Ceramic Materials

6.1 INTRODUCTION

Ceramic materials are defined as those containing phases that are

compounds of metallic and nonmetallic elements.

The science of ceramics, nearly as old as mankind, is the processing of

earthly materials by heat. The crude cooking utensils of early man were
the first application of the materials now used in jet engines and atomic
reactors. All the early ceramic products were made from clay because the
ware could be easily formed. It was then dried and fired to develop the
permanent structure. Because the other ceramic materials lacking
plasticity also have desirable properties, other methods of forming and
processing have been developed. Other forming methods used for
ceramic materials are injection molding, sintering and hot pressing. In
other cases, the formed materials are allowed to harden on the job by the
addition of water, as in case of cements.
6.2. CLASSIFICATION OF CERAMICS

A. Classification of Ceramic Materials:

Ceramic materials are classified as follows:

1. Functional Classification:

(i) Abrasives: Alumina, carborundum

(ii) Pure oxide ceramics:
(iii) Fire-clay products:
(iv) Inorganic glasses:
(v) Cementing materials:
(vi) Rocks:
(vii) Minerals:
(viii) Refractories:
MgO, Al2O3, SiO2
Bricks, tiles, porcelain etc.
Window glass, lead glass etc.
Portland cement, lime etc.
Granites, sandstone etc.
Quartz, calcite, etc.
Silica bricks, magnesite, etc.

2. Structural Classification:

(i) Crystalline ceramics: Single-phase like MgO or multi-phase from the

MgO to Al2O3 binary system.

(ii) Non-crystalline ceramics: Natural and synthetic inorganic glasses.

(iii) "Glass-bonded" ceramics: Fire clay products-crystalline phases are

held in glassy matrix.

(iv) Cements: Crystalline or crystalline and non-crystalline phases.

B. Classification of Ceramic Products:

A general classification of 'ceramic products' is difficult to make because

of the great versatility of these materials, but the following list includes the
major groups:
1. Whitewares. 2. Bricks and tiles. 3. Chemical stoneware.

4. Cements and concretes. 5. Abrasives. 6. Glass.

7. Insulators. 8. Porcelain enamel. 9. Refractories.

10. Electrical porcelain. 11. Mineral ores. 12. Slags and fluxes.

6.3. ADVANTAGES OF CERAMIC MATERIALS

The ceramic materials entail the following advantages:

1. The ceramics are hard, strong and dense.

2. They have high resistance to the action of chemicals and to the

weathering.
3. Possess a high compression strength compared with tension.

4. They have high fusion points.

5. They offer excellent dielectric properties.

6. They are good thermal insulators.

7. They are resistant to high temperature creep.

8. Availability is good.

9. Good sanitation.

10. Better economy.

6.4. APPLICATIONS OF CERAMICS

The applications of ceramics are listed below:

1. The whitewares (older ceramics) are largely used as/in:

●Tiles; ● Sanitary wares; ● Low and high voltage insulators;

• High frequency applications;

• Chemical industry-as crucibles, jars and components of chemical
reactors;
• Heat resistant applications-as pyrometers, burners, burner tips, and
radiant heater supports.

2. Newer ceramics (e.g., borides, carbides, nitrides, single oxides, mixed

oxides, silicates, metalloid and intermetallic compounds) which have the
high hardness values and heat and oxidation values are largely used
as/in:
 • Refractories for industrial furnaces.
• Electrical and electronic industries--as insulators, semiconductors,
dielectrics, ferro-electric crystals, piezo-electric crystals, glass,
porcelain alumina, quartz and mica etc.
• Nuclear applications--as fuel elements, fuel containers, moderators,
control rods and structural parts. Ceramics such as UO2, UC, UC2
are employed for all these purposes.
• Ceramic metal cutting tools--made from glass free Al2O3.
• Optical applications=Ytralox, a comparative newcomer in the
ceramic material field, is useful since it is as transparent as window
glass and can resist very high temperature.

3. Advanced ceramics (e.g., SiC, Si3N4, ZrO2, B4C, SiC, TiB2 etc.)

The advanced ceramics are utilized as/in:

• Internal combustion engines and turbines, as armor plate;

• Electronic packaging;
• Cutting tools;

• Energy conversion, storage and generation.

6.5. PROPERTIES OF CERAMIC MATERIALS

1. Mechanical Properties:

The ceramic materials possess the following mechanical properties:

(i) The compressive strength is several times more than the tensile
strength.

(ii) Non-ductile/brittle. Stress concentration has little or no effect on

compressive strength.

(iii) The ceramic materials possess ionic and covalent bonds which impart
high modulus of elasticity. The modulus decreases with increase in
temperature (due to increase in interatomic distance at elevated
temperature).

(iv) As compared to pure metals, more force is required to cause slip in

diatomic ceramic materials, because diatomic material consists of a
mixture of positively and negatively charged ions which have strong
forces of attraction between them.

(v) Below recrystallisation temperature, non-crystalline ceramics are fully

brittle. The cleavage failure occurs along crystallographic planes and
propagation of the crack takes place at high speed.

(vi) At high temperature rigidity is high.

(vii) In case of alloy consisting of two or metals, each phase may have
appreciable difference of coefficient of thermal expansion which
generate stress. This stress may then cause the metal to fail.

2. Electrical Properties:

The electrical properties of ceramic products vary from the low loss, high
frequency dielectrics to semiconductors. Electrical insulators fall into two
general classifications, the classical electrical porcelain for both high- and
low-tension service and the special bodies such as steatite, rutile,
cordierite and high alumina for high frequency insulation.

[By mass, "pure" steatite is roughly 63.37% silica, 31.88% magnesia, and
4.74% water].

Cordierite is a magnesium iron aluminum cyclosilicate.

Dielectric constant:

• Dielectric constant is the ratio of the capacitance of a dielectric

compared to the capacitance of air under the same conditions.
• A low dielectric constant contributes to low power loss and low loss
factor; a high dielectric constant permits small physical size.
• The dielectric constant for electrical porcelain varies between 4.1 and
11.0. Some special bodies have reported values of several
thousands.
• Porcelain has large positive temperature coefficient.
• Rutile bodies have large negative coefficients.
• By combining capacitor dielectrics having different temperature
coefficients it is possible to reduce effect of the temperature change.

Dielectric strength:

• The dielectric strength of a material is defined as the ability of a

material to withstand electrical breakdown.
• The specific values of dielectric strength vary from 100 V per mil for
low-tension electrical porcelain to 500 V per-mil for some special
bodies.
• Rutile bodies show higher breakdown strength at higher frequencies.
Volume and surface resistivity:

• A volume resistivity of 106 ohms/cm3 is considered the lower limit for an

insulating material. At room temperature practically all ceramic materials
exceed this lower limit. As the temperature of ceramic materials is raised,
the volume resistivity decreases; the volume resistivity of sida-lime
glasses decreases rapidly with temperature, whereas some special
bodies are good insulators (above 106 ohms/cm3) at 700oC. Crystallized
alumina has a volume resistivity of 500 ohms/cm3 at 1600oC.

• Surface resistivity for dry, clean surface is 1012 ohms/cm3. At 98%

humidity, the surface resistivity may be 1011 ohms/cm3 for a glazed piece
or 109 ohms/cm3 for an unglazed piece. The presence of dissolved gases
and other deposits also tends to decrease the surface resistivity of
ceramic materials.

3. Thermal Properties:

Since the ceramic materials contain relatively few electrons, and ceramic
phases are transparent to radiant type energy, their thermal properties
differ amply from that of metals. The following are the most important
thermal properties of ceramic materials (which vary from material to
material and from condition to condition):

(i) Thermal capacity

(ii) Thermal conductivity

(iii) Thermal shock resistance,

(i) Thermal capacity:

• The specific heats of fine clay bricks are 0.25 and 0.297 at 1000oC and
1400oC respectively.
• Carbon bricks possess specific heats of about 0.812 at 200oC and 0.412
at 1000oC.

(ii) Thermal conductivity:

• The ceramic materials possess a very low thermal conductivity since

they do not have enough electrons (for bringing about thermal
conductivity). The conduction of heat takes place by phonon
conductivity and the interaction of lattice vibration, while at elevated
temperatures conduction takes place by the transfer of radiant
energy.
• The impurity content, porosity and temperature decrease the thermal
conductivity.
• In order to have maximum thermal conductivity, it is imperative to
have maximum density which most of the ceramic materials do not
possess.

(iii) Thermal Shock:

Thermal shock resistance is the ability of a material to resist cracking or

disintegration of the material under abrupt or sudden changes in
temperature.

Thermal shock is developed primarily because of thermal expansion or

contraction. which is largely a function of internal structure particularly the
inter-atomic bonding. Loosely packed structures can provide internal
expansion. Thus, the coefficient of expansion is low.

• Lithium compounds are used in many ceramic compounds to reduce

thermal expansion and to provide excellent thermal shock resistance.

• Common ceramic materials graded in order of decreasing thermal shock

resistance are given below:'
(i) Silicon nitride (ii) Fused silica (iii) Cordierite

(iv) Zircon (v) Silicon carbide (vi) Beryllia

(vii) Alumina (viii) Porcelain (ix) Steatite.

4. Chemical, Optical and Nuclear Properties:

Chemical Properties:

• Several ceramic products are highly resistant to all chemicals except

hydrofluoric acid and to some extent, hot caustic solutions. They are not
affected by the organic solvents.

• Oxidic ceramics are completely resistant to oxidation, even at very high

temperatures.

• Zirconia, magnesia, alumina. graphite etc., are resistant to certain molten

metals and are thus employed for making crucibles and furnace linings.

• Where resistance to attack from acids, bases and salt solutions is

required, ceramics like glass are employed.

Optical Properties:

• Several types of glasses have been employed for the production of

windows, subjected to high temperatures and optical lenses.

• Special glasses, in large number, have also been used for selective
transmission or absorption of particular wavelengths such as infrared
and ultraviolet.

Nuclear Properties:

As ceramics are refractory. chemically resistant and because different

compositions offer a wide range of neutron capture and scatter
characteristics. they are finding nuclear applications and are being used
as: Fuel elements, moderators. controls and shielding.

6.6. STRUCTURE OF CRYSTALLINE CERAMICS

Most ceramic phases, like metals, have crystalline structure. Ceramic

crystals are formed by either a pure ionic bond, a pure covalent bond or
by bonds that possess-the ionic as well as covalent characteristics.

• Ionic bonds give ceramic materials of relatively high stability. As a class,

they have a much higher melting point, on the average, than do metals
or organic materials. Generally speaking, they are also harder and more
resistant to chemical reaction.

• Covalent crystals usually also possess high hardness, high melting

point and low electrical conductivity at room temperature.

The ceramics crystals structures are, however, invariably more complex

as compared to those of metals, since atoms of different sizes and
electronic configurations are assembled together.

Common crystal structures found in crystalline ceramics particularly those

of oxide type include the following:

(i) Rock salt structure (cubic) (ii) Cerium chloride structure (Hexagonal)

(iii) Zinc blende structure (fcc) (iv) Wurtzite structure (Hexagonal)

(v) Spinel structure (fcc) (vi) Fluorite structure (cubic)

(vii) Ilmenite structure (Rhombohedral)

6.7. SILICATE STRUCTURES

The silicates are co-ordinate structures based upon large anions arranged
about small cations. The dimensions of the lattice in general are controlled
by the anions rather than cations because of the larger sizes of the former.
Most important are the si+4 and O-2 ions. In all silicates the basic unit is the
SiO4 tetrahedron. This appears to remain essentially unaltered regardless
of the other materials present.

Silicates are important constituents of most of the ceramic materials since

they are plentiful, cheap and have certain distinct properties, necessary
for certain engineering applications.

• Portland cement is the most widely known silicate. It has the very
advantage of forming a hydraulic bond.

• Certain other construction materials made of silicates are brick, tile,

glass, vitreous enamels etc.

• Silicates are also used as reinforcing glass fibers, chemical wares and
electrical insulators.

6.7.1. Types of Silicate Structures

The various silicate structures are:

I. Silicon-oxygen tetrahedron (SiO4)4- structure.

2. Double and poly-tetrahedral structures.

3. Chain structures. 4. Sheet structures.

5. Framework structures. 6. Vitreous structures.

1. Silicon-oxygen tetrahedron (Si04)4- structure:

Refer Fig. 6.1. In this structure (primary structural unit of silicates) one
silicon atoms fits interstitially among four oxygen atoms.

Example: Forsterite (Mg2Si04), a mineral which is a high temperature

refractory.
2. Double and poly-tetrahedral structures:

Refer Fig. 6.2.

• This type of structure results when three or more tetrahedral units link
together (a ring type structure is produced). One of the oxygens is a
member of two units.

• The composition of a three polyhedral unit is Si3O9, which produces

(Si3O9)6- ions.

Fig. 6.1 Fig. 6.2

Example: Polysilicates (double tetrahedral structure).

3. Chain structure:

• A chain structure is formed when two corners of each tetrahedra are

linked.

A single chain structure (Fig. 6.3) can be noticed in pyroxenes.

Fig. 6.3

A double chain structure (Fig. 6.4) results when two parallel identical
chains are polymerized by sharing oxygen to every alternate tetrahedral.
Example: Amphiboles.
 Fig. 6.4

Theoretically, the length of these chain structures can be almost infinite.

4. Sheet structure:

Refer Fig. 6.5.

• When the double chain structure extends infinitely in a two dimensional

plane, a sheet structure results.

• This structural arrangement provides certain important properties, e.g.,

the lubricating characteristics of tale and plasticity of clay, the cleavage of
mica etc.

• The sheet structure is found in ceramic materials which as clays, micas

and tale.

5. Framework structure:

• This type of structure is an extension of silicate tetrahedral unit into three

dimensions.

• A framework structure is generally hard, has low atomic packing factors

and possesses relatively low densities.

Examples: Quartz, feldspar, cristobalite etc.

6. Vitreous structure:

• Fig. 6.6 shows a vitreous form of silica (glass) in two dimensions.

• Glass is a vitreous silicate, having a vitreous structure. Glass has a
three-dimensional frame work structure containing covalent bonds.

6.8. POLYMORPHISM

Depending on the conditions one and the same substance may crystallize
in different forms, this is called polymorphism usually referred to as
allotropy. The two or more types of crystals which have the same
composition are called polymorphs. Polymorphism is found in pure
elements as well as among chemical com ponds both organic and
inorganic. According to the number of distinct polymorphic forms a
substance may be known as di-or trimorphic.

• In nature, the phenomenon of polymorphism is- widespread. Silica is an

important ceramic and it undergoes polymorphic changes. The
tetrahedral units of silica, (SiO4)4-, are arranged in a hexagonal pattern
and this is stable at room temperature. At higher temperatures different
transformations takes place and the bonds which excited earlier are
broken to form new ones. Three modifications of silica generally
observed are: (i) Quartz, (ii) Tridymite, (iii) Cristobalite.
• In aluminosilicates (Al2SiO5) three different crystalline forms viz.,
sillimanite, andalusite, and kyanite are formed from the compound
mullite (3Al2O32SiO2) which is stable at the liquidus.

• Similarly, alpha and gamma forms of alumina are obtained from fused
alumina.

• Among metals, the most important example of polymorphism is iron.

• Among non-metallic elements, polymorphism is found in phosphorus

and carbon.

Polymorphic transformations are usually brought about by temperature

changes, but several have been induced by high pressure or drastic cold
work treatment also.

6.9. GLASS

6.9.1. Introduction

• Glass is any substance or mixture of substances that has solidified from

the liquid state without crystallization. Elements, compounds and
mixture of wide varying composition can exist in the glass state, but the
term "glass" as ordinarily used refers to material which is made by the
fusion of mixture of silica, basic oxides and a few other compounds that
react either with silica or with the basic oxides. No definite chemical
compounds can be identified in glass. Many of its properties correspond
to those of a supercooled liquid whose ingredients cannot be identified
because they have not separated from the solution in crystalline form.

• Glass may also be defined as a hard, brittle, transparent or translucent

material chiefly compound of silica, combined with varying proportions
of oxides of sodium, potassium, calcium, magnesia, iron and other
minerals.
• Glass is an amorphous substance having a homogeneous texture.

Structure of glass:

The glass is a random arrangement of molecules, the great majority of

which are oxygen ions bounded together with the network forming ions of
silicon, boron or phosphorus. A glass made of silica alone has many
desirable characteristics but unfortunately the high temperatures involved
make it expensive, and difficult to prepare. In order to reduce the
temperature, required network-modifying ions are added. Sodium.
potassium. and calcium are the most common. The network-modifying
ions increase the competition for the oxygen ions, thus loosening the Si-
O bonds. Certain other ions may substitute for either the network-forming
ions or network-modifying ions; aluminum. zinc. beryllium. lead and ion
are a few of these intermediate ions.

6.9.2. Constituents of Glass and their Functions

The various constituents of glass and their functions are described below:

1. Silica:

• It is the principal constituent of glass.

• If silica alone is used in the manufacture of glass, it could be fused only

at a very high temperature, but it would give a good glass on cooling.
However, it is imperative to add some alkaline materials (sodium or
potassium carbonate) and lime in suitable proportions to make the
molten silica glass sufficiently viscous to make it amply workable and
resistant against weathering agencies.

2. Sodium or potassium carbonate:

• It is an alkaline material-and forms an essential component of glass.

• It is added in suitable proportion to reduce the melting point of silica and
to impart viscosity to the molten glass.

3. Lime:

• It is added in the form of chalk.

• It imparts durability to the glass.

In place of lime, sometimes, lead oxide is also added; it makes the glass
bright and shining.

4. Manganese dioxide:

• It is added in suitable proportion to correct the color of glass due to the

presence of iron in raw materials of glass.

• It is also called 'Glass maker' soap.

5. Cullet

• It is the old broken glass of the same type as that which is intended to
be prepared.

• It is added in small quantity to provide body to the glass.

6. Coloring substance:

While manufacturing a colored glass, a' suitable coloring substance is

added at fusion stage to provide the desired color to the glass.

The various coloring substances for manufacturing glass of different

colors are given below:

Color Coloring substance Color Coloring substance

1. Black Cobalt, nickel and manganese 4. Violet Manganese dioxide
oxide
2. Green Chromic oxide 5. White Cryolite, tin oxide
3. Red Cuprous oxide, selenium 6. Yellow Cadmium sulphate
6.9.3. Properties of Glass

Following are the properties of glass:

1. No definite crystalline structure.

2. No sharp melting point.

3. Absorbs, refracts or transmits light.

4. Affected by alkalis.

5. An excellent electrical insulator at elevated temperatures.

6. Extremely brittle.

7. Available in beautiful colors.

8. Not affected by air or water.

9. Not easily attacked by ordinary chemical reagents.

10. Capable of being worked in several ways.

11. Can take up a high polish (and may be used as substitute for very
costly gems).

12. Possible to weld pieces of glass by fusion.

13. As a result of advancement made in the science of glass production,

it is possible to make glass lighter than cork or softer than cotton or
stronger than steel.

14. Glass can be cleaned easily by any of the following methods:

(i) Applying methylated spirit.

(ii) Rubbing finely powdered chalk.

(iii) Rubbing damp salt for cleaning paint spots.

 (iv) Painting the glass panes with lime-wash and leaving it to
dry and then washing with clean water.

Commercial glass must meet the following requirements:

1. The material must melt at commercially obtainable temperature. Fused

silica cools to a glass that is superior to ordinary glass, but the
temperature required to melt it is so high that its production is
expensive, and its use restricted.
2. The molten mixture must remain in the amorphous. or non-crystalline
condition after cooling.

3. The fluidity of molten glass must persist to a sufficient extent to permit

the formation of desired shapes while the glass is cooling.

4. The glass must be reasonably permanent in the use for which it is

intended. Glass with a high proportion to sodium oxide is more readily
attacked by water and acids than glass that contains less sodium oxide
and more lime and magnesia. Glasses low in basic oxides are less
readily attacked.

Mechanical Properties:

Strength: Glass is weak in tension and it always falls in tension no matter

how stress is applied. Nevertheless, glass is four to six times as strong in
compression as it is in tension and it should, therefore, be used under
compressive loads. Strength depends upon the factors such as surface
conditions, cross-section and amount of addition etc.

Hardness and brittleness: The hardness of glass cannot be measured

by the Brinell or Rockwell machines because the test specimen fails when
the surface is ruptured. Yet some glasses will scratch steel. The relative
value of hardness can be evaluated by scratch or abrasion test. For
ordinary purpose the hardness of glass is a function of its tensile strength.

The concept of brittleness has not been clearly defined. When glass is
fixed it bends only a little, then shatters. There is no plastic deformation,
and the curve of the stress-strain diagram is straight until the test
specimen breaks.

Thermal endurance: The lower the coefficient of expansion and the

thinner the piece the less likely it is to break under thermal shock. Glass
does not break from thermal causes but from the tensile stresses set up
by the temperature gradient.

Electrical Properties:

Conductivity: Conductivity depends on composition, temperature and

surface conditions. Sodium and potassium ions are largely responsible for
imparting electrical conduction, but the function of the calcium ions or the
mechanism of conduction in an alkali-free glass is not known. Na2O and
K2O increase the conductivity. Al2O3 increases the conductivity slightly;
ZnO, PbO, MgO, Fe2O, BaO, B2O2 and CaO decrease the conductivity.

The presence of a-film on the surface glass affects the surface resistivity
to a marked degree. In high alkali glasses, the surface conductivity may
exceed the volume conductivity. The presence of CO2, SO2, H2S solids
and mineral soils also affects the surface conductivity.

In making conductivity tests on glass a precise value is seldom obtained

because of the influence of the surrounding medium. ·Even oil immersion
will not give the true value because it has been shown that such a test is
a measure of the oil, which fails first, bringing about the failure of the glass.
Care in eliminating the edge effects and other conditions show that glass
has puncture values several times higher than that obtained in service.
The practical limit must take the operating conditions into account.

In the usual method of testing glass for its electrical conductivity the glass
specimen is placed between electrodes. Such a system consists of a
capacitor with glass as the dielectric medium. Upon charging such a
capacitor, the initial charging current is high and then drops off. The
charging current rapidly diminishes and straightens out, approaching a
low but finite value. The discharge current behaves in like manner. If the
charged capacitor is short circuited, the initial discharge current is high
and drops off rapidly, approaching a low but finite value. The residual
charge may be removed by short-circuiting the capacitor. It may be
necessary to repeat this process several times. Because of this behaviour,
the measurement of electrical resistance may be in error, and the time
interval should be stated.

Dielectric constant, power factor, dielectric loss: The dielectric

constant K of glass varies from 3.7 to 16.5 and remains relatively constant
over a wide frequency, the square of the voltage gradient, and to the
product of dielectric constant and the power factor. For conditions of high
frequency or high voltage or both, the value of K should be kept as low as
possible. Both the dielectric constant and $e power factor can be varied
by changes in the glass composition by a ratio of more than 200 to 1. Two
general glasses are available: those with high dielectric constant and low
power factor, and those with low dielectric constant and low power factor.

Dielectric strength: Electrical breakdown is int1uenced by the

characteristics of the dielectric, the thickness, the duration of the stress,
temperature and edge effects, the surrounding medium and
characteristics of the voltage, whether direct or alternating; thermal failure
of dielectric is a result of internal heating, which causes it to become a
conductor. Alternating currents causes failure at a lower voltage than
direct currents do.

6.9.4. Glass Furnaces

For the manufacture of glass two types of finances are used:

1. Pot furnaces. 2. Tank furnaces.

1. Pot Furnaces:

This type of furnace is used to make small amounts of glass such as

optical glass that require careful control of ingredients and of melting and
fining operations. The pots are fire clay crucibles ranging up to 0.9 metres
in height and up to 1.5 metres in diameter. They are arranged on edges
in a circular or oblong furnace where they are exposed to a steadily
increasing temperature.

2. Tank Furnaces:

In a continuous tank a constant level of molten glass is maintained by the

addition of raw material or "batch" at the proper rates. The furnace is
divided into two compartments: the large melting compartment and the
smaller working compartment from which the molten glass is withdrawn.
Molten glass flows from the melting to the working compartment through
a small opening at the bottom of the dividing wall. The "day tank" is a
smaller tank, designed to complete melting of a small charge in one day.
It is a particularly useful type of tank in cases where frequent changes in
glass composition are required.

Melting:

When the well-mixed raw materials are heated in the glass furnace, those
substances with the lower melting points liquify and act as solvents for
other substances, at the same time reacting with them and enabling them
to react with each other. The system is very complicated one and the exact
sequence of events cannot be determined. The temperature during
melting is kept as high as practicable (1400 to 1500°C) in order to reduce
the viscosity. Bubbles of gas (carbon dioxide, steam etc.) that are formed
during the healing must escape, and their escape will be slower from a
more viscous liquid. In order to remove the gases entirely, the glass must
be held sometime at the highest possible temperature. This is called
plaining or fining. Additions are often made to the batch to lower its
viscosity and to generate gas in large volumes at later stages in the
melting process, thus sweeping out the small bubbles along with large
ones. Salt cake is often used for this purpose. The under composed
portion forms a liquid layer on the surface of be glass and reacts with the
scum of siliceous material that tends to collect there. The working
temperature, i.e., the temperature at which the glass has the proper
viscosity for the shaping operations, is much lower than the highest
temperature during melting, the actual working temperature being
dependent on the kind of glass and the type of machine used. The range
is roughly from 1000 to 1300°C or higher.

5.9.5. Fabrication of Glass

The various processes involved in the fabrication of glass are enumerated

and described below:

1. Blowing 2. Flat drawing 3. Rolling

4. Pressing into moulds 5. Casting 6. Spinning.

1. Blowing

In this process, a blow-pipe, 1.5 m to 2 m long and 12 mm diameter is

used. One end of the blow-pipe is dipped in a molten mass of glass and a
lump (of about 50 N weight) is taken out. The operator then blows
vigorously from other end of the blow pipe (it can also be done with the
help of a compressor); this blowing causes the molten mass of assume a
cylindrical shape. It is then heated for ten seconds and is blown again.
The blowing and heating are continued till the cylinder of required size is
formed. It is then kept on an iron plate disconnected from the blow pipe
and a cut is made on its top surface longitudinally by a diamond glass
cutter so that by gravity the two ends of the cut cylinder will fallout, forming
a rectangular thin sheet of glass.

2. Flat drawing:

In this process, the molten glass in viscous form is drawn in the form of a
plate by moving an iron bar side way through it. The plate is then passed
over a large rotating roller which helps it in spreading out in a thin sheet.

3. RoIling:

Rolling is a carried out in two ways:

(i) In one method the molten glass is poured on a flat iron casting table
and it is then turned flat with the aid of a heavy iron roller.

(ii) In another method, the molten mass of glass is passed between

heavy iron rollers and flat glass plate of uniform thickness is obtained.

4. Pressing into molds:

In this process, the molten glass is pressed into molds by machines. Such
a glass is stronger and more durable than un-pressed glass. This process
is used for hollow glass articles, ornamental articles etc.

5. Casting: In this process, molten glass is poured in molds and then

allowed to cool down slowly. This method is used to prepare large pieces
of glass of simple design, mirrors, lenses etc.
6. Spinning: In this process, the molten glass is drawn into threads or is
spun on a high-speed wheel operated by power, to produce even finer
than cotton threads.

The spun glass has tensile strength equal to that of mild steel. It is very
soft and flexible and does not fade. decay or shrink. It is not attacked by
acids, fire and vermin.

It is used for producing insulation against heat. sound and electricity.

6.9.6. Classification of Glass

As per composition and properties glass may be classified as:

I. Soda-lime or crown glass

2. Flint glass

3. Pyrex or heat-resistant glass.

1. Soda-lime or crown glass:

• It is the cheapest quality of glass.

• Its composition, like that of most glass, is not rigidly fixed, but can be
varied both as to the amount of ingredients and chemical compounds
used.

Composition by weight: Sand 75 parts; lime 12.5 parts; soda 12.5 parts;
alumina 1 part and waste glass 50 to 100 parts.

• It is easily fusible at comparatively low temperatures.

• It is available in clean and clear state.

• It is possible to blow or to melt articles made from this glass with the help
of simple sources of heat.
Uses: Its principal uses are for window glass, plate glass and container
glass (bottles, glass etc.)

2. Flint glass:

• It contains varying proportion of lead oxide to make it suitable for various

purposes. Lead provides brilliance and high polish which makes the glass
available for special purposes.

Composition by weight: Sand 100 parts; red lead 70 parts; potash 32

parts; waste glass 10 parts.

• It liquifies at lower temperature than soda-lime glass and has better

luster.

• Owing to the ease with which lead compounds are reduced, the glass
must be melted in an oxidizing atmosphere.

Uses: This is potash-lead glass used for better quality of table-wares and
for optical glass. It is also used for electric lamps, thermometers, electron
tubes, laboratory apparatuses, containers for foods etc.

3. Pyrex or heat resistant glass:

Both soda-lime and flint glasses are unable to withstand sudden

temperature changes because of their large coefficients of thermal
expansion. The basic oxides that they contain make them susceptible to
chemical attack by water and acids. Elimination of the basic oxides and
inclusion of boron oxide produce a glass that is very resistant to thermal
shock and to attack by water and acids. The temperature required to melt
and fine such a glass is so high that it has to be heated in the electric arc.
The familiar Pyrex glasses, which are used extensively for cooking
utensils and laboratory wares, are borosilicate glasses.
Composition by weight: Silica 80 parts; boron oxide 14 parts; sodium
oxide 4 parts; alumina 2 parts,

with traces of a potassium oxide, calcium oxide and magnesium oxide.

Special Types of Glasses

1. Annealing glass:

To prevent glass articles becoming too brittle and falling into pieces at the
slightest shock, they are kept while still hot in an annealing furnace to cool
very slowly. The longer the annealing period, the better, the quality of the
glass.

2. Sheet Glass:

• It is roughly composed of 100 parts sand, 35 parts limestones or chalk,

40 parts soda and 50 parts waste glass.

• It is made by blowing glass into hollow cylinder, splitting the cylinder and
finally flattening it over a plane surface. It is manufactured in thickness
varying from 1.5 to 5 mm and sizes upto 1.5 x 1 meter.

Uses: It is generally used for doors and windows.

3. Plate glass:

• Its composition is: White sand 100 parts; soda carbonate 33 parts;
slaked lime 14 parts; manganese peroxide 0.15 part and waste glass 100
parts.

• It is made by pouring white hot glass over an iron table and rolling it to a
uniform thickness under heavy roller.

• It is thicker than sheet glass, and its thickness varies from 5 to 25 mm

and sizes upto 275 cm x 90 cm.
• It is stronger and more transparent to sheet glass.

In modern glass-fabrication, rolled plate glass is annealed because glass

cooled normally is brittle.

• Plate glass includes transparent, translucent, opaque and structural

glasses.

Uses: (i) It is used for making looking-glass, wind screens of motors, car
skylights and glass houses.

(ii) It is also used for sales counter and table tops after being laminated
with plywood or metal sheet.

4. Fluted glass:

When there are corrugations on one side of the plate glass then it is known
as fluted glass. The other side is wavy but smooth. The light is admitted
without glare of the sun.

Uses: It is used in situations where it is desirable to secure privacy without

obstruction of light. Horizontal ribs give more light in the middle and less
at the sides, while upright ribs give more light at the sides and less in the
middle. It is thus more used for skylight roofs and for windows of railway
stations and factories.

5. Ground glass:

• It is made either by grinding (usually by sand blasting) one side, or by

melting powdered glass upon it.

• This glass is mostly translucent.

• This type of glass is also known as frosted glass or obscured glass.

Uses: This glass is used in situations where light is required without
transparency. It is normally used for window panes and bath room
ventilators etc.

6. Wired glass:

• It is glass with wire netting or similar strengthening material embedded

in it during manufacture.

This is why this glass is known as reinforced glass.

• It resists fire better than ordinary plate glass.

• In case the glass is fractured it does not fall into pieces.

Uses: It is used for skylight and roofs, also for fire- resisting doors and
windows.

7. Safety glass:

• This type of glass is produced by sandwiching sheets of celluloid or other

transparent plastic between two sheets of glass and sticking the whole
combination together by means of colorless and heat resisting glue.

• Wired glass falls into the category of safety glass.

8. Bullet-proof glass:

• This glass is made of several layers of plate glass and alternate layers
consist of vinyl-resin plastic. The outer layers of plate glass are made
thinner than the inner layers. The special care is to be taken for heating
and cooling of layers during manufacture.

• The thickness of this type of glass may vary from 15 mm to 75 mm or

more.

• This glass will not allow bullet to fierce through it.

Uses: It is extensively used for glazing bank teller, cages, cashier booths,
jewelry stores, display cases etc.

9. Insulating glass:

It is transparent glass unit composed of two or more plates of glass

separated by 6 to 13 mm of dehydrated captive air, hermetically sealed
inside, is scientifically cleaned and dried.

Insulating glass provides a high resistance to heat-flow. The sealed air

makes the coefficients of heat transmission of the glass low and hence
keeps the apartment cool in summer and warm in winter.

10.Foam glass:

• It is prepared from powdered glass to which is added the desired quantity

of carbon or any gas which makes the mass porous and light in weight.

• This glass is water-proof also.

• It can be easily cut and worked with common masonry tools.

Uses: It is used for sound and heat insulation purposes. It is specially

recommended for use in air-conditioning of buildings.

11.Glass blocks:

• These consist of two halves so fused together as to form a hollow inside.

• They provide insulation against heat, cold and noise and are easy to
clean.

Uses: They are widely, used for constructing wall partitions.

12.Soluble glass:

• It is prepared by melting quartz sand, grinding and thoroughly mixing it

with soda ash, sodium sui phase or potassium carbonate. The melting is
carried out in glass tank at a temperature between 1300oC to 1400oC and
it takes about 7 to 10 hours. The resultant glass mass flows out from the
furnace and it cools rapidly and breaks up into pieces, known as silica
lumps.

• It is soluble in water, under normal conditions.

• The soluble glass in the form of silicate lumps is transported in containers

and in the form of liquid, it is transported in barrels or glass bottles.

Uses: It is used for preparing acid-resistant cement.

13.Ultra-voilet glass:

• It transmits ultra-violet rays effectively even though it is not in the

direction of the rays of sun.

• It is made from the raw mixture with minimum admixtures of iron, titanium
and chrome.

Uses: It is used in the windows of schools, hospitals etc.

14. Structural glass:

• This type of glass is available in the form of glass-Crete square blocks,

tiles or lenses in thicknesses varying from 5 mm to 30 mm.

• These glass products are hollow, light and transparent.

• This type of glass can be sawn. placed and drilled like wood work. in
spite of having general properties of glass.

Uses: Widely used for pavement lights, partitions. lantern lights; also used
for roof covering material in industrial buildings. factories etc.
Glass-Fiber or Glass-Wool

• The usual composition of glass-fibers is that of a soda-lime glass, but it

may be varied for different purposes.

• The glass-fibers are made by letting the molten glass drop through tiny
orifices and blowing with air or steam to attenuate the fibers.

• They have very high tensile strengths. upto about 2750 N/mm2•

• Glass-fiber or glass-wool differs from mineral wool in that it is a glass

made to a definite formulation with a uniformity not found in mineral wool.

6.9.7. Uses of Glass

Besides other uses. some of the important uses of glass, based on the
recent development in the glass industry, are as follows:

1. The fiber glass reinforced with plastics can be used in the construction
of furniture, cars, trucks, lampshades, bath room fittings etc.

2. Glass is used to form a rifle barrel which is lighter and stronger than
conventional type.

3. Thousands of items in the body of a guided missile are made of glass.

4. Glass is used in the construction of noses of deep-diving vehicles.

5. Optical glass is finding wide application for the development and

advancement of sciences of astronomy and bacteriology.

6. The glass linings are applied on equipment likely to be affected-by the

chemical corrosion such as valves, pipes, pumps etc.

7. Hollow glass blocks can be used for the construction of the walls and
ceilings of the modem homes.
8. These days, it is possible to prepare the color-changing glass; a window
with such a glass will be transparent during the day and it will be a source
of light at night.

6.9.8. The Glass Industry in India

Names/addresses of some important glass manufacturing concerns in

India are given below:

6.10. ADVANCED CERAMICS

1. Glass Ceramics:

• These are special glass compositions that are thermally treated prior to
forming operations to de vitrify or precipitate a crystalline phase from the
material; this phase gives that material special properties such as zero
thermal expansion for applications involving high thermal-shock
application.

• The compositions (typical of glasses) in which nucleation and

crystallization have been commercially produced are: MgO-Al2O3- SiO2;
LiO2-Al2O3-SiO2; LiO-MgO-Si02.

Characteristics:

(i) Very low coefficient of thermal expansion.

(ii) Relatively high mechanical strengths.

(iii) High thermal conductivities.

(iv) Can be easily fabricated (conventional glass-forming techniques

may be employed conveniently in the mass production of nearly
pore-free ware).
Uses:

(i) Owing to their excellent resistance to thermal shock and their high
conductivity, glass ceramics are used as ovenware and tableware.

(ii) As insulators.

(iii) As substrates for printed circuit boards.

2. Dielectric Ceramics:

• The use of ceramic materials is made both as electrical insulators and

as functional parts of an electrical circuit. Since the electrical insulators
can breakdown under high electrical voltages, the insulators are designed
with lengthened surface paths to decrease the possibility of surface
shorting. Since internal pores and cracks provide opportunity for additional
surface failure, the insulators are glazed to make them non-absorbent.

• Non-linear dielectric ceramics are suitable in the miniaturization of

electronic parts which have led to the development of increasingly
sophisticated electrical circuitry.

• These "Ceramics are also used in capacitors.

• Some typical non-linear dielectric ceramics are: Lead zirconate-titanate,

lead niobates, barium titanate, etc.

3. Electronic Ceramics:

Ferrites ferro-electric ceramics etc. are the ceramic materials with unusual
properties that are of specific use in electronic circuits.

• Ferrites are mixed-metal-oxide ceramics (almost completely crystalline).

They assimilate high electric resistivity and strong magnetic properties.
Soft ferrites can be used for specific uses such as memory cores for
computers and cores for radio and television loop antennas. Barium and
lead ferrites are widely used in permanent-magnet motors in automobiles,
portable electrical tools and small appliances.

• Ferro-electric ceramics can convert electrical signal into mechanical

energy (such as sound); and can also change sound, pressure or motion
into electrical signals. Thus, they function as transducers.

Examples: Barium titanate (most common), tantalates, zirconates,

niobates, etc.

4. Cermets:

• Cermets are ceramic-metal composites.

• Cermets contain alumina (Al2O3) and chromium in varying proportions.

• These are used in brake shoe linings. oxidation-resistant parts and inject
engines.

• The most common cermet is cemented carbide and such like composites
are extensively used as cutting tools for hardened steels.

6.11. ROCKS AND BUILDING STONES

6.11.1. Sources of Stones

The stones are derived from rocks which form the earth's crust and have
no definite shape or chemical composition but are mixtures of two or more
minerals. The mineral is substance which is formed by the natural
inorganic process and possesses a definite chemical composition and
molecular structure.

The rocks from which stones are obtained are classified in the following
four ways:
1. Geological

2. Physical

3. Chemical

4. Practical.

1. Geological Classification: Geologically the rocks are classified into

three different types:

(i) Igneous rocks

(ii) Sedimentary rocks

(iii) Metamorphic rocks.

The igneous rocks are formed by cooling of the molten lava on or inside
the earth' s surface during the volcanic eruption. The portion of lava, which
comes outside the surface, cools quickly and forms the rock of non-
crystalline nature called as Trap or Basalt. The rest of the portion which
remains inside the earth undergoes cooling at a slow rate and results in
formation of a rock of crystalline variety known as Granite.

Sedimentary rocks are formed by gradual deposition of disintegrated

rocks (due to the atmospheric action such as rain, wind and temperature),
vegetable matter and clay at the bottom of rivers, lakes or sea. These are
also called stratified because these rocks are formed in layers. Limestone
and sandstone belong to this category of rocks.

When sedimentary or even igneous rocks are subjected to great heat and
pressure inside the earth. A new variety of rock is formed which is known
as metamorphic rock. This change of structure is called metamorphism.
For example, limestone changes to marble. slate changes to Gneiss etc.
2. Physical Classification: The basis of the classification are physical
properties of rocks. the manner and arrangement of different particles and
mass forming a stone. Physically the rocks are classified as:

(i) Stratified rocks

(ii) Unstratified rocks.

Stratified rocks are those which exhibit distinct layers which can be
separated. The plane along which the separation of the layers can be
carried out is called 'cleavage plane'. Lime stone. slate and sand stone
are the examples.

Unstratified rocks do not show any sign of strata and cannot be easily
split into slabs. Examples are granite. trap. marble etc.

3. Chemical Classification: The chemical constituents (in the rocks) are

the basis of this classification. Chemically the rocks are classified as:

(i) Silicious

(ij) Agrillaceous

(iii) Calcarious.

In case of Silicious rocks silica is the main constituent. The silica in free
state is called 'sand' and in combined state ‘silicate’. The rocks containing
silica in free form are harder. While those having silica in combined from
are likely to be disintegrated. Examples are sandstone, quartzite etc.

In argillaceous rocks clay or alumina is the main constituent. Slate,

laterite, kaolin etc. belong to this category.

Calcarious rocks have calcium carbonate or lime as their leading

constituent. These rocks are readily acted upon by even dilute
hydrochloric acid. Limestone and the marble are the important examples.
4. Practical Classification: Practical classification is based on the usage.
Practically stones have been classed as : Granites, basalts, laterites,
marbles, limestones, sandstones, slates.

6.11.2. Common Rock Forming Minerals

The common rock forming minerals are discussed below:

Silica: Quartz is pure or nearly pure silica and is a hard and glassy
mineral. It occurs in granite in grey, white or colorless lumps which are
sometimes crystalline. It is unaffected by weather. Quartz has a hardness
of 7 and specific gravity of 2.66. Due to the presence of small quantities
of metallic oxides it has varying transparency and colors.

Felspar: Felspar are the silicates of alumina, with alkaline substances like
potassium, sodium and calcium. In a sound granite, it occurs in the form
of grey or reddish-brown bright crystals, in a bad sample of granite the
felspar is earthly in appearance. The hardness of felspars is 6 and specific
gravity varies from 2.5 to 2.7. A stone readily meets the decay if it contains
large proportions of felspars mixed with other softer minerals.

Mica: It contains silicate of aluminum with potassium. It is of dark grey,

black or brown color. It is very soft and readily affected by atmosphere
and chemicals. It has a perfect cleavage and could be split into very thin
laminate or flakes. It has a hardness of 2.5 and specific gravity of about
3. The mica occurs in granite as semitransparent, glistening scales, which
are sometimes dark grey, brown or black.

Hornblende: It is a very complex silica and its color varies from dark
green to black. It has hardness of 5.5 and specific gravity of 3.2.
Calcite: It is the leading constituent of the limestones and marbles. It"
color varies from white to grey and luster varies from vitreous dull to
earthy. Hardness = 3 and specific gravity = 2.7.

Dolomite: It is CaMg(CO3)2 or magnesian carbonate. It is commonly

found in dolomitic limestone and dolomitic marbles. Its stability and
weather resisting property is better than pure calcium carbonate.

6.11.3. Characteristics of Good Building Stones

Stones find their applications in the construction of heavy structures such

as dams, docks and harbors, weirs, bridge piers, building etc. To find the
suitability of stones under different conditions, the following characteristics
should be considered:

1. Appearance and color: The stones which are to be employed for

decoration work should have uniform and appealing color and should be
free from flaws and clay holes. The use of stones which contain much iron
should be discouraged as the foundation of iron oxide disfigures it and
brings about disintegration. The stones should also have the ability to
receive good polish.

2. Weight: The specific gravity hence the weight of the good building
stone should be high as heavier stones can resist the force of bigger
magnitude. A heavy stone possesses more compactness and less
porosity.

3. Porosity and absorption: Porosity (which is decided by the number of

pores) exists in all the stones but if it is present in greater extent it makes
the stone unsuitable for building construction because during rain, water
seeping into pores contains acids and fumes (absorbed from atmosphere)
which destroy the stone. When the climate is cold, water entering the
pores may even freeze and split the stone.

4. Fineness of grain: The stones which are tine grained are suitable for
molding works. If the stones are non-crystalline, they are likely to
disintegrate under the action of natural agencies.

5. Compactness: Stone' s durability is decided by their compactness or

density of composition. A compact stone can withstand the effects of
external agencies effectively.

6. Resistance to fire: For resistance against tire, the stone (i) should
have homogeneous composition and (ii) should be free from calcium
carbonate or oxide of iron.

7. Electrical resistance: The electrical resistance of a stone decreases

when it gets wet. Thus to have steady and high electrical resistance, the
stone must be non-absorbent like slate.

8. Hardness and toughness: The stone must be adequately hard and

tough so that they may resist wear and tear (as in the .case of railway
ballast, road metal etc.). Hardness may be tested by scratching with a pen
knife which should not be able to produce an impression on hard stone
like granite. Toughness of the stone can be tested by subjecting it to a
hammer action.

9. Strength: Stones used in the structures are usually subjected to

compression; so they should have sufficient strength to cope with the
requirements. Generally, all the stones possess a reasonable degree of
strength as far as their use in building work is concerned but for heavy
structures only those stones are suitable which have high strength
comparatively.
10. Durability: A stone is more durable in case it is (i) compact, (U)
homogeneous and (iii) free from any material affected by dilute
hydrochloric and sulphuric acids. It should also have negligible water
absorption.

11. Dressing: The art of shaping a stone is known as dressing. Stones

should possess uniform texture and softness so that they may be easily
dressed, if it is too hard, finish will be poor and dressing uneconomical.

6.11.4. Uses of Stones and Their Selection

In the table below are given the important uses and the selection of stones
for variety of works.

No. Use Name of stone Reason for selection

1 Construction of building Granite and sand- Hardness due to presence
exposed to high wind stone. of silica
blowing particles.
2 For general building work, Sandstone Hard and durable.
i.e., walls, foundations and
super-structure
3 For heavy engineering work Granite and Gneiss Strong, durable, capable of
such as docks, bridges and resisting thrust.
light houses.
4 Building exposed to tire Compact sandstone Fire resisting property.
5 For buildings in industrial Granite and compact Acids and smoke proof.
town sandstone
6 For road metal and railway Granite and basalt Hard, tough and possesses
ballast abrasion resistance.
7 Electrical switch boards Slabs of marble and Possesses electric
slate resistance, non-absorbent
of water and easily cut into
pieces.
8 Manufacture of lime Limestone Decomposed into quick lime
on heating
9 As flux in the manufacture of Limestone Special characteristics.
Iron

6.11.5. Deterioration of Stones

The various agencies which bring about the deterioration of stones are as
follows:

1. Rain: A stone gets wet due to rain and becomes dry due to sun; this
alternate wetting and drying go a long way in deteriorating the stone. The
harmful gases and acids contained in rain water also exercise a damaging
effect on the stone.

2. Temperature: The stone also gets deteriorated due to frequent

changes in temperature of atmosphere (due to these changes expansion
and contraction take place frequently, which results in the production of
cracks).

3. Wind: A strong wind carrying with it grits and dust strikes the stones
and brings about the wear of the stones. Also, the water particles in the
wind penetrate into the pores of the stones and cause dampness which
results in deterioration.

4. Frost: When the stone is used in the cold climatic conditions, the water
in the pores freezes; consequently, it expands and thereby splits the
stone. Therefore, porous stones should not be used in very cold places.

5. Atmospheric impurities: In an Industrial town the presence of acids

and fumes adversely affect the stones containing carbonate of lime.

6. Vegetable growth: Certain acids secreted by the roots of certain plants

and trees in the joints of the stone, attack it. The vegetable growth also
keeps the stone in wet condition; this constant dampness decays the
stone.

7. Living organism: In the stones, sometimes holes are bored by certain

insects due to which they become weak. These insects are found in sea
and thus stones near shores are affected by them.

6.11.6. Preservation of Stones

The durability of stone increases to a considerable extent if it is properly

preserved. Preservation means making the stone strong enough to face
the atmospheric agencies which are the root cause of its deterioration and
can be affected in the following ways:

1. Filling up the stone pores.

2. Providing the stone with a coat of preservative to prevent the ingress of

moisture into the pores.

3. The use of stones containing carbonate of lime in industrial town should

be discouraged.

4. In a structure, as far as possible limestone and sandstones, magnesium

limestone and granular limestone should not be laid close to each other.

5. Only that binding material, which does not have any adverse effect on
a particular stone, should be employed.

6. Growth of plants and trees on the stone should be checked.

Some of the preservatives are: (i) Coal tar, (ii) Linseed oil, (iii) Bartya
solution, (iv) Sczerelmy's solution and Alum soap solution.

6.11.7. Tests of Stones

To determine the suitability of a stone for its use in engineering works, the
following tests are performed:
1. Hardness test: Hardness of a stone is tested by a pen knife which will
not be able to produce a scratch on a hard stone (like granite). Hardness
is determined with aid of the Moh's scale of hardness. If a pocket knife
makes a mark on a fresh surface of a stone say on limestone, (he
hardness of that limestone may be taken as H = 3, a scratch with the aid
of a finger nail indicates a hardness of H = 2. Hard siliceous rocks which
cannot be scratched by a knife, represent a hardness of H = 7.

2. Crushing test: This test in particular, is performed for the stone which
is to be used under high compression (such as the stone to be used at the
bottom of a heavy structure). It is carried out on blocks, 10 cm cube, in a
testing machine.

3. Toughness test: Toughness of a stone can be determined by

subjecting it to a hammer blow.

4. Fire resistance test: The stone which is free from calcium carbonate
can resist the fire. The presence of calcium carbonate in the stone can be
detected by dropping a few drops of dilute sulphuric acid which will
produce bubbles.

5. Attrition test: This test also known as abrasion test is carried out in
Deval's testing machine. Broken pieces of stone nearly 5 kg in weight are
placed in a cylinder along with cast iron balls. The cylinder is kept at
inclination of 30° with the horizontal and is rotated at 30 r.p.m. for 5 hours.
At the end of this interval the pieces are removed, cleaned and weighed.
Loss of weight determines the abrasion resistance property of the stone.
The stones which undergo a heavy loss of weight are not suitable for road
metal.

6. Acid test: In this test, a stone is kept for one week in the solution of
sulphuric acid and hydrochloric acid having 1% strength. The corners of
stones which have high alkaline content turn roundish and loose particles
will get deposited on its surface. Such type of stones are unsuitable for
smoky atmosphere. The stones having high percentage of lime content
exhibit efflorescence when subjected to action of acids.

7. Electrical resistance test: As the electric resistance of a wet stone is

less, therefore, the stone should be non-absorbent. Sandstones should
not absorb more than 10 percent of water, 17 percent in case of
limestones and 1 percent in granites of their volume of water when dipped
for 3-4 hours.

8. Smith's test: This test indicates the presence of earthly matter. The
stone's sample is broken into small pieces and put into a test tube
containing clear water. It is then shaken vigorously, the dirty color will
show presence of argillaceous matter.

9. Crystallization test: This test determines the durability or weathering

quality of a stone. A sample of stone is immersed in the solution of sodium
sulphate at room temperature and dried in hot air. The process of wetting
and drying is carried out for two hours; the difference in weight if any is
recorded. Little difference in weight indicates durability and good
weathering quality of the stone.

10. Porosity or absorption test: In this test the stone is first weighed
when, dry and weighed again after immersing it in water for a few hours.
The percentage of absorption, then is given by:
Weight of water absorbed
× 100
Weight of stone when dry

If this percentage does not exceed 5, the stone is suitable for use.

6.11.8. Common Building Stones, their Compositions, Properties,

Uses and Occurrence
1. Granite

(a) Composition: It is igneous rock. Its main constituent minerals are

Quartz, (hard and least affected by carbon dioxide and water) Felspar
(crystalline, lustrous, readily attacked by atmospheric agencies) and Mica
(dark grey, black or brown in color, soft, readily affected by chemicals and
atmospheric agencies).

(b) Characteristics:

(i) Its specific gravity is 2.64 and absorption less than 1%.

(ii) It has mottled appearance.

(iii) Significantly strong and durable.

(iv) Finely grained granite takes a fine polish.

(v) Crushing strength varies from 110 to 140MN/m2.

(vi) It has least tire resistance as it cracks under a strong tire.

(vii] Its color depends. upon that of felspar.

(e) Uses:

(i) Fine grained granite is suitable for ornamental columns, plinth etc. as
it takes a polish.

(ii) Owing to the hardness, weight and durability of granite it is considered

most suitable for the construction of sea walls, light houses, bridge piers
etc.

(iii) Large pieces are used as building blocks, the smaller as road metals
or railway ballast and the chippings for the manufacture of concrete or
artificial stone.

2. Basalt or Trap
(a) Composition: It is an igneous rock (siliceous variety). The main
constituents are silica. Alumina and felspar.

(b) Characteristics:

(i) Very hard and tough.

(ii) Heavier than granite.

(iii) Has greenish grey to dark grey color.

(iv) Crushing strength varies from 70 to 80 MN/m2.

(v) Specific gravity = 2.96.

(e) Uses:

(i) Suitable for paving sets and as a road metal.

(ii) Used for the manufacture of artificial stone.

(iii) Used as aggregate in concrete.

3. Slate

(a) Composition: It is a metamorphic rock (Argillaceous variety). It is

composed of alumina mixed with sand or carbonate of lime.

(b) Characteristics:

(i) Its specific gravity is 2.8.

(ii) A good slate is hard, tough and fine grained.

(iii) It has grey or dark blue color.

(iv) It can be split into thin sheets.

(v) Its crushing strength varies from 60 to 70 MN/ml.

(vi) It is non-absorbent.
(vii) When struck with a light hammer, it produces a sharp metallic ring.

(viii) Its durability is good.

(e) Uses:

(i) Used for making electrical switch boards.

(ii) Because of its non-absorbent property, it is suitable for use in cisterns,

urinals partitions, etc.

4. Gneiss

(a) Composition: It is a metamorphic rock. It is also sometimes called

stratified granite as it occurs in somewhat parallel layers. Its constituents
are the same as granite, i.e., quartz and felspar.

(b) Characteristics:

(i) It can be readily split into slabs.

(ii) It is more easily worked than granite.

(iii) As it is available in different colors, it is used for ornamental and

decorative purposes.

(iv) It is reasonably good material for street paving.

5. Sandstone

(a) Composition: It is a sedimentary rock of siliceous variety. It contains

sand or quartz cemented by lime, mica, magnesium, aluminum, oxide of
iron or by a mixture of these materials. Sometimes fragments of lime
stone, mica or felspar are also present.

(b) Characteristics:

ii) Its structure shows sandy grains.

(ii) Its usual colors are white, grey, brown, pink etc.

(iii) Its specific gravity is 2.25.

(iv) Crushing strength varies from 35 to 40 MNllm2.

(v) Fine grained stones are strong and durable.

(vi) The sandstone of thin-bedded variety is called flag stone. It splits

easily into large slabs along

the bedding.

(vii) The rock composed of angular sharp-edged sand grains is called grit;
it is adequately strong and

heavy and is used in heavy engineering works.

(viii) The sandstone that can be cut easily with mallet and hammer into
blocks for building is referred as free stone.

(ix) Its durability depends upon the nature of cementing material. The
quantity of sandstone is poor if it is porous or contains lime.

(e) Uses:

(i) The fine grained and compact variety is suitable for ashlar work,
moldings, carvings etc.

(ii) The rough and coarse-grained stone is employed for rubble work.

6. Limestone

(a) Composition: It is a sedimentary rock of calcareous variety. When in

pure state it contains CaCO3 but frequently is mixed with MgCO3 and
small amount of silica and alumina. When both MgCO3 and CaCO3 are
present nearly in equal proportion it is known as Dolomite.

(b) Characteristics:
(i) Its specific gravity is 2.6.

(ii) It is available in brown, yellow and dark grey colors.

(iii) Crushing strength = 52 MN/m2

(c) Uses:

(i) It is used in large quantities in blast furnaces, bleaching, tanning and

other industries.

(ii) If compact and fine grained it may be used as stone masonry for walls
and paving set in floor.

(iii) It is used as road metal (when better materials like trap, basalt or
granite are not available).

7. Marble

(a) Composition: It is metamorphic rock of calcareous verity. It is

changed from limestone. It is crystalline hard compact stone having
CaCO3 as the main constituent.

(b) Characteristics:

(i) It is available in white, yellow, grey, green, red, blue and black colours.

(ii) It is very hard and takes a fine polish.

(iii) Its specific gravity is 2.72.

(iv) Crushing strength varies from 50 to 60 MN/m2

(v) It can be easily worked.

(c) Uses:

(i) It is used for carving and decoration work.

(ii) It is also used for steps, wall linings, electrical switch boards, table
slabs and columns.

8. Kankar

(a) Composition: It is an impure limestone containing 30 percent of clay

and sand.

(b) Characteristics:

(i) It is available in grey or khaki color.

(ii) It has porous structure.

(iii) It occurs in solid layers or as irregular shaped modules a few metres

below the surface.

(iv) Hard kankar is adequately durable.

(c) Uses:

(i) Nodular kankar when burnt yields excellent hydraulic lime; when clean.
hard and tough is used

as road metal.

(ii) Hard kankar is employed for foundations of buildings.

9. Laterite

(a) Composition: It is basically igneous but not completely metamorphic.

It is sandy claystone containing high percentage of iron oxide.

(b) Characteristics:

(i) It has a porous and cellular structure.

(ii) It is readily quarried in blocks.

(iii) It is of reddish. brown. yellow. drak brown and black colours.

(iv) Its specific gravity varies from 2 to 2.2.

(c) Uses:

(i) Laterite blocks are suitable as building stones.

(ii) Nodular laterite proves a very good road metal.

10. Moorum

(a) Composition: It is a decomposed laterite.

(b) Characteristics: It has deep brown or red colour.

(c) Uses:

(i) Due to its rich red color. it is used in surfacing fancy paths and garden
walks.

(ii) It serves as a tine blindage for metalled rods.

11. Gravel

It is mixture of rounded water worn pebbles of any kind of stone with sand.
It is usually available in river beds. The size of the pebble varies from
minute grains to 8 cm in diameter. It is suitable for surfacing road and is
also used in concrete.

12. Chalk

It is pure. white limestone. It is soft and can be easily powdered. It is

largely used for the manufacture of Portland cement. It is also used for
marking and as a coloring matter. It is unsuitable for building purposes.

13. Shingles

These are large water-worn pebbles found in river beds. Broken shingles
are used in concrete and as road metal when no better stuff is available
at reasonable cost.
14. Quartzite

It is composed of silica and is dense. hard and glassy in structure. Some

of the varieties are considered as the hardest and strongest type of
building stones. It is strong and durable and used as road metal or railway
ballast or in concrete.

6.11.9. Natural Bed of Stone

Natural bed of stone is the original position occupied by the strati tied rock
from which the stone is obtained. It is also known as the plane of cleavage.
The strength and durability of the stratified stone depends on its position
in a structure, i.e., how it is placed. It should always be placed in such a
fashion that the load or thrust acts perpendicular to 'natural bed of stone
or plane of cleavage. If the stone is placed with its natural bed parallel to
the direction of load, it will get destroyed by the effects of frost and rain
(which scale off the face layer by layer). In case of a column or a wall
where the load line is vertical, the stones should be placed with the planes
of bedding radial so that thrust acts normal to the bedding plane while in
cornices with undercut moldings, the natural bed should be placed
vertically and perpendicular to the face otherwise the layers of
overhanging portions being horizontal will drop off.

6.12. REFRACTORIES

6.12.1. General Aspects

The term "refractories" embraces all materials used in the arts for the
construction of heat resisting containers, using the word in its broadest
sense, whether it be to afford space for the evolution of gases in
combustion processes or the holding of molten charges or of solids
undergoing heat-treatment. The two principal functions involved in the use
of refractory materials are to those of thermal insulation and conduction.
In the outside walls of a furnace, refractories serve tile purpose of
confining the heat and preventing excessive loss to the atmosphere; in a
muffle or retort, they serve to conduct the heat through the walls to the
charge.

Although, in general, the heat resisting quality of refractories is of

paramount importance, this is by no means the only requirement and may
at times be only a secondary consideration. Refractories may be expected
to be relatively unaffected by high temperatures under stress whether
negligible or heavy; to resist mechanical abrasion at various
temperatures; to resist the intrusion of molten metals, slags Or metallic
vapors, as well the action of superheated steam and hydrocarbons, sulfur
oxide, chlorine or other gases; and to withstand sudden temperature
changes. Under one set of conditions, high thermal conductivity may be
required and under another high insulation value, while in still other cases
high electrical resistance at moderately high temperatures may be
demanded. It is obvious that no single refractory will completely fulfil all
these functions, and hence the proper selection of a suitable material is
often a complicated task.

6.12.2. Properties of Refractories

A good refractory material should have the following properties:

I. It should be able to withstand high temperatures generated in the

furnace.

2. It should be able to withstand sudden alternating heating and cooling,

i.e., thermal shocks.

3. It should be able to withstand abrasion and rough usage.

4. Its contraction and expansion due to the inevitable temperature
variation should be minimum possible.

5. It should be able to withstand fluxing action of the slags and the

corrosive action of gases.

6. It should have good heat insulating properties.

7. It should be chemically inactive at elevated temperatures.

8. It should be impermeable to gases and liquids as far as possible.

9. If used in electric furnaces, it must have low electrical conductivity.

6.12.3. Types of Refectories

According to their chemical behavior, the refractory materials which are

mainly oxides or carbides of metals or non-metals or their mixtures, are
classified as follows:

1. Acid refractories.

2. Basic refractories.

3. Neutral refractories,

6.12.4. Acid Refractories

Acid refractories are those which really combine with bases and are
therefore. termed "Acid". They are materials consisting of silica or
containing silica as their chief constituent greatly in excess of the bases
present. The important acid refractories are quartz. sand, ganister, dinas
rock etc. Most tire-clays contain SiO2 in excess of the amount indicated
by the formula Al2O3 . 2SiO2 . 2H2O and are therefore. classed as acid.

Silica: When pure silica fuses at a very high temperature, viz., 1713°C,
but when heated in contact with basic substances it forms silicates, some
of which fuse easily. Therefore, the presence of bases in silica to be used
as refractory materials is to be guarded against. Silica occurs as quartzite,
Dinas rock and ganister. Ganister is a naturally occurring high siliceous
rock (98% Si02). In the prepared state it is used in the form of bricks.

Silica bricks are made from hard, dense fine-grained quartzite (known as
ganister). After crushing. The rock is ground with water and mixed with
about 2 percent lime. From this mixture, bricks may be molded by hand or
by power press; after drying in hot air, they are baked for proper time and
at the proper temperature. The lime being base reacts chemically with
acidic Si02 and fuses at a number of places in the brick and gives its
strength. The bricks expand 3.5 percent after the baking is finished.

Silica bricks possess the following properties:

1. Low porosity and free from air pockets.

2. Good thermal expansion and conductivity.

3. Remarkable load bearing capacity especially at high temperatures.

4. Not susceptible to thermal spalling at temperatures above 400C.

5. Ability to withstand thermal shock poor.

Silica bricks are extremely suitable for those parts of a furnace which are
subjected to uniformly high temperature. e.g., fire bridges, roofs of Acid
and Basic Open and Hearth, Electric furnaces, copper smelting and
refining furnaces etc.

Fire Clay: The main constituent of fire-clay is kaolinite, Al2O3 . 2SiO2 .

2H2O. The tire clays, however, contain varying proportions of alumina and
silica. Impurities in fire clays such as alkalis, sand, oxides of iron and
silicates of calcium and magnesium adversely affect their properties. At
high temperature the fire clays lose their water of hydration and mainly
consist of alumina and silica.

The fireclay bricks are manufactured in the same manner as silica bricks.
The clay in a finely crushed state is mixed with a definite amount of water
in a pugmill. The mixture is then pressed into molds, dried and finally
burnt. To control the shrinkage, and accelerate the rate of production
about 20 to 80% of burnt or calcined clay called Grog is mixed in the clay,
while using flint clay, plastic clay is employed as binder. By altering the
properties of flint clay and plastic clay in the brick mixture the properties
of the bricks made can be controlled.

Important properties of fire-clay bricks are:

1. Coefficient of thermal expansion low.

2. Sufficient strength at high temperature.

3. Resist spalling.

4. Not so refractory as silica bricks but much cheaper.

Fire clay bricks are used for the following:

1. Linings of blast furnaces for the melting of iron, copper, lead ores etc.

2. The linings of flues and shocks.

3. Heat treatment furnaces.

4. Glass furnaces.

5. Checker-work of regenerative furnaces.

6. Reverberatory furnaces.

7. Pottery kilns.

6.12.5. Basic Refractories

Basic refractories consist mainly of basic oxides without free silica and
resist the action of bases. The most common basic refractories are
Magnesite. Dolomite. lime etc. But lime, because of its dehydrating
tendency is never used as a refractory.

Magnesite: This is most important basic refractory material. It is made by

"dead burning" the mineral magnesite which is essentially magnesium
carbonate. At any temperature above about 700°C, magnesite is
dissociated to magnesia and carbon dioxide, but the properties of the
resultant product differ greatly according to the temperature of burning.
Below 900°C the product is "caustic magnesia", which is readily hydrated
to magnesium hydroxide, and is used in cement. Microscopic examination
shows no crystals, so that it is often called amorphous magnesia.
Prolonged firing at I 800°C gives an insoluble, unreactive "dead burnt"
magnesite, easily recognized as the crystalline mineral.

In the manufacture, magnesite is first "dead burnt" to remove shrinkage

as much as possible, then crushed, graded for minimum porosity, bonded,
and molded under hydraulic pressure. Bonding is done by adding an
organic binder, or by use of a little caustic magnesia, which sets to a
hydrated cement with water, or the crushed, deal burnt magnesite itself is
allowed to stand in water for some days until the surface of the particles
has undergone hydration.

Magnesite possesses the following properties:

I. Thermal conductivity greater than that for fire-clays and silica.

2. Highly resistant to the action of basic slags and iron oxide.

3. Starts losing strength at temperatures above 1500°C.

Magnesite bricks are not capable of resisting sudden changes of
temperature and show a tendency to spall under such conditions. They
are costlier than silica and fireclay bricks and used in the construction of
those parts of a furnace which are required to withstand the corrosive
action of basic slags.

They are used for:

1. Hearths of basic open-hearth and copper reverberatory furnaces.

2. Electric arc and induction furnaces.

3. Lining of L.D. crucible (in the manufacture of steel).

Dolomite: It is a double carbonate of calcium and magnesium and occurs

abundantly in India. It is burnt generally in shaft furnaces. Dolomitic bricks
have low conductivity and refractoriness as compared to magnesite
bricks. Calcium oxide present in the bricks has a tendency to combine with
water and carbon dioxide present in the atmosphere and causes
disintegration of the bricks. They are cheaper than magnesite bricks but
are poor in performance. It is extensively used for repairing the banks and
the bottoms of the Basic Open-hearth furnaces.

Burned bricks made from dolomite have not been successful in service. It
is possible to produce brick that will not hydrate under reasonable
treatment, but the stabilizing agents added cause high shrinkage when
the brick is heated to high temperature. Such bricks are also sensitive to
spalling influences.

6.12.6. Neutral Refractories

Neutral refractories are substances which do not combine with either

acidic or basic oxides and for this reason constitute the most satisfactory
furnace lining, e.g., chromite and carbon in graphite form.
Chromite: Chormite refractories are made from core ores which mainly
contain chromite, FeO.Al2O3. The ore is finely powdered and mixed with
a small amount of binding material, such as fire-clay, bauxite and
magnesia. The mixture is molded into bricks, dried and burnt in a kiln at a
temperature of about 1500oC to 1700oC.

Chrome bricks possess the following properties:

1. Low porosity.

2. High resistant to both acid and basic slags.

3. High thermal conductivity.

4. Low resistance to spalling.

Chrome bricks are extensively used in steel industry for lining open
hearths and also in the bottom of soaking pits.

Graphite: It is a form of pure carbon and is natural product. It occurs

mixed with calcareous and siliceous rocks. It is employed in making
graphite crucibles using clay as the bond.

Graphite bricks have the following properties:

I. Reduced oxidizing action (on the metal) at high temperatures.

2. Resist acid and basic slags.

3. Free from scaffolds formation due to the adherence of metals to the

lining.

Kaynite: Its composition is Al2O3.SiO2 (Disthene) and crystals are

triclinic. It decomposes at a temperature of 1350°-1330oC. Its, hardness
is 5 to 7 mhos.
Sillimanite: Its composition is Al2O3.Si2: (fibrolite) and occurs as long
needle-shaped crystals. It has high softening point (above 1800°C). It has
very low electrical conductivity. It is employed for making blocks, bricks,
crucibles, refractory fittings for electrical goods and tubes for surface
combustion.

In the Table 6.1 are shown the common refractory materials with their
chemical composition, melting point etc.

Table 6.1. Common Refractory Materials

Name Formula Composition Melting Class

point
Silica SiO2 100% SiO2 1713°C Acid
Kaolin (Fire- Al2O3.2SiO2.2H2O 4.50% Al2O3 About Acid (when
clay) 54.1% SiO2 1775°C pure)
Sillimanite Al2O3.2SiO2 63% Al2O3 About Acid
37% SiO2 1800°C
Mullite 3Al2O3.2SiO2 72% Al2O3 1900°C Acid
28% SiO2
Alumina Al2O3 100% Al2O3 2050°C Acid
(Corundum)
Lime CaO 100%CaO 2570oC Basic
Magnesia MgO 100% MgO 2800oC Basic
Chromite FeO. Cr2O3 32% FeO 2180oC Neutral
68% Cr2O3
Zirconia ZrO2 100% ZrO2 2700oC Neutral
Graphite C 100% C 3000oC Neutral

6.12.7. Refractory Fibers

• These are made from high purity alumina and silica grains melted in
electric furnace and blasted by high velocity gases into light fibers.

• Ceramic fibers are available in the form of felts, blocks and blankets.
• The heat losses through ceramic fibers are low compared to other
refractory materials.

They have excellent temperature resistance, outstanding thermal stability

and good resistance to vibration.

• Refractory fibers, in general, are considered in four broad categories

namely:

(i) Alumina silica fibers,

(ii) Pura silica fibers,

(iii) Pure metal oxide fibers,

(iv) High silica leached fired glass fibers.

Uses:

I. Because of low thermal conductivity the refractory ceramic fibers are

fast replacing and are used for lining of furnaces, kilns and other high
temperature equipment.

2. Silica fibers are very expressive, hence. limited industrial use. They find
applications in aerospace industry.

3. Alumina silica fibers are generally used from 1000 to 1500°C

temperature because of their low cost and good thermal properties (they
have average diameter ranging from 1.5 to 3.0 microns).

4. Metallic oxide, alumina fibers are used for 1500 to 1600°C.