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IMPERFECTIONS & APPLICATION OF CERAMIC

Assumed: ceramic perfect order exists throughout crystalline materials on an atomic scale, however, such an idealized solid does not exist

All contain large numbers of various defects or imperfections

• Assumed: ceramic  perfect order exists throughout crystalline materials on an atomic scale, however, such

Many of the properties of materials are sensitive to deviations from crystalline perfection; the influence is not always adverse

crystalline defect a lattice irregularity having one or more of its dimensions on the order of an atomic diameter

Classification : point defects(those associated with one or two atomic positions), linear (or one-dimensional) defects, as well as interfacial defects and impurities in solids

• Assumed: ceramic  perfect order exists throughout crystalline materials on an atomic scale, however, such

Point defect

Point defects are localized disruptions in an otherwise perfect atomic or ionic arrangements in a crystal structure.

may be introduced by movement of the atoms or ions when they gain energy by heating, during processing of the material or by introduction of other atoms.

The distinction between an impurity and a dopant :

Impurities element/compounds that are present from raw materials or processing (e.g. Si single crystals grown in quartz crucibles contain oxygen as an impurity)

Dopants elements/compounds that are deliberately added, in known concentrations, at specific locations in the microstructure, with an intended beneficial effect on properties or processing (e.g. P & B are added to Si crystals to improve or alter the electrical properties of pure silicon

the effect of impurities is deleterious, whereas the e¤ect of dopants on the properties of materials is useful

Type: vacancies, interstitial & substitutional

vacancies

The simplest of the point defects is a vacancy, or vacant lattice site

A vacancy is produced when an atom or an ion is missing from its normal site in the crystal structure

All crystalline solids contain vacancies and, in fact, it is not possible to create such a material that is free of these defects.

vacancies • • • The simplest of the point defects is a vacancy, or vacant lattice

Interstitial defect

An (self) interstitial defect is formed when an extra atom or ion is inserted into the crystal structure at a normally unoccupied position

Interstitial atoms or ions, although much smaller than the atoms or ions located at the lattice points, are still larger than the interstitial sites that they occupy.

Consequently, the surrounding crystal region is compressed and distorted.

Interstitial atoms such as hydrogen are often present as impurities; whereas carbon atoms are intentionally added to iron to produce steel.

Unlike vacancies, once introduced, the number of interstitial atoms or ions in the structure remains nearly constant, even when the temperature is changed.

Atomic defects involving host atoms for each ion vacancies & interstitial are possible since ceramic materials contain ions of at least two kinds (+ & -), defects for each ion type may occur NaCl : Na & Cl each interstitials & vacancies highly improbable that there would be appreciable concentrations of anion (Cl) interstitials. The anion is relatively large, and to fit into a small interstitial position, substantial strains on the surrounding ions must be introduced.

 Atomic defects involving host atoms  for each ion  vacancies & interstitial are possible

Because the atoms exist as charged ions, when defect structures are considered, conditions of electroneutrality must be maintained.

Electroneutrality the state when there are equal numbers of positive and negative charges from the ions.

consequently, defects in ceramics do not occur alone

in AX materials, defect is a cation vacancy –anion vacancy pair known as a Schottky defect

created by removing one cation and one anion from the interior of the crystal and then placing them both at an external surface.

Since both cations and anions have the same charge, and since for every anion vacancy there exists a cation vacancy, the charge neutrality of the crystal is maintained

• Defect of a cation–vacancy and a cation–interstitial pair  a Frenkel defect • formed by

Defect of a cation–vacancy and a cation–interstitial pair a Frenkel defect

formed by a cation leaving its normal position vacant and moving into an interstitial site.

There is no change in charge because the cation maintains the same positive charge as an interstitial.

The ratio of cations to anions is not altered by the formation of either a Frenkel or a Schottky defect

If no other defects are present, the material is said to be stoichiometric.

Stoichiometry as a state for ionic compounds wherein there is the exact ratio of cations to anions predicted by the chemical formula.

For example, NaCl is stoichiometric if the ratio of Na+ ions to Cl− ions is exactly 1:1.

A ceramic compound is nonstoichiometric if there is any deviation from this exact ratio

Nonstoichiometry may occur for some ceramic materials in which two valence (or ionic) states exist for one of the ion types.

Iron oxide (FeO) can be present in both Fe2+ and Fe3+ states; depends on temperature and the ambient oxygen pressure.

The formation of an Fe3+ ion disrupts the electroneutrality of the crystal by introducing an excess +1 charge, which must be offset by some type of defect.

This may be accomplished by the formation of one Fe2+ vacancy (or the removal of two positive charges) for every two Fe3+ ions that are formed

The crystal is no longer stoichiometric because there is one more O ion than Fe ion; however, the crystal remains electrically neutral.

 Nonstoichiometry may occur for some ceramic materials in which two valence (or ionic) states exist

Substitutional Defects

introduced when one atom or ion is replaced by a different

type of atom or ion which occupy the normal lattice sites. may either be larger than the normal atoms or ions, in which

case the surrounding interatomic spacings are reduced, or smaller causing the surrounding atoms to have larger interatomic spacings. alter the interatomic distances in the surrounding crystal.

introduced either as an impurity or as a deliberate addition

once introduced, the defects is relatively temp. independent

Examples dopants such a (P) or boron (B) into Si.

Whether atoms or ions go into interstitial or substitutional sites

depends upon the size and valence of guest atoms or ions compared to the size and valence of host ions. The size of the available sites also plays a role in this.

Impurities in ceramics

impurity or foreign atoms will always be present, and

some will exist as crystalline point defects. Type: solid solutions of both substitutional and interstitial

For an interstitial, the ionic radius of the impurity must be relatively small in comparison to the anion.

A substitutional impurity will substitute for the host ion (c/a) to which it is most similar in an electrical sense:

if the impurity atom normally forms a cation in a ceramic material, it most probably will substitute for a host cation.

For example, in NaCl, impurity Ca2+ and O2− ions would most likely substitute for Na+ and Cl− ions, respectively.

To achieve any appreciable solid solubility of substituting impurity atoms, the ionic size and charge must be very nearly the same as those of one of the host ions

For an impurity ion having a charge different from the host ion for which it substitutes, the crystal must compensate for this difference in charge so that electroneutrality is maintained with the solid.

One way this is accomplished is by the formation vacancies or interstitials of both ion types

 To achieve any appreciable solid solubility of substituting impurity atoms, the ionic size and charge

APPLICATIONS

APPLICATIONS
Glasses • The glasses are a familiar group of ceramics; e.g. containers, lenses, window and fiberglass

Glasses

The glasses are a familiar group of ceramics; e.g. containers, lenses, window and fiberglass

Non crystalline silicates with other oxide (e.g. CaO, Na2O, K2O & Al2O3) influence the glass properties.

Glasses • The glasses are a familiar group of ceramics; e.g. containers, lenses, window and fiberglass

A typical soda–lime glass consists of approximately 70 wt % SiO3, the balance being mainly NaO (soda) and CaO (lime)

Optical transparency & relative ease to fabricated

Glasses • The glasses are a familiar group of ceramics; e.g. containers, lenses, window and fiberglass

Glass Ceramics

Glass can be transformed to crystalline by high T heat treatment crystallisation

Product: glass-ceramics (fine-grained polycrystalline)

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Process involves nucleation & growth stage (30-90 % crystallinity)

A nucleation agent (frequently TiO2) is addded to promote crystallization

Because there is usually no pressing and sintering, glass-ceramics have, unlike sintered ceramics, no pores

share many properties with both glasses and ceramics

Commonly used as ovenware, tableware, oven window etc

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Clay Products

Very popular products (abundant, inexpensive, easy to be formed)

Contain nonplastic ingredient which affect the change that take place during the drying and firing processes the characteristics of the finished piece

two broad classifications: the structural clay products and the whitewares.

Structural clay products include bricks, tiles, and sewer pipes—applications in which structural integrity is important.

whiteware ceramics become white after the high- temperature firing group are porcelain, pottery, tableware, china, and plumbing fixtures, sanitary ware

Refractories

Properties: the capacity to withstand high temperatures

without melting or decomposing, endure at high T, capacity to remain inert in severe enviroment, provide thermal insulation Common product bricks

Application: metal refining, glass manufacturing,

metallurgical heat treatment, power generation the performance of a refractory ceramic, to a large degree,

depends on composition. there are several classifications:

Refractories • Properties: the capacity to withstand high temperatures • without melting or decomposing, endure at

For many commercial materials, the raw ingredients consist of both large and fine particles, which may have different compositions.

Upon firing, the fine particles normally are involved in the formation of a bonding phase, which is responsible for the increased strength of the brick

The service temperature is normally below that at which the

refractory piece was fired. Porosity must be controlled to produce a suitable refractory brick.

Strength, load-bearing capacity increase with porosity reduction.

At the same time, resistance to thermal shock are diminished. the optimum porosity depends on the conditions of service

• For many commercial materials, the raw ingredients consist of both large and fine particles, which
• For many commercial materials, the raw ingredients consist of both large and fine particles, which

Abrasives

used to wear, grind, or cut away other material, which necessarily is softer.

Properties: hardness/wear resistance, tough, not easily fractured

Diamond, silicon carbide, tungsten carbide, aluminium oxide, silica sand

used in several forms: 1) bonded to grinding wheels, 2) as coated abrasives, and 3) as loose grains.

Abrasives • used to wear, grind, or cut away other material, which necessarily is softer. •
Abrasives • used to wear, grind, or cut away other material, which necessarily is softer. •
Abrasives • used to wear, grind, or cut away other material, which necessarily is softer. •

In the first case, the abrasive particles are bonded to a wheel by means of a glassy ceramic or an organic resin

Coated abrasives are those in which an abrasive powder is coated on some type of paper or cloth material; sandpaper is probably the most familiar example. Wood, metals, ceramics, and plastics are all frequently ground and polished using this form of abrasive.

Grinding, lapping, and polishing wheels often employ loose abrasive grains that are delivered in some type of oil- or water-based vehicle.

Cements

cement, plaster cement of paris, and lime

Characteristic: form paste when mixed with water subsequently set & hardens

act as a bonding phase that chemically binds particulate aggregates into a single cohesive structure at Tr

the role of the cement is similar to that of the glassy bonding phase that forms when clay products and some refractory bricks are fired

One important difference is that the

cementitious bond develops at room temperature

The properties of portland cement, including setting time and final strength, to a large degree depend on its composition.

Cements • cement, plaster cement of paris, and lime • Characteristic: form paste when mixed with
Cements • cement, plaster cement of paris, and lime • Characteristic: form paste when mixed with
Cements • cement, plaster cement of paris, and lime • Characteristic: form paste when mixed with