Banda, Marybeth Hope T.

Bautista, Rajane Faith T.

Chemistry
Catarata, Antonio Perseus Prometheus O.
2014

Chemistry 81
Industrial
December

Ceramic Industry
Introduction

The traditional ceramic industries have as their finished materials a variety of

products that are essentially silicates.
In recent years, new products have been developed as a result of the
materials that withstand higher temperatures, resist greater pressures, etc.

What are Ceramics?

pots and other articles made from clay hardened by heat.
A ceramic is an inorganic non-metallic solid made up of either metal or nonmetal compounds that have been shaped and then hardened by heating to
high temperatures. In general, they are hard, corrosion-resistant and brittle.
Ceramic comes from the Greek word keramikos meaning pottery. The
clay-based domestic wares, art objects and building products are familiar to
us all, but pottery is just one part of the ceramic world.
Nowadays the term ceramic has a more expansive meaning and includes
materials like glass, advanced ceramics and some cement systems as well.
What is Pottery?
pots, dishes, and other articles made of earthenware or baked clay. Pottery
can be broadly divided into earthenware, porcelain, and stoneware.
Pottery is generally considered to be containers made from clay. "Pot" is a
term used for any number of container forms.

History

Burnt clayware has been found dating from about 15,000 BC

Well developed in Egypt in 5, 000 BC
Various ancient races were found to have created clay products
independently of each other
The advent of cross-fertilization of silicate chemistry, metallurgy, solid-state
physics, computer-controlled processes, and advanced automation
modernized methods of fabrication.
It is now possible to produce ceramics with superior qualities.
Recently, new processes have been developed for brickmaking from inorganic
wastes (fly ash, foundry sand, mine tailings, furnace slag, etc.)

Human Utilization

Building brick
Sewer pipe
Drain tile

Filler in paper
Filler in rubber
Filler in plastics

Filler in paint
Aerospace
Filler in fertilizers
Electronics
Fridge magnets
Automotive
Metals production
Personal protection
In modern medicine, advanced ceramics often referred to as bioceramics
play an increasingly important role. Bioceramics such as alumina and zirconia
are hard, chemically inert materials that can be polished to a high finish.
They are used as dental implants and as bone substitutes in orthopaedic
operations such as hip and knee replacement.

Basic Raw Materials

Clay
Feldspar
Sand
Clay
Impure hydrated aluminum silicates
Resulted from the weathering of igneous rocks in which feldspar was a
noteworthy component

K 2 O Al 2 O3 6 Si O 2 +CO 2+ 2 H 2 O K 2 CO3 + Al 2 O 3 2 Si O 2 2 H 2 O+4 SiO 2

Potash feldspar:

Kaolinite:

Silica:

K 2 O Al 2 O3 6 SiO2

Al 2 O3 2 SiO2 2 H 2 O

4 Si O2

Clay minerals:
Mixture of:

Al 2 O3 2 SiO2 2 H 2 O

Kaolinite:

Montmorillonite:

( Mg , Ca ) O Al 2 O3 5 SiO2 nH 2 O

Illite: K2O, MgO, Al2O3, SiO2, H2O (in varialble amounts)

Plastic and moldable when pulverized and wet
Rigid when dry
Vitreous when fired at a suitably high temperature
Accompanied by varying amounts of feldspar, quartz, and other impurities
(oxides of iron)
Kaolinite China clay the basic clay mineral present in nearly all the clays
used in the ceramic industry
Chosen for particular properties
Frequently blended to give the most favorable result
Physical Properties and impurities vary from clay to clay
It is necessary to upgrade them by beneficiation process
Feldspar

Common types:

Potash:

Soda:

Na 2 O Al2 O3 6 SiO2

Lime:

CaO Al 2 O3 6 SiO2

Fluxing constituent in ceramic formulas

Sand
Flint
the skeletal structure upon which clays and flux components attach
used to modify thermal expansion, regulate drying and shrinkage, and
improve structural integrity and appearance
Word of the moment: Fluxing
To treat (a metal object) with a flux to promote melting.
Table 1. Summary of the Properties of the basic raw materials of the ceramic
industry

K 2 O Al 2 O3 SiO2

Kaolinite

Feldspar

Sand
or
Flint

SiO2

Formula

Plasticity

Plastic

Nonplastic

Nonpl
astic

Fusibility

Refractory

Easily fusible
binder

Refrac
tory

Melting Point

1785C

1150C

1710
C

Shrinkage
burning

Much
shrinkage

Fuses

No
Shrink
age

on

Al 2 O3 2 SiO2 2 H 2 O

K 2 O Al 2 O3 SiO2

Additional Raw Materials

Fluxing agents lower vitrification temperature, melting temperature,
reaction temperature
Borax
Fluorspar
Boric Acid
Cryolite
Soda Ash
Iron oxides
Sodium nitrate
Antimony oxides
Pearl ash
Lead oxides
Nepheline syenite
Lithium minerals
Calcined bones
Barium minerals
Apatite

Refractory ingredients retains the strength of the material at high

temperatures
Alumina
Hydrous
magnesium
silicates
Olivine
Aluminium silicates
Chromite
Dumortierite
Magnesite
carborundum
Lime and limestone
Mullite
Zirconia
Dolomite
Titania
thoria

Chemical Conversions and Basic Ceramic Chemistry

All ceramic products are made by combining various amounts the

aforementioned materials, shaping and firing to temperatures (700C 2000C)
Chemical conversions:
Dehydration: chemical smoking 150 - 650C
Calcination: 600 - 900C
Oxidation of ferrous iron and organic matter: 350 - 900C
Silicate formation: 900C and higher
Phase-rule studies have been of importance in interpreting empirical
observations in the ceramic industries and in making predictions for
improvements

Figure 1. Phase Diagram of Basic Raw Materials

Ceramic products are all more or less refractory and the degree of
refractoriness of a given product is determined by the relative quantities of
refractory oxides and fluxing oxides
The common ingredient of all ceramic products is clay, and therefore the
chemical reactions which occur on heating clay are important
The first effect of the heat is to drive off the water of hydration (600 - 650C)
The clay absorb more heat, leaving an amorphous mixture of alumina and
silica

Al 2 O 3 2 SiO2 2 H 2 O Al 2 O 3 +2 SiO2 +2 H 2 O

A large proportion of the alumina can be extracted with hydrochloric acid in

this stage
As heating is continued, the amorphous alumina changes sharply at 940C to
a crystalline form of alumina, -alumina, with the evolution of considerable
heat

At 1000C, the alumina and silica combine to form mullite (

3 Al 2 O3 2 SiO2

At a still higher temperature, the remaining silica is converted into crystalline

cristobalite
Overall reaction in the heating of clay:

3 ( Al 2 O3 2 SiO2 2 H 2 O ) 3 Al 2 O3 2 SiO2 +4 SiO2 +6 H 2 O

An actual ceramic body contains many more ingredients than clay itself.
The chemical reactions are more involved and there will be other chemical
species besides mullite and cristobalite present in the final clay product
All ceramic bodies undergo a certain amount of vitrification, or glass
formation, during heating, and the degree of vitrification depends upon the
relative amounts of refractory and fluxing oxides in the composition, the
temperature, and the time of heating
The vitreous phase imparts desirable properties to some ceramic bodies by
acting as a bond and imparting translucency in chinaware.
In refractories, some vitrification is desirable to act as a bond
Extensive vitrification destroys the refractory property
As a result, any ceramic body is composed of a vitreous matrix plus crystals
(mullite and cristobalite)
The degree of vitrification provides the basis for useful classification of
ceramic products
Word of the moment: Vitrification
The process of converting materials to glass
The point at which a pot loses its porosity

Classification of ceramic products based on degree of

vitrification

Whitewares
Heavy-clay products
Refractories
Enamels
Glass

Table 2. Summary of the Properties of Types of Ceramic Products based

on vitrification

A
m
ou
nt
of
flu
x

Heating
Tempera
ture

Vi

Whitewa
res

Va
rie
s

Moderate

Va

Heavyclay
products

Ab
un
da

Low

Lit

nt

Refracto
ries

Fe
w

High

Lit

Enamels

Ve
ry
ab
un
da
nt

Moderate

Co

Glass

Mo
de
rat
e

High

Co

Whitewares

Whiteware is a generic term for ceramic products which are usually white and
of fine texture
Because of the different amounts and kinds of fluxes, there is a corresponding
variation in the degree of vitrification among whitewares.
Types:
Earthenware semivitreous dinnerware. Porous and nontranslucent
with a soft glaze
Chinaware vitrified translucent ware with a medium glaze which
resists abrasion to a degree. Used for nontechnical purposes
Porcelain vitrified translucent ware with a hard glaze which resists
abrasion to the maximum degree. Includes chemical, insulating, and
dental porcelain
Sanitary ware formerly made from clay, usually porous. Prefired and
sized vitreous grog is sometimes included in the triaxial composition
Stoneware one of the oldest ceramic wares. Crude porcelain not so
carefully fabricated from raw material of a poorer grade
Whiteware tiles generally classified as floor tiles. Resistant to
abrasion and impervious to stain penetration. May be glazed or
unglazed

Glazing
Important in whitewares and in tableware
A glaze is a thin coating of glass melted onto the surface of more-or-less
porous ceramic ware
A glaze contains ingredients of two distinct types in different proportions:
Refractory materials (feldspar, silica, china clay)
Fluxes (soda, potash, flourspar, and borax)
glost firing technical term for the firing of the glaze
Earthenware should be glazed between 1050 1100 C
Stoneware 1250 to 1300C

STRUCTURAL-CLAY PRODUCTS

Ceramic products intended for use in building construction.

Low-cost but durable products.
Frequently manufactured from the cheapest of common clays.
Made from commonly occurring natural materials, which are mixed with water,
formed into the desired shape, and fired in a kiln in order to give the clay
mixture a permanent bond.
The type of clay locally available often determines the ceramic product which
can be made economically.
Structural-clay product fabrication has become highly mechanized;
unmodernized
plants
cannot
remain
competitive.
Finished products display such essential
properties as:
load-bearing strength
resistance to wear
resistance to chemical attack
attractive appearance
ability to take a decorative finish.

MANUFACTURE
BUILDING BRICK

OF

Face Brick Clay

Requirements:
Freedom from warping
Absence of soluble salts
Sufficient hardness when burned at a moderate temperature
General uniformity in color upon burning
Brick
Red burning clay is usually used.
Manufactured by one of three processes:
Soft mud
Stiff mud
Dry-press
May be re-pressed to make face
brick.
Are dried in various ways:
Outdoors
In sheds
In tunnel bricks
After drying, they are fired in kilns.

Stiff mud

 Employed for the manufacture of practically every clay product.

The clay is wet enough to stick together when worked.

Figure 2. Stiff-Mud Process of Brickmaking

REFRACTORIES

Those materials used to withstand the effect of thermal, chemical, and

physical effects met with in furnace procedures.

PROPERTIES OF REFRACTORIES
In making the refractory best suited for a definite
operation it is necessary to consider:
The materials
The working temperature of the furnace where the
refractory is needed
The rate of temperature change
The load applied during heats
The chemical reactions encountered

Chemical Properties
Can be divided into acid, basic, and neutral groups.*
Depends upon the relative silica-alumina content.*
It is usually inadvisable to employ an acid brick in
contact with alkaline product, or vice versa.*

 Chemical action may be due to contact with slags, fuel

ashes, and furnace gases as well as with products such
as glass or steel.
Porosity
Directly related to many other physical properties of
brick.*
The higher the porosity of the brick, the more easily it is penetrated by
molten fluxes and gases.
Those bricks with the lowest porosity have the greatest strength, thermal
conductivity, and heat capacity.

Fusion Points
It is found by the use of pyrometric cones of predetermined softening
points.
Most commercial refractories soften gradually over a wide range and do
not have sharp melting point.*
Spalling
A fracturing , or a shaking off , of a refractory brick, or block, due to
uneven heat stresses or compression caused by heat.
Refractories usually expand when heated.
Bricks that undergo the greatest expansion at the least uniform rate are
the most susceptible to spalling when subjected to rapid heating and
cooling.
Strength
Cold strength usually has only a slight bearing on strength at high
temperatures.
Resistance to abrasion or erosion is also important for many furnace
construction.
Resistance to Temperature Change
Bricks with the lowest thermal expansion and coarsest texture are the most
resistant to rapid thermal changes.
Bricks that have been used for a long time are often melted to glassy slags
on the outside surface or even more or less corroded away.
Thermal conductivity
The densest and least porous bricks have the highest thermal conductivity.
Heat Capacity
Furnace heat capacity depends upon the thermal conductivity, the specific
heat, and the specific gravity of the refractory.
Conversely, dense, heavy fire-clay brick is best for regenerator
checkerwork, as in coke ovens, glass furnaces, and stoves for blast
furnaces.

MANUFACTURE OF REFRACTORIES
Grinding

It is known that a mixture in which the proportion of coarse and fine

particles is about 55:45, with only few intermediate particles, gives the
densest mixures.
Careful screening, separation, and recycling are necessary for close
control.
Mixing
The real function f mixing is the distribution of the plastic material so as to
coat thoroughly the non-plastic constituents.
This serves the purpose of providing a lubricant during the molding
operation and permits the bonding of the mass with a minimum number of
voids.
Molding
The great demand for refractory bricks of greater density, strength,
volume, and uniformity has resulted in the adoption of the dry-press
method of molding with mechanically operated presses.
The dry-press method is particularly suited for batches that consist
primarily of non-plastic materials.
In order to use high-pressure forming, it is necessary to de-air the bricks
during pressing to avoid laminations and cracking when the pressure is
released.
When pressure is applied, the gas is absorbed by the clay or condensed.
Vacuum is applied through vents in the mold box
Large species shapes are not easily adapted to machine molding.
Drying
It is used to remove the moisture added before molding to develop
plasticity.
The elimination of water leaves voids and cuases high shrinkage and
internal strains.
In some cases drying is omitted entirely, and the small amount necessary
is accomplished during the heating stage.
Burning
It may be carried out in a typical round, downdraft kilns or continuoustunnel kilns.
Two important things takes place during burning:
The development of a permanent bond by partial vitrification
The development of stable mineral forms for future service
The changes that takes place are:
Removal of water of hydration
Calcination of carbonates
Oxidation of ferrous iron
During these changes the volume may shrink as much as 30%, and severe
strains are set up in the refractory.
This shrinkage may be eliminated by prestibilization of the materials used.

Grinding

Mixing

Burning

Molding

Drying

Figure 3. Manufacture of Refractories

VARIETIES OF REFRACTORIES
95% of the refractories manufactures are non-basic, with silica (acid) and fireclay (neutral) brick predominant. *
It is really only in exceptional cases that heat is the sole agent that affects
the final destruction.
It is usually caused by chemical reaction at the operating temperature.

Fire-Clay Brick
Most widely used of all available refractory material.*
The steel industries are the largest consumers of this refractory.
Other industries having use for them are pottery kilns, brass and copper
furnaces, and glass furnaces.
Silica Brick
Contains approximately 95-96% of SiO2 and about 2% lime added during
grinding to furnish the bond.
It undergo permanent expansion.*

When reheated, it expand again about 1.5% but the effect is reversible and
the bricks return to size when cooled. SiO 2
They have a very homogeneous texture, are free from air pockets and
molding defects, and possess low porosity.
Furnaces using these must be heated and cooled gradually to lessen
spalling and cracking.

High-Alumina Refractories
They are used increasingly to meet the demand for materials that can
withstand severe conditions for which the older fire-clay and silica bricks
are not suitable.
Made from clays rich in bauxite and diaspore.
They are also practically inert to carbon monoxide and not disintegrated by
natural-gas atmospheres up to 1000C
High alumina bricks are employed in the cement industry and paper-mill
refractories. Also in the lining of glass furnaces, oil-fires furnaces, etc.
Basic Refractories
Important basic bricks are made from magnesia, chromite, and forsterite.
To achieve the required strength and other physical properties, they are
usually power-pressed and are either bonded or hard-burned.
Magnesia Refractories
Made from domestic magnesites or magnesia extracted from brines.
They do not stand much load at elevated temperatures, but this difficulty
has been overcome by blending with chrome ores.
They are among the most expensive bricks. There is a large price variation
because of the composition variation.
Forsterite which is the most stable silicate at high temperature is employed
both as a base for high-temperature refractories.
In the manufacture of forsterite refractories, dead-burned magnesites is
usually added to convert some accessory minerals to forsterite.
For example, estatite or clinoenstatite, occuring in the rock olivine, as
mined, is converted to forsterite:
MgOSiO2 + MgO

2MgOSiO2
Bricks with
a high precentage of alumina are classed among the
superrefractories, and those of almost-pure alumina (+97%) may be
considered among the recently special refractories, termed pure oxide.
Superrefractories have the advantages of a high melting point, no
transformation during heating, and unsurpassed volume stability at high
temperatures.
Insulating Brick
2 types:
For backing refractory bricks
For use in place of regular refractory brick
For instance, waste cork is ground and sized; then it is mixed with fire clay,
molded, and burned. In the kiln the cork burns out, leaving a highly porous,
light brick.

These lightweight refractories may be used safely for 1350-1600C,

whereas diatomaceous-earth brick are not suitable above 1100C under
ordinary conditions.
Silicon Carbide
Superrefractories are noted for their chemical resistance and ability to
withstand sudden temperature changes.
They are strong mechanically and withstand loads in furnaces to
temperatures up to 1400C.
Their ability to absorb and release heat rapidly and their resistance to
spalling under repeated temperature changes make them desirable for
recuperators.
They are replacing carbons and aluminosilicate products in iron-making
blast furnaces because of their stability under reducing conditions and
good alkali resistance.
Refractories from Crystalline Alumina or Aluminum Silicates
High-temperature kilns now furnish alumina bricks that closely approach
pure corrundum in properties and mullite bricks.
Research has revealed that mullite and corundum have high slag
resistance and remain crystalline state at temperatures of 1600C and
higher.
Electrocast or Cohart Refractories
The blocks cannot be cut or shaped, but may be ground on Alundum
wheels, however, skills in casting has progressed rapidly, and now many
sizes and intricate shapes are available.
This electrocast has only 0.5% voids, in contrast to the usual 17-29% of
fire-clay blocks.
Pure Oxide Refractories
The refractory industry is constantly faced with increased demands for
products which will withstand higher temperature and more severe
operating conditions.
To meet this requirements, a group of special pure oxide refractories has
been developed.
Their superior qualities are based mostly on freedom from fluxes.
Refractory oxides of interest in order of increasing cost per unit volume
include alumina, magnesia, zirconia, beryllia, and thoria.
All have been developed commercially for light refractory products.
The first three have certain properties in common:
They are of high purity
They are principally composed of electrically fused grains
Beryllia is not used commercially for heavy wear because of its high cost
and volatilization above 1650C in the presence of water vapor.
Thoria has a number of disadvantages, perticularly since its radioactivity
places it under the control of the Atomic Energy Comission.
Magnesia is a basic refractory and is easily reduced at high temperatures.
Its application is limited to oxidizing atmospheres at temperatures not
much over 2200C.

 Pure zirconia undergoes a crystalline change from monoclinic to tetragonal

form at 980C, accompanied by a drastic volume change on inversion,
stabilization of the crystal structure to the cubic form, is necessary.
Sinter alumina has the widest application among these pure oxide
refractories.
It is used successfully at temperatures up to 1870C.

Specialized ceramic products

Ceramic Composites
Ferroelectric and Ferromagnetic
High Alumina

Ceramic Composites

Structures of metallic honeycombs or webbing impregnated with a

ceramic phase
Carbon (C), special silicon carbide (SiC), alumina (Al 2O3) and mullite
(Al2O3SiO2)
Ceramic Composite armor is 30 to 50% lighter and meets the international
standards for safe protection
UN and NATO uses Ceramic Composite in bullet-proof vests and tanks

1. Roving (Fiber reinforcement)= Fiber-perform

2. Ceramic Filling (Matrix filling)
i. Deposition
ii. Pyrolysis
iii. Chemical Reaction
iv. Sintering (1000-1200C)
v. Electrophoretic deposition
2.) Machining (diamond tool or with water jet/ laser)
i. Grinding
ii. Drilling
iii. Lapping/Milling

MultiFerroic material

Is a material that shows both magnetism and polar order, which are
seemingly contradictory properties
Ferroelectric- (Barium titanate) [BaTiO3]
o coupling of charge polarization and electric field
Ferromagnetic- television set, computers
o coupling of magnetic momentum and magnetic field
Scientists at Argonne National Lab and the Researchers from the
University of Pennsylvania, Chicago and Cornell confirmed that Iron
Titantium oxide (FeTiO3) or ilmenite has multiferroic properties, which are
seemingly contradictory properties. The material is a promising
exploration for the next generation of handheld electronics.

Figure 4. Multiferroicity

The figure explains the various possible scenarios. While there are a
large number of magnetically and electrically polarizable materials,
there are only a few materials which show ferroelectric and
ferromagnetic ordering. Magnetoelectric materials are those materials
which are simultaneously
electrically and magnetically polarizable,
while Multiferroics are strictly those materials which show
ferroelectric and ferromagnetic ordering.

High Alumina

A material that can withstand very high temperature under reducing, inert
or high vacuum condition. It remains good chemical resistance under high
temperature and has excellent wear and abrasion resistance.

Porcelain or Vitreous Enamel

Is a ceramic mixture containing a large proportion of fluxes, applied cold

and fused to the metal at moderate red heat.
Used in Cooking utensils, industrial equipment and glass-enameled steel
for chemical use, electroluminescent lighting and automobile industry

Manufacture of Porcelain

1.
2.
3.
4.
5.

Raw Materials
Manufacture of the Frit
Preparation of metal Parts
Application of the Enamel
Firing

Raw Material
Is not just highly pure but also fineness.
The material used is dependent to the enamel to be used.
Is not just highly pure but also fineness.
Six different Materials
1.) Refractories Quartz, Clay, Feldspar

- Acidic part of the melt

- body glass
2.) Fluxes Borax, Soda Ash, Cryolite, Fluorspar

- Basic character

- reacts with the Acidic part to form glass

3.) Opacifiers give the opaque white color

- Insoluble (titanium dioxide)

- Devitrification (Cryolite)
4.) Colors oxides materials, elements, salts or frits

- may act as refractories or fluxes

5.) Floating Agents clay and gums

- to suspend the enamel in water

6.) Electrolytes Borax, Soda Ash, Magnesium sulfate and or carbonate

Manufacture of the Frit

Frits- the shattered
material product produce by the mixed
melted materials
- It is produce by mixing the materials in proper proportions and charged into
the melting furnace at 1300C from an hour to three, after the batch is then
poured in a tank of cold water.

Preparation of Metal Parts

The metal should be clean from all foreign matter in order for the enamel
coat to adhere well to it.
The metal is cleaned by pickling in diluted hydrochloric or sulfuric acid at
60C.
The success of enameling is dependent on the nature and uniformity of
the metal base.

Application of the Enamel

Conventional Process

The enamel is applied air-dried and the colors are brushed and
stenciled on. Enamel is applied twice to assure the quality.
Electrostatic Sprayer
o when the steel is powder processed it is coated using the spray, in
which consist of two-coat, one- fire system that consist of a thin
powder base coat and the other is a powder cover coat. This process
produces a good quality at a lower cost.

Firing
Successful firing and good enamel:

1.) Proper Firing temperature (700-800C)

2.) Time (1-15mins)

3.) Proper support of the Ware

4.) Uniform heating and cooling of the ware

5.) Free dust atmosphere

Kilns

A furnace for firing or burning or drying things such as porcelains or

bricks.

Continuous Kilns
Succession of burning or heating chamber with one cooling chamber it is
usually using in bricks and tile production and utilizes a roller hearth kiln.
Two types:
a. Direct-fired type
b. Indirect-fired type

Periodic Kilns
Not as efficient as the first one but it is more versatile
Two types:
1. Downdraft- Face brick, Stoneware, tile and common brick
2. Updraft (Tunnel Kilns) Pottery