Notes on CERAMICS, 2022

Pls go through the book Shreves Chemical Process Industries, 5th Edition for
details about ceramic industry

This note has been collected from net and will help you to prepare yourself for
exam only.

Ceramics can be defined as heat-resistant, nonmetallic, inorganic

solids that are (generally) made up of compounds formed from metallic
and nonmetallic elements. Although different types of ceramics can
have very different properties, in general ceramics are corrosion-
resistant and hard, but brittle. Most ceramics are also good
insulators and can withstand high temperatures. These properties have
led to their use in virtually every aspect of modern life.

The two main categories of ceramics are traditional and advanced.

Traditional ceramics include objects made of clay and cements that
have been hardened by heating at high temperatures. Traditional
ceramics are used in dishes, crockery, flowerpots, and roof and wall
tiles. Advanced ceramics include carbides, such as silicon carbide,
SiC; oxides, such as aluminum oxide, Al2O3; nitrides, such as silicon
nitride, Si3N4; and many other materials, including the mixed oxide
ceramics that can act as superconductors. Advanced ceramics require
modern processing techniques, and the development of these techniques
has led to advances in medicine and engineering.

Glass is sometimes considered a type of ceramic. However, glasses and

ceramics differ in that ceramics have a crystalline structure while
glasses contain impurities that prevent crystallization. The structure
of glasses is amorphous, like that of liquids. Ceramics tend to have
high, well-defined melting points, while glasses tend to soften over a
range of temperatures before becoming liquids. In addition, most
ceramics are opaque to visible light, and glasses tend to be
translucent. Glass ceramics have a structure that consists of many
tiny crystalline regions within a noncrystalline matrix. This
structure gives them some properties of ceramics and some of glasses.
In general, glass ceramics expand less when heated than most glasses,
making them useful in windows, for wood stoves, or as radiant glass-
ceramic cooktop surfaces.

Composition

Some ceramics are composed of only two elements. For example, alumina, Al2O3 is
aluminum oxide,; zirconia, ZrO2;is zirconium oxide, Ceramics are good insulators
and can withstand high temperatures.
A popular use of ceramics is in artwork.
silicon dioxide, SiO2. Other ceramic materials, including many
minerals, have complex and even variable compositions. For example,
the ceramic mineral feldspar, one of the components of granite, has
the formula KAlSi3O8.

The chemical bonds in ceramics can be covalent, ionic, or polar

covalent, depending on the chemical composition of the ceramic. When
the components of the ceramic are a metal and a nonmetal, the bonding
is primarily ionic; examples are magnesium oxide (magnesia), MgO, and
barium titanate, BaTiO3. In ceramics composed of a metalloid and a
nonmetal, bonding is primarily covalent; examples are boron nitride,
BN, and silicon carbide, SiC. Most ceramics have a highly crystalline
structure, in which a three-dimensional unit, called a unit cell, is
repeated throughout the material. For example, magnesium oxide
crystallizes in the rock salt structure. In this structure, Mg2+ ions
alternate with O2− ions along each perpendicular axis.

Manufacture of Traditional Ceramics

Traditional ceramics are made from natural materials such as clay that
have been hardened by heating at high temperatures (driving out water
and allowing strong chemical bonds to form between the flakes of
clay). In fact, the word "ceramic" comes from the Greek keramos, whose
original meaning was "burnt earth." When artists make ceramic works of
art, they first mold clay, often mixed with other raw materials, into
the desired shape. Special ovens called kilns are used to
"fire" (heat) the shaped object until it hardens.

Clay consists of a large number of very tiny flat plates, stacked

together but separated by thin layers of water. The water allows the
plates to cling together, but also acts as a lubricant, allowing the
plates to slide past one another. As a result, clay is easily molded
into shapes. High temperatures drive out water and allow bonds to form
between plates, holding them in place and promoting the formation of a
hard solid. Binders such as bone ash are sometimes added to the clay
to promote strong bond formation, which makes the ceramic resistant to
breakage. The common clay used to make flowerpots and roof tiles is
usually red-orange because of the presence of iron oxides. White
ceramics are made from rarer (and thus more expensive) white clays,
primarily kaolin.

The oldest known ceramics made by humans are figurines found in the
former Czechoslovakia that are thought to date from around 27,000
B.C.E. It was determined that the figurines were made by mixing clay
with bone, animal fat, earth, and bone ash (the ash that results when
animal bones are heated to a high temperature), molding the mixture
into a desired shape, and heating it in a domed pit. The manufacture
of functional objects such as pots, dishes, and storage vessels, was
developed in ancient Greece and Egypt during the period 9000 to 6000
B.C.E.

An important advance was the development of white porcelain. Porcelain

is a hard, tough ceramic that is less brittle than the ceramics that
preceded it. Its strength allows it to be fashioned into beautiful
vessels with walls so thin they can even be translucent. It is made
from kaolin mixed with china stone, and the mixture is heated to a
very high temperature (1,300°C, or 2,372°F). Porcelain was developed
in China around C.E. 600 during the T'ang dynasty and was perfected
during the Ming dynasty, famous for its blue and white porcelain. The
porcelain process was introduced to the Arab world in the ninth
century; later Arabs brought porcelain to Spain, from where the
process spread throughout Europe.

Manufacture of Advanced Ceramics

The preparation of an advanced ceramic material usually begins with a

finely divided powder that is mixed with an organic binder to help the
powder consolidate, so that it can be molded into the desired shape.
Before it is fired, the ceramic body is called "green." The green body
is first heated at a low temperature in order to decompose or oxidize
the binder. It is then heated to a high temperature until it is
"sintered," or hardened, into a dense, strong ceramic. At this time,
individual particles of the original powder fuse together as chemical
bonds form between them. During sintering the ceramic may shrink by as
much as 10 to 40 percent. Because shrinkage is not uniform, additional
machining of the ceramic may be required in order to obtain a precise
shape.

Sol-gel technology allows better mixing of the ceramic components at

the molecular level, and hence yields more homogeneous ceramics,
because the ions are mixed while in solution. In the sol-gel process,
a solution of an organometallic compound is hydrolyzed to produce a
"sol," a colloidal suspension of a solid in a liquid. Typically the
solution is a metal alkoxide such as tetramethoxysilane in an alcohol
solvent. The sol forms when the individual formula units polymerize
(link together to form chains and networks). The sol can then be
spread into a thin film, precipitated into tiny uniform spheres called
microspheres, or further processed to form a gel inside a mold that
will yield a final ceramic object in the desired shape. The many
crosslinks between the formula units result in a ceramic that is less
brittle than typical ceramics.

Properties and Uses

For centuries ceramics were used by those who had little knowledge of
their structure. Today, understanding of the structure and properties
of ceramics is making it possible to design and engineer new kinds of
ceramics.

Most ceramics are hard, chemically inert, refractory (can withstand

very high heat without deformation), and poor conductors of heat and
electricity. Ceramics also have low densities. These properties make
ceramics attractive for many applications. Ceramics are used as
refractories in furnaces and as durable building materials (in the
form of bricks, tiles, cinder blocks, and other hard, strong solids).
They are also used as common electrical and thermal insulators in the
manufacture of spark plugs, telephone poles, electronic devices, and
the nose cones of spacecraft. However, ceramics also tend to be
brittle. A major difficulty with the use of ceramics is their tendency
to acquire tiny cracks that slowly become larger until the material
falls apart. To prevent ceramic materials from cracking, they are
often applied as coatings on inexpensive materials that are resistant
to cracks. For example, engine parts are sometimes coated with
ceramics to reduce heat transfer.

Composite materials that contain ceramic fibers embedded in polymer

matrices possess many of the properties of ceramics; these materials
have low densities and are resistant to corrosion, yet are tough and
flexible rather than brittle. They are used in tennis rackets,
bicycles, and automobiles. Ceramic composites may also be made from
two distinct ceramic materials that exist as two separate ceramic
phases in the composite material. Cracks generated in one phase will
not be transferred to the other. As a result, the resistance of the
composite material to cracking is considerable. Composite ceramics
made from diborides and/or carbides of zirconium and hafnium mixed
with silicon carbide are used to create the nose cones of spacecraft.
Break-resistant cookware (with outstanding thermal shock resistance)
is also made from ceramic composites.

Although most ceramics are thermal and electrical insulators, some,

such as cubic boron nitride, are good conductors of heat, and others,
such as rhenium oxide, conduct electricity as well as metals. Indium
tin oxide is a transparent ceramic that conducts electricity and is
used to make liquid crystal calculator displays. Some ceramics are
semiconductors, with conductivities that become enhanced as the
temperature increases. For example, silicon carbide, SiC, is used as a
semiconductor material in high temperature applications.

High temperature superconductors are ceramic materials consisting of

complex ionic oxides that become superconducting when cooled by liquid
nitrogen. That is, they lose all resistance to electrical current. One
example is the material YBa2Cu3O7−x, which crystallizes to form
"sheets" of copper and oxygen atoms that can carry electrical current
in the planes of the sheets.

Some ceramics, such as barium ferrite or nickel zinc ferrites, are

magnetic materials that provide stronger magnetic fields, weigh less,
and cost less than metal magnets. They are made by heating powdered
ferrite in a magnetic field under high pressure until it hardens.
Ceramic magnets are brittle, but are often used in computers and
microwave devices.
The properties of piezoelectric ceramics are modified when voltage is
applied to them, making them useful as sensors and buzzers. For
example, lead zirconium titanate is a piezoelectric ceramic used to
provide "muscle action" in robot limbs in response to electrical
signals.
Some ceramics are transparent to light of specific frequencies. These
optical ceramics are used as windows for infrared and ultraviolet
sensors and in radar installations. However, optical ceramics are not
as widely used as glass materials in applications in which visible
light must be transmitted. An electro-optic ceramic such as lead
lanthanum zirconate titanate is a material whose ability to transmit
light is altered by an applied voltage. These electro-optic materials
are used in color filters and protective goggles, as well as in memory-
storage devices.

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Sintering and microstructure of ceramics
Sintering is at the heart of ceramic processes. However, sintering takes place only
in
the last of the three main stages of the process (powders → forming → heat
treatments).
Sintering involves scientific considerations more directly, whereas the other two
stages often stress more technical observations and involve manufacturing secrets.
Generally, the success of the powder treatment is validated by the performances of
the sintered part.
During sintering, the non-cohesive granular medium becomes a cohesive material;
the consolidation takes place, and organizing the microstructure (size and shape of
the grains, amount and nature of the porosity, etc.). However, the microstructure
determines, to a large extent, the performances of the material. This is the reason
Sintering is the basic technique for the processing of ceramics, but other materials
can also use it: metals, carbides bound by a metallic phase and other cermets …
etc.
Experimental aspects of sintering
The parameters available to us to regulate sintering and control the development of
the microstructure are primarily the composition of the starting system and the
sintering conditions:
– composition of the system:
i) chemical composition of the starting powders,
ii) size and shape of the particles, and
iii) compactness rate of the pressed powder;
– sintering conditions:
i) treatment temperature,
ii) treatment duration,
iii) treatment atmosphere and,
iv) pressure during the heat treatment (for pressure sintering).
Sintering with and without reaction
We can speak of reactive sintering for traditional ceramics, where the starting raw
materials are mixtures of crushed minerals that react with one another during
sintering. The presence of a liquid phase often favors the chemical reactions
between the liquid and the solid grains. However, for solid phase sintering, reactive
sintering is generally
avoided: either we have the powders of the desired compound already, or sintering
is
preceded by calcination, i.e. a high temperature treatment of the starting raw
materials
Sintering with liquid phase: vitrification
Parameters of the liquid phase
In general, the presence of a liquid phase facilitates sintering. Vitrification is the
rule
for silicate ceramics where the reactions between the starting components form
compounds melting at a rather low temperature, with the development of an
abundant
quantity of viscous liquid. Various technical ceramics, most metals and cermets are
all
sintered in the presence of a liquid phase. It is rare that sintering with liquid phase
does
not imply any chemical reactions, but in the simple case where these reactions do
not
have a marked influence, surface effects are predominant. The main parameters are
therefore:

Refractory Materials
Refractory Materials Contents: Role of refractory What is a refractory? Why
required? Refractory requirements Melting point of some pure compounds used to
manufacture refractory Properties required in a refractory Types of refractory
materials Insulating materials Key words: Refractory, steelmaking, furnaces Role
of refractory Refractory materials have a crucial impact on the cost and quality of
steel products. The diversification on steel products and their cleanliness
requirement in recent years have increased the demand for high quality refractory.
Steelmaking requires high temperatures of the order of 1600 degree centigrade. In
addition steelmaking handles high temperature phases like molten steel, slag and
hot gases. These phases are chemically reactive; refractory materials are required
to produces steels. High quality refractory at a cheaper cost is the main
requirement because cost of refractory adds into the cost of product. What is a
refractory? Refractories are inorganic nonmetallic material which can withstand
high temperature without undergoing physico – chemical changes while remaining
in contact with molten slag, metal and gases. It is necessary to produce range of
refractory materials with different properties to meet range of processing
conditions. The refractory range incorporates fired, chemically and carbon bonded
materials that are made in different combinations and shapes for diversified
applications. Why required? • To minimize heat losses from the reaction chamber •
To allow thermal energy dependent conversion of chemically reactive reactants
into products because metallic vessels are not suitable. In steelmaking, the physico-
chemical properties of the following phases are important: Slag: Mixture of acidic
and basic inorganic oxides like SiO2, P2O5, CaO, MgO, FeO,etc.; temperature
varies in between 1400℃ to 1600℃. Molten steel: Iron containing carbon, silicon,
manganese, phosphorous, tramp elements, non metallic inclusions, dissolved gases
like nitrogen, oxygen and hydrogen and different alloying elements like Cr,Ni,Nb,
Mo, W, Mo etc.; temperature 1600℃ Gases: CO, CO2,N2,Ar containing solid
particles of Fe2O3, Fe3O4 etc.; temperature 1300 ℃ to 1600 ℃ . The above phases
are continuously and constantly in contact with each other and are in turbulent
motion. Refractory requirements: The refractory materials should be able to
withstand • High temperature • Sudden changes of temperature • Load at service
conditions • Chemical and abrasive action of phases The refractory material should
not contaminate the material with which it is in contact. Melting point of some
pure compounds used to Manufacture refractory Compounds Melting point ( ℃)
MgO (pure sintered) 2800 CaO(limit) 2571 SiC pure 2248 MgO (90-95%) 2193
Cr2O3 2138 Al2O3(pure sintered) 2050 Fireclay 1871 SiO2 1715 Kaolin (Al2O3.
SiO2) 1816 Chromite (FeO. Cr2O3) 2182 Properties required in a refractory The
diversified applications of refractory materials in several different types of
industries require diversified properties to meet the physico-chemical and thermal
requirements of different phases. In some industrial units more than one phase are
present e.g. in steel-making vessels slag /metal /gases are simultaneously present in
the vessel at high temperatures. In the heat treating furnaces solid/reducing or
oxidizing gases are simultaneously present. Below are briefly described the
properties of the refractory materials: Refractoriness Refractoriness is a property at
which a refractory will deform under its own load. The refractoriness is indicated
by PCE (Pyrometric cone equivalent). It should be higher than the application
temperatures. Refractoriness decreases when refractory is under load. Therefore
more important is refractoriness under load (RUL) rather than refractoriness.
Porosity and Slag permeability Porosity affects chemical attack by molten slag,
metal and gases. Decrease in porosity increases strength and thermal Conductivity.
Strength It is the resistance of the refractory to compressive loads, tension and
shear stresses. In taller furnaces, the refractory has to support a heavy load; hence
strength under the combined effect of temperature and load, i.e. refractoriness
under load is important. Specific gravity Specific gravity of the refractory is
important to consider the weight of a brick. Cost of bricks of higher specific
gravity is more that of lower specific gravity. But strength of bricks of higher
specific gravity is greater than one with lower specific gravity. Spalling Spalling
relates to fracture of refractory brick which may occur due to the following
reasons: • A temperature gradient in the brick which is caused by sudden heating or
cooling. • Compression in a structure of refractory due to expansion • Variation in
coefficient of thermal expansion between the surface layer and the body of the
brick • Variation in coefficient of thermal expansion between the surface layer and
the body of the brick is due to slag penetration or due to structural change. On
sudden heating Spalling tendency ∝ coeff . of thermal expansion max m shearing
strain �thermal diffusivity On sudden cooling Spalling tendency ∝ coeff . of
thermal expansion max m tensile strength �thermal diffusivity Permanent Linear
change (PLC) on reheating In materials certain permanent changes occur during
heating and these changes may be due to • Change in the allotropic form •
Chemical reaction • Liquid phase formative • Sintering reactions PLC(%)linear =
Increase /decrease in length original length × 100 PLC%(volume) = Increase
/decrease in volume original volume × 100 These changes determine the volume
stability and expansion and shrinkage of the refractory at high temperatures.
Thermal conductivity Thermal conductivity of the bricks determines heat losses.
Increase in porosity decreases thermal conductivity but at the same time decreases
strength also. Bulk density: Decrease in bulk density increases volume stability,
heat capacity. Types of refractory materials This can be discussed in several ways,
for example chemical composition of refractory or use of refractory or method of
manufacture or in terms of physical shape. Below is given type of refractory
depending on its chemical composition and physical shape. A) Chemical
composition Refractories are composed of either single or multi-component in
organic compounds with non metallic elements. Acid refractory The main raw
materials used are SiO2, ZrO2 and alumino- silicate. They are used where slag and
atmosphere are acidic. They cannot be used under basic conditions. Typical
refractories are fireclay, quartz and silica. Basic refractory Raw materials used are
CaO, MgO, dolomite and chrome-magnesite. Basic refractories are produced from
a composition of dead burnt magnesite, dolomite, chrome ore. a) Magnesite:
Chrome combinations have good resistance to chemical action of basic slag and
mechanical strength and volume stability at high temperatures. b) Magnesite:
Carbon refractory with varying amount of carbon has excellent resistance to
chemical attack by steelmaking slags. c) Chromite- Magnesite refractory: used in
inner lining of BOF and side walls of soaking pits.( basic refractory) d) Magnesite:
Basic refractory in nature. Magnesite bricks cannot resist thermal stock, loose
strength at high temperature and are not resistant to abrasion. Neutral refractory
Neutral refractory is chemically stable to both acids and bases. They are
manufactured from Al2O3, Cr2O3 and carbon. For details readers may see the
references given at the end of lecture 10. B) Physical form Broadly speaking
refractory materials are either bricks or monolithic. Shaped refractories are in the
form the bricks of some standard dimensions. These refractories are machine
pressed and have uniform properties. Special shapes with required dimensions are
hand molded and are used for particular kilns and furnaces. Different types are: i.
Ramming refractory material is in loose dry form with graded particle size. They
are mixed with water for use. Wet ramming masses are used immediately on
opening. ii. Castables refractory materials contain binder such as aluminate cement
which imparts hydraulic setting properties when mixed with water. These materials
are installed by casting and are also known as refractory concretes. iii. Mortars are
finely ground refractory materials, which become plastic when mixed with water.
These are used to fill the gap created by a deformed shell, and to make wall gas
tight to prevent slag penetration. Bricks are joined with mortars to provide a
structure. iv. Plastic refractories are packed in moisture proof packing and pickings
are opened at the time of use. Plastic refractories have high resistance to corrosion.
Monolithic refractories Monolithic refractories are replacing conventional brick
refractories in steelmaking and other metal extraction industries. Monolithic
refractories are loose materials which can be used to form joint free lining. The
main advantages of monolithic linings are • Grater volume stability • Better
spalling tendency • Elimination of joint compared with brick lining • Can be
installed in hot standby mode • Transportion is easier Monolithic refractories can
be installed by casting, spraying etc. Ramming masses are used mostly in cold
condition so that desired shapes can be obtained with accuracy. Insulating
materials The role of insulating materials is to minimize heat losses from the high
temperature reactors. These materials have low thermal conductivity while their
heat capacity depends on the bulk density and specific heat. Insulating materials
are porous in structure; excessive heat affects all insulating materials. Choice of
insulating materials would depend upon its effectiveness to resist heat conductivity
and upon temperature. High alumina with thermal conductivity 0.028 kcal m ℃ ,
and silica with thermal conductivity 0.04 kcal m ℃ etc are amongst others, used as
insulating materials. Ceramic fibres are important insulating materials and are
produced from molten silica, titania, Zirconia etc in the form of wool, short fibres
and long fibres. They have excellent insulation efficiency. They are long weight.
References: O.P.Gupta: Fuels, Furnace and refractory