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CHAPTER # 1
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INTRODUCTION

1.1 CERAMICS
The word ceramic is derived from the Greek word (keramikos)
meaning of pottery or for pottery. So, ceramic can be defined as an inorganic
nonmetallic solid prepared by the action of heat and subsequent cooling. Ceramic
materials may be crystalline, partially crystalline or amorphous material (Bello, 2003).
Elements of metals and non-metals as shown in Table 1.1 can be combined to form an
enormous range of ceramic materials.

1.2 CERAMIC COMPOUNDS

In the old age human made ceramics uncovered by archeologist about 24000 BC.
These are found in the form of animal and human shapes, slabs and balls. First use of
ceramic was as pottery vessels is about 9000 BC. While second use was glazed and fired
to produce colored and smooth surfaces. About 1500 BC the glass was produced as a
separate item of ceramic and is closely related to the manufacturing of pottery vessels
(Richerson, 2000).
1.3 TYPES OF CERAMICS
Ceramic materials are grouped into different types according to their properties.
These properties of some ceramic compounds are discussed below. Classification scheme
of ceramics is given in Figure 1.1.
1.3.1 Alumina
Its chemical formula is Al2O3 and is called as Aluminum Oxide (Skinner et al.,
2013). It shows some distinct properties which are wear resistance, corrosion resistance
and strength (Kyocera, USA).
1.3.2 Silicon Nitride
Its chemical formula is Si3N4 (Mellor, 1947). Distinct properties are thermal
shock resistance, low density, high strength, low thermal expansion and good corrosion
resistance (Kyocera, USA).
1.3.3 Silicon Carbide
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Its chemical formula is SiC and is also known as Carborundum (Weimer, 1997).

It has high corrosion resistance and show high strength at about 1400 (Kyocera,

USA).

Table 1.1 Periodic table with ceramics compounds indicated by a combination of one or more
metallic elements (in green color) with one or more nonmetallic elements (in blue color) (Altinoz
et al., 2009).
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CERAMICS

Silicate Ceramics Non-Silicate Ceramics

Bricks, Tiles, Tera-cotta

Non-Oxide Ceramics
Oxides of Ceramics SiC, Si3N4, BN, B4C
Al2O3, MgO, Be2O3

Family of Oxides
3CaO.Al2O3

CaO.Al2O3 12CaO.7Al2O3

Aluminate Family

CaO.6Al2O3 CaO.2Al2O3
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Figure 1.1 Classification of ceramics.

1.3.4 Zirconia
Chemical formula of Zirconia is ZrO 2 (Nielsen et al., 2005). It has high strength
and toughness at room temperature and fine grains give smooth surface and Sharpe edges
(Kyocera, USA).
1.3.5 Calcium Oxide
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It is also known as quicklime and its chemical formula is CaO. It survives

processing without reacting in building products such as cement is known as free lime
(Miller, 2007).

1.4 CALCIUM ALUMINATE CEMENTS

It consists of hydraulic calcium aluminate (Hewlett, 2006). Its formulation from
limestone and low silica bauxite is patented in France in 1908 (Taylor, 1990).

1.5 PROCESS OF PREPARATION

Calcium Aluminate cement can be prepared by mixing the limestone (CaO) and
bauxite (Al2O3) in liquid phase. The mixture is cooled to produce final product and it is
settled down. To melt the lump of raw materials a special type of kiln may be used called
Reverberatory furnace in which lump is of raw material goes upward while hot gasses
pass downward (Taylor, 1990).

1.6 CHARACTERISTICS
Calcium Aluminate cement has a lot of characteristics in which some are given
below,
Rapid strength development at low temperature.
High chemical resistance.
Strength is maintained at high temperature.
Controlled expansion (Washingtonr, 1970).

1.7 CALCIUM ALUMINATE SYSTEM

There are five stable phases in CaO-Al2O3 family. These are given below.
3CaO.Al2O3 (C3A)
12CaO.7Al2O3 (C12A7)
CaO.Al2O3 (CA)
CaO.2Al2O3 (CA2)
CaO.6Al2O3 (CA6) (Medvedeva et al., 2007).
1.7.1 3CaO.Al2O3 (C3A)
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It has cubic crystalline structure. It has smallest valance band width (VBW) 3.5

eV. It has lowest band gape E g 3.86 eV. It is also seem that non uniform distribution

of carrier donors like as oxygen defects or aliovalent substitutional dopants occur by

doping of this structurally anisotropic material (Medvedeva et al., 2007).
1.7.2 CaO.Al2O3 (CA)
It has monoclinic crystalline structure. Anisotropic value for (CA) is large enough
(Medvedeva et al., 2007).
1.7.3 CaO.2Al2O3 (CA2)
It has monoclinic crystalline structure. Anisotropic factor for (CA2) is 10.71. So
the value of hole effective mass is small. It is seem that non uniform distribution of
carrier donors like as oxygen defects or aliovalent substitutional dopants occur by doping
of this structurally anisotropic material (Medvedeva et al., 2007).
1.7.4 CaO.6Al2O3 (CA6)
It has highest melting point 2156 among five lime alumina compounds

comparable to pure alumina 2327 . It also has the largest valance band width

(VBW) 7.8 eV. It has hexagonal type crystal structure and has higher crystal symmetry
and provides larger overlap between the orbitals of neighboring atoms. It has largest

band gape E g 5.38 eV. Anisotropic value for (CA6) is large enough while the value of

hole effective mass is small. It is also seem that non uniform distribution of carrier
donors like as oxygen defects or aliovalent substitutional dopants occur by doping of this
structurally anisotropic material (Medvedeva et al., 2007).
1.7.5 12CaO.7Al2O3 (C12A7)
It has cubic crystalline structure. It has lowest melting point 1722 among

five lime alumina compounds. This material show opto-electronic property. Its
conductivity is about 1700 S/cm due to the presence of oxygen ions in cages of diameter

5.6 . Introduction of other ions like H , OH , Cl and F or reduction

leads to semiconducting to metallic behavior and it changes with the concentration of

ions (Washingtonr, 1970). Figure 1.2 is the representative of the popular phase diagram
of calcium aluminate system showing all the five stable phases.
8
CaO.6Al2O3
or
CA6 9

CaO.Al2O3
or
CA

Figure 1.1 Phase diagram of calcium aluminates before hydration present in the
anhydrous calcium aluminate cement.
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1.8 12CaO.7Al2O3 (C12A7) AS AN ELECTRIDE

It is a wide band insulator but there are two methods to introduce conduction
property in it. First is introducing electrons at oxygen vacant places and the second is
introducing electron hopping along framework lattice sites. It is suggested that in both
conducting and insulating C12A7 consist of a narrow conduction band between the
valance and conduction band. Due to various properties it is used as structural material,
used in electronics and as a catalyst and also investigated as a candidate material for
organic light material diode, resistive random access memory and as a substrate for nano
circuit.
4+

The unit cell of C12A7 consist of two components and Ca24 Al28 O 64 has

2
a three dimensional lattice framework containing 12 cages and two O ions

containing extra framework species occupying some cages. They are more loosely bound
than framework ones, so they are act as free ions. Different monovalent anions can be

replaced by these species but H and O ions gives novel properties to the

material such as oxidation power and persistent light induced electronic conduction
respectively. It was also reported that by replacing the free oxygen ions with electrons
the material will converted into n- type material using chemical reaction with Ca and Ti
metals.
When the concentration of free oxygen ions (replaced by electrons at room

temperature) is increased to 2 1021 cm3 then the conductivity changes from 10 -10

Scm-1 to1.5 103 Scm-1 and the critical concentration for metal-insulator transfer is about
1x1021 cm-3. As the temperature of C12A7.e- drops the resistivity of the material also
drops and it will show superconducting property at T c 0.14-0.4 K depending upon
concentration of free electron anions (McLeod et al., 2012).

1.9 ELECTRIDE FORMATION

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A free or ionized electron introduced or trapped into a polar solvent by

reorientation on of the polar molecules it is firstly described by Sir Humphery Davy in
1808. Karus in 1914 described the negative electrons surrounded with envelop of solvent
molecules. After two years Gibson and Argo gives these electrons the name of solvated
electrons and is described as the simplest an ion in solution. From a chemical stand point
electron doped mayenite considered as a best electride. Kim et al wanted to introduce
excess electrons and then stabilized them as solvated electrons in high temperature. Kim
et al reported partially replacement of oxygen ions with negative electrons through high

Figure 1.2 Conduction setting in. Modals of solvated electrons in (A) Alkali metal
Ammonia Solution (B) C12A7.e- melt (C) C12A7.e- glass (Edwards, 2011).
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temperature chemical reduction with Titanium. These introduced electrons are trapped at

+
oxygen ion vacancy in the melt with the cage structure is so called F like center.

The transparent and insulator oxide is transferred into a highly colored and
electron doped conducting liquid. These solvated electrons survive and indeed thrive at
high temperature up to 1873 K. Solvated electrons in the cages of mayenite results
partially filled conduction band. As the concentration of solvated electrons increases
above to a critical concentration turning liquid cement into a liquid metal.
The rapid quenching of the high temperature melt leads to C12A7.e- glassy
materials but the high majority exist as a diamagnetic spin paired state. Carefully study
show that glass transition temperature for highly conducting C12A7.e - electride melt is
160 K lower than that for the parent C12A7 glass. Thats why; the network structure of
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the electride glass is fundamentally different from that of the parent cement glass (Kim et
al., 2011).

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