials to control frequencies in electronic
circuits, as in quartz watches and ultrasonic generators.
One of the most highly publicized uses of ceramic materials is in the
manufacture of ceramic tiles for the surfaces of space shuttle vehicles to
protect against overheating on reentry into Earth's atmosphere (Figure
12.28). The tiles are made of short, high-purity silica fibers reinforced with
aluminum borosilicate fibers. The material is formed into blocks, sintered at
over 1300C, and then cut into tiles. The tiles have a density of only 0.2
g/cm3, yet they are able to keep the shuttle's aluminum skin below 180C
while sustaining a surface temperature of up to 1250C.
Superconducting Ceramics
In 1911 the Dutch physicist H. Kamerlingh Onnes discovered that when
mercury is cooled below 4.2 K, it loses all resistance to the flow of an
electrical current. Since that discovery, scientists have found that many
substances exhibit this "frictionless" flow of electrons. This property has
become known assuperconductivity. Substances that exhibit
superconductivity do so only when cooled below a particular temperature,

called the superconducting transition temperature, Tc. The observed

values of Tc are generally very low. In fact, before the 1980s, the highest
value that had been observed for Tcwas about 23 K for a niobium-germanium
compound.
In 1986 J. G. Bednorz and K. A. Mller, working at the IBM research
laboratories in Zrich, Switzerland, discovered superconductivity above 30 K
in a ceramic oxide containing lanthanum, barium, and copper. This material
represents the first superconducting ceramic. That discovery, for which
Bednorz and Mller received the Nobel Prize in 1987, set off a flurry of
research activity all over the world. Before the end of 1986 scientists had
verified the onset of superconductivity at 95 K in yttrium-barium-copper
oxide, YBa2Cu3O7. At the time of this writing, the highest temperature
observed for onset of zero resistance at 1 atm pressure has been 133 K,
which was achieved in another complex copper oxide,
HgBa2Ca2Cu3O8+x, where x represents a slight excess of oxygen.
The discovery of so-called high-temperature (high-Tc) superconductivity is of
great significance. Using materials that carry electrical current with zero
resistance could save great amounts of energy in many applications,
including electrical generators and large electric motors, and could lead to
the production of smaller and faster computer chips. In addition,
superconducting materials exhibit a property, called the Meissner
effect (Figure 12.29), in which they exclude all magnetic fields from their
volume. For this reason, engineers might be able to use these materials to
design magnetically levitated trains. All these applications became feasible
only with the discovery of high-temperature superconductivity, because the
cost of maintaining extremely low temperatures is very high. The only readily
available safe coolant at temperatures below 77 K is liquid helium, which
costs about $2.50 per liter. However, for materials that undergo the
superconducting transition at temperatures well above 77 K, liquid nitrogen,
which costs only about $0.05 per liter, can be used.
One of the most widely studied ceramic superconductors is YBa2Cu3O7,
whose structure is shown in Figure 12.30. The unit cell is defined by the lines;
a few oxygen atoms that lie outside the unit cell are also shown to illustrate
the arrangement of oxygens about each copper atom. Extensive work on
modifying this and related copper oxide superconductors by introducing
other atoms, called dopants, in various atomic positions indicates that the
conductivity and superconductivity take place in the copper oxygen planes.
At temperatures above Tc the electrical conductivity parallel to the copperoxygen planes is 104 times greater than in the perpendicular direction. The
Cu2+ ions have a [Ar]3d9 electron configuration with a single electron in the
3dx2 - y2 orbital. Although the mechanism of conduction and superconduction
is not yet well understood, the fact that the lobes of the 3dx2 - y2 orbital point
toward the neighboring O2 ions is believed to be important.

Figure 12.30 Unit cell of YBa2Cu3O7. A few oxygen atoms that fall outside
the unit cell are also shown to illustrate the arrangement of oxygen atoms
about each copper atom. The unit cell is defined by the lines that describe a
rectangular box.
The new superconducting ceramic materials have immense promise, but a
great deal of research is needed before they can be applied on a practical
basis. At present it is difficult to mold ceramics, which are brittle materials,
into useful shapes like tapes or wires on a large scale. Progress in this area
has been made (Figure 12.31), although the attainable current densities (the
current that can be carried by a wire of a certain cross-sectional area) are
still not high enough for many applications. A related problem is the
tendency of ceramics to interact with their environment, particularly with
water and carbon dioxide. For example, the reaction of YBa2Cu3O7 with
atmospheric water liberates O2 and forms Ba(OH)2, Y2BaCu3O5, and CuO.
Because these materials are so reactive, they must be protected against
long-term exposure to the atmosphere.
The discovery of new high-temperature superconducting materials with
superior properties and the fabrication of useful devices from the known
superconducting materials are subjects of very active research. Even so,
scientists estimate that the new discoveries will not be translated into major
practical applications for several years. In time, however, this new class of
ceramic materials will likely become part of our everyday lives.