MMMD-103

Q.2

Laws of Crystallography
Crystallography is based on three fundamental laws.
(i) Law of constancy of interfacial angles: This law states that angle
between adjacent corresponding faces is inter facial angles of the crystal of a
particular substance is always constant inspite of different shapes and sizes
and mode of growth of crystal. The size and shape of crystal depend upon
the conditions of crystallisation. This law is also known as Steno's Law.

(ii) Law of rational indices: This law states that the ratio of intercepts of
different faces of a crystal with the three axes are constant and can be
expressed by rational numbers that the intercepts of any face of a crystal
along the crystallographic axes are either equal to unit intercepts (i.e.,
intercepts made by unit cell) a, b, c or some simple whole number multiples
of them e.g., na, n' b, n''c, where n, n' and n'' are simple whole numbers.
The whole numbers n, n' and n'' are called Weiss indices. This law was given
by Hauy.
(iii) Law of constancy of symmetry: According to this law, all crystals of a
substance have the same elements of symmetry is plane of symmetry, axis
of symmetry and centre of symmetry.

Q.4

Imperfections of crystal structure

There are three conventional types of crystal imperfections:

 Point defects

 Line defects

 Planar defects
Point defects
The simplest point defects are as follows:

 Vacancy – missing atom at a certain crystal lattice position;

 Interstitial impurity atom – extra impurity atom in an interstitial position;

 Self-interstitial atom – extra atom in an interstitial position;

 Substitution impurity atom – impurity atom, substituting an atom in crystal lattice;

 Frenkel defect – extra self-interstitial atom, responsible for the vacancy nearby.

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Line defects
Linear crystal defects are edge and screw dislocations.
Edge dislocation is an extra half plane of atoms “inserted” into the crystal lattice. Due to the edge
dislocations metals possess high plasticity characteristics: ductility and malleability.

 Screw dislocation forms when one part of crystal lattice is shifted (through shear) relative to the

other crystal part. It is called screw as atomic planes form a spiral surface around the dislocation

line.
For quantitative characterization of a difference between a crystal distorted by a dislocation and the
perfect crystal the Burgers vector is used.

The dislocation density is a total length of dislocations in a unit crystal volume. The dislocation density
of annealed metals is about 1010 - 1012 m−². After work hardening the dislocation density increases
up to 1015 - 1016 m-². Further increase of dislocation density causes crackes formation and fracture.

Planar defects
Planar defect is an imperfection in form of a plane between uniform parts of the material. The most important
planar defect is a grain boundary. Formation of a boundary between two grains may be imagined as a result of
rotation of crystal lattice of one of them about a specific axis. Depending on the rotation axis direction, two ideal
types of a grain boundary are possible:

 Tilt boundary – rotation axis is parallel to the boundary plane;

 Twist boundary - rotation axis is perpendicular to the boundary plane:

 An actual boundary is a “mixture” of these two ideal types.

Grain boundaries are called large-angle boundaries if misorientation of two neighboring grains exceeds 10º-15º.
Grain boundaries are called small-angle boundaries if misorientation of two neighboring grains is 5º or less.
Grains, divided by small-angle boundaries are also called subgrains.
Grain boundaries accumulate crystal lattice defects (vacancies, dislocations) and other imperfections, therefore
they effect on the metallurgical processes, occurring in alloys and their properties.

Since the mechanism of metal deformation is a motion of crystal dislocations through the lattice, grain boundaries,
enriched with dislocations, play an important role in the deformation process.
Diffusion along grain boundaries is much faster, than throughout the grains.
Segregation of impurities in form of precipitating phases in the boundary regions causes a form of corrosion,
associated with chemical attack of grain boundaries. This corrosion is called Intergranular corrosion.

Q.5
Interstitial Solid Solutions
Interstitial Solid Solutions :- shows that solute atoms in interstitial alloys must be small in size. -
Extensive interstitial solid solutions occur only if the solute atom has an apparent diameter
smaller than 0.59 that of the solvent. - The 4 most important interstitial atoms are carbon,
nitrogen, oxygen, and hydrogen, all of which are small in size. - Small interstitial solute atoms
dissolve much more readily in transition metals than in other metals. The ability of transition
elements to dissolve interstitial atoms is believed to be due to their unusual electronic structure.
All transition elements possess an incomplete electronic shell inside of the outer, or valence,
electron shell. The nontransition metals, on the other hand, have filled shells below the valence
shell. The extent to which interstitial atoms can dissolve in the transition metals depends on the
metal in question, but it is usually small.
Interstitial atoms can diffuse easily through the lattice of the solvent. Diffusion occurs not by a
vacancy mechanism, but by the solute atoms jumping from one interstitial position to another.

Substitutional solid solutions and the Hume-Rothery rules -

Humer-Rothery pointed out that an extensive solid solubility of one metal in another only occurs
if the diameters of the metals differ by less than 15%. This criterion for solubility is known as the
size factor and is directly related to the strains produced in the lattice of the solvent by the solute
atoms. - One of the most important requirements is the relative positions in the electromotive
series. When metals lie close to each other in the electromotive series, they tend to act as if they
were chemically the same, which leads to metallic bonding instead of ionic. - Two other factors
are of importance, especially when one considers a completely soluble system. Even if the size
factor and electromotive series positions are favorable, such a system is only possible when both
components (pure metals) have the same valence, and crystallize in the same lattice form.

(ii)
Diifferent Between Point Defects and Line Defect

The key difference between point defect and line defect is that the point defects occur only at or around a
certain point of the crystal lattice whereas the line defects occur in a plane of atoms in the middle of the crystal
lattice.

Crystallographic defects are the imperfections of the repeating pattern of a crystal lattice. These defects
interrupt the regular pattern of the lattice. There are several types of crystallographic defects such as point
defects, line defects, planar defects and bulk defects. It is easy to visualise a point defect, but the visualization of
a line defect is difficult.

Point defects are irregularities that occur at or around a single point of the crystal lattice. Typically, this type of
defect forms either due to the presence of extra atoms or due to the loss of atoms from the lattice. Therefore,
these defects are considerably small. However, sometimes there are some larger defects as well. We call them
dislocation loops.
 Figure 01: Different Point Defects

Several forms of point defects can occur in a crystal lattice.

 Vacancy defects
 Interstitial defects
 Frenkel defects
 Substitutional defects
 Schottky defect

Line Defect

Line defects are a form of crystallographic defects in which the defects occur in a plane of atoms in the middle
of the crystal lattice. Therefore, these are linear defects. There the atoms of the lattice are misaligned. The two
major forms of these defects are;

 Edge dislocation
 Screw dislocation

Sometimes we can see a combined effect of both these defects. We call it a mixed dislocation. Edge dislocations
occur due to the loss of a plane of atoms in the middle of the crystal. In these dislocations, the adjacent planes
of atoms become not straight; bend around the missing plane to make the crystal structure well-ordered on
either side.
 Figure 02: Edge Dislocation

A screw dislocation is difficult to envision. There, the planes of atoms in the crystal trace a helical path around
the dislocation line.
D

Difference Between Schottky Defect and Frenkel Defect

Schottky defect occurs when oppositely charged atoms (cation and anion) leave their corresponding lattice sites and
create a pair of Vacancy Defects. Since both cation and anion leave the lattice sites at the same time, so overall electrical
neutrality of the crystal is maintained; however, density reduces because of the vacancies. Schottky defects occur in ionic
crystals where the size of anion is almost same with the size of the cation. Read more about Schottky defect.

Frenkel Defect is one type of point defect where an atom (better to say ion, especially cation) leaves its original lattice site
and occupies an interstitial position on the same crystal. Usually, this type of defect is observed in ionic solids, where size
of anion is substantially larger than the size of cation. Read more about Frenkel defect.
Although both Schottky defect and Frenkel defect are point defects and occur only in ionic materials, there exists a big
margin between them. Differences between Schottky defect and Frenkel defect are portrayed in the following table.

Schottky Defect Frenkel Defect

Schottky defect occurs in those ionic Frenkel defect usually occurs in those
crystals where difference in size between ionic crystals where size of anion is quite
cation and anion is small. large as compared to that of the cation.

In Schottky defect, both cation and anion In Frenkel defect, only the smaller ion
leave the solid crystal. (cation) leaves its original lattice site;
whereas, the anion remains in original
lattice sites.

The atoms permanently leave the crystal. Here, atoms leave the original lattice site
and occupy interstitial position. So atoms
reside within the solid crystal.

One Schottky defect leads to the One Frenkel defect creates one vacancy
formation of two vacancies. and one self-interstitial defect.

Two atoms reduce from the crystal for The number of atoms present in the
each Schottky defect. crystal before and after Frenkel defect
remains same.

Due to vacancy formation, Schottky Density of the solid crystal before and
defect reduces density of the solid. after Frenkel defect remains same as no
atom leaves the solid.

Common materials where Schottky Common materials where Frenkel defect

defect can be found are: can be found are:

 Sodium Chloride (NaCl)  Zinc Sulfide (ZnS)

 Potassium Chloride (KCl)  Silver Chloride (AgCl)
 Potassium Bromide (KBr)  Silver Bromide (AgBr)
 Silver Bromide (AgBr)
 Cerium Dioxide (CeO2)
 Thorium Dioxide (ThO2)