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PHYSICS OF CRYSTALS
1. Crystallography.
2. X-Ray Diffraction.
3. Defects in Crystals.
4. Diffusion.
Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 97

CRYSTAL STRUCTURE
10.1 Introduction order. The crystalline structure, being orderly and
The matter, in general, can exist in three states periodic arrangement of atoms, is characterized by
namely solid, liquid and gaseous. The matter can sharp transition temperature (also called melting
be transformed from gaseous to liquid or liquid to point) to liquid. However an amorphous solid,
solid by decreasing the motion of atoms through when heated, softens over a range of temperature
cooling or any other process of retrieving energy before getting transformed to liquid. The
from the system. In a similar spirit, the transition crystalline state is the lowest energy state of a
from solid to liquid or liquid to gaseous or solid to solid.
gaseous state is possible by increasing the atomic
motion.
10.2 The Crystalline State
When liquid cools, two types of solids can be
A solid is said to be in the crystalline state, if a
formed. If the liquid is cooled slowly so that the
basic unit (which may be a single atom or a group
atoms get sufficient time to assume an orderly
of atoms or an ion) is repeated periodically
arrangement, then a crystal structure results. On
throughout the volume of solid. The idea of
the other hand if the temperature of liquid is
periodicity can be had from the figure 10.1, shown
lowered abruptly thereby arresting the motion of
below.
atoms before they reorganize themselves, then a
mixed-up structure called glass or amorphous solid
may result. The glass is different from liquids in the
fact the relative motion of atoms is ceased, a
property which can be best described by viscosity.
In a crystalline structure, the orderly arrangement
or the periodicity of atoms is repeated over large
distance (i.e. very large number of inter-atomic
separations) which is also referred to as long range
Figure 10.1: A crystalline solid with atoms
order. In contrast to this, regularity or orderly
arranged periodically.
arrangement, if any, may exist in amorphous solid
but it does not persist beyond few inter-atomic
The distance between two nearest neighbours
separations before it changes to another order of
along x-direction is a while that along y-direction is
arrangement. This is referred to a short range
b. The concept of exact periodicity is also

expressed by saying that a crystal possesses the the volume of the crystal. This is an inherent
translation symmetry, which means that if a crystal limitation of a crystalline solid.
is translated by a vector joining two atoms as (ii) Another source of imperfection arises due to
shown in figure 10.1, its surroundings remains the thermal vibration of atoms about their mean
exactly the same as it was before the translation positions (also referred to as lattice
operation. This periodicity, in crystalline solids, vibration) at any finite temperature. These
prevails over a very large distance and is also lattice vibrations distort the periodicity
referred to as long range order. characterizing the crystal structure
The crystals can be grown from a gas by continuously.
sublimation or from a liquid by crystallization. (iii) The third kind of imperfection arises due to
When a crystal grows from a vapor or liquid, its the impurity, which may be in traces but
continued growth depends upon the sufficient remains in the crystal even when grown in
supply of growth units (i.e. the atoms required to the best controlled conditions.
make up its structure). If the supply is Hence the perfect crystal can be thought of an
overabundant, then crystal may grow extremely approximation of very large crystal (whose ratio of
fast and in many directions at once thereby giving surface area to volume is very small) maintained at
a branchlike appearance. Such a crystal, referred very low temperature and having impurities in
to as poly-crystal, has many orderly arrangements trace amounts. However these imperfections can,
of atoms, having different orientations, which in certain cases, play a role in customizing the
interpenetrate into each other. In case the supply material properties for technological applications.
of growth units is insufficient then the crystal
starts dissolving back into its mother solution. 10.3 Basic Definitions
During the process of crystal growth, many errors The study of crystal structure requires
in periodicity occur. Strictly speaking one can not
acquaintance with certain terms which form the
grow a perfect crystal. The following can be
language of crystallography. These terms are
considered as limitations or imperfections in a
usually referred to for one- and two-dimensional
crystal:
cases for the simplicity of understanding but can
(i) The surface of a crystal itself forms an
be easily extended to the actual three dimensional
imperfection as the surface atoms cases.
experience altogether a different
10.3.1 Crystal Lattice
environment than those lying deep within
In crystallography, only the geometrical properties
of the crystal are of interest, rather than those

arising from particular atoms (or group of atoms or form one kind of lattice while A’, B’ and C’
molecule or ions) constituting the crystal. If each constitutes another kind of lattice. These two non-
atom in the crystal is replaced by a geometrical equivalent sets of points together constitute a
point located at its equilibrium position, then the non-Bravais lattice.
resulting pattern is called a lattice.
Mathematically the lattice is periodic arrangement 10.3.2 Basis Vectors
of geometrical points in a line (linear or 1- Consider the lattice shown in the figure 10.3
dimensional lattice) or plane (planar or surface or below. Let A be the origin of coordinates for the
2-dimensional lattice) or space (space or 3- lattice points. The position vector for any lattice
dimensional lattice). point, in the plane, can be written as:
There are two different kinds of lattice: r r r
Rn = n1a + n2 b (10.1)
Bravais lattice which has all lattice points
equivalent and hence these points are occupied by
atoms of same kind. In the figure 10.1, the lattice
points A, B and C are equivalent and form the
Bravais lattice.
Non-Bravais lattice may have two or more sets of
equivalent lattice points, which implies that such a
lattice can be considered to be resulting due to
inter-penetration of two or more Bravais lattices.
In the figure10.2, the lattice points A, A’; B, B’; and Figure 10.3: Bravais lattice demonstrating the
C, C’ form non-equivalent sets of points. Hence A, basis vectors.
B and C
r r r
The a and b are called basis vectors. The Rn is
called lattice translation vector which can

accomplish translation from one lattice point to
another with the appropriate choice of integers set
(n 1 , n 2 ). Hence a Bravais lattice can be considered
to be invariant under group of all translations
expressed by equation (10.1). The choice of basis
Figure 10.2: The crystal lattice demonstrating the
vectors for a lattice is not unique but is guided by
non-Bravais lattice.

the convenience. For a three dimensional lattice procedure is called Wigner-Seitz cell. The
r r r procedure is sequentially spelled out as follows:
a , b and c form the basis vectors and lattice
Taking one lattice point as centre, it is connected
translation vector is expressed as:
r r r r through line segments to all its nearest neighbors.
Rn = n1a + n2 b + n3c (10.2)
Each line segment is bisected by a perpendicular
plane. These perpendicular bisector planes will
10.3.3 Unit Cell
enclose a volume, which is referred to as Wigner-
In case of two dimensional lattices, the
Seitz cell. This cell is characterized by occupying
parallelogram subtended by basis vectors as its
minimum volume and also possessing one lattice
adjacent sides is called a unit cell. The unit cell is
point per unit cell. This procedure is illustrated
usually the smallest area whose translation by
diagrammatically in figure 10.4, shown below.
using equation (10.1) spans whole lattice once and
only once. The choice of the unit cell for one and
the same lattice is however not unique. However
all the unit cells representing same lattice must
obey the following characteristic features:
(i) They must have same area.
(ii) They should have one lattice point/unit cell.
The unit cell obeying the above mentioned
properties is called a primitive cell. However
Figure 10.4: The geometrical procedure to
certain choice of a unit cell can be such that (i)
construct Wigner Seitz cell.
area of unit cell is some multiple of that of
primitive cell and (ii) in addition to lattice points at
10.5 Symmetries In Crystals
its vertices has one or more lattice points at body
Crystals have a regular repetitive internal
or face centre. These are called non-primitive cell.
structure. The repetition of internal structure is
For a three dimensional lattice, the unit cell is a
best described by concept of symmetry. The study
parallelepiped in contrast to a parallelogram for
crystallography is concerned with exploring for
two dimensional case. Such a unit cell will be
different symmetries exhibited by crystals and
characterized by three basis vectors.
cataloging them. This catalogue is further used to
The geometrical procedure of obtaining a primitive
infer crystal structure and also predict properties
cell from a given lattice was devised by Wigner and
on its basis. A symmetry operation is defined as
Seitz. The primitive cell, so obtained from this
the action that leaves the system or object

unchanged. A symmetry element can be a point or symmetry is an essential requisite for a Bravais
line or plane through which the operation is lattice.
performed to leave the crystal structure
unchanged. The study of crystallography is based 10.5.2 Inversion Symmetry
upon the idea of translational, rotational and The Bravais lattices usually have an inversion
inversion or mirror symmetry. Various kinds of centre as there always exists a pair of lattice points
symmetries observed in crystals can be broadly satisfying the mathematical relation:
classified in two catagories which are discussed in r r
R( n1 , n2 , n3 ) = − R( −n1 ,−n2 ,−n3 ) (10.4)
this section.
As can be understood from the translation
Point group consists of symmetry operations in
symmetry of bravais lattices, inversion centre will
which at least one point remains fixed and
always exist. The existence of inversion centre in a
unchanged in space. The symmetry operations,
non-bravais lattice is not an essential requisite.
constituting point group, can be proper symmetry
if it doesn’t alter the handedness of the object
10.5.3 Rotational Symmetry
being operated otherwise it is referred to as
As seen above, it is clearly evident that the
improper symmetry it is changes the handedness
translational periodicity of lattice points is an
of the object.
essential requirement for bravais lattice. Similarly
Space group comprises of both translational and
there exist one or more axes about which if the
rotational symmetry operations of a crystal.
crystal is rotated, it remains invariant (i.e the
Each of the Bravais lattice is characterized with a
environment, the basis atom or group of atoms
set of symmetry properties, which help in
under rotation, observes before and after rotation
understanding the underlying periodicity in lattice.
are identical). In case the character of the basis
The various symmetries are discussed below:
does not change on rotation {i.e the right handed
(left handed) object gets repeated as right handed
10.5.1 Translation Periodicity
(left handed)}, then the basis forms a congruent
A lattice is said to possess translational symmetry
set. If rotation of a crystal, leads to repetition of
or periodicity if a translation represented by
r r congruent basis set, then it is called proper
r r
Rn = n1a + n2 b + n3c (10.3) rotation. However if rotation leads to change of
carries it from one lattice point in the crystal to handedness of the basis (from right handed to left
another lattice point such that environment handed character or vice versa), then it is referred
around two points is identical. The translational to as an improper rotation.

The axis of rotation is said to be n-fold if a rotation Accordingly two opposite rotations by an amount
2π ϕ about two axes are shown in the figure 10.5.
through an angle of keeps the unit cell
n Two new lattice points P and Q are produced
invariant. In bravais lattice 1-, 2- 3-, 4- and 6-fold which must be equidistant from the original
rotation axes are allowed as per their symmetry. lattice. The line joining P and Q must be parallel to
The symbolic representations of different linear lattice translation t and also some integral
permitted rotational symmetries is given below:
P Q
Figure 10.5: The diagram depicting the rotation of

lattice about a lattice position by an angle.
The 5 fold rotation and those higher than 6 folds
do not yield any symmetry. This is also multiple of t. If it is not, then line joining P and Q is
qualitatively justifiable from the fact that if not a translation of lattice and the linear array is
pentagonal unit cells or those with more than six not periodic. Hence we can write, in general that
sides are packed then they result in either PQ =mt which is related as:
overlapping or empty intermittent spaces. This mt = t + 2t cos ϕ m = 0,±1,±2,...
clearly implies that such unit cells can’t repeat to m −1 N
cos ϕ = = (10.5)
2 2
generate crystal structure.
Since m is an integer so must be N. The possible
solutions of equation (10.5) will be exhausted by
10.5.3 Prohibited Rotational Symmetries
range − 2 ≤ N ≤ 2 as cosine function’s value
To discover the permissible throws that rotation
can’t exceed unity. Hence we will have:
axes can have, let’s consider a linear lattice of
N cosφ Φ N
periodicity a and place an n-fold rotation axis at
-2 -1 180o 2
each lattice point. Since n rotations by an amount
-1 -1/2 120o 3
ϕ cause superposition, it does not matter
0 0 90o 4
whether rotation proceeds in clockwise or
+1 +1/2 60o 6
anticlockwise manner.
o o
+2 +1 360 or 0 1

allowed rotational axes and are represented as
Hence 5 fold rotational symmetry and those higher (~ ) (~ )
one fold 1 , two-fold 2 , etc to distinguish from
than 6 fold are not allowed.
proper rotation axes.
10.5.4 Reflection Symmetry Roto-Inversion Symmetry: In the similar manner,

It is an imaginary plane passing through the unit the improper rotation followed by inversion leads
cell, over which when a mirror reflection is to another element of hybrid symmetry referred to
performed, it remains invariant. The triclinic lattice as roto-inversion symmetry. Corresponding to five
has no reflection plane. The cubic lattice has in rotational axes, there exist five roto-inversion axes
total nine reflection planes of which three are
()
which are represented as one fold 1 , two-fold
parallel to faces while remaining six pass through
opposite edges.
(2 ) etc.
Screw Axis: A kind of hybrid symmetry is generated

10.5.5 Hybrid Symmetries
by combining proper improper rotation with
These are the symmetries arising out of complex
translation parallel to the axis of rotation. The
mathematical operations on the crystal lattice.
combination of two operations is equivalent to a
Such symmetries involve improper rotation as one
screw motion which is shown for 3 1 screw axis in
of the operations which results in change in
the figure 10.6 below.
handedness of the object. The improper rotation
can be followed by another operation, which
restores the handedness of the object and hence
defines the symmetry. Some of these symmetries
are explained in the remaining portion of this
subsection:
Roto-Reflection Symmetry: The improper rotation

Figure 10.6: The diagram depicts the sequence of
repeats a left handed object from right handed
operations underlying the 3 1 screw axis symmetry.
one and vice versa. If the improper rotation
The overall operation involves the translation of
operation on a crystal is followed by reflection,
crystal lattice by 1/3 of basis vector magnitude
then crystal symmetry is observed. This is referred
along the direction of screw axis followed by
to as roto-reflection symmetry. There exist roto-
rotation by 2π/3 of the lattice about the same axis.
reflection axes corresponding to each of the five

For an n-fold axis, each rotation through an angle of the lattice in the direction of glide. Hence axial
2π glides will correspond to translation (
ϕ= must lead to translation T along
n a b c
T= or or ) while diagonal glides will
rotational axis. Hence one complete revolution 2 2 2
(involving n rotations) will result in integral correspond to  1 1 1 .
 T = ( a + b) or (c + b) or (a + c) 
 2 2 2 
number of the translations (nT), which further
must be equal to integral number (m) of lattice
r r r r 10.5.6 Point and Space Group Symmetries
translation vector Rn = n1 a + n 2 b + n3 c . Hence
In a non-bravais lattice, each lattice point is
we have:
associated with the cluster of atoms called the
nT = mRn basis or motif. The symmetry of such a lattice is
mRn
∴T = (10.6) specified by the symmetry of basis, in addition to
n
the symmetry of bravais lattice. The symmetry of a
As can be seen from equation (10.6), there are
basis is called point-group symmetry, such as all
eleven possible screw axes which are
possible rotations, reflection and inversion centre,
21 ,31 ,3 2 ,41 ,4 2 ,4 3 ,61 ,6 2 ,6 3 ,6 4 ,6 5 . In equation
which leave the basis invariant. There are possible
(10.6), the subscript denotes the value of m and
32 point-group symmetries which are consistent
number denotes the fold of axis of rotation. The
with the requirement of translation symmetry for
m=0 and m=n correspond to the cases of purely
the lattice as a whole. The limit on the number of
proper rotations. The following symbol notations
point-group symmetry is understood as the shape
are used to depict the screw axis symmetries.
and structure of basis can’t be arbitrarily complex
which would become incompatible with the
symmetry of inter-atomic forces operating
between the basis atoms (or atomic groups or
ions) at various lattice sites. The space-group
symmetries arise when rotation symmetries of
point-group are combined with translation
symmetry. This generates a large number of space
Glide Planes: Another kind of hybrid symmetry group (72 exactly) symmetries. Further the
arises when reflection is combined with translation consideration of hybrid symmetries leads to 230
parallel to the reflection plane. This forms the glide space group symmetries.
plane. The translational component of T of a glide
plane is equal to one half of the normal translation

10.6 Characteristics of Unit Cell Centred Rectangle: It is characterized by basis
vectors a≠b which are orthogonal. It also forms a
10.6.1 Bravais Lattices in a Plane
non-primitive or conventional unit cell having
A planar lattice which has all lattice positions
lattice points at centre of rectangle in addition to
equivalent is referred to as a bravais lattice. Such a
those at four vertices. The figure 10.9 depicts the
lattice is characterized by two basis vectors (a and
centred rectangular lattice.
b) and angle (θ) between them. The planar lattices
which obey the translation periodicity fall into five
broad classes:
Square Lattice: It is characterized by basis vectors
a=b which are orthogonal. It forms a primitive unit
cell and has lattice points only at vertices. Such a
lattice is shown in the figure 10.7 below:
Figure 10.9: The centred rectangular lattice with

its non-primitive unit cell.
Oblique: This unit cell is characterized by basis

vectors which may or may not be equal and angle
Figure 10.7: The square planar lattice having a
between them is other than 90o. This is a primitive
primitive unit cell.
unit cell. The oblique lattice with its unit cell is
Rectangular lattice: It is characterized by basis
shown in the figure 10.10.
vectors a≠b which are orthogonal. It also forms a
primitive unit cell and has lattice points at vertices.
Such a lattice is shown in the figure 10.8.
Figure 10.10: The oblique unit cell with its

Figure 10.8: The rectangular lattice with a

Hexagonal: This is a planar lattice with a hexagonal types of lattices. The unit cells of these lattices
unit cell characterized by a=b and θ=120o. This obey the following:
shown in the figure 10.11. • They are simplest repeating unit in a crystal.
• Its opposite faces are parallel.
• Its edges are connected to equivalent points.
• The lattices obey translation symmetry.
These lattices along with crystal systems are
tabulated below in table 10.1 along with their
Figure 10.11: The hexagonal planar lattice with

unit cell.
10.6.2 Bravais Lattices in Space

The unit cell in space is defined by its basis vectors
r r r
a , b and c and inter-planar (inter-facial) angles
α , β and γ . These are shown for a three
dimensional unit cell in the figure 10.12 below:
Table 5.1: The tabulation of seven crystal systems,

falling into 14 Bravias lattices, along with their
shape characteristics and symmetries.
Figure 10.12: The characteristic parameters characteristics and possible symmetries. The unit
describing the three dimensional unit cell. cells of above mentioned fourteen lattices are of
three types which are: (a) Simple lattice having
10.6.3 Crystal Systems lattice points only at vertices and is primitive in
In 1848, Auguste Bravais demonstrated that the nature (b) Side centered having lattice points at
point symmetry operations in three dimensions centre of a pair of opposite faces in addition to
lead to seven crystal systems having 14 distinct those at vertices (c) Body centered having one

lattice point at body centre in addition to those at a 2 = 4 RBCC
vertices. (d) Face centered having one lattice at a 2
RBCC = (10.8)
centre of each face in addition to those at vertices. 4
These 14 lattice types exhaust all the possibilities In FCC, the length of face diagonal is exhausted by
for Bravais lattices. Any other type of lattice, on radius each of the vertex atom and two radii of
reduces to one of them. face centered atom. Hence we have:
a 3 = 4 RFCC
10.7 Cubic Unit Cell a 3
RFCC = (10.9)
The cubic unit cell is characterized by a=b=c and 4
α=β=γ=90o. Cubic unit cells exist in three forms as 10.7.2 Atoms per Unit Cell
(i) Simple Cubic Cell, which has one atom at each In SCC, each atom at its vertex is shared by eight
vertex of the cube (ii) Body Centered Cubic Cell, adjacent unit cells. Hence total number of atoms
which has eight atoms at vertices of the cube and 1

associated with each cell is 8 × = 1.
one atom at the body centre of the cube (iii) Face 8
centered Cubic Cell, which have eight atoms at Similarly in BCC, vertex atoms together contribute
vertices of cube and one atom at centre of each one atom per cell while the atom at the body
face of the cube. centre is not shared by any other unit cell. Hence
1
number of atoms per unit cell are 8 × +1 = 2.
8
10.7.1 Atomic Radius
In FCC unit cell, vertex atoms together contribute
The atoms in a unit cell are closely packed and
one atom while atoms at center of each face are
hence touch each other. In a simple cubic cell, the
shared by two adjacent unit cells. Hence atoms per
atoms forming the vertices of side of cube in same
1 1
plane touch each other. If a is the lattice constant unit cell are 8 × + 6 × = 4 . Hence FCC forms
8 2
of the cell, then we can write:
most efficient way of arrangement of atoms.
a = 2 RSCC
a
RSCC = (10.7) 10.7.3 Atomic Packing Factor (APF)
2
It is defined as the fraction of total volume of unit
The above expression gives the radius of atom in
cell which gets occupied by atoms. In general it can
SCC. Similarly for BCC, the length of the body
be expressed mathematically as:
diagonal is exhausted by one radius each of vertex
No. of atoms in unit cell × Vol. of atom
atoms and two radii of body center atom. If lattice APF = (10.10)
Volume of unit cell
constant of cell is a, then we have;

The APF for various types cubic cell are triangular vertex pointing up are designated B,
( APF ) SCC = 0.52  while those with vertices pointing down are
( APF ) 
 BCC = 0.68 (10.11) labeled C as shown in the part (a) of the figure
( APF ) FCC = 0.74 10.13.
The above mentioned values show that atoms are A second close-packed plane may be positioned
most efficiently packed in FCC lattice. with the centers of its atoms over either B or C
type trigonal voids. Both of the arrangements are
10.8 Closest Packing Morphologies equivalent in all respects. Suppose that the B type
trigonal voids are chosen and the stacking
Although their exists infinite number of possible
sequence is AB, which is shown part (b) of the
ways of closely packing the basis (which may be
figure 10.13.
atoms or ions or group of atoms or molecules) to
form a crystalline solid, only a very small number
of them get actually realized in nature. In fact most
of the closest packing morphologies observed in
nature are hexagonal and cubical close packing. All
the metallic crystals have their constituent atoms
arranged in one of these two structures, which are
the most efficient ways of packing of identical
spherical atoms. These two packing morphologies
can be conveniently depicted as close-packed
planes of atoms placed as layers one over the
other. The difference in two structures lies in the Figure 10.13: The stacking sequence of closely
stacking sequence of stacking the closely packed packed layer of atoms in hexagonal closed packing
atomic layers. morphology.
10.8.1 Hexagonal Close Packing (HCP) The real distinction lies in where the third close-
Let the centers of all the atoms lying in the one packed plane is positioned. For HCP, the center of
close-packed plane be labeled A. Associated with atoms of third layer is positioned directly over
this plane are two sets of equivalent triangular original A positions. This leads to stacking
depressions or trigonal voids formed between sequence ABABAB…… which repeats after every
three adjacent atoms, into which next close- alternate layer of atoms.
packed plane of atoms may rest. Those having

10.8.2 Cubical Close Packing (CCP)
In other kind of close-packed structure, referred to 10.9.2 Number of Atoms per Unit Cell
as cubical (or Face Centered) close-packing, center The top layer contains seven atoms. Each of the
of atoms of third layer are positioned over the C atoms occupying the vertex position, in regular
sites of the first layer. This leads to a sequence hexagon forming top or base plane, is shared by six
ABCABCABC….. wherein the stacking layers repeat adjacent unit cells. The atom, lying at the centre of
after every third layer. regular hexagon, is shared by two unit cells. The
three atoms with in the body solely contribute to
10.9 Hexagonally Close Packed Unit Cell the cell. Thus total number of atoms in a
hexagonal unit cell are:
10.9.1 Structure of Hexagonal Unit Cell
1 1
In hexagonally closed packing, the top and bottom N = 12 × + 2 × + 3 × 1 = 6 (10.13)
6 2
face of the unit cell contains one atom at each of
the six vertices and an atom at centre of the
10.9.3 Volume of Hexagonal Unit Cell
regular hexagonal face. Three more atoms are
Let a and c be the edge and height of unit cell
positioned within the body which forms the
respectively. Three atoms lie in a horizontal plane
central plane of the cell. Each atom in top or
at perpendicular distance of c/2 from the
bottom plane (See figure 10.14) touches three
orthocenter of alternate equilateral triangles
atoms in the layer just below or above its plane
formed in the top or base plane of the hexagonal
and six atoms in its own plane. Further the atoms
cell. These three body atoms just rest in the
touch each other along the edge of the regular
trigonal void formed by three atoms arranged at
hexagon. Thus we have
the vertex of the equilateral triangles formed in
a = 2R
a base and top hexagonal planes of unit cell. The
⇒R= (10.12)
2 figure 10.15 shown below, gives the bottom layer
of the HCP structure. The distance AZ between the
vertex atom A and body centered atom Z is
a = 2R .
In triangle ABY
AY
cos 300 =
AB
a 3
Figure 10.14: The atomic arrangement in a AY = AB cos 300 = (10.14)
2
hexagonal unit cell.

Va π
APF = = = 0.74 (10.17)
V 3 2
It is surprising to observe that despite having
larger number of atoms per unit cell, the
hexagonal unit cell exhibits same APF as face
Figure 10.15: The geometry atomic arrangement in centered cell involved in cubical close packing.
hexagonal plane and central plane.
In triangle AXZ, we have: 10.10 Voids in Closest Packed

( AZ ) 2 = ( AX ) 2 + ( ZX ) 2 Structures
2 2a 3 a
AX = AY = ⋅ = It has been observed that large number of known
3 3 2 3
inorganic compounds have structures which
AZ = a ZX = c / 2
slightly distorted closed packing or are related to
a2 c2
∴ a =
2
+ closest packing in another way. In such structures,
3 4
c 8 usually one kind of atoms are arranged as closed
⇒ = (10.15)
a 3 packed structures while other kind of atoms
Volume of unit cell is given as the product of area occupy voids created in closest packed structure of
of the hexagonal base and height of unit cell. first ones. Common example of this kind of
Hence have arrangement of atoms is metal oxides where
V = 6 × Area ( ∆AOB ) × c oxygen atoms are arranged in closest packed
1  structure while the metal atoms occupy voids in
= 6 ×  AY × BO  × c
2  this structure. Another good example is the steel
1 a 3 c alloy, where small sized foreign atoms (such as
= 6 ×  a × × ×a
 a
 2 2  carbon) get distributed in voids created in the
= 3 2a 3
(10.16) body centre cubic packing of iron. It should not be
borne in mind by the reader that the HCP or CCP
10.8.4 Calculation of Atomic packing Fraction morphologies exhaust the efficient methods of
Volume of all the atoms in the hexagonal cell is atomic packing in the solids. However it must be
given as clearly borne in mind that small number of the
4 4 a available voids also get filled either through
Va = 6 × πR 3 = 6 × π ( ) 3 = πa 3
3 3 2
The APF for the hexagonal cell is

natural arrangement of interstitial impurities or
imperfections. 10.10.2 Octahedral Void
Hence the voids play important role in the If the trigonal void pointing up in one closest
formation of closely packed crystalline structure packed layer is covered by another such void
and also influence the overall properties. Further pointing down in an adjacent layer, then the void
the preference of alloys over pure metals can be pointing upward gets surrounded by six atoms (see
owed to the better properties exhibited by alloys figure 10.17). These six atoms are arranged at
due to occupation of voids by solute atoms, corners of an octahedron and such a void is called
thereby freezing many degrees of freedom of octahedral void.
neighbouring solvent atoms. This has play role in
customizing or tailoring the properties of crystals.
There are two kinds of voids that we come across
in closest packed structures. These voids and their
related aspects are discussed below:
10.10.1 Tetrahedral Voids
If the identical spheres are packed closely over a
plane then triangular voids are created between
the surfaces of three spheres in mutual contact
with each other. These are called trigonal voids. If Figure 10.17: The arrangement of atoms around
another sphere is placed over this trigonal void octahedral voids.
then it results in a void with four spheres around it
(see figure 8) and this is referred to as tetrahedral 10.10.3 Coordination Number of Voids
void. The centres of these four spheres occupy the A sphere, in a closest packed layer, is surrounded
vertices of a tetrahedron. by six trigonal voids of two kinds, which is clearly
revealed in the figure 10.17, of which three are
pointing in upward direction while remaining three
are pointing in downward direction. When the
second layer of atoms is added over this layer,
then atoms may occupy one of these two kinds of
voids in first layer. The voids occupied by second
Figure 10.16: The arrangement of atoms around a
layer become tetrahedral in nature while
tetrahedral void.
remaining three unoccupied voids assume

octahedral shape. In similar manner, the layer volume, hence one sphere in a closest packing
below the first layer will also result in three belongs to the octahedral void. The radius of
tetrahedral and three octahedral voids. In addition largest sphere that can be accommodated in the
to these voids, the considered sphere sits over a octahedral void is 0.414R (R=radius of identical
tetrahedral void in both the layers below and surrounding atoms).
above it. Hence an atom in the closest packing is
surrounded by eight tetrahedral voids and six 10.9.5 Voids in Body Centre Cubic Packing
octahedral voids. Since each tetrahedral void is In the body centre cubic structure (see Figure
surrounded by 4 spheres so number of tetrahedral 10.18), the packing of atoms is not the closest but
voids per sphere is 2. In the similar sense, the it becomes interesting to study the voids that
octahedral void is surrounded by six atoms leading occur in such structures. Two kinds of voids occur
to one octahedral void per sphere in closest in this type of close packing of atoms of which one
packing. is octahedral in nature while the other is
tetrahedral.
10.10.4 Number of Voids around a Sphere
The number of spheres that are arranged around
each void is called its coordination number. If the
void is also represented as a sphere, then the
collection of spheres coordinating the sphere
(representing void) forms the coordination
polyhedron.
Figure 10.18: The BCC unit cell showing various
The tetrahedral void has a coordination number of
voids that exist.
four spheres. Each of these spheres contributes its
one eighth of volume to the coordination
The octahedral voids occur at the centre of face of
polyhedron which implies that one half of volume
cubic cell (see figure 10.19). It is coordinated by
of sphere belongs to a tetrahedral void. The radius
four atoms at vertices of the face and two atoms
of largest sphere that can be accommodated in
located at the body centre of two adjacent cubes.
tetrahedral void is 0.255R (R=radius of identical
This void
surrounding atoms).
The octahedral void is surrounded by six spheres
leading to coordination number of 6. Since each of
the six spheres contribute one-sixth of their

are four sphere surrounding each void and 24
voids surrounding each sphere, so the ratio of
spheres to voids is 1:6. These tetrahedral voids are
larger than octahedral voids.
10.11 Indexing in Crystals

Figure 10.19: Octahedral void in BCC unit cell.
In describing physical phenomena, we require the
knowledge of directions and planes in crystals as
forms irregular octahedron of atoms around it. It
they are anisotropic in nature. The directions and
can accommodate a largest sphere of radius
orientation of crystal planes are specified using
0.154R (R=radius of the coordinating sphere).
well defined prescription.
There are six spheres coordinating the void and 18
voids coordinating each sphere, so the ratio of
spheres to voids is 1:3. 10.11.1 Indexing of Crystal Directions
The second kind of void, tetrahedral in nature (See Consider a straight line joining certain atoms in the
figure 10.20), exists in between two atoms forming crystal. Consider one of the atoms as origin and
the edge of the cube and other two lying at the translate from this atom to next using the
r r r r
body translation vector Rn = n1 a + n2 b + n3 c . The
triplet of indices [n1 , n 2 , n3 ] in lowest possible
integer ratio gives the direction of line joining the

considered atoms. This direction does not mean a
particular straight line but a family of parallel lines.
Due to rotational symmetry of crystal, there may
exist several non-parallel directions which are
equivalent. For example in a cubic crystal the
Figure 10.20: The tetrahedral void in the BCC directions [100], [010] and [001] are equivalent
unit cell.
and are represented together as 100 .
centre positions of adjacent cubic cells. The

10.11.2 Indexing of Crystal Planes
coordination of spheres around this void forms the
The orientation of the plane in a lattice is specified
irregular tetrahedron. A sphere of largest radius
by its Miller indices.
0.291R can be accommodated in this void. There

• Set up three coordinate axes along edges of the inverted. This is useful as in the analysis of x-ray
unit cell. diffraction spectrum of a crystal, one needs not
• Note the intercepts (x,y,z) of the plane (to be the direct lattice but the reciprocal one, whose
indexed) on three coordinate axes. lattice constants are related to these inverted
• Divide these intercept values with edge lengths intercepts. The set of Miller’s indices are not
of unit cell along respective coordinate axis. restricted to one plane but a family of parallel
x y z planes. This is because all these planes scatter
 , , 
a b c incident x-rays in an identical manner as far as
• Invert the resultant triplet of ratios. angle and phase of scattering are concerned and
a b c lead to constructive interference of scattered x-

 , , 
x y z rays thereby yielding maxima of intensity in the
• Use a common multiplier (n) such that the diffraction pattern.
triplet of inverted coordinates form the set of
lowest integers (h,k,l) given as: 10.11.3 Indexing in Hexagonal Cells
 a For hexagonal crystals, a problem arises in that
h = n x 
  the some equivalent directions will not have same
k = n b  (10.18)
 y
  set of indices. This is circumvented by using a set
l = n 
c
 z  of four indices instead of three and this system of
• Triplet (hkl) denotes the Miller’s indices for the prescription is called Miller-Bravais indices. The
plane. three axes a 1 , a 2 , a 3 are contained in the same
plane and are at 120o to each other (see figure
The set of Miller indices specify not one plane but 10.21). The z-direction is perpendicular to this
a set of parallel planes or family of planes which basal plane formed by three axes.
are either parallel to each other or are equivalent
by virtue of symmetry. For example the planes
(100), (010), (001), ( 1 00), (0 1 0), (00 1 ) are equivalent

in a cubic cell and hence are represented in
condensed form as {100} .
The prescription of specifying Miller’s indices for

planes has good reasons. The intercepts of the
Figure 10.21: The axes for the Miller-Bravais
plane with three principal axes, expressed in units
prescription of planes in hexagonal unit cell.
of lattice constants along respective axes, are

The direction indices are obtained using same 1
d hkl = (10.20)
procedure as for Miller’s indices. Out of the four 1 1 1
2
+ 2 + 2
x y z
indices (h' , k ' , i ' , l ') , first three pertain to
The intercepts x,y and z are related to Miller’s
projections along three axes in basal plane and
indices (h, k , l ) as
fourth one is related to projection on the
perpendicular axis. These are related to three  a
h = n x 
index system of Miller as follows:  
k = n b  (10.21)
 n 
 y
 
h ' = 3 ( 2h − k )  l = n c 
   z 
k ' = n ( 2k − h )  (10.19)
 3  Solving for x, y and z from above equation (10.21)
i ' = −( h + k ) 
  and inserting it in expression (10.20) for d hkl , we
l ' = nl 
get:
The n denotes the integer which reduces the
n
indices (h, k , l ) to smallest set of integers. d hkl = (10.22)
h2 k 2 l 2
+ +
a 2 b2 c 2
10.10.4 Inter Planar Spacing where n denotes the order of the plane w.r.t the
In case of x-ray diffraction studies one need to plane passing through origin having n=0.
know the spacing ( d hkl ) between the successive
planes labeled by same Miller indices (h, k , l ) . To 10.11.5 Results from Miller’s Prescription
calculate this spacing, let’s consider another plane, (a) The angle between orientation of two planes
having same indices and oriented parallel to first (hkl) and (h’k’l’) is given as:
one, passing through the origin. The distance h1h2 + k1k 2 + l1l2
cos θ =
between these two planes is d hkl , which is the
(h 2
1 + k12 + l12 )(h22 + k 22 + l22 )
(b) The direction [uvw] is normal to the plane

length of the normal between two planes. If this
(hkl) if u=h, v=k and l=w.
normal makes angles α , β and γ with X, Y and Z
(c) The direction [uvw] is parallel to the plane
axes respectively, then we can write
(hkl) if we have uh+vk+wl=0.
d hkl = x cos α = y cos β = z cos γ
(d) Two planes (hkl) and (h’k’l’) are normal to
Since cos 2 α + cos 2 β + cos 2 γ = 1
each other if they satisfy the condition that
2
 d hkl   d hkl   d hkl 
2 2
  +   +   =1 hh’+kk’+ll’=0.
 x   y   z 

(e) Two directions [uvw] and [u’v’w’] are normal a = 2( RNa + RCl ) (10.23)
if they satisfy the condition that
uu’+vv’+ww’=0.
10.12.2 Structure of CsCl
The crystal structure of CsCl, shown in figure
10.12 Simple Crystal Structures 10.23, has chlorine ions placed at corners of the
cube while the Cs+ ion is located at the body centre
10.12.1 Structure of NaCl of unit cell. Each of the Cs+ and Cl- ions lie at vertex
The structure of NaCl is cubic and is such that of its simple cubic cell but two unit cells are
along three principal directions, there is an interpenetrated along lines directed along four
alternation of Na+ and Cl- ions as shown in the body diagonals of the cube. There are, one Cs+ ion
figure 10.22 below. The cell is FCC in nature. per unit cell located at point (0, 0, 0) and one Cl-
The position of four Na atoms are (0,0,0), (1/2, ion per unit cell located at (1/2, ½, ½). This is a
½,0) , (1/2, 0, ½) and (0, ½, ½) while those of four non-Bravais lattice composed of two simple cubic
chlorine atoms are (1/2, ½, ½), (0, 0, ½), (1/2, 0, 0) lattices which are displaced relative to each other
and (0, ½, 0). The NaCl is a non-Bravais structure by an amount equal to half the length of the body
composed of two interpenetrating lattices of Na+ diagonal.
and Cl-, which are displaced relative to each other

by a/2.
Figure 10.23: The crystal structure of CsCl.
10.11.3 Polymorphic Forms of Carbon

Diamond Crystal Structure
The unit cell for the diamond crystal is FCC cell
Figure 10.22: The Crystal Structure of NaCl.
(shown in figure 10.24) with a basis of two carbon
atoms associated with each lattice site. The
In this crystal structure the unlike ions touch each
position of these two basis atoms are (0, 0, 0) and
other and size of the unit cell can be obtained from
(1/4, ¼, ¼). In this structure each atom has 4
the relation given as:

nearest neighbors, forming a regular tetrahedron Structure of Graphite
having atom in question at its apex. Hence total The graphite is a polymorph of carbon whose
number of atoms per unit cell are crystal structure is different from that of diamond.
1 1 The structure of graphite is more stable as
8 × + × 6 + 4 = 8 . The crystal structure is
8 2 compared to that of diamond at ambient
shown below in the figure 10.23. temperature and pressure. The graphite is
To determine the APF of diamond crystal, the composed of layers of hexagonally arranged
atomic radius is evaluated by considering that the carbon atoms; within the layers each carbon atom
centre of two carbon atoms, located at vertex of is bonded to three other coplanar neighboring
cube and at one fourth distance from this vertex carbon atoms through strong covalent bonds. The
along body diagonal is equal to a. Hence we have: fourth bonding electron participates in a weak van
2R =
3
a der Waals type of bond. It results in some of the
4
3 important properties of graphite: (i) easy
∴R = a (10.24)
8 interplanar cleavage (ii) excellent lubricant (iii) high
4
8 × πR 3 electrical conductivity along the direction parallel
APF = 3
a3
to planes. The layered structure of graphite is
π 3
= = 0.34 (10.25)
16 shown in the figure 10.25 below:
Figure 10.25: The arrangement of carbon atoms in

Figure 10.24: The arrangement of carbon atoms in graphite structure.
the unit cell of diamond.
Structure of Fullerene
Although the unit cell of diamond crystal has 8 Another polymorphic form of carbon was
carbon atoms per unit cell but still it is a loosely discovered in 1985. It exists in discrete molecular
packed structure. This is owing to large unit cell of form and consists of a hollow spherical cluster of
carbon. 60 carbons atoms which is represents a single

molecule C 60 . Each molecule consists of group of concentric cylinders of graphite sheets are also
carbon atoms that are bonded to one another to found to exist.
form both hexagon (6 carbon atoms) and
pentagon (5 carbon atoms) geometrical
configurations. One such molecule shown below in
the figure 10.26 consists of 20 hexagons and 12
pentagons, which are arrayed in such a manner
that no two pentagons share a common side. The
surface of this molecule appears to be like a soccer
Figure 10.27: The structure of a carbon nanotube.
ball and is
The nanotubes are extremely strong and stiff but

relatively ductile. These tubes have relatively low
densities due to which they are considered as
ultimate fiber having promising reinforcement
properties. The nanotubes have unique and
structure sensitive electrical characteristics.
Figure 10.26: The arrangement of carbon atoms in
Depending upon the orientation of the hexagonal
the fullerene molecule.
units in the graphite plane with the tube axis, it
called buckminsterfullerene after the name
may behave as either metal or a semiconductor.
Buckminster Fuller who invented it.
10.11.4 Structure of Zinc Blende (ZnS)

Structure of Carbon Nanotube
The crystal structure of ZnS is similar to diamond
Another molecular form of carbon has been
except that now basis of two atoms is formed by
discovered and is fast turning into an important
different atoms (Zn and S). Each cell contains four
material for future technological growth. It is
ZnS molecules and each Zn or S finds itself at the
composed of a single graphite sheet rolled into a
apex of tetrahedron formed by atoms of opposite
cylinder and is capped on both its ends by C 60
kind. The crystal structure of ZnS is shown in the
fullerene hemispheres. This is called carbon
figure 10.28.
nanotube (See figure 10.27). Each nanotube is a
single molecule of millions of atoms and length of
this tube is much greater than its diameter (100nm
or less). Multiwalled nanotubes, consisting of

Silica
The simplest silicate material is silicon dioxide
(SiO 2 ). It is generated as a three dimensional
network of SiO44− tetrahedron when every oxygen
atom, lying at the vertex of a tetrahedron, is

shared by the adjacent tetrahedral structures. If
Figure 10.28: The arrangement of atoms of Zn and
these tetrahedrons are arranged in regular and
S in unit cell of zinc blende.
ordered manner, then it forms the crystalline
structure. There exist three crystalline polymorphs
10.11.5 Structure of Silica of silica which are quartz, cristobalite and
Silicate Ceramic tridymite. Their structures are complicated but
Silicates are materials primarily composed of loosely packed leading to low relative density. The
silicon and oxygen and are found in soils, clays, Si-O bond is highly strong which is reflected in high
rocks and sand. The basic unit of silicate ceramics melting temperature of silica.
is SiO44− tetrahedron which has silicon sits at
centre of tetrahedron and is bonded to four Silica Glasses
oxygen atoms lying at vertices of the tetrahedron Silica can also exist as a non-crystalline solid or
(see figure 10.28). This arrangement has 4 negative glass which has a degree of atomic randomness.
charges since each of the oxygen atoms requires Such silica structures are also called fused or
one extra electron to achieve stable electronic vitreous silica. These structures are also generated
configuration. This constitutes the basic unit which by networking of SiO44− tetrahedron but results in
combines into one-, two- and three-dimensional disorderly arrangement. Some other materials like
arrangements. B 2 O 3 and GeO 2 also form glassy structures due to
their networking. Hence such materials (SiO 2 ,
GeO 2 , B 2 O 3 ) are also called network formers.
Certain oxides like CaO and Na 2 O when added in
glassy structures do not form polyhedral structures
but modify them. Hence they are also called
network modifiers. Still other oxides like Al 2 O 3 and
Figure 10.28: The structure of Silicate ion. TiO 2 become part of polyhedral network and
stabilize the structure. These are called

intermediates. These are commonly used in and 3Ǻ respectively, in a tetragonal crystal
amorphous silica to obtain different structures. with c/a ratio of 1.5.
10. A plane includes points (0,0,0), (0.5,0.25,0) and
Numerical Problems Set I (0.5,0,0.5). What are its Miller indices.

11. In an orthorhombic unit cell a :b : c = 1:2:3.
1. Taking the edge of its unit cell of diamond to
The magnitude of a = 2Ǻ. What are the
be 3.57Ǻ long, evaluate its density.
intercepts of a plane having Miller indices
2. Bunsenite (NiO) has FCC structure with O2- in
(230).
all face centre sites. The radii of Ni2+ and O2-
12. Calculate the density of MgO, which has
are 1.40Ǻ and 0.69Ǻ respectively. What is the
packing factor. What would be this factor if anions in FCC packing while cations are placed
in octahedral voids. The radii of Mg2+ and O2-
radii ratio R(O)/R(Ni) = 0.41.
3. Titanium has HCP structure with a density of ions are 0.78Ǻ and 1.32Ǻ respectively.
4.5g/cm3. What is the volume of this cell. 13. A substance with FCC lattice has density
6250kg/m3 and molecular weight 60.2.
4. Find the Miller indices of a set of parallel
planes which make intercept in the ratio 3a:4b Calculate its lattice constant a.
on the X and Y axes and are parallel to Z axis. 14. Metallic iron changes from BCC to FCC at
Given the lattice is simple cubic. 910oC. The atomic radii in two structures are
5. A certain orthorhombic crystal has a ratio of a: 1.258Ǻ and 1.292Ǻ respectively. Calculate the
b: c of 0.428:1:0.376. Find Miller indices of the volume change during this structural change.
faces with intercepts (i) 0.214:1:0.188 (ii) Also calculate the change in density.
0.858:1:0.754 (iii) 0.429: ∞ : 0.126. 15. Zinc has HCP structure. The height of the unit
cell is 0.494nm. The nearest neighbor distance
6. Draw (232) plane in the cubic crystal and (2 ī 1)
plane in orthorhombic crystal. is 0.27nm. The atomic weight of zinc is 65.37.
Calculate the volume of unit cell and density of
7. Lead has FCC structure with atomic radius
zinc.
1.746Ǻ. Find the spacing between (200) and
16. Show that for
(220) planes.
(a) simple cubic system
8. In a unit cell of SCC, find the angle between
d 100 : d 110 : d 111 = √6 : √3 : √2.
the normal lines to the planes having Miller
indices (121) and (111). (b) face centred cubic system
9. Find the Miller indices of a plane that makes d 100 : d 110 : d 111 = 1 : √2 : (√3)/2.
intercepts on a, b and c axis equal to 3Ǻ, 4Ǻ (c) body centred cubic system
d 100 : d 110 : d 111 = 1 : 1/√2 : √3.

17. Show that for trigonal, tetrahedral and accommodated in the octahedral void in the
octahedral voids can be just filled by spheres BCC unit cell. Further prove that there is a
having radii not larger than 0.155r, 0.225r and ratio of 1:3 spheres to octahedral voids in BCC
0.414r respectively, where r = radius of larger unit cell.
sphere involved in closed packing of these 20. Show that a largest sphere of radius 0.291R
structures. (R=radius of the coordinating sphere) can be
18. Show that the maximum radius of a sphere accommodated in the tetrahedral void in the
which can just fit into the empty space at the BCC unit cell. Further prove that there is a
centre of SCC structure is 0.732r, where r is the ratio of 1:6 spheres to tetrahedral voids in BCC
radius of the atom. unit cell.
19. Show that a largest sphere of radius 0.154R
(R=radius of the coordinating sphere) can be

X-RAY DIFFRACTION
11.1 Introduction intensity is mostly concentrated in central maxima
and falls off rapidly in secondary maxima.
When light passes through a fine aperture and falls
The three dimensional crystal lattice has atoms
on a screen, it is observed that an interference
arranged in a regular and periodic manner which is
pattern is observed. This pattern is in the form of
central bright spot which represents the image of the analogous to the system of multiple slits. The inter-
planar distance in crystals is of order comparable to
aperture and alternate dark and bright annular rings
the wavelength of x-rays. When x-rays are incident
of rapidly falling intensity. Such a pattern depicting
on the crystal, then they suffer diffraction from the
modification of light intensity distribution on passing
crystal lattice. The intensity distribution observed on
through an aperture is called diffraction and is
a screen is similar to that observed light illuminating
observed only if the size of aperture is comparable to
the wavelength of light. As interpreted by wave a system of multiple fine slits.
theory of light, the diffraction phenomenon is The diffraction pattern of x-rays, so observed, can be
used to extract lot of information of crystal structure
described as modification of light intensity
such as shape and size of unit cell, arrangement of
distribution resulting from interference between
contents in the unit cell, symmetries observed by the
light waves reaching the screen from different
unit cell and defects or imperfection or dislocations.
portions of the same wave front. The typical
This has led to rapid growth of field of x-ray
diffraction pattern observed on illumination of a
system of fine slits is shown in the figure 11.1 diffraction in the pursuit to have insight into crystal
structures. Following x-rays as incident beam, the
electrons and neutrons have also been employed to
probe structure of crystals.
11.2 Bragg’s Law

Figure 11.1: The diffraction pattern observed due to When monochromatic x-rays are incident on the
illumination of fine aperture. surface of a crystal, reflection occurs only at certain
angles of incidence, which depend on lattice
It can be observed that the diffraction pattern differs constant of crystal and wavelength of incident x-rays.
from that due to interference in the fact that light This selective reflectivity can be understood by
considering the crystal as a set of parallel atomic

planes acting as partially reflecting mirrors. Each have a common wave-front only at these angles.
atomic plane reflects the incident beam partially and Consequently the amplitudes of scattered waves
reflected waves from different atomic planes reinforce to yield maximum possible value. At other
interfere at the detector. The interference is angles, the waves emanated from different atoms
constructive only if the path difference, between two are not in phase with each other resulting in their
waves reflected from successive planes, is integral destructive interference.
multiple of wavelength. The figure 11.2 shows the The intensity of the beam decreases as order of
reflection from two successive atomic planes. plane increases, which makes it more appropriate to
treat this process as diffraction rather than
interference. The wavelength (λ ) and glancing angle
(θ ) can be measured independently, hence the

Bragg’s law gives a method to evaluate lattice
constant (d ) of the crystal. The diffraction is possible
Figure 11.2: The diagram representing the reflection only if λ < 2d , which implies that crystal diffraction
of x-rays from different atomic planes and is not possible with optical waves.
subsequently interfering to produce the diffraction However, the Bragg’s law is an oversimplified model
pattern. to study the features of x-ray diffraction using crystal
The path difference (∆ ) between rays 1 and 2 as a three dimensional grating. The atomic planes,
constituting the crystal, are considered to be
(shown in the figure 11.2) is given as:
continuous but the scattering of x-ray beam is
∆ = AB + BC − AC ' = 2 AB − AC ' = 2d sin θ
actually caused by discrete atoms. The diffraction
Here d is the spacing between two successive planes
condition given in the Brigg’s law considers only the
and θ is the glancing angle of incident ray with the
path difference but phase component of these
surface of crystal. The integer n = 1, 2, 3,.. refers to
waves are not included in the treatment. X-ray
the order of planes.
diffraction from discrete atoms may not give
2d sin θ = nλ (11.1)
complete picture until and unless the structure of
The equation (11.1) is called the Bragg’s law. The
atom, their arrangement in the unit cell and the
meaning of this equation is that the intensity of
shape of the unit cell are incorporated appropriately
scattered x-rays build up only at certain values of
into the diffraction condition.
angle θ , corresponding to a specific value of
λ and d . This can be attributed to the fact that the
x-rays scattered from various atoms in the crystal

11.3 Theory of X-Ray Scattering where f e is called scattering length of the electron,
11.3.1 Scattering from an Atom D is the distance of observation point from the
In order to understand the phenomenon of electron and k (=2π/λ) is the wave number of
diffraction of x-rays from a crystal structure, it is scattered wave whose magnitude is same as k 0 due
instructive to study the scattering of x-rays by an to elastic nature of scattering. The quantity D arises
atom. Further the knowledge of scattering from in the denominator because of the fact that
individual atom can be utilized in order to assess the scattered radiation will obey the inverse square law
situation arising from interference of radiation of intensity.
scattered from different atoms constituting the If we consider that incident wave acts on two
crystal. electrons as shown in the figure 11.3, then both the
When x rays fall on an atom, the electrons suffer electrons emit spherical waves and scattered
oscillations under the influence of alternating intensity at any distant point is determined by sum
electric field of the radiation. These oscillating of two partial fields scattered by each of them.
electrons behave like an oscillating dipole and emit

radiation in all possible directions. This is referred to
as scattering. As the electrons form a charge cloud
around the nucleus, so the scattering of x -rays from
an atom as a whole must account for phase of
radiation scattered from different portions of charge
cloud.
If we consider a single electron on which a
monochromatic plane wave is incident, then incident Figure 11.3: The scattering of x-rays from the system
wave will have a form given as: of two electrons.
r r
i ( k 0 ⋅ r − ωt )
u = Ae (11.2)
The scattered wave observed at a distance D is given
This incident wave will be scattered uniformly in all
as:
directions, thereby resulting in spherical wave font
[
A ikr ⋅ Dr
]
r r
emerging as a scattered wave which is expressed u' = f e e + e i ( k ⋅ D + δ ) e − iωt (11.4)
D
mathematically as:
A i ( kr ⋅ Dr −ωt ) where δ is the phase lag of electron 2, shown in the
u' = f e e (11.3)
D figure 11.3, from that of electron 1 taken to be at
origin. The phase (δ ) is expressed as:

f = f e ∑ e irl ⋅ s
r r r r
δ = ( P1 M − P1 N )k = ( r ⋅ Sˆ − r ⋅ Sˆ0 )k (11.12)
r l
= r ⋅ ( Sˆ − Sˆ0 )k (11.5)
The intensity I of the scattered wave is proportional
From the figure 11.3 shown above, we can write:
r r to the absolute square of scattering length and is
r
s = ( Sˆ − Sˆ0 )k = k − k 0 expressed as:
s = k + k − 2kk 0 cos 2θ
2 2
0 (11.6) 2
∑e
r r
irl ⋅ s
r r I = f 2
= f e
2
(11.13)
Since scattering is elastic in nature, then k = k0 l
The interference of waves, scattered from different

∴ s = 2k sin θ (11.7)
r r electrons, will be meaningful if and only if the
δ = r ⋅s (11.8)
scattering electrons maintain a definite phase
The scattered wave amplitude is represented as
relation with each other, otherwise time average will
u' = f e
A i ( kr ⋅ Dr − ωt )
D
e [
r r
1 + eir ⋅ s ] (11.9) smoothen the intensity variation of resultant
In deriving the equation (11.9), we have considered scattered wave obtained by superposition. Further
that electron 1 is at origin of coordinates. If we chose the electrons have been considered as discrete
an arbitrary position to be the origin of coordinates points rather than spread of electronic charge cloud
r r over whole volume of the atom. If the continuous
such that electron 1 and 2 have positions r1 and r2
distribution of electronic charge is included in this
respectively, then the above equation gets
treatment
generalized as:
r rr
f = f e ∑ e irl ⋅s = f e ∫ ρ ( r )e is ⋅r d 3 r
r r
[e ]
A r r
i ( k ⋅ D − ωt )
r r
ir1 ⋅ s
r r
ir2 ⋅ s
(11.14)
u' = f e e +e (11.10) l
D
The atomic scattering factor ( f a ) is defined as:
Now with the change of reference, the equation
r r r
∫ ρ ( r )e
is ⋅ r
(11.10), representing scattered wave amplitude, can fa = d 3r (11.15)
be extended to any number of scattering electrons. f = fe fa (11.16)
Hence we can write for a system of electrons as:

If the charge distribution around the nucleus of an
A i ( kr ⋅ Dr −ωt )
∑
r r
u' = f e e e irl ⋅ s atom is spherically symmetric, then the integral
D l
 r r  A r r (11.15) representing the atomic scattering factor

=  f e ∑ e irl ⋅ s  e i ( k ⋅ D −ωt ) (11.11)
 l D simplifies to the form:
R r Sinsr 3
Comparing equations (11.3) and (11.11), the
fa = ∫ 0
4πr 2 ρ ( r )
sr
d r (11.17)
scattering length of system of discrete electrons is where R is the radius of atom. The atomic scattering
given as: factor, given by equation (11.17), depends on the

following factors:

(i) Scattering angle through the factor s = 2kSin θ . (11.16) for a system of electrons, we can extend the
As 2 θ increases, so does s and hence atomic definition as:
f cr = f e ∑ eis ⋅ rl
r r
scattering factor decreases. (11.19)
l
(ii) Wavelength of incident radiation: The term
In equation (11.19), the summation extends over all
Sinsr
is an oscillating in nature and its the electrons in the crystal. However this summation
sr
process is too complicated to be handled practically.
wavelength is inversely proportional to s. Hence
For this purpose, the equation (11.19) can be
larger value of s yields shorter wavelength and
rewritten by first summing the scattering
Sinsr
faster oscillations in leading to a smaller contribution from all the electrons constituting single
sr
value of atomic scattering factor. atom and then summing over all the atoms in the
The above integral in equation (11.17) requires the crystal lattice. The first summation can be introduced
knowledge of density function which can be in (11.19) using the previously defined atomic
evaluated from considerations of forward scattering. scattering factor and we get:

r r
In this limit we have: f cr = f e ∑ f al e is ⋅Rl (11.20)
l
Sinsr
θ = 0 , s = 0 and =1 The term f al denotes the atomic scattering factor
sr
r
for the l th atom and Rl denotes the position of this
fa = ∫ 4πr ρ ( r )d 3 r = Z
2
(11.18)
atom relative to some chosen reference or origin.
If density is expressed as the number of electrons
The equation (11.20) can more conveniently be
per unit volume, then atomic scattering factor for
expressed as a product of two terms: Geometrical
forward scattering, given by equation (11.18), is
structure factor (F) which is the sum of the
equal to number of electrons. This is because all the
scattering contribution from atoms constituting a
radiations scattered from different electrons will
unit cell and Lattice structure factor (S) denoting the
have the same phase and hence they will interfere
sum of scattering contribution from all the unit cells
constructively.
comprising the crystal lattice. These factors are
expressed as:
11.3.3 Scattering from a Crystal r r
F = f e ∑ f aj e
is ⋅δ j
(11.21)
To obtain the amplitude of scattered waves from the j
r r
crystal, we have to consider the scattering S = ∑el

is ⋅Rl
(11.22)
contribution from all the electrons constituting In equation (11.21), f aj and δ j represent the
various atoms of the crystal. In analogy with the
atomic scattering factor and position for jth atom in
definition of scattering length given by equation

r r
unit cell relative to some chosen origin. In the  Ns ⋅ a 
Sin 
r
S=  2 
equation (11.22), Rl denotes the position of l th unit r r (11.24)
s ⋅a
Sin 
cell. The factor S depends solely on the crystal  2 
system while F depends upon geometrical shape as The term S2 plays an important role in calculating the
well as contents of the unit cell. By segregation into intensity of scattered x-rays and is expressed as:
r r
geometrical and lattice structure factors, the  Ns ⋅ a 
Sin 2 
scattering contributions have been separated S2 =  2  (11.25)
r r
2s ⋅a
Sin 
explicitly into structural properties of the lattice and  2 
properties of constituent atoms. It is a ratio of two oscillating functions with
numerator oscillating rapidly than denominator
11.3.3 Laue’s Equations because of multiple N, which itself is a large number.
The lattice structure factor (S) plays an important r r
The quantity S2 depends on s ⋅ a as is shown in the
role in the discussion of x-ray scattering theory. Let’s figure 11.5 below:
evaluate the lattice structure factor for x-ray beam
scattered from a mono-atomic linear lattice with
basis vector a, as shown in the figure 11.4:
Figure 11.5: The diagram depicting the oscillations of

S2 with s.a.
Figure 11.4: The scattering of x-rays from a
monoatomic linear lattice.
r r
This plot of S 2 vs s ⋅ a shows the following features
The lattice structure factor becomes: of interest:

N (i) There exist principal maxima at
∑e
r r
is ⋅la
S= (11.23) r r r r
l =1 s ⋅ a = 0, 2π ,4π ,6π ,..... i.e. s ⋅ a = 2nπ
Here N is the total number of atoms constituting the (ii) In addition, there are present many secondary
lattice. The series in equation (11.23) forms a maxima of much reduced intensity between
r r
is ⋅ a
geometric progression with a common ratio e and successive principal maxima.
its summation yields the resultant as:

(iii) If N is very large, as is expected for number of will give rise to a diffracted beam on superposition.
atoms in a crystal, the secondary maxima have The main problem at this juncture is to determine
r
negligible size as compared to the principal the scattering vector s , which satisfies the
maxima. conditions that:
(iv) The principal maxima get sharper in width as r r
 s ⋅ a = 2πh 
value of N increases. r r 
 s ⋅ b = 2πk  (11.30)
As the principal maxima should exist with the  sr ⋅ cr = 2πl 
 
periodicity of 2π , we must have
r r
s ⋅ a = 2πh h = any int eger (11.26)
We can write:
11.4 Reciprocal Lattice
Let’s start with a lattice having basis vectors
r r 2π ˆ ˆ r
s ⋅a =
λ
( )
S − S 0 ⋅ a = 2πh (11.27) r r r
a , b and c and define another set of basis vectors
The equation (11.27), for a given value of h, is valid r r r
A, B and C as following:
for infinite number of directions forming a cone
r 2π r r 
whose axis lies along the lattice line (see in the figure A = r r r (b × c ) 
 a ⋅ (b × c ) 
11.5 above). Hence (11.27) can be rewritten as: r 2π r r 
B = r r r (c × a )  (11.31)
2πa  a ⋅ (b × c ) 
(cos α 0 − cos α ) = 2πh (11.28) r 2π r r 
λ C = r r r (a × b )
 a ⋅ (b × c ) 
where α 0 and α are the respective angles made
The vectors defined in equation (11.31) are called
by incident and scattered x-rays with the lattice line.
reciprocal lattice vectors and the lattice so formed is
Thus for a given value of h and α 0 , the beam referred to reciprocal lattice. The translation vector
diffracts along all those directions for which α for such a basis of vectors is expressed as:
satisfies the equation (11.28). r r r r
G = n1 A + n2 B + n3C (11.32)
Similar arguments can be extended for three
The reciprocal lattice vectors are related to direct
dimensional lattice and obtain the conditions that:
lattice vectors as:
a (cos α 0 − cos α ) = hλ  v
av ⋅ A = 2π
r r r r
  A⋅b = A⋅ c = 0
b(cos β 0 − cos β ) = kλ  (11.29) r r r r r r 
c(cos γ − cos γ ) = lλ  b ⋅ B = 2π B ⋅ a = B ⋅ c = 0 (11.33)
  r r r r r r 
c ⋅ C = 2π C ⋅ b = C ⋅ a = 0
0
The set of equations (11.29) gives Laue’s equations,

The following are the important properties of
which define the various possible directions for the
reciprocal lattice:
constructive interference of partial waves scattered
from various constituent atoms of the crystal which

(i) Orthogonality of Basis Vectors: If the direct crystal systems remains same although Bravais
lattice vectors form an orthogonal set of basis structure may not be same.
vectors then reciprocal lattice vectors also form (v) Interplaner Spacing: The reciprocal lattice vector
r r r r r r
an orthogonal set with a parallel to A and so Ghkl = hA + kB + lC is normal to the crystal plane
on. defined by Miller’s indices (hkl ) .The spacing
(ii) Generation of Reciprocal Lattice: The reciprocal
(d hkl ) between two crystal successive planes
lattice corresponding to a direct lattice can be
defined by Miller’s indices (hkl ) is related to
formed by evaluating the reciprocal basis vectors
using equation (11.31). These basis vectors are reciprocal lattice vector (G hkl ) as
r
used to obtain translation vector G , given by 2π
d hkl = (11.35)
Ghkl
equation (11.32), which further generates whole
of the reciprocal lattice.
(iii) Brillouin Zones: The primitive cell using 11.5 Diffraction Condition & Bragg’s Law
reciprocal basis vectors is formed by drawing 11.5.1: Bragg’s Law from Lattice Structure
basis vectors to connect the nearest lattice point Factor
in their respective directions. Then planes are The important applications of reciprocal lattice
drawn, which form perpendicular bisectors to r r r r
vector G hkl = hA + kB + lC lies in obtaining
each basis vector. These planes enclose a
summation involved in the evaluation of the lattice
volume, which is the primitive cell for reciprocal
factor S. For this purpose, let’s consider an arbitrary
lattice, also called Brillouin zone. This primitive r r r r
lattice translation vector R = l1 a + l 2 b + l 3 c , then
cell is a parallelepiped of edges having length
we have:
2π 2π 2π
, , and is also called the first N vr
a b c S = ∑e
iR ⋅Ghkj
= Nδ Rr ,Gr hkl (11.36)
Brillouin zone (FBZ). In a similar manner higher j =1
BZ can be constructed using multiple of The quantity δ Rr ,Gr is called Kroneckor’s delta
hkl
reciprocal basis vectors in above prescription. function which is non-vanishing and equal to unity
(iv) Reciprocal lattice for Various Crystal Systems: r r
only when R = G hkl .
The reciprocal lattice for SCC of lattice constant a r r
Since S2=N2 when s ⋅ a = 0, 2π and lattice structure
2π
is SCC with lattice constant . The reciprocal factor (S) vanishes everywhere except when
a
r r
lattice for BCC and FCC are FCC and BCC R = Ghkl . Hence we can write that scattering vector
respectively. The reciprocal lattice for other (sr ) must satisfy the condition:
r r However it is also observed that Bragg’s diffraction
s = Ghkl (11.37)
 2π  from certain family of planes is missing which is
s = 2k 0 sin θ = 2  sin θ
 λ  because of vanishing value of geometrical structure
2π
= Ghkl = factor Fhkl . Let’s obtain the condition using
d hkl
2d hkl sin θ = λ (11.38) geometrical structure factor:
r r
Fhkl = f a ∑ e
is ⋅δ j
Hence equation (11.38) gives the Bragg’s law. (11.41)
j
r r r r r
s = Ghkl = hA + kB + lC
11.5.2 Bragg’s Diffraction Pattern r r r r
Let δ j = na + mb + zc
From the above analysis, the condition for the r
where δ j denotes the position of atoms in the unit
diffraction is that when the magnitude of the
r cell. Hence we get general condition (11.41) as:
scattering vector s equals that of the reciprocal
( ) Fhkl = f a ∑ e 2πi ( hn +km+lz )

r
lattice vector G hkl then the lattice structure factor (11.42)
assumes the value

BCC Lattice: It has two atoms per unit cell, the
S hkl = N position of atoms are (0,0,0) and (1/2, ½, ½), we get
Substituting this in equation given as: (11.42) as:
f cr = Fhkl S hkl = NFhkl (11.39) Fhkl = f a ∑ (1 + eπi ( hn +km +lz ) ) (11.43)
The intensity of the scattered x-ray beam will be
The equation (11.43) gives non-zero values only
given as:
when (h+k+l) is even and zero if (h+k+l) is odd. Hence
I ≈ f cr ≈ N 2 Fhkl
2 2
(11.40)
for BCC lattice Bragg’s diffraction peaks are observed
The scattered x-ray intensity vanishes in all directions for those planes for which the sum of Miller’s indices
except those in which lattice structure factor S is (h+k+l) is even.
non-vanishing. These are therefore the directions FCC Lattice: In a similar analysis for FCC lattice,
along which constructive interference between Bragg’s diffraction peaks are observed for planes
scattered x-rays takes place. When the Bragg’s having all the three Miller’s indices odd or all of them
condition is satisfied, then whole of the incident are even.
beam is diffracted into a single beam producing a
spot on the film, which represents a set or family of
11.5.3 Physical Meaning of Scattering Vector
reflecting planes (hkl ) . If the crystal is rotated now, We can give an important meaning to scattering
a new set of planes will satisfy the Bragg’s condition vector which is expressed mathematically as
producing another spot representing this new set. r r r r
s = k − k0 = G

r r r
k = k0 + G certain limitations or demerits. These techniques are
r r r
hk = hk 0 + hG (11.44) discussed in subsections to follow:
According to equation (11.44), the term on LHS
denotes the momentum of scattered x-ray photons 11.6.1 Rotating Crystal Method
v r
while the terms hk 0 and hG denote the This method is used for the analysis of structure of
single crystal. The experimental arrangement is
momentum of incident photon and momentum
shown in figure 11.6 below. The crystal is usually
associated with recoil of crystal due to collision of x-
about 1mm in diameter and is mounted on a spindle
ray photon with it. Hence this equation represents
which can be rotated.
momentum conservation for interaction of x-ray
photon with the crystal lattice. Since the crystal is
massive, it carries negligible recoil energy and
collision is practically elastic in nature.
11.6 Experimental Techniques for X-Ray

Diffraction
The experimental techniques used to study crystal
Figure 11.6: The experimental arrangement for
structure have an objective of measuring the
rotating crystal method of x-ray diffraction.
following quantities in general:
(i) The scattering angle 2 θ between diffracted and
A photographic plate is placed on the inner side of
incident beams. By substituting sin θ in Bragg’s
the cylinder concentric with the axis of rotation. A
law, one can determine inter-planar spacing and
the orientation of those crystal planes which play
monochromatic beam of wavelength (λ ) is
collimated and made to impinge on the crystal. The

an active role in diffraction.
specimen is then rotated, if necessary, until
(ii) The intensity of the diffracted beam, which
diffraction condition is satisfied (i.e.
determines cell geometrical structure factor Fhkl
λ and θ satisfy Bragg ' s law ). When this
and hence yields information about arrangement
occurs, diffracted beam emerges from the crystal
of atoms in the unit cell.
and is recorded as a spot on the film. By recording
The different experimental techniques are employed
the diffraction pattern (both angle and intensities)
to quantitatively study the crystal structure. Each of
for various crystal orientations, one can determine
these techniques have their merits and also offer

the shape and size of unit cell and also the part (b) of figure 11.7, the crystal exhibits 6-fold
arrangement of atoms inside the cell. symmetry.
11.6.2 Laue’s Method 11.6.3 Powder Method

This method can be used for rapid determination of This method is used to determine crystal structure
symmetry or orientation of a single crystal. The even if the specimen is not a single crystal. The
experimental arrangement is shown in figure 11.7 specimen may be made up of fine grained powder
below. The white x-ray beam is made to fall on the packed into a small cylindrical glass tube or it may be
crystal, which has a fixed orientation relative to the polycrystalline having large number of micro-crystals
incident beam. Flat films are placed in front and which are more or less randomly oriented. A
behind of the specimen. Since the incident x-ray monochromatic x-ray beam impinges on the
have a continuous range of wavelengths, a family of specimen and the diffracted beam spots are
crystal planes select a particular wavelength which recorded on a cylindrical film surrounding it. Since
satisfies the Bragg’s law at the present orientation. the crystallites are randomly oriented, there are
always enough of crystal planes which satisfy the
Bragg’s condition and hence diffracted beam emerge
at the corresponding angle. Since wavelength and
angle are measurable, the inter-planar spacing can
be determined. Other sets of planes lead to other
diffracted beams corresponding to different planar
spacing for the same wavelength. Thus one can
Figure 11.7: The experimental arrangement for determine the lattice parameter accurately if the
Laue’s method. crystal structure is known.
The diffracted beam emerges at a corresponding Numerical Problem Set II

angle and gets recorded as a spot on the film. Since 1. A unit cell has the dimensions a=0.4nm,
the wavelength is not known, only ratios of inter- b=0.6nm, c=0.8nm, α = β = 90 0 , γ = 120 0 .
planar spacing are measurable. These ratios enable
Determine (i) lattice constants for the reciprocal
us to ascertain the shape of the unit cell but not its
cell (ii) The volumes of reciprocal and real unit
size. If the direction of the beam is along the axis of
cells (iii) The spacing between (210) planes. (iv)
symmetry of the crystal, then the diffracted pattern
Bragg angles for reflection from the (210) planes.
exhibits the symmetry of the crystal. As shown in

2. Show that the reciprocal lattice for FCC is BCC 6. An X-ray analysis of a crystal is made with
and that for BCC is FCC. monochromatic X-rays of λ = 0.58Ǻ. Bragg’s
3. Calculate the glancing angles of a cube (100) of a reflections are observed at angles of 6.45o, 9.15o
rock salt (a=0.2814nm) corresponding to second and 13o. Calculate the inter-planer spacing.
order diffraction maxima for x-rays of 7. From a powder camera of diameter 114.6mm,
wavelength 0.071nm. using x-ray beam of wavelength 1.54Ǻ, the
4. Monochromatic X-rays of λ = 1.5Ǻ are incident following s values (in mm) are obtained for a
on a crystal face having inter-planer spacing of material : 86, 100, 148, 180, 188, 232 and 272.
1.61Ǻ. Find various orders at which Bragg’s Determine the structure and lattice parameter of
reflection takes place. the material.
5. A diffraction pattern of a cubic crystal structure 8. A diffraction pattern of a cubic crystal of lattice
of lattice parameter 3.16Ǻ is obtained with parameter a = 3.16Ǻ is obtained with a
monochromatic X-ray beam of wavelength monochromatic x-rays of wavelength 1.54Ǻ. The
1.54Ǻ. The first line on this pattern was observed first four on this pattern were observed to have
o
at 20.3 . Determine the inter-planer spacing and the respective values of 20.3o, 29.2o, 36.7o and
Miller’s indices of the reflecting plane. 43.6o. Determine the inter-planer spacing and
Miller indices of the reflecting planes.

DEFECTS IN SOLIDS
12.1 Imperfections in Crystals defects are discussed in the remaining portion of this
section. Depending upon the type of above-
The perfect crystal is a mathematical idealization
mentioned irregularity, the point defects are
which can be visualized as a regular and periodic
classified as:
three dimensional array formed by repetition of a
basis (which may an atom or ion or molecule). In real 12.2.1 Impurity or Interstitial Atoms
situations such crystals are difficult to grow and This defect is caused by an irregularity in the crystal
employing sophisticated techniques of crystal structure localized to a lattice position or interstitial
growth can considerably reduce defects and space, for example presence of a foreign or an
impurities but can never eliminate them completely. impurity atom. Many impurity atoms of small size,
Certain defects such as binding surface of crystal, present in atmosphere (such as hydrogen, oxygen
creeping of impurities or vacancies are associated and nitrogen), get embedded in the crystal during
inherently with techniques employed in growing the process of crystallization. Such atoms can occupy
crystals and metallurgical operations over them. In regular lattice sites which are referred to as
many situations, the defects are induced in the substitution impurities or they may lie in the
crystal to customize some of its properties. interstitial spaces (called interstitial impurities). An
A defect is defined as a break or irregularity in the appreciable number of substitution impurities may
long range order or periodicity observed in a crystal be present if the size of impurity atoms is not far
structure. These defects can be classified as (i) point different from that of regular atoms. In the similar
or zero order defects (ii) line or first order defects or spirit, it can be argued that only small atoms can
dislocations (iii) surface or second order defects and possibly be present in interstitial spaces.
(iv) volume or third order defects.
12.2 Point Defects

These are defects which can be caused as a result of
(i) presence of foreign or impurity atoms in crystal,
(ii) presence of vacancies at lattice sites (iii)
displacement of regular lattice atoms to interstitial Figure 12.1: The crystal structure showing different
spaces and (iv) formation of color centre. These kinds point defects.

12.2.2 Vacancies crystal has N atoms, then number of vacancies, at
An empty lattice site, from where a regular atom has any temperature T, are
been displaced or removed, leads to formation of −
Qv
N v = Ne kT
(12.1)
vacancy. These vacancies are created due to thermal
Here N o denotes the total number of lattice
excitations at very high temperatures, where the
positions in a unit volume of crystal, N v is the total
vibrating atoms acquire sufficient energy to leave
number of vacant positions in unit volume of the
their regular lattice positions. Other possible sources
crystal, Q v is the activation energy required for
of vacancy production in the crystal are related to
formation of vacancy and k is the Boltzmann
the extensive plastic deformation and high energy
constant. Hence as T increases, number of vacancies
particle bombardment of crystals. The presence of
increase in exponential manner. At room
vacancy results in distortion in its immediate
temperatures, the fraction of lattice position
neighborhood because of local lattice relaxation. It is
remaining vacant may be as high as 0.1%.
very common in the crystals to have large number of
vacancies in them at room temperatures.
12.2.3 Defects in Ionic Crystals
The energy required to create a vacancy, called the
formation energy (Q v ), can be evaluated by the In ionic crystals, the lattice positions are occupied by
knowledge of coordination number of atom when ions. These ions can get dislocated from their regular
placed at regular site and average bond energy. The lattice positions either due to thermal excitations or
average number of vacancies created in crystal high energy particle bombardment. If the displaced
specimen, due to thermal excitations, can be atom diffuses to the surface of crystal, then such a
estimated from the knowledge of the formation defect is referred to as Schottky defect. In such a
energy of vacancy, temperature of crystal and total defect the cation and anion vacancies are produced
number of atoms constituting the specimen. The together so as to maintain charge neutrality.
vibrating atoms in the crystal, at any temperature T,

have an average energy 3kT which is usually
significantly smaller than energy Q v (formation
energy) for room temperatures. However the
vibrating atoms in the crystal can have all possible
energies and their distribution is guided by Maxwell-
Boltzmann distribution. Hence the probability that a
Qv
−
vibrating atom has energy Q v is e kT
. Hence if a Figure 12.2: The crystal lattice depicting ionic
defects.

However in certain circumstances, the removed due to anion (halogen ion) vacancy created by
atoms move through the interstitial spaces within irradiation of the crystal. The valence electron of cat-
the deeper volume of the crystal and such a defect is ion (alkali ion) suffers attraction and gets trapped in
called Frenkel defect. The Schottky defects are vacant site. The orbital motion of this electron
characterized by presence of pair of ion vacancies around vacancy (acting as positively charged) is
while the Frenkel defect is characterized by presence quantized and has a series of discrete levels in
of ion vacancy which corresponds to missing ion and optical frequency region. Hence such an orbiting
an interstitial ion displaced from the regular lattice electron suffers excitation on absorption of light and
site. The Frenkel defects are energetically less re-emits on its de-excitation thereby giving
favorable due to strain energy required in distorting characteristic color to the crystal.
the lattice at the site of vacancy as well as around
the atom displaced to the interstitial space. The 12.3 Line Defects
Frenkel defects are usually caused either thermally
The line defects, also called dislocations, arise due to
at temperatures close to the melting point or due to
presence of additional linear array of atoms
external radiation which may knock out an atom
extending over a considerable distance inside a
from regular lattice site. The Schottky and Frenkel
lattice. These defects are of two types (a) Edge
defects are shown in the figure 12.2.
dislocation and (b) screw dislocation.
12.2.4 Color Centers

12.3.1 Edge Dislocation
These set of defects arise because of charge
The figure 12.3 shown below depicts the edge
compensation. If a crystal is irradiated by neutrons,
dislocation
electrons and gamma-rays, their color suffers a
change. For example a diamond crystal turns blue on
electron bombardment and brown on neutron
irradiation. The color change takes place because of
crystal damage caused by irradiation, leading to
formation of various types of point defects. The color Figure 12.3: The diagram depicts the edge
centre is a lattice defect that absorbs the visible dislocation.
light.
The most extensively studied color centre is F-centre The extra half plane of atoms AB has been
(F stands for Farbe meaning color in German) which embedded into the upper half of the crystal as
is common in alkali halide crystals. They originate shown in the cross-sectional view of crystal in the

figure 12.3. The half plane terminates at A, which in of dislocation and it lies at end of the step BAB’. This
two dimensions, represents a linear array of atoms in is referred to as screw dislocation because of the fact
direction normal to the plane of paper and this array that if one moves in the atomic plane around the axis
form the edge referred to as the dislocation. The of dislocation, the plane actually follows a spiral (see
region in the neighborhood of dislocation suffers figure 12.5).
distortion which extends over many atomic lengths.
The upper region, having extra half atomic plane
introduced, suffers compression while lower region
is somewhat expanded. The strain caused by such a
dislocation fades far away from the site of
dislocation. The formation energy or elastic strain
energy for this dislocation is considerably high and
consequently such dislocations can’t be caused by
thermal means but they are formed as a result of
Figure 12.5: The diagram depicts the spiral ramp
mechanical treatment such as hammering or
formed as a result of screw dislocation.
bending.
In such a dislocation, the crystal suffers shear strain

12.3.2 Screw Dislocation
due to slippage of plane. The volume of the crystal
The screw dislocation is observed in the figure 12.4
does not suffer any alteration unlike in the edge
shown below. To visualize the nature of this
dislocation. These dislocations involve large energy
dislocation, let’s consider a planar cut ABCD made in
of formation and are not possible by thermal means.
the crystal. The left side is then slipped up with
respect to the right side. The line AD is called the axis
12.4 Surface Defects
In such defects, the crystalline irregularity extends in
plane and hence are referred to as surface defects.
The following figure 12.6 describes the classification
into different kinds of surface defects. The surface
defects may arise within pure crystal or even may
Figure 12.4: The diagram depicts the screw arise because compositional changes observed
dislocation. within in a crystal.

The crystals can be grown from a gas by sublimation
or from a liquid by crystallization. When a crystal
grows from a vapor or liquid, its continued growth
depends upon the sufficient supply of growth units
(i.e. the atoms required to make up its structure). If
the supply is overabundant, then crystal may grow
extremely fast and in many directions at once
thereby giving a branchlike appearance. Such a
Figure 12.6: The diagram depicts different types of crystal, referred to as poly-crystal, has many orderly
surface defects. arrangements of atoms, having different

orientations, which interpenetrate into each other.
The surface defects are classified into the following Each of the orderly arrangement is called a crystal
types: grain and common interface of two adjacent grains is
12.4.1: External Surface Imperfections referred to as a grain boundary. One such
The binding surface of the crystal itself, as shown in polycrystalline structure composite of many grains in
the figure 12.7, is a surface defect as surface atoms shown in the figure 12.8 below:
have much different environment than those lying in

deeper volume of the crystal.
Figure 12.8: The polycrystalline structure composed

Figure 12.7: The diagram depicts a different atomic
of main grains having different orientations.
environment for surface atom which is a king of
imperfection.
The shape of the grain is usually influenced by
presence of its surrounding grains. The boundary
12.4.2 Grain Boundaries
atoms in two randomly oriented grains can’t have
Most of the solids are not purely mono-crystalline
perfect complement of surrounding atoms and a
rather are polycrystalline in nature. A given crystal is
transition occurs in atomic packing which is the
usually composed of large number of single crystal
cause of imperfection. At each grain boundary, the
grains which are joined together.
crystal suffers change in orientation and

consequently this boundary behaves as a surface 12.4.3 Twin Boundaries
defect. The grain boundaries are the surfaces along Another planar surface imperfection is a twin
which the crystal can be cleaved with little effort boundary. The atomic arrangement on one side of
because of weak cohesivity. At such boundaries, the twin boundary is the mirror reflection of the
atomic arrangement suffers a disorder and these arrangement on the other side. Twin boundaries
regions are characterized by low atomic densities. appear in pairs such that orientation change,
Due to disorder and low density, these regions have introduced on one side, is restored on other side.
high mobility, diffusivity and chemical activity. These The region between twin boundaries is called
defects have a strong influence on properties of a twinned region. The twin boundary is shown in the
poly-crystal. figure 12.10 below:
The boundaries where the crystal orientation suffers
a change of more than 10o are called high angle
grain boundaries. These boundaries have less
efficient packing of atoms and atoms forming the
boundary have higher energy than those within the
grains. In certain cases of surface defects, the
orientation difference between two adjacent grains
Figure 12.10: The diagram depicts the twin
is less than 10o, which is referred to as low angle
boundary.
grain or tilt boundaries. The tilted boundaries can be
The phenomenon of twinning occurs when a crystal
described by an array of edge dislocations lying one
planes suffer a slip because of applied shear stress
above the other as shown in the figure 12.9 below.
(mechanical twin which is quite common in BCC and
HCP crystal structures) or during annealing
treatment (annealing twin observed in FCC crystals).
12.4.4 Stacking Faults

A stacking fault occurs when in the regular stacking
sequence of the crystal, one plane is out of
Figure 12.9: The low angle grain boundary can be
sequence, while the lattice on either side of the fault
described as an array of close lying edge dislocations.
is perfect. These faults occur during crystal growth
phase when close packed layers grow over one
another. It results when a layer starts incorrectly. For

example in FCC close packing, instead of regular 12.5 Volume Defects
sequence of layers ABCABCABCA…. the sequence
The volume or bulk defects in the crystals arise due
gets changed to ABCABABCA….. The plane of atoms to the following reasons:
A after second B layer in latter sequence constitutes • Occurrence of small electrostatic dissimilarity
a thin region of HCP stacking in FCC crystal which
between stacking sequence of close packed
lead to significantly weak cohesivity. Such type of
planes in metals.
interruption of stacking is also referred to as
• Presence of a large void due to group or cluster of
deformation fault.
atoms missing.
• Presence of group of atoms which are termed as
12.4.5 Slip in Crystals precipitates.
The crystals, when subjected to shear stress, result in
restricted motion of certain atomic planes relative to
12.6 Strength of Metals
others. This is same as distortion produced in the
The metals have many distinctive properties such as
deck of cards when certain cards are forced to
elasticity, ductility and malleability, which make
protrude out. The phenomenon of slip occurs along a
them highly useful for industrial applications. The
plane in the crystal and this is referred to as slip
metals in their pure state are soft and easily
plane. If the atomic planes suffer shear stress
deformable. We wish to understand the mechanical
exceeding the critical value, then one or more atomic
strength of metals using the microscopic picture and
plane get displaced relative to other. The slip in a
study the influence of dislocations and impurities on
crystal is realized through motion of dislocations of
their mechanical strength.
both type and this phenomenon plays an important
When a metal is subjected to small amount of stress,
role in defining the plastic deformation in the
they suffer strain but recover completely when the
crystals.
imposed stress is withdrawn completely. This is
It has been observed that the crystal planes having
referred to as elasticity of metal. During application
low values of Miller’s indices are characterized by
of stress in the elastic region of metal, the atomic
greater atomic planar density and are more prone to
planes are pulled apart and their separation is
slip. The BCC and FCC systems have large number of
proportional to the magnitude of stress applied. On
such planes and hence they can suffer extensive
withdrawal of applied stress, these planes are
plastic deformation resulting in greater malleability
restored to their equilibrium positions and
and ductility. However the HCP crystal systems have
orientations.
lesser number of such planes and hence are brittle in
nature.

However when the metal is subjected to shear stress crosses the atom of stationary plane, it has to
beyond the elastic limit, then it suffers shearing overcome a potential barrier. Since the slippage of
strain and does not recover even when the stress is one atomic plane over the other will lead to
completely removed. This is called plastic overcoming very large number of such potential
deformation of metal. During plastic deformation, barriers so the critical stress becomes much higher
various regions of crystal appear to slip against each than observed experimentally. Consequently this
other. The crystalline regions undergoing slippage picture is not capable to explain surprising softness
form slip bands which slide past each other. and a general tendency of metals towards plastic
To understand the slip process, let’s consider that a flow.
force F is applied over a surface having area of cross- When a metal crystal is grown a large number of
section A such that it makes an angle θ with the dislocations are formed in the process. If an edge
normal to surface. The shear force will be given by dislocation is considered in the volume of crystal,
the component Fsin θ while the effective area over then applied shear stress shifts the extra half plane
A by one inter-atomic separation past the lower half
which it acts is . Hence shear stress is given as:
cosθ plane. Consequently the half plane gets shifted to
F sin θ F surface of crystal (see figure 40).
τ= = sin θ cos θ
A A
cos θ
σ
τ= sin 2θ (12.2)
2
Hence the shear stress is maximum when force is
inclined at an angle of 45o to the normal to the
surface. As a result, slippage must occur when
σ Figure 12.11: The slip of crystals described as motion
τ > along that plane. Since crystals are
2 of edge dislocations under the influence of shear
anisotropic, there are plane which have lower critical
stress.
value of shear stress to suffer slip and they usually
have higher atomic concentrations. They are called
Since the dislocation region is already strained so
easy slip planes.
they are not in stable equilibrium and lower stress is
If one plane of atoms is to slip over the other,
required to shift the upper half plane. This requires
theoretically predicted values of critical stress are
much lower shear stress than sliding of one whole
much higher than those observed experimentally.
atomic plane over the other. Hence dislocations
This is because each time atom of slipping plane
make the crystal much softer and increase their

tendency towards plastic flow. A metallic crystal, if greater resistance to plastic deformation and is said
grown free of dislocations, will require very large to be pinned down by impurities or defects. This
shearing stress for causing even very small plastic phenomenon is called impurity hardening.
deformation. This explain as to why the perfect Another interesting effect observed is that metals
crystals are highly resistant to plastic deformation. become hardened after being strained. This
The impure metals or alloys are usually stronger than phenomenon is called work hardening. This happens
pure metals because of the fact the impurity atoms because the strain produces very large number of
or defects have a strong tendency to accommodate dislocations. These dislocations interfere with each
in the region of dislocations. The dislocation is now other and prohibit the relative motion of each other.
loaded with impurity atoms or defects and it
becomes difficult to move it readily as it has to carry
the impurities along with it. Such a crystal shows

DIFFUSION
13.1 Introduction pharmaceutical applications is undisputed through
the drug therapy curing a specific portion of body.
In a sample having non-uniform composition of
certain kind of atoms, a concentration gradient is set
in, which leads to migration of atoms from region of 13.2 Basics of Diffusion
their higher concentration to the region of lower The process of diffusion involves two components: (i)
concentration. This phenomenon is referred to as solvent is the medium in which atoms of similar or
Diffusion and continues till atomic distribution different kinds are to be diffused and (ii) solute are
becomes homogeneous throughout. the atoms of one or more kinds which are to be
The diffusion process plays an important role in the diffused into the environment of solvent. The solute
field of metallurgy and fabrication of extrinsic atoms migrate and distribute themselves in solvent
semiconductors. The technology of controlled in process of which they may become interstitial
diffusion plays a sensitive role in accomplishment of impurity (occupying interstitial spaces in solvent
desired devices. The metals, in their pure form, are lattice) or substitution impurity (substituting the
soft and do not possess large tensile strength. Their solvent atom from its regular position in lattice).
properties can be modified by the process of alloying The process of diffusion can be classified into two
in a controlled manner. The desired properties of types which are (a) Self-diffusion in which solute and
alloys are achieved by proper choice of solute (atoms solvent atoms are identical. For example diffusion of
to be diffused) and their amount to be diffused. This copper in copper (b) Inter-diffusion in which the
is accomplished through sophisticated techniques solute atoms are different from the solvent atoms as
and instruments. Further the dynamical processes of in the case steel where solvent is iron whereas solute
bio-systems utilize the phenomenon of diffusion in atoms are those of carbon and many other elements.
wide variety of ways which include the role of blood The phenomenon of diffusion of solute atoms into
circulation leading to nourishment of various body the solvent environment may occur through the
organs and also waste disposal from them. The following mechanisms:
control of heart beat through hormonal diffusion and (a) Vacancy mechanism where the solute atoms lie in
digestion of food through enzymatic action are some the vacancy and moves to other available
of the examples. Further the role of diffusion in vacancy. Atoms can move from one site to
another if there are vacancies and the atom has

sufficient energy to overcome a local activation structure of solvent, imperfections in crystal and
energy barrier. The activation energy for diffusion concentration of diffusing species.
is the sum of energy required to form a vacancy The Fick’s law can be understood to a greater extent
and further cause its motion. through a kinetic model. Let’s consider a one
(b) Interstitial Mechanism is applicable in case of dimensional flow of solute atoms in normal direction
small atoms like hydrogen, helium, carbon, through section S as shown in the figure 13.1 below:
nitrogen diffuse through the interstitial spaces in
a
a crystal. The activation energy for diffusion is the
energy required for these atoms to squeeze
through the small voids between the host lattice
atoms. S
13.3 Macroscopic Model of Diffusion c1 c2
13.3.1 Fick’s First Law Figure 13.1: The diagram showing the one
The basic process of diffusion kinetics is described by dimensional flow of atoms through the intermediate
Fick’s first law which states that the diffusion current plane S through their jumping in either of two
(J) is directly proportional to the concentration possible directions.
 ∂c 
gradient  . Hence we express this
 ∂x  The concentration of solute atoms in adjacent planes
mathematically as: are indicated by c 1 and c 2 (c 1 > c 2 ) respectively. The
∂c atoms on both the planes jump randomly to right as
J = −D (13.1)
∂x well as left. The atoms of plane 1 which jump to right
The negative sign indicates that solute atoms
and those of plane 2, which jump to left will cross
migrate down the concentration gradient. The
the section S in opposite directions. Since the net
diffusion current is defined as the mass of solute
flow of solute atoms will be towards right so we can
atoms migrating in one second through a unit area of
write diffusion current as:
cross-section placed normally to the direction of
1 1
flow. The constant D is called diffusion coefficient
J = n1v − n2 v (13.2)
2 2
which is characteristic of solute atoms and solvent In the equation (13.2), n 1 and n 2 represent planar
environment, depends upon temperature of solvent densities of solute atoms at planes 1 and 2
medium, mechanism of diffusion, type of crystal respectively while v represents the jump frequency.
The factor of half accounts for equal probability of

jumping in one of the two possible directions leading 13.3.2 Fick’s Second Law
to net rate of flow through section S. The The diffusion of solute atoms in solvent environment
concentrations c 1 and c 2 are defined as number of obeys the continuity equation given as:
solute atoms per unit volume at plane 1 and 2 ∂c ∂J
+ =0 (13.7)
respectively. Hence we can have relation between ∂t ∂x
atomic density and concentration of solute atoms at Putting equation (13.1) in (13.7), we get:
a plane as n = ca. Using this relation in (13.2), we get: ∂c
=−
∂  ∂c 
− D 
∂t ∂x  ∂x 
1
J = av ( c1 − c2 ) (13.3) ∂c ∂ 2c
2 =D (13.8)
∂t ∂x 2
If the concentration does not vary rapidly between The equation (13.8) is called the Fick’s Second law.
the planes 1 and 2, then we can write as: The solution of equation (13.8) for the one
∂c dimensional case of diffusion being studied is
c1 − c2 = − a (13.4)
∂x
x2
Putting (13.4) in (13.3), we get: A − 4 Dt
c( x, t ) = e (13.9)
t
1 ∂c
J = − a 2v (13.5) The depth of diffusion as a function of time is
2 ∂x
Comparing the equations (13.1) and (13.5), the evaluated by root mean square value of x and is
diffusion coefficient D in one dimensional case can given as:

∞
be expressed as:
∫x
2
c( x, t )dx
1 2 x= 0
(13.10)
D= va (13.6) ∞
2 ∫ c( x, t )dx
0
If we consider the three dimensional case then the
The above integral, with use of equation (13.9),
atom can jump in any random direction and its
yields x as
1
probability of crossing the section S will be
6 x = 2Dt (13.11)
instead of half and the diffusion coefficient will Hence the diffusion front advances into the solvent
become: environment with distance traversed proportional to
1 2 square root of time. The diffusion coefficient being
D= va (13.7)
6 very small, the process of diffusion is an extremely
-20 -50 2
The values of D can range from 10 –10 m /s slow in nature.
which correspond to jumping frequencies ranging
from 10-20Hz to 1Hz. This indicates that the diffusion
is an extremely slow process.

13.4 Microscopic Model of Diffusion R2
have x = y = z =
2 2 2
and equation (13.13)
In the microscopic picture, the diffusion is migration
3
takes the form as
of atoms between adjacent lattice sites. The atomic
motion is random but leads to slow and organized nd 2
x= (13.14)
macroscopic motion down the concentration 3
gradient. To understand the atomic picture of the Using equations (13.11) and (13.14), we get diffusion
diffusion process, let’s consider one dimensional coefficient as:
lattice with an atom placed at position x=0. The atom vd 3

D= (13.15)
hops to adjacent lattice site at frequency v but at 6
every lattice site the direction of hopping is The equation (13.15) gives same result as obtained
completely random. Hence it may jump to left or using macroscopic model.
right with equal probability. If d is the distance

between adjacent sites, then position ( xn ) after n 13.5 Diffusion: Temperature Effects
jumps will be given as: The diffusion in a solid may take place through any of
xn = d 1 + d 2 + .......... + d n (13.12) the following mechanisms:

(a) The solute atom, if small in size that it can be
The d i may be +d or –d depending upon the
accommodated in interstitial spaces, jumps from
direction of hopping. Since the overall motion of
one interstitial space to another. This is common
atoms leads to displacement so we can express it as
case in the diffusion of carbon atoms in the
root mean square value of ( xn ) . Hence we can write
formation of steel alloy.
as: (b) The solute atoms, in case of substitution alloys or
L impurities, diffuse through the exchange of
x= x n2 = nd 2 = (13.13)
n positions with other neighbouring regular atoms.
where L=nd is the distance travelled in n jumps along (c) The migration in case of vacancy is by succession
one direction only. For n very large, we have x << L of many atoms filling the vacancy which migrates
which implies that diffusion is very slow due to in this process in opposite direction.
random motion of atoms. All these mechanisms may occur simultaneously too.
If the atom is allowed to move in all directions then When the atom or vacancy moves from one position
x will be replaced by R since the atoms would now to another, it pushes other atoms sideways resulting
move radially outwards. In symmetrical case we will in local elastic strain. As a result, the process of atom
making a transition from one to other lattice site
requires at least energy equal to elastic strain

energy, which is also referred to atomic transition −
Q
D = D0 e kT
(13.16)
energy (Em ) and is of the order of 1eV roughly. Q
ln D = ln D0 −
Another energy required by atom to make transition kT
Hence one observes that the diffusion coefficient
is that required to create vacancy at its initial site
varies rapidly with temperature. The plot of
(Ev ) and is called vacancy formation energy. Thus
1
total energy, also called activation energy, required log e D vs gives D o as intercept and -Q/k as
T
is sum of energy of formation of vacancy and atomic
slope.
transition energy i.e. Q = Ev + Em .
The atom oscillates at frequency v0 around its Numerical Problem Set III
equilibrium position and energy possessed by it is far 1. Calculate the equilibrium number of vacancies
less than that required to cause jumping to per cubic meter for copper at 1000oC. The
neighbouring site. However for a fraction of time, energy for vacancy formation is 0.9eV/atom; the
Em
− atomic weight and density (at 1000oC) for copper
equal to Boltzmann factor e kT
, the atom gets
are 63.5 g/mole and 8.4 g/cm3 respectively. (2.2
sufficient energy required for atomic transition.
x 1025 /m3)
Hence if the atom oscillates at frequency v0 , then
2. Calculate the percentages of interstitials and
Em
−
jumping frequency at any temperature is v = v0e kT
. vacancies at the melting point in Cu (1356K). The
formation energy for these defects in Cu are
This atom, in three dimensional crystal, can jump to
4.5eV and 1.5eV respectively.
any of its z neighbouring sites provided there is a
3. A plate of iron is exposed to carburizing (carbon
vacancy in them. The probability of a neighbouring
Ev
rich) atmosphere on one side and a
−
site having vacancy is e kT
. Hence total probability decarburizing (carbon deficient) atmosphere on
of jumping is the other side at 700oC. If the condition of steady
 − Em  − kT
Eν
 (E +E )
− m ν state is achieved, calculate the diffusion flux of
v =  v0 e kT  ze

 = zv0 e kT

   carbon through the plate if the concentration of
−
Q
carbon at position of 5mm and 10mm beneath
= zv0 e kT
the carburizing surface are 1.2 and 0.8kg/m3,
The diffusion coefficient D is given as:
respectively. Assume diffusion coefficient= 3 x
Q
1 −
D= zv0 a 2 e kT 10-11m2/s at this temperature. (J=2.4 x 10-9
6
kg/m2s)
1
If D0 = zv0 a 2 then
6

4. The diffusion coefficients for diffusion of Cu in Al
at 500oC and 600oC are 4.8 x 10-14 m2/s and 5.3 x
10-13 m2/s that will produce the same diffusion
result (in terms of concentration of copper at
some specific point in Al) as a 10h heat
treatment at 600oC. (110.4h)
5. Nitrogen from a gaseous phase is to be diffused
into pure iron at 700oC. If the surface
concentration is maintained 0.1wt%N, what will
be concentration 1mm from the surface after 10
hours. The diffusion coefficient for nitrogen in
iron at 700oC is 2.5 x 10-11m2/s.
6. At approximately what temperature would a
specimen of γ − iron have to be carburized for 2
hours to produce same diffusion result as at

900oC for 15 hours.
7. The activation energy for the diffusion of Cu in
Ag is 193kJ/mole. Calculate the diffusion
coefficient at 1200K if diffusion coefficient at
1000K is 1.2x10-14m2/s.
8. The diffusion coefficients for carbon in nickel is
at 600oC and 700oC are 5.5 x 10-14 m2/s and 3.9 x
10-13 m2/s respectively. Find the value of Q and
D o . What is the diffusion coefficient at 850oC.

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PHYSICS OF CRYSTALS

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 97

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 98

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 99

called lattice translation vector which can

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 100

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 101

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 102

Figure 10.5: The diagram depicting the rotation of

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 103

10.5.4 Reflection Symmetry Roto-Inversion Symmetry: In the similar manner,

Screw Axis: A kind of hybrid symmetry is generated

Roto-Reflection Symmetry: The improper rotation

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 104

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 105

Figure 10.9: The centred rectangular lattice with

Oblique: This unit cell is characterized by basis

Figure 10.10: The oblique unit cell with its

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 106

Figure 10.11: The hexagonal planar lattice with

10.6.2 Bravais Lattices in Space

Table 5.1: The tabulation of seven crystal systems,

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 107

which has eight atoms at vertices of the cube and 1

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 108

atomic layers. morphology.

packed plane of atoms may rest. Those having

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 109

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 110

In triangle AXZ, we have: 10.10 Voids in Closest Packed

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 111

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 112

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 113

10.11 Indexing in Crystals

triplet of indices [n1 , n 2 , n3 ] in lowest possible

integer ratio gives the direction of line joining the

centre positions of adjacent cubic cells. The

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 114

a b c lead to constructive interference of scattered x-

(100), (010), (001), ( 1 00), (0 1 0), (00 1 ) are equivalent

The prescription of specifying Miller’s indices for

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 115

(b) The direction [uvw] is normal to the plane

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 116

composed of two interpenetrating lattices of Na+ diagonal.

and Cl-, which are displaced relative to each other

Figure 10.23: The crystal structure of CsCl.

10.11.3 Polymorphic Forms of Carbon

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 117

Figure 10.25: The arrangement of carbon atoms in

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 118

The nanotubes are extremely strong and stiff but

10.11.4 Structure of Zinc Blende (ZnS)

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 119

network of SiO44− tetrahedron when every oxygen

atom, lying at the vertex of a tetrahedron, is

is SiO44− tetrahedron which has silicon sits at

centre of tetrahedron and is bonded to four Silica Glasses

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 120

Numerical Problems Set I (0.5,0,0.5). What are its Miller indices.

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 121

Dr. J.K.Goswamy’s Lecture Notes: Physics of Crystals. Page 122

11.2 Bragg’s Law