UNIT II

Crystallography and X-ray diffraction

CO 2: Familiarize with the basics of crystals and their structures
Course content:
Crystallography:
 Space lattice, Basis, Unit Cell and lattice parameters
 Seven crystal systems (3D) fourteen Bravais Lattices
 Coordination number - packing fraction of SC, BCC & FCC
 Miller indices – separation between successive (hkl) planes.
X-ray diffraction:
 Bragg’s law
 X-ray Diffractometer
 Crystal structure determination by Laue’s and
 Crystal structure determination by powder methods.

Crystallography
Crystallography: It is the branch of science which deals with the study of geometric form and other
physical properties of crystalline solids by using x-rays, electron beams and neutron beams.

Solid: A Solid consists of a large number of closely packed atoms or molecules.

Solids are classified into two categories based on the arrangement of atoms. They are
1. Crystalline Solids
2. Amorphous solids
Comparison between crystalline solids and amorphous solids:
Crystalline solids Amorphous solids
When the atoms or molecules in solids When the atoms or molecules in solids
are arranged regularly and the are arranged irregularly and the
environment about each atom is same, environment about each atom is not
then the solids are called crystalline same, the solids are called amorphous
solids solids.

The two dimensional patterns of two The two dimensional patterns of two
crystalline solids are shown in above amorphous solids are shown in above
Fig. Fig
Crystalline solids have regular and Amorphous solids have irregular
periodic arrangement of atoms arrangement of atoms
Crystalline solids are anisotropic in Amorphous solids are isotropic in
nature. ( having different properties in nature. ( having same properties in all
different directions) directions)
Crystalline solids have very sharp Amorphous solids do not have sharp
melting points. melting points
Crystalline solids have long range order Amorphous solids have short range

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 of atomic interaction. order of atomic interaction
The cooling curve of crystalline solids The cooling curve of amorphous solids
has breaks is smooth

Crystalline solids have low lattice Amorphous solids have high lattice
energy enery
Ex: Rock salt, calcite, sugar, quartz etc., Ex: Glass, rubber, plastic, silica etc.,

Fundamental definitions of crystallography:

Crystal structure: The atomic arrangement in a crystal is called crystal structure.

Lattice point: Lattice point denotes the position of atoms or molecules site in the crystal.

Space Lattice (or) crystal lattice: A space lattice is defined as an array of lattice points in space
such that the environment about each point is the same.
(or)
It is also defined as an infinite three dimensional array points showing how atoms are arranged in a
crystal.
Basis: In order to obtain a crystal structure, an atom or a group of atoms must be place at each
lattice point in a regular fashion; such group of atoms are called Basis.
(or)
A group of identical atoms or molecules in composition is called basis.
Crystal Structure:
A crystal structure is obtained by arranging the basis in each and every lattice point.
𝐬𝐩𝐚𝐜𝐞 𝐥𝐚𝐭𝐭𝐢𝐜𝐞 + 𝐛𝐚𝐬𝐢𝐬 = 𝐜𝐫𝐲𝐬𝐭𝐚𝐥 𝐬𝐭𝐫𝐮𝐜𝐭𝐮𝐫𝐞
The generation of a crystal structure from a two dimensional lattice and a basis is illustrated in the
following figure.

Translation Vector:
The periodically repeating arrangement of points in space lattice can be described by the operation
of parallel displacement called translation vector.
Explanation:
Consider the case of a two dimensional array of lattice points as shown in figure.

2
Let ‘a’ and ‘b’ are called lattice parameters along X- and Y- directions. When the periodicity is also
extended into Z-direction, its periodicity is given as ‘c’.
Let n1 be the number of translations along X-direction each of magnitude ‘a’, then its translation
vector T⃗ = n a⃗
Let n2 be the number of translations along y-direction each of magnitude ‘b’ then its translation
vector is T⃗ = n b⃗
Let T⃗ be the resultant translation vector in two dimension so that
𝑇 = 𝑇⃗ + 𝑇⃗

𝑇 = 𝑛 𝑎⃗ + 𝑛 𝑏⃗

Where n1 and n2 are integers and a⃗ and b⃗ are translation vectors along X and Y directions
For a three dimensional lattice, the translational vector
T = n a⃗ + n b⃗ + n c⃗
Unit Cell:
The unit cell is the smallest geometric figure, the repetition of which in three dimensions will gave
the actual crystal structure.
(Or)
The unit cell may also be defined as the fundamental elementary pattern with minimum number of
atoms, molecules or group of molecules which represents the total characteristics of the crystal.
Explanation:

Figure: various ways to consider the Unit cell

Let us consider a two dimensional crystal lattice as shown in figure. Let us consider a parallelogram
ABCD of side AB = a and AD = b.
When the parallelogram ABCD is rotated repeatedly by any integral multiple of vectors 𝑎⃗ and 𝑏⃗,
then the whole array may be obtained. The region ABCD is called an unit cell and 𝑎⃗ and 𝑏⃗ are
called lattice vector.

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  The choice of a unit cell is not unique.
 It can be constructed in many numbers of ways like A 1B1C1D1 (or) A2B2C2D2 (or)
A3B3C3D3 etc. without affecting the symmetry of the crystal.

In two dimensional, a unit cell is called as a parallelogram where as in three dimensions it is called a
parallelepiped.

Primitive cell or simple cell:

The primitive cell is defined as a unit cell which contains lattice points at corners only.
It contains only one lattice point per cell.
Ex: simple cube
Non-primitive cell:
If a unit cell contains more than one lattice point then it is called a non-primitive cell.
Ex: BCC and FCC.

Lattice parameters:

A unit cell can be completely described by three fundamental vectors 𝑎⃗ , 𝑏⃗ and 𝑐⃗ called lattice
vectors. The angle between the vectors 𝑏⃗ and 𝑐⃗ is , the angle between the vectors 𝑐⃗ and 𝑎⃗ is  , and
the angle between the vectors 𝑎⃗ and 𝑏⃗ is . The angles , ,  are called interfacial angles.
The lattice vectors 𝑎⃗ , 𝑏⃗ and 𝑐⃗ and the interfacial angles , ,  are called lattice parameters of the
unit cell. The size and shape of the unit cell depends upon the values of lattice parameters.

4
Crystal systems:

Taking different symmetries and structures into consideration, all structures are classified into
seven crystal systems.
Each system is characterized by the values of lattice parameters a, b, c and , , 
S.No Name of the Relation between No. of Lattices Examples
system lattice vectors and possible
interfacial angles lattice
1 Cubic a = b =c 3 Primitive Au, Ag, Cu,
0
 = = =90 Body Nacl
centered
Face centered
2 Tetragonal a=b≠c 2 Primitive SnO4,
0
 = = =90 Body TiO2,Tin,
centered KH2PO4
3 Orthorhombic a≠b≠c 4 Primitive PbCO3,
0
 = = =90 Body SrSO4,
centered Mg2SiO4,
Face centered K2SO4,
Base centered KNO3
4 Monoclinic a≠b≠c 2 Primitive Borax,
0
 =  = 90 ≠  Base centered Cryolite,
Gypsum
5 Triclinic a≠b≠c 1 Primitive K2Cr2O7,
 ≠ ≠  ≠ 900 H3BO3,
CuSO4.5H2O
6 Hexagonal a=b≠c 1 Primitive Zn, Cd,
0 0
==90 =120 SiO2, AgI
7 Trigonal a = b =c 1 Primitive As, Sb, Bi,
(Rhombohedral)  = =  ≠ 900 quartz

Bravais Lattice:

Bravais in 1948, showed that there are 14 different types of space lattices under the seven crystal
systems as shown in following
1. Cubic system: a = b =c;  = = =900

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 2. Tetragonal: a = b ≠ c;  = = =900

3. Orthorhombic: a ≠ b ≠ c;  = = =900

4. Monoclinic: a ≠ b ≠ c;  = =900 ≠ 

900

7. Trigonal: a = b = c;  =  =  ≠ 900
5. Triclinic: a ≠ b ≠ c;  ≠  ≠  ≠ 900
6. Hexagonal: a = b ≠ c;  = = 900; 
=1200

Properties of unit cell:

1. Co-ordination Number (N):
The number of nearest neighbouring atoms around any atom in the crystal is called co-ordination
number.
The co-ordination number of SC, BCC & FCC structure is 6, 8, 12 respectively.
2. Nearest neighbouring distance:
The distance between two nearest neighbouring atoms in a crystal lattice is known as the nearest
neighbouring distance.
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 √
In SC, BCC & FCC structures these values are a, 𝑎& respectively.
√
3. Atomic packing fraction (or) packing density:
Atomic packing fraction is defined as the ratio of the volume occupied by the atoms in a unit cell to
the volume of the unit cell.
𝑉𝑜𝑙. 𝑜𝑐𝑐𝑢𝑝𝑖𝑒𝑑 𝑏𝑦 𝑡ℎ𝑒 𝑡𝑜𝑡𝑎𝑙 𝑛𝑜. 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑝𝑒𝑟 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
𝐴𝑃𝐹 =
𝑇𝑜𝑡𝑎𝑙 𝑣𝑜𝑙. 𝑜𝑓 𝑡ℎ𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙

𝑇𝑜𝑡𝑎𝑙 𝑛𝑜. 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑋 𝑣𝑜𝑙. 𝑜𝑓 𝑜𝑛𝑒 𝑎𝑡𝑜𝑚

𝐴𝑃𝐹 =
𝑇𝑜𝑡𝑎𝑙 𝑣𝑜𝑙. 𝑜𝑓 𝑡ℎ𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙

Generally, it varies from 0.54 to 0.74 for different crystal structures.

4. No. of atoms per unit cell (or) effective no.:
The total no. of atoms present in or shared by an unit cell is known as no. of atoms per unit cell. It is
also called effective mass.
In case of SC, BCC and FCC structures, these values are 1, 2and 4 respectively.
5. Atomic radius(r):
The atomic radius is defined as half of the distance between the nearest neighbouring atoms in a
crystal.
Generally, the atomic radius ‘r’ is expressed in terms of lattice constant.
6. Lattice constant:
The edge of the cube is equal and constant, it is known as lattice constant (a).
Consider a unit cell with lattice parameters a=b=c and  = = =900.
Let ‘ρ’ be the density of the crystal.
Volume of cubic cell =a3
Mass of unit cell = ρ a3
Let ‘M’ be the molecular weight of the cell and NA be the Avogadro’s number
∴Mass of each atom in unit cell =
If ‘n’ is no. of atoms in unit cell
∴Mass of unit cell =
𝑛𝑀
ρa =
𝑁
𝑛𝑀
a =
ρ𝑁
𝑛𝑀
a=
ρ𝑁
Crystal structure of materials:
Simple cubic structure:
A simple cubic crystal unit cell consists of eight corner atoms as shown in figure.

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1. Co-ordination number:
The co-ordination number for simple cubic is six.

2. Nearest neighbouring distance:

In SC, the atoms are along the edge of the cube. So the nearest neighboring distance is
‘a’.
3. Atomic radius:
In SCC structure the corner atom touch each other along the edges as shown in figure.
The nearest neighbouring distance = a= 2r
 r = a/2
4. No. of atoms per unit cell:
In SC structure, there are only 8 atoms, one at each corner of the cube (or) unit cell.
But in actual crystals, each and every atom is shared by 8 adjacent unit cells. Hence each
corner atom contributes only 1/8th of its part to a single unit cell.
Therefore, total number of atoms per SC unit cell = 1/8*total no. of corner atoms
= 1/8 * 8
= 1 atom

5. Packing faction:

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 Examples: Polonium

Body Centered Cubic structure (BCC):

It has eight atoms at eight corners of the cube and one atom at center of the cube as shown in
the figure.

1. Co-ordination number: In BCC structure, the corner atoms do not touch each other. But
each corner atom touches the body centred atom along the body diagonal.
Thus, the co-ordination number is 8
2. Atomic radius: For a BCC unit cell, the atomic radius can be calculated for following
figure.

From figure AD = 4r
CD = a
AB = a
From ∆ACD, AD2 = AC2 + CD2 ----(1)
But from ∆ ABC, AC2 = AB2 + BC2 ----(2)
Using (1), AD2 = AB2 + BC2 + CD2
 (4r)2 = a2 + a2 + a2
 16 r2 = 3 a2
 𝑟 =
√
 𝑟=

9
  𝑎=
√
3. No. of atoms per unit cell:

In BCC, there are eight atoms one at each corner of the cell, but each and every corner
atom is shared by 8 adjacent cells.

∴ The total no. of corner atoms per unit cell = 1/8 * 8 = 1 atom

But the In BCC, there is an one body centred atom at the center of the unit cell. This atom is
shared by that particular unit cell.
∴ The no. of body centred atoms per unit cell= 1 atom
Hence, the total no. of atoms per unit cell in BCC = 1+1 = 2 atoms
4. Packing fraction:

Examples: Lithium, sodium, potassium, chromium etc.,

Face Centered Cubic structure (FCC):
It has eight atoms at eight corners of the cube and six atoms at center of six faces of the cube
as shown in the figure.

1. Co-ordination number:
For FCC, each corner atom has four face centred atoms as nearest neighbouring in its
own plane. It has four another face centred atoms as nearest neighbouring in a plane which
lie just above this corner. Similarly in a plane which lies just below this corner atom it has 4
more face centred atoms as nearest neighbours.
Therefore the total no. of nearest atoms in FCC = 4+4+4 = 12.
2. Atomic radius: For a FCC unit cell, the atomic radius can be calculated for following
figure.
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3. No. of atoms per unit cell:
An FCC unit cell consists of eight corner atoms and each and every corner atoms is
shared by eight adjacent unit cell.
Therefore, each and every corner atom contributes 1/8 of its part to one unit cell.
The total number of atoms by corner atom = 1/8 x 8 = 1 atom.
In addition, there are 6 atoms at the face centers of the cube. Each face-centered atom
is shared by two surround unit cells.
Hence, the number of face centered atoms in unit cell, =1/2 x 6 =3 atoms.
Therefore, total number of atoms in one unit cell = 1 + 3 = 4 atoms .
4. Packing Factor:
The number of atoms present in an FCC unit cell is four.

Example: copper, gold and aluminium etc.,

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 .Comparison between SC, BCC and FCC structure:

Property SC BCC FCC

Volume of unit cell a3 a3 a3

No of atoms per unit cell 1 2 4

No. of nearest neighbours 6 8 12
Atomic radius (r) 𝑎 𝑎 √3 𝑎√2
2 4 4
Packing fraction 0.52 0.68 0.74
Example polonium sodium copper

Planes in crystals:

A crystal is made up of a large no. of parallel equidistant planes passing through lattice points called
lattice planes.

Inter planer spacing:

The perpendicular distance between two adjacent crystal planes is called inter planar spacing. It is
denoted by ‘d’.
Miller indices:
Miller in 1839 derived a method of representing the orientation of a crystal plane.
The reciprocals of the intercepts made by the plane on crystallographic axis are called
Miller Indices. (Or) Miller indices are three smallest integers which have same ratio as the
reciprocals of the intercepts of the crystal plane with co-ordinate axes.
Procedure to Find Miller Indices:
(1) Note down the intercepts
(2) Take the reciprocals of the intercepts
(3) Find the LCM of the denominators
(4) Reduce the reciprocal intercepts in to integers by multiplying them with LCM
(5) These obtained integers enclosed in brackets without comma seperation
represent the Miller Indices (h k l) for a given plane.
Example: If a plane makes intercepts as 2,3 and 4 along x,y and z-axes
respectively then steps to find Miller Indices
Step 1: Intercepts are 2, 3, 4
Step 2: Reciprocal intercepts 1/2,1/3,1/4
Step 3: LCM of denominators 12
Step 4: Multiply the reciprocal intercepts with LCM 1/2*12 1/3*12 1/4*12
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Step 5: Miller Indices are (6 4 3)
Important Salient Features of Miller Indices:
(1).Miller Indices give the orientation of crystal plane
(2).Plane parallel to any coordinate axes will have infinite intercept
(3).Plane passing through origin is defined in terms of a parallel plane having non-zero
intercepts.
(4).All parallel planes have same Miller Indices
(5).If the intercept is negative then its corresponding Miller Index value is represented
by bar over it.
(6). If (h k l) are the Miller Indices then a/h, b/k and c/l are the intercepts for
corresponding lattice parameters a,b and c.
Various planes in crystal:

Relation between inter planer distance and lattice parameters:

Consider a plane ABC making intercepts on the co-ordinate axes OX, OY, OZ at distances OA,
OB, OC respectively as shown in figure.
Let us consider any set of parallel planes with miller indices (h k l) and any other plane which is
parallel to the plane ABC , passing through the origin ‘O’ as the reference plane. The Plane ABC
makes intercepts , , on X, Y and Z axes respectively.
i.e., OA = , OB = , OC =

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A normal ON is drawn to the plane ABC from the origin. The distance of the plane ABC from the
origin is the inter planer spacing ‘d’ (ON). Let the angles made by the normal with the X, Y, and Z
axes be 𝛼, 𝛽 𝑎𝑛𝑑 𝛾 respectively. Then the interplaner spacing ‘d’ between the origin and the plane is
derived as follows
𝑂𝑁 𝑑
𝐶𝑜𝑠 𝛼 = =𝑎 − − − −(1)
𝑂𝐴 ℎ
𝐶𝑜𝑠 𝛽 = = − − − − (2)
𝑂𝑁 𝑑
𝐶𝑜𝑠 𝛾 = = 𝑐 − − − −(3)
𝑂𝐶 𝑙
According to the law of directional cosines
𝑐𝑜𝑠 𝛼 + 𝑐𝑜𝑠 𝛽 + 𝑐𝑜𝑠 𝛾 = 1 − − − −(4)

Using equ.s (1), (2), (3) in equ. (4)

⎡ ⎤
𝑑 𝑑 𝑑
+ ⎢ ⎥ + =1
𝑎 𝑐
ℎ ⎢𝑏 𝑘 ⎥ 𝑙
⎣ ⎦

ℎ 𝑘 𝑙
𝑑 + + =1
𝑎 𝑏 𝑐

1
𝑑 =
ℎ 𝑘 𝑙
+ +
𝑎 𝑏 𝑐
1
𝑑 =
ℎ 𝑘 𝑙
+ +
𝑎 𝑏 𝑐

This is the general expression for interplanar separation for any set of planes. For a cubic system a=
b= c. Hence the expressions becomes

1
𝑑 =
[ℎ + 𝑘 + 𝑙 ]

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 X-ray diffraction
Introduction to Diffraction of X-rays:

 Von Laue first discovered the diffraction of X-rays in 1912; later, it was tested by Kuipping
and Freidrich.
 X-ray, electromagnetic radiation of extremely short wavelength and high frequency,
with wavelengths ranging from about 10−8 to 10−12 metre and corresponding frequencies
from about 1016 to 1020 hertz (Hz)
..

 Waves exhibit interference, diffraction and polarization. Like all waves, X-rays also exhibit
diffraction effects.
 Diffraction is defined as bending or spreading of light waves around an obstacle. The
obstacle can be an aperture or slit whose size is approximately the same as the wavelength of
light.

 Average wavelength of man-made sharp edges, slits, diffraction gratings that are normally
used in regular diffraction experiments have dimensions comparable to wavelengths of
visible light waves. Hence these obstacles easily produce diffraction effects with visible
light.
 X-ray wavelengths are extremely short of the order of 1Ǻ. It is virtually impossible to make
obstacles with dimensions comparable to a few Angstroms.
 In crystals, there is a regular and periodic arrangement of atoms in different planes, with inter
planar separation around 2Ǻ and interatomic spacing's 3 to 5Ǻ.
 Hence crystals suit well to diffract X-rays.
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  Crystals act as three-dimensional space gratings and the diffraction pattern then produced
reveals the internal arrangement of atoms in the crystals.
 Bragg’s law is the governing law in x-ray diffraction by crystal planes.
Bragg’s Law Statement:
Bragg’s law states that X-rays reflected from different parallel planes of a crystal interfere
constructively when the path difference is an integral multiple of the wavelength of X-rays.

2𝑑𝑠𝑖𝑛𝜃 = 𝑛𝜆

Where, ‘d’ is the inter planar spacing, θ is the glancing angle, λ the wavelength of X-rays,
and n is the order of diffraction.
Bragg’s law is a consequence of the periodicity of the crystal lattice.
Derivation for the Bragg’s Equation:
Consider a set of parallel lattice planes of a crystal in which spacing between the successive
planes is ‘d’. Let a narrow beam of X-rays of wavelength ‘λ’ be incident on the planes of a crystal
with glancing angle ‘θ’ as shown in the figure.

Consider the ray XO and X′O′ incident on two consecutive planes AA′ and BB′ reflected as OY and
O′Y′ respectively. OP and OQ are perpendiculars drawn from O on the rays X′O′ and O′Y′
respectively.

The path difference between the reflected rays is

Δ = 𝑃𝑂 + 𝑂 𝑄 ---(1)

From the ∆le OPO′, sin 𝜃 = = ⇒ 𝑃𝑂 = 𝑑 𝑠𝑖𝑛𝜃 ---(2)

From the ∆le OQO′, sin 𝜃 = = ⇒ 𝑂 𝑄 = 𝑑 𝑠𝑖𝑛𝜃 ---(3)

Substituting equ. (2) & (3) in (1)

We get the path difference Δ = 𝑑 𝑠𝑖𝑛𝜃 + 𝑑 𝑠𝑖𝑛𝜃 = 2𝑑 𝑠𝑖𝑛𝜃 ---(4)

If this path difference is an integral multiple of the wavelength ‘λ’, the reflected beam will interfere
constructively giving maximum intensity. Hence the condition for maximum intensity is

2𝑑 𝑠𝑖𝑛𝜃 = 𝑛𝜆—(5)
Where n is an integer(n =1, 2, 3 ---)
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(This above equation is called Bragg’s equation.
For First order maxima, n=1 ∴ sin 𝜃 =
For second order maxima, n=2 ∴ sin 𝜃 =
For third order maxima, n=3 ∴ sin 𝜃 = and so on

𝜆 2𝜆 3𝜆
∴ sin 𝜃 : sin 𝜃 : sin 𝜃 : … = : : :…
2𝑑 2𝑑 2𝑑
sin 𝜃 : sin 𝜃 : sin 𝜃 : … = 1 : 2 3: … )
Bragg’s X-ray Spectrometer:

Bragg’s X-ray Spectrometer is device designed by the Bragg to study the structural properties of the
crystals by diffracting X-rays from the crystal.

The experimental arrangement of Bragg’s spectrometer was as shown in the figure.

The X-rays from an X-tube are allowed to pass through slits S1 and S2, to become a fine beam and
allowed to incident on a crystal which is placed at the center of the turn table.
This table is mounted on a graduated scale.
Bragg used an ionization chamber as a detector to measure the intensities of the X-rays which are
scattered from the crystal.
The crystal is rotated by means of the turn table so as to increase the glancing angle at which X-rays
are incident at the exposed face of the crystal.
The angle, for which the reflection intensities become maxima, gives the values of θ of equation .
2𝑑 𝑠𝑖𝑛𝜃 = 𝑛𝜆
Where n is order of the spectrum.
If θ1, θ2 and θ3 are the glancing angles for first, second and third order reflections respectively then,
sin 𝜃 : sin 𝜃 : sin 𝜃 : … = 1 : 2 3: …
Therefore, by measuring the glancing angles at which reflections occur, we can determine the inter-
planer spacing knowing the wavelength of the X-rays.

17
If a graph is plotted between the ionization current and the glancing angle, some peaks are obtained,
which represent the values of glancing angles satisfying the Bragg’s law.

The experimental results from the Bragg’s method shown that if X-rays from a palladium
anticathode are used, the first order maxima occurred at 5.9O, 8.4O and 5.2O for (100). (110) and
(111) planes respectively. Now from Bragg’s equation, for first order reflections, n=1,

1
2𝑑𝑠𝑖𝑛𝜃 = 𝜆 ⟹ 𝑑 𝛼
sin 𝜃

Therefore, 𝑑 :𝑑 :𝑑 = ∶ ∶
. . .

= 9.73 ∶ 6.84: 11.04

= 1.00: 0.703 ∶ 1.14

1 1
𝑑 :𝑑 :𝑑 = 1∶ ∶
√2 √3
This ratio shows that NaCl crystal has a face centered cubic structure. Similarly, it is possible to
determine the structure other crystals also.

Determination of crystal structure by Powder crystal method (Debye Scherrer method):

 The powder method was developed by Debye and Sherrer in Germany and by hill
in America simultaneously.
 This method is used to study the structure of crystals which cannot be obtained in the form of
perfect crystals of appreciable size.
 This method can be used for pure metals, compounds and alloys.
Basic Principle:
 The basic principle underlying this powder technique is that, the specimen contains a large
number of micro crystals (~ 12 10 in 1 mm3 of powder sample) with random orientations,
almost all the possible q and d values are available. The diffraction takes place for these
values of q and d which satisfy Bragg’s condition, i.e., 2d sin = n.
Experimental arrangement:-
 The experimental arrangement is shown in figure.

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  Finely powdered sample is filled in a thin capillary tube and mounted at the center of the
drum shaped cassette with photographic film at the inner circumference.
 Collect the X-rays (non-monochromatic or heterogeneous or white or continuous) from the
X-ray tube.
 Heterogeneous can be converted into monochromatic X-Rays by passing through the filter.
 This monochromatic (or homogenous) x-rays can be converted into fine pencil beam by
passing through the lead sheet.
 The pencil beam of X-rays is allowed to fall on the powder specimen (sample).
Theory:
 The diffraction takes place for these values of  and d which satisfy Bragg’s condition,
i.e.,. 2𝑑 𝑠𝑖𝑛𝜃 = 𝑛𝜆
 Reflection takes place at the lattice planes, which satisfy the Bragg’s condition. For the value
of  , the beam appears at the corresponding 2 deviation.
 The pattern recorded on the photographic film is shown in the figure.
 When the film is laid flat. Due to the narrow width of the film, only parts of circular rings are
register on it. The curvature of arcs reverses when the angle of diffraction exceeds 90 o.

 Knowing the distances between the pair of arcs, various diffraction angles  can be
calculated by using the formula.

Where D, is the diameter of the cylindrical film.

 Then the inter-planer spacing for various sets of parallel planes can be evaluated from the
Bragg’s law as follows
𝜆
𝑑=
2 sin 𝜃
 Knowing all the parameters, the crystal structure can be determined.
Determination of crystal structure by Laue method:
Basic principle
The basic Principe underlying this Laue technique is that, each reflecting plane selects a wave
length according with the Bragg’s relation, i.e., 2d sin = n .
The resulting diffraction is recorded on the photographic plate.
Experimental arrangement
The experimental arrangement of the Laue technique is shown in the figure.

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  Collect the X-rays of wavelength 0.2 Ao to 2.0 A0 from X-ray tube.
 Collected X-rays are converting in to fine pencil beam by passing through the pin-hole
arrangements in lead diaphragms.
 The size of pin hole should be kept very small to get sharp interference pattern.
 The smaller is the pinhole diameter, sharper is the interference pattern.
Theory
 The fine pencil beam of X-rays is allowed to fall on the single crystal.
 The X-rays are diffracted and recorded on the photographic plate. The diffraction pattern
consists of a bright central spot and a set of spots arranged in a definite pattern about the
central spot.
 The symmetrical pattern caused by X-rays by crystal planes is called the Laue pattern.
 Each spot in the Laue pattern corresponding to an interference maximum for a set of planes
satisfying the Bragg’s relation 2d sin = n.

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 UNIT-II Crystallography and X-ray diffraction
Question Bank
Long Answer Questions:

1. Name the seven types of crystal systems and give the relation of lengths of axes and the
relation of angles between the axes of a unit cell in each type.
2. What is a Bravais lattice? Describe the 14 Bravais lattice with suitable diagrams.
3. What is meant by atomic packing factor? Calculate atomic packing factor for SC, BCC
and FCC structures.
4. Calculate a) Number of atoms per unit cell b) Coordination number c) Atomic radius for
SC, BCC and FCC structures.
5. What are Miller indices? How are they determined?
6. What do you mean of miller indices? What are their significances?
7. Draw the planes (100), (101), (110) and (111) in a simple cubic structure.
8. Deduce the relation inter planar distance and Miller indices of the planes for a cubic
system.
9. State and deduce Braggs’ law in X-ray diffraction
10. Describe a Bragg’s spectrometer.
11. Explain how Bragg’s spectrometer can be used to determine the inter planar distance.
12. Describe with suitable diagram, the powder method for determination of crystal
structure.
13. Describe with suitable diagram, the Laue method for determination of crystal
structure.
Very Short Answer Questions
1. What is crystallography?
2. Distinguish between crystalline and amorphous solids.
3. Define the terms lattice and basis.
4. What is Bravais lattice?
5. What is a unit cell?
6. Define primitive and non-primitive cells.
7. What is coordination number?
8. Define packing fraction or density of packing.
9. What are Miller indices?
10. Give the relation between inter-planar distance and lattice parameters.
11. State Bragg’s law?

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