2.

0 CRYSTALLINE STRUCTURE OF MATERIALS

Solids in which atoms are arranged in a three-dimensional pattern that repeats itself regularly
are called Crystals, whereas those in which the internal structures are not based upon regular
repetition pattern are called Amorphous.

The atomic arrangement of atoms in a crystal will give the crystal its characteristic
properties; in particular that of growing in the form of polyhedra.

Defn:
A polyhedron – a solid figure bounded by plane faces
The faces of a crystal are defined by surface layers of atoms and lie at angles to one another,
exhibiting definite characteristic values. The characteristic lattice parameters or inter-atomic
distances of elements is the basis of identifying them by X-ray diffraction analysis.

Crystal Patterns.

Crystallographic structures may exhibit either point symmetry or lattice symmetry.

Crystals can be classified into six crystal systems; i.e Triclinic, Monoclinic, Orthorhombic,
Tetragonal, Hexagonal and Cubic.

Triclinic

No symmetry or centre of symmetry

No restriction on the axes
Inter-axial Angles α = β = γ
a, b, c are unequal

Monoclinic

A single mirror plane or a single 2 fold axis

a and c must lie in the plane perpendicular to the
mirror plane or parallel to the
second fold axis.
a and c must lie in a plane perpendicular to b but they
can make an arbitrary angle
β with each other.

Orthorhombic

Has either a second 2-fold axis or a second mirror plane

perpendicular to the first.

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Tetragonal
a2
Has a 4-fold axis
a1 = b = a2 = a
c

b
a1

Hexagonal
Has 3 or six fold axis
a = b = a1 = a2
θ = 120o

Cubic

Has three equal axes

a3 a = a1 = a2 = a3
a2
a1

Other unit cells which satisfy the point symmetry requirements include:-

i) Body-centered
ii) Face centered
iii) Primitive
iv) End Centered
v) Rhombohedral

i) Body Centered Cubic (BCC)

Has a lattice point at its centre

Examples: Vanadium, Chromium, α-Iron,
Molybdenum, Tungsten.

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ii) Face Centered (FCC)
Has lattice points at the centre of all faces
Examples:- γ-Iron, Aluminium, Gold, Copper,
Lead, Nickel

iii) Primitive Cell

A cell is primitive if the lattice points appear at
the corners only.

iv) Rhombohedral

A modification of the hexagonal system where

the cell has 3 equal axes “a” making three equal
angles “α” with one another.
Can be derived from the hexagonal cell.

Number of Atoms in a Unit Cell & Atomic radius

Assumptions
Atoms are spherical in nature
Each is always in contact with its neighbour

Examples:-

i) Simple Cube

Let a = Lattice Constant

r = Radius of atom

a = 2r
r = a/2
Number of atoms = ½ (1/4) x 8 = 1

Therefore, Number of atoms per unit cell = 1

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ii) FCC

The system has 8 corner atoms plus 1 atom at the centre of each face. Corner atoms don’t
touch but each corner atom touches the central atom on each face

BD2 = AD2 + AB2

But BD = 4r and AD = AB = a

⇒ (4r)2 = 2a2 ⇒ 4r = √2 . a

r = √2 . a = a
4 2√2

Number of atoms per Unit cell = (1/2) x (1/4) x 8 = 4

(iii) Body Centered Cubic

BD2 = BC2 + CD2

= AB2 + AC2 + CD2

But BD = r + 2r + r = 4r
And AB = AC = CD = a

(4r)2 = a2 + a2 + a2

4r = √3 . a
r = (√3)/4 . a

Number of atoms per unit cell = (1/2) x (1/4) x 8 + 1

= 2
Co-ordination Number

This is the number of nearest atoms directly surrounding a given atom

Crystal Structure Co-ordination Number(CN)

Simple Cube 6
Face Centered Cube 12
Body Centered Cube 8

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Packing Fraction or Packing Density.

This is the ratio of the volume of atoms in a unit cell to the total volume of the cell

volume of atoms
apf =
volume of unit cell

(i) Face Centered Cube

apf = 4 x 4/3πr3
a3
Where r = atomic radius
a = Lattice Constant

Substituting a for r

apf = 4 x 4/3π(a/2√2)3
a3

(√2)/6 x π

= 0.74

(ii) Simple Cube

Has one atom per unit cell

apf = 1 x 4/3πr3
a3

π/6 = 0.53

(iii) BCC Structure

Contains 2 atoms per unit cell

apf = 2 x 4/3πr3 = 0.68

a3

iii) Hexagonal close packed (hcp).

The CN is 12 (consider atom at centre of hexagon - 6 neighbours in the same plane, 3 below
and 3 above). Two lattice constants, (a) and (c) are required to define the dimensions of the
unit cell.
There are 6 atoms/unit cell [3 (cell centre) + 1/2 x 2 (hexagon centre) + 1/6 x 12 (hexagon
corner) = 6].

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 F

O
B D C

The apf can be calculated as:

2 2
AD = 4R - R = R 3

Area of hex. base = 6 x Area ABC = 6 x 1/2 x Rx31/2 x 2R = 6 x 31/2 x R2

2 2
OA = AD = R
3 3

(since atom F lies at the centroid of ABC)

2 2 4R 2
c = 2 OF = 2 4R - R =
3

Vol. of unit cell = area of base x c

3
6 x 4/3π R
apf = 2
= 0.74
6 3 x R x 4R 2/3

Among the common metals with hcp structure are Mg, Zn, Co, Be.
The crystal structures may be visualized as alternate layers of planes of spheres. In the case
of bcc and sc, the planes have a square arrangement. To get the sc structure, the next plane is
placed such that its atoms are on top of the atoms of the lower plane. With the second plane
placed such that its atoms are at the centroid of four atoms of the lower plane, we get a bcc
structure.

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In the case of fcc and hcp structures, the spheres have a hexagonal arrangement and the
planes are close packed (see next section). The next plane of atoms is placed such that its
atoms are at the centroid of 3 atoms of the lower plane. Then in the case of hcp, the third
layer is placed such that its atoms are directly above those of the 1st layer (the so called
ABABAB stacking). Each hexagon has 6 "centroids" into which atoms could fit but only 3
can be simultaneously filled. In the case of fcc, the 3rd plane has its atoms corresponding to
the 3 "centroids" which were not filled by the second layer -- hence it is only the 4th plane
whose atoms corresponds to those of the 1st plane (called ABCABC stacking).

Crystal Structures of Selected Compounds/Elements

NaCl CsCl

ZnS
diamond

Polymorphism
Some elements exhibit different crystal structures with each structure existing over well
defined physical conditions. The phenomenon is called polymorphism and each structure is
termed a polymorph. (When polymorphism occurs in metals, the word allotropy is also
used.) Examples are: carbon which may exist as diamond (tetragonal crystal structure) or
graphite (hexagonal structure) and iron which has the temperature based polymorphs α-Fe
(bcc), γ-Fe (fcc) and δ-Fe (bcc).

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Crystal Planes and Directions
From the previous sections, we observe that the distance between successive atoms differs in
different directions and that some planes are close packed while others are not. The strength
of the bond between atoms depends on the distance between atoms and hence crystals are
anisotropic (i.e., have different properties in different directions). Polycrystalline materials
are however isotropic (or quasi-isotropic) if the arrangement of their crystals is random and
anisotropic if the crystals have a preferred orientation.

It is thus important to be able to identify crystal planes and directions and the most often used
system is the Miller index system. Here, after drawing the unit cell, an origin is chosen at
one corner of the uc and 3 perpendicular axes, x, y and z drawn from it. Then, for planes, the
intercepts of the plane on the axes u.a, v.b, and w.c (where a, b and c are the lattice constants)
are determined. The Miller indices (hkl), of the plane are then 1/u, 1/v, 1/w. For example the
plane shown in the last sketch of fig. 2.10 intercepts the x axis at 1/2a, the y-axis at 1 b and z-
axis at infinity. Hence, the Miller indices are (2 1 0) (the indices are reduced to the nearest
whole number). The indices for individual planes are given in ordinary brackets and with no
commas i.e. (h k l), and negative numbers are indicated with a bar over the numeral.

All parallel planes have the same index. Further, some planes, though not parallel, are
crystallographically equivalent. An example is the six faces of the cube in a cubic system:
(100), (100), (010), (001), (010), 001). This family of planes are represented in curly
brackets as {h k l} - in the above case {1 0 0}.
For ease of handling, planes in the hexagonal unit cell are given four indices, (h k i l),
corresponding to the 4 axes.
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Crystallographic directions are similarly indexed: the coordinates of any point through
which the direction passes are taken and reduced to the lowest integers. The direction is then
given in square brackets as [h k l]. For example, the indices of a direction passing through
(1/4, 1/2, 1) are [1 2 4]. Crystallographically equivalent directions are given in pointed
brackets: <h k l>.
The Miller index notation makes calculations involving planes and directions easy. From the
law of cross product in vector geometry, the line of intersection between two planes (h1 k1
l1) and (h2 k2 l2) is given by:

(h1k1l1) x (h2k2l2) = [h k l]

i.e. h = k1 l2 - l1 k2; k = l1 h2 - h1 l2 and l = h1 k2 - k1 h2

A plane will have the same indices as a direction normal to it and hence if [h k l] lies in plane
(h1 k1 l1) the dot product (h k l).(h k l) = 0 (since the plane normal and [h k l] are

perpendicular).[Dot product a.b = |a|*|b|cosθ]

The angle, θ , between two directions (h1 k1 l1) and (h2 k2 l2) can be found from the dot

product i.e.,
hh +k k +l l
1 2 1 2 1 2
Cos θ =
2 2 2 2 2 2
h +k +l h +k +l
1 1 1 2 2 2

The linear density of equivalent sites in a direction is a measure of how close atoms are to
each other in the given direction and is given by 1/bhkl, where bhkl = shortest distance
between equivalent sites. The direction with the highest linear density is termed the close
packed direction (usually the direction in which the atoms are in contact). It is also possible
to get the planar density of atoms in a plane (the proportion of the area occupied by atoms).

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X--Ray Diffraction
The crystal structures detailed above are determined by X--ray diffraction studies. The
wavelength of X--rays are the same order of magnitude as interatomic spacing in crystals -
hence X--rays are diffracted by alternative crystal planes. With reference to fig. 2.11,
constructive interference will occur only if the path difference between the rays reflected
from the first and second planes is a whole number of wavelengths. From the figure below,
path difference = PQ + QR

d P R

⇒ dSin θ + dSin θ = nλ
nλ = 2dSin θ
where d is the inter-planar spacing.
The above equation is called Bragg's law. d can then be related to the indices of the plane.
For cubic crystals:

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 a
d =
2 2 2
h +k +l
Several methods are used for X--ray diffraction in practice. In the powder pattern,
monochromatic X--rays are directed at the material (which is in powder form -- mixed with a
cement and made into a thin filament). The sample is placed at the centre of a circular
camera and the diffracted rays are captured on X--ray film. Several lines representing
various diffraction orders, are obtained.

3 a2 c2
For the hexagonal structure d hkl = +
4 h 2 + hk + k 2 l 2

Schematic example of a diffraction experiment using the powder method.

(a) diffraction cones from a powder specimen shown intercepting the film
(b) powder photograph showing diffraction lines for tungsten

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