HISTORY

28,000 BCE Oldest known artifact (from the late Paleolithic period) is a
statuette of a woman, named the Venus of Dolní Věstonice, from
a small prehistoric settlement near Brno, in the Czech Republic.
These ceramics were made of animal fat and bone mixed with
bone ash and a fine claylike material. After forming, the
ceramics were fired at temperatures between 500 -800°C in
domed and horseshoe shaped kilns partially dug into the ground
with loess walls.

7,000 – 5,000 BCE People were already using sharp tools made from obsidian, a
natural occurring volcanic glass. The Roman historian Pliny
reported that the first man-made glass was accidentally produced
by Phoenician merchants. While firing pottery, the presence of
calcium oxide (CaO) containing sand combined with soda and
the overheating of the pottery kiln may have resulted in a colored
glaze on the ceramic pot.

1,500 BCE Egyptians started building factories to create glassware for

ointments and oils. Glass was produced independently of
ceramics and fashioned into separate items. This primitive glass
consisted of a silicate glaze over a sinte red quartz body and was
primarily used fro jewelry.

6th – 5th BCE The apex of evolution where ceramic potteries are decorated by
oxidizing and reducing atmosphere during firing to achieve
special effects.

50 BC – 50 AD Optical glass (lenses and mirrors), window glass and glass

blowing production began in Rome and spread around the world
with the Roman empire.

16th century CE The Chinese were the first to introduce high temperature kilns
capable of reaching up to 1350°C. Refractories (synthetic
materials with better resistance to high temperatures) were
developed during the industrial revolution. These refractories
created the necessary conditions for melting metals and glass on
an industrial scale, as well as for the manufacture of coke,
cement, chemicals, and ceramics.

15th century CE The earliest blast furnaces were developed in Europe, capable of
reaching up to 1,500°C. They were used to melt iron and were
initially constructed from natural materials.

1965 The development of photovoltaic cells which converts light into

electricity opens a new way to access solar energy.
(https://ceramics.org/about/what-are-engineered-ceramics-and-glass/brief-history-of-ceramics-and-
glass
https://depts.washington.edu/matseed/mse_resources/Webpage/Ceramics/ceramicproperty.htm)

CERAMIC
WHAT IS A CERAMIC?

Ceramics are classified as inorganic and nonmetallic materials that are essential to our daily
lifestyle.  Ceramic and materials engineers are the people who design the processes in which these
products can be made, create new types of ceramic products, and find different uses for ceramic products
in everyday life. Ceramics are generally made by taking mixtures of clay, earthen elements, powders, and
water and shaping them into desired forms.  Once the ceramic has been shaped, it is fired in a high
temperature oven known as a kiln.  Often, ceramics are covered in decorative, waterproof, paint-like
substances known as glazes.

(https://depts.washington.edu/matseed/mse_resources/Webpage/Ceramics/ceramicproperty.htm)

CERAMIC PROPERTIES

The properties of ceramic materials, like all materials, are dictated by the types of atoms present, the
types of bonding between the atoms, and the way the atoms are packed together. This is known as the
atomic scale structure. Most ceramics are made up of two or more elements. This is called a compound.
For example, alumina (Al2O3), is a compound made up of aluminum atoms and oxygen atoms.

The atoms in ceramic materials are held together by a chemical bond. The two most common chemical
bonds for ceramic materials are covalent and ionic. For metals, the chemical bond is called the metallic
bond. The bonding of atoms together is much stronger in covalent and ionic bonding than in metallic.
That is why, generally speaking, metals are ductile and ceramics are brittle. Due to ceramic materials
wide range of properties, they are used for a multitude of applications. In general, most ceramics are:

 hard,

 wear-resistant,

 brittle,

 refractory,

 thermal insulators,

 electrical insulators,

 nonmagnetic,

 oxidation resistant,
  prone to thermal shock, and

 chemically stable.

EXAMPLE OF CERAMIC CRYSTAL STRUCTURE

Perovskite Structure

Rock Salt Stucture

Fluorite Structure

CERAMIC PROCESS
Ceramic processing is used to produce commercial products that are very diverse in size, shape, detail,
complexity, and material composition, structure, and cost.  The purpose of ceramics processing to an
applied science is the natural result of an increasing ability to refine, develop, and characterize ceramic
materials. 

Ceramics are typically produced by the application of heat upon processed clays and other natural raw
materials to form a rigid product. Ceramic products that use naturally occurring rocks and minerals as a
starting material must undergo special processing in order to control purity, particle size, particle size
distribution, and heterogeneity. These attributes play a big role in the final properties of the finished
ceramic. Chemically prepared powders also are used as starting materials for some ceramic products.
These synthetic materials can be controlled to produce powders with precise chemical compositions and
particle size.

The next step is to form the ceramic particles into a desired shape. This is accomplished by the addition of
water and/or additives such as binders, followed by a shape forming process. Some of the most common
forming methods for ceramics include extrusion, slip casting, pressing, tape casting and injection
molding. After the particles are formed, these "green" ceramics undergo a heat-treatment (called firing or
sintering) to produce a rigid, finished product. Some ceramic products such as electrical insulators,
dinnerware and tile may then undergo a glazing process. Some ceramics for advanced applications may
undergo a machining and/or polishing step in order meet specific engineering design criteria.

(https://depts.washington.edu/matseed/mse_resources/Webpage/Ceramics/ceramicprocessing.htm)

REFRACTORIES
(https://www.refractoriesinstitute.org/tri-pages/tri-what-are-refractories.asp)

WHAT ARE REFRACTORIES?

Refractories are ceramic materials designed to withstand the very high temperatures (in excess of 1,000°F
[538°C]) encountered in modern manufacturing. More heat-resistant than metals, they are used to line the
hot surfaces found inside many industrial processes.

In addition to being resistant to thermal stress and other physical phenomena induced by heat, refractories
can withstand physical wear and corrosion caused by chemical agents. Thus, they are essential to the
manufacture of petrochemical products and the refining of gasoline.

WHAT ARE REFRACTORIES MADE OF?

Refractories are produced from natural and synthetic materials, usually nonmetallic, or combinations of
compounds and minerals such as alumina, fireclays, bauxite, chromite, dolomite, magnesite, silicon
carbide, and zirconia.

WHAT ARE REFRACTORIES USED FOR?

From the simple (e.g., fireplace brick linings) to the sophisticated (e.g., reentry heat shields for the space
shuttle), refractories are used to contain heat and protect processing equipment from intense temperatures.
In industry, they are used to line boilers and furnaces of all types (reactors, ladles, stills, kilns, etc.).

It is a tribute to refractory engineers, scientists, technicians, and plant personnel that more than 5,000
brand name products in the United States are listed in the latest “Product Directory of the Refractories
Industry.”

PHASES

The following phases are important in high temperature processing to design the refractory for a given
requirement:

a) Slag:  It is a mixture mostly molten oxides and sulphides, in some processes phosphate is also a
constituent of slag. Oxides are either acidic such as silica, fireclay or basic like MgO, MgO ‐C, alumina,
FeO. Among sulphides CaS, MnS, FeS, PbS etc, are prominent phases. The slag is molten and its
temperature in different processing lay within the range 1200‐1600°C.

b) Liquid metal  

In metal extraction from ores, metal is extracted in the liquid stage. Composition of metal, and its
temperature are important. For example in iron and steel industry, hot metal is a mixture of iron, carbon,
silicon, manganese and phosphorus. The temperature varies in between 1300 °C to 1600°C. In copper ‐
making the temperatures are within the range 1100‐1200°C. Molten aluminum is produced at700‐750°C,
and likewise other nonferrous metals.

c) Matte: it is a high temperatures molten phase and consists of a mixture of molten sulphides like Cu2 S,
Fe S, Ni3 S2 etc. The temperatures vary within the range 1100°C to 1250°C.

d) Gases: Several different types of gases like CO, CO2, N2 H2O (vapor), argon, O2 are used at high
temperatures in several unit processes like roasting, calcination, smelting, refining, converting etc. The
temperatures may vary in between 600O C to1500°C. The gases like CO2, H2O, and O2 are oxidizing,
wheras the gases like  CO, and H2 are reducing.  N2 and argon are inert.

e) Speisses are molten solutions of arsenides, or arsenides and antimonides when the materials being
treated contain large quantities of As and Sb.

f) Drossses are heterogeneous products skimmed or driven form the surface of molten metal during
refining. They are mixtures of precipitated solid and liquid compounds with substantial proportion of
mechanically trapped molten metal.

(http://14.139.172.204/nptel/CSE/Web/113104058/mme_pdf/Lecture14.pdf)

PROPERTIES

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.

Thermal Conductivity Thermal conductivity of the bricks determine 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.

(http://14.139.172.204/nptel/CSE/Web/113104058/mme_pdf/Lecture14.pdf)

CLASSIFICATION OF REFRACTORY MATERIALS

Refractories can be classified on the basis of: (I) Chemical composition(their chemical behaviour, i.e.
their reaction to the type of slags.) (II) The methods of manufacture (III)Physical form(shaped and
unshaped Refractories).

Classification Based on Chemical Composition

(I) Acid Refractories: Acid refractories are those which are attacked by alkalis (basic slags). These are
used in areas where slag and atmosphere are acidic. Examples of acid refractories are: Silica (SiO2),
Zirconia (ZrO2).

(II) Basic Refractories: Basic refractories are those which are attacked by acid slags but stable to alkaline
slags, dusts and fumes at elevated temperatures. Since they do not react with alkaline slags, these
refractories are of considerable importance for furnace linings where the environment is alkaline. for e.g.
Dolomite (CaO*MgO)

(III) Neutral Refractories: Neutral Refractories are chemically stable to both acids and bases and are used
in areas where slag and atmosphere are either acidic or basic. The common examples of these materials
are: Carbon graphite, Chromites (Cr2O3),Alumina. Out of these, graphite is the least reactive and is
extensively used in metallurgical furnaces where the process of oxidation can be controlled.

Classification Based on Physical Form

(I) Shaped Refractories: Shaped refractories are those which have fixed shaped when delivered to the
user. These are what we call bricks. Brick shapes maybe divided into two: standard shapes and special
shapes. Standards shapes have dimension that are conformed to by most refractory manufacturers and are
generally applicable to kilns and furnaces of the same type. Special shapes are specifically made for
particular kilns and furnaces. This may not be applicable to another furnaces or kiln of the same type.
Shaped refractories are almost always machine pressed, thus, high uniformity in properties are expected.
Special shapes are most often hand-molded and are expected to exhibit slight variations in properties.

(II) Unshaped Refractories: Unshaped refractories are without definite form and are only given shape
upon application. It forms joint less lining and are better known as monolithic refractories. These are
categorized as Plastic refractories, ramming mixes, gunning mixes.

TYPES OF REFRACTORIES

Refractories are classified as dense or insulating types. The most high-temperature refractories, such as
firebricks, are high-density (>120 lb/ft3). They offer excellent resistance in challenging operating
environments, such as slags with different chemical compositions, fumes, dust, and gases. Insulating
refractories have lower densities (4 to 70 lb/ft3) and provide insulating properties, while offering
resistance to corrosion and chemical reactions with the operating environment.

Fire-clay brick Refractories

Fire-clay brick comprise about 75% of the production of refractories on a volume basis and are essentially
hydrated aluminum silicates with minor proportions of other minerals. Typical composition consists of:
(I) SiO2 <78% and (II) Al2O3 < 44%. They are extremely versatile; least costly of all refractory bricks
and are extensively used in the iron and steel industry, non ferrous metallurgy, glass industry, cement
industry etc.

Characteristically, fire-clay brick begin to soften far below their fusion temperature and under load actual
deformation takes place. The amount of deformation depends upon the load, and, once started, this
deformation is a slow but continuous process unless either the load or the temperature is reduced.

High Alumina Refractories

Alumina refractory which consists of aluminum oxide and traces of other materials is the most mature of
the engineering ceramics. Alumina is one of the most chemically stable oxides known, which offers
excellent hardness, strength and spalling resistance. It is insoluble in water and super heated steam, and in
most inorganic acids and alkalis. Alumina refractories carry the all purpose characteristics of fire-clay
brick into higher temperature ranges that makes it suitable for lining furnace operating up to 3350°F. It
has a high resistance in oxidizing and reducing atmosphere and is extensively used in heat processing
industries.

Mullite refractory:
Mullite brick is about 72% alumina with 28% silica. These have excellent volume stability and strength at
high temperatures.

Corundum refractories

The 99% alumina class of refractories is called corundum. These refractories comprise single phase,
polycrystalline, and alpha-alumina. High alumina bricks are most commonly used in cement, lime and
ceramic kilns, glass tanks, crucibles for melting a wide range of metals, hearth & shaft of blast furnaces
and in lead drossing furnaces.

Silica Brick

Silica Brick is a refractory material containing at least 93% SiO2. They have one major drawback too.
Their weakness lies in their susceptibility to spalling at temperatures below 1200°F.

Magnesite

Magnesite refractories are chemically basic materials, containing at least 85% magnesium oxide. These
are made from naturally occurring magnesite (MgCO3) and Silica (SiO2).

Monolithic Refractories

Monolithic refractory, the name generally given to all unshaped refractory products, are materials
installed as some form of suspension that ultimately harden to form a solid mass. Various means are
employed in the placement of monolithic refractories like ramming casting, spraying, sand slinging etc.

The main advantages of this are:

1) It eliminates joints which is an inherent weakness

2) Method of application is faster and skilled measures in large number are not required

3) Properties can be better than pressed bricks

4) Transportation and handling are simple

5) Offers considerable scope to reduce inventory and eliminate special shapes

6) Has better spalling resistance and volume stability