UES012 – ENGINEERING

MATERIALS PROJECT (2018)

Determination of crystal structure of the

given specimens by XRD method

Submitted By: Submitted To:

Dr. Mukesh Kumar
Rakshit Sharma-101708150
Ravi Mehta-101708151
Ravinder Pal Singh-101708152
Rishab Sud-101708153

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 ACKNOWLEDGEMENT
We take this opportunity to express our profound gratitude and deep regards to
our Professor Dr. Puneet Sharma and our Lab teachers Mr. Mukesh and Ms.
Yashpreet for their exemplary guidance, monitoring and constant
encouragement throughout the course. The blessing, help and guidance given by
them time to time shall carry us a long way in the journey of life on which we
are about to embark.

We are obliged to all our friends and teachers, for the valuable information
provided by them in their respective fields. We are grateful for their cooperation
during the period of our assignment. We are making this project not only for
marks but to also increase our knowledge.

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 TABLE OF CONTENTS

S.NO. PARTICULARS PAGE NO.

1 Aim 4

2 Theory / Introduction 4

3 Formation of Crystal Lattice 6

4 Structure Determination by X-ray Diffraction 7

5 Production of X-rays 8

6 Bragg’s Law of X-ray Diffraction 9

7 Crystal Structure Determination 10

8 The Powder Method 11

9 Graph 13

10 Analysis and Calculations 14

11 Result and Conclusion 15

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AIM: To determine crystal structure of the given specimens by using X-ray diffraction
method.

INTRODUCTION/THEORY:
Materials can be broadly classified as crystalline and amorphous solids. In a crystalline
material, the arrangement of atoms is in a periodically repeating pattern, whereas no such
regularity of arrangement is found in an amorphous material. A crystalline solid can be either
a single crystal, where the entire solid consists of only one crystal, or an aggregate of many
crystals separated by well-defined boundaries. In the latter form, the solid is said to be
polycrystalline.

MATERIALS

CRYSTALLINE AMORPHOUS

SPACE LATTICE: A space lattice can be defined by referring to a unit cell. The unit cell is
the smallest unit which when repeated in space indefinitely, will generate space lattice.

CRYSTAL STRUCTURE: A space lattice is combined with a basis to generate crystal

structure.

Space lattice + Basis  Crystal structure

In many elemental crystals, the basis is simple and consists of one atom per lattice point. In
such cases, the crystal is generated by just positioning one atom of the element at each lattice
point. For example, the crystal structures of chromium and copper are generated as:
BCC space lattice + 1 Cr atom per lattice point  BCC crystal of Cr
FCC space lattice + 1 Cu atom per lattice point  FCC crystal of Cu

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UNIT CELL: It is basic building block of lattice. The unit cell is the smallest unit which
when repeated in space indefinitely, will generate space lattice.

TYPES OF UNIT CELL:

1. SIMPLE CUBIC : Atoms at eight corners of unit cell

Fig: Simple Cubic Unit Cell

2. FACE CENTERED : Atoms at eight corners and at six face centers

3. HEXAGONAL CLOSED PACK: The top and bottom faces of the unit cell consist
of six atoms that form regular hexagons and surround a single atom in the center.
Another plane that provides three additional atoms to the unit cell is situated between
the top and bottom planes.

Fig: FCC and HCP unit cell

4. BODY CENTERED : Atoms at eight corners and at body center

Fig: BCC unit cell

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 5. END CENTERED /BASE CENTERED / SIDE CENTERED : Atoms at eight
corners and at two face centers (faces opposite to each other)

Fig: End Centered unit cell

6. DIAMOND CUBIC: Just like face centered but with four additional atoms in 4
tetrahedral voids.

Fig: Diamond Cubic unit cell

FORMATION OF CRYSTAL LATTICE

Formation of unit cells takes place in seven forms, namely:

 Cubic Lattice
 Tetragonal Lattice
 Orthorhombic Lattice
 Monoclinic Lattice
 Hexagonal Lattice
 Rhombohedral Lattice
 Triclinic Lattice

A crystal is a homogeneous portion of a solid substance made by regular pattern of

structural units bonded by plane surface making definite angles with each other. 

And the smallest repeating unit in space lattice which when repeated over and over again
results in a crystal is known as a unit cell. 

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 Table: Types of Bravais lattice

STRUCTURE DETERMINATION BY X-RAY DIFFRACTION:

X-ray diffraction (XRD) relies on the dual wave/particle nature of X-rays to obtain
information about the structure of crystalline materials. A primary use of the technique is the
identification and characterization of compounds based on their diffraction pattern.

PRINCIPLE:

It is well known that, for visible electromagnetic radiation to be diffracted, the spacing
between lines in a two-dimensional grating must be of the same order as the wavelength
range for light (3900–7800 Å). The same principle holds good for diffraction by the three-
dimensional grating of the periodic array of atoms in crystals. The typical interatomic spacing
in crystals is 2–3 Å. So, the wavelength of the radiation used for crystal diffraction should be
in the same range. X-rays have wavelengths in this range and are, therefore, diffracted by
crystals. This property is widely used for the study of crystal structures.

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PRODUCTION OF X-RAYS:

When electrons moving at high speeds are directed to a metal target, a small percentage of
their kinetic energy is converted into x-rays.
To understand it better let’s see continuous and characteristic X-ray. The spectrum from an
X-ray tube contains two distinct parts:
 
(i) Continuous X-ray spectra It consists of radiations of all possible wavelengths, from a
certain lower limit to higher value continuously, as in the case of visible light. 
Origin - Continuous X-ray spectra
X-rays are produced, when high velocity electrons strike the target material of high atomic
number. It has also been mentioned in the production of X-rays, that most of the energy of
the electrons goes into the heating of the target material.

A few fast moving electrons penetrate deep into the interior of the atoms of the target
material and are attracted towards the nuclei by the attractive forces of their nuclei. Due to
these forces, the electrons get deflected from their original path. As a result of this, the
electrons are decelerated, and hence energy of the electron decreases continuously. This loss
of energy during retardation is given off in the form of X-rays of continuously varying
wavelength. The minimum wavelength in the continuous spectrum is inversely proportional
to the applied voltage which accelerates the electrons towards the target.

(ii) Characteristic X-ray spectra

 It consists of definite, well defined wavelengths superimposed on the continuous spectrum.
These spectral lines generally occur in the form of small groups and are characteristic of the
material of the target.

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Origin - Characteristic X-ray spectra

 Few of the fast moving electrons having velocity of about (1/10) th of the velocity of light
may penetrate the surface atoms of the target materials and knock out the tightly bound
electrons even from the inner most shells (like K, L shells) of the atom. Fig. shows the case,
when the fast moving electrons knock off one electron from K-Shell and the vacancy is filled
by the nearby electron from the L shell. During this transition, the energy difference is
radiated in the form of X-rays of very small wave length. This corresponds to K α - line of the
series. The frequency ν1 of this line is given by the relation (E K - EL) = hν1. Suppose, the
electron from M shell jumps to the K shell, it gives out K β line and so on. If an electron jumps
from the M-Shell to the vacant state in L-Shell, it contributes Lα line and if the vacancy in L-
Shell is filled up by an electron of N shell, it contributes L β and so on. The frequency of
radiation depends upon the target material. The X-ray spectra consists of sharp lines and is
the characteristic of target material. Hence this spectra is known as characteristic
spectra.Therefore, on combining the both we get following graph. The radiation emitted by a
molybdenum target at 35 kV includes both types of radiation as illustrated below.

THE BRAGG’S LAW OF X-RAY DIFFRACTION:

A beam of x-rays directed at a crystal interacts with the electrons of the atoms in the crystal.
The electrons oscillate under the impact and become a new source of electromagnetic
radiation. The waves emitted by the electrons have the same frequency as the incident x-rays.
The emission is in all directions. As there are millions of atoms in a crystal, the emission in a
particular direction is the combined effect of the oscillations of electrons of all the atoms. The
emissions will be in phase and reinforce one another only in certain specific directions, which
depend on the direction of the incident x-rays, their wavelength as well as the spacing
between atoms in the crystal. In other directions, there is destructive interference of the
emissions from different sources. The easiest way to visualize the diffraction effects
produced by the three-dimensional grating provided by the crystal is to consider the Bragg
law.

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A beam of x-rays of wavelength λ is directed towards the crystal at an angle Ɵ to the atomic
planes. In Bragg law, the interaction described above between x-rays and the electrons of the
atoms is visualized as a process of reflection of x-rays by the atomic planes. This is an
equivalent description of the diffraction effects produced by a three-dimensional grating. The
atomic planes are considered to be semi-transparent, that is, they allow a part of the x-rays to
pass through and reflect the other part, the incident angle (called the Bragg angle) being equal
to the reflected angle. Referring to Fig., there is a path difference between rays reflected from
plane 1 and the adjacent plane 2 in the crystal. The two reflected rays will reinforce each
other, only when this path difference is equal to an integral multiple of the wavelength. If d is
the interplanar spacing, the path difference is twice the distance d sinƟ, as indicated in Fig.
The Bragg condition for reflection can therefore be written as:
2 d sinƟ = nλ

CRYSTAL STRUCTURE DETERMINATION

HOW IS CRYSTAL STRUCTURE DETERMINED?
Now through some methods which are written in later part of report, we can easily determine
various parameters of the below given formulas and hence we may extract info that we want
2 d sinƟ = nλ
a
d=
√ h +k 2+l2
2

On combining both we get,

( h 2+ k 2 + l 2)
sin2 Ɵ= λ2
4 a2
METHOD:
In diffraction studies, in order to increase the probability that crystals with the right
orientation for Bragg reflection are available, one of the following procedures is adopted:
(i) A monochromatic x-ray beam of a specific wavelength is combined with numerous
possible values so that reflection occurs at the right combination that satisfies the Bragg law.

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This is done by placing thousands of crystals of random orientation in the path of the beam.
The crystals are usually in powder form.
(ii) A single crystal is held stationary in the path of the beam so that is kept constant. A white
radiation is then directed at the crystal so that numerous values of the wavelength are
available, and again the right combination will lead to the diffraction condition. This method
is called the Laue technique.
(iii) A single crystal is held in the beam of a monochromatic radiation and is rotated such that
at some position of the crystal, the diffraction condition is satisfied. This method is known as
the rotating crystal method. Even though this is not the most widely used method, it provides
greater certainty in identification, as well as more accurate measurement of the intensities of
the reflected beam.

THE POWDER METHOD:

The powder method is a widely used experimental technique for the routine determination of
crystal structures. It is highly suitable for identification and for determination of the structures
of crystals of high symmetry.
HOW IT WORKS?
Here, a monochromatic x-ray beam, usually of K-alpha radiation, is incident on thousands of
randomly oriented crystals in powder form. The powder camera, called the Debye-Scherrer
camera, consists of a cylindrical cassette, with a strip of photographic film positioned around
the circular periphery of the cassette. The powder specimen is placed at the centre of the
cassette in a capillary tube or pasted on a thin wire. The tube, the wire and the paste material
must be of some non-diffracting substance such as glass or glue. The x-ray beam enters
through a small hole, passes through the powder specimen and the unused part of the beam
leaves through a hole at the opposite end.
Consider a set of parallel crystal planes making an angle Ɵ with the incident direction. When
this angle satisfies the Bragg equation, there is reflection. By virtue of the large number of
randomly oriented crystals in the powder, there are a number of possible orientations of this
set of planes in space for the same angle Ɵ with the incident direction. So the reflected
radiation is not just a pencil beam like the incident one; instead, it lies on the surface of a
cone whose apex is at the point of contact of the incident radiation with the specimen. Also,
the interplanar spacing d being the same for all members of a family of crystal planes, they all
reflect at the same Bragg angle Ɵ , all reflections from a family lying on the same cone. After
taking n = 1 in the Bragg equation, there are still a number of combinations of d and Ɵ that
would satisfy the Bragg law. For each combination of d and Ɵ, one cone of reflection must
result and, therefore, many cones of reflection are emitted by the powder specimen. If the
reflected cones were recorded on a flat film placed normal to the exit beam, they will be in
the form of concentric circles. In the powder camera, however, only a part of each reflected
cone is recorded by the film strip positioned at the periphery of the cylindrical cassette. The

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recorded lines from any cone are a pair of arcs that form part of the circle of intersection.
When the film strip is taken out of the cassette and spread out.
After the film is exposed and developed, it is indexed to determine the crystal structure. It is
easily seen that the first arc on either side of the exit point corresponds to the smallest angle
of reflection. The pairs of arcs beyond this pair have larger Bragg angles and are from planes
of smaller spacing, recall that d =λ / (2 sinƟ). The distance between any two corresponding
arcs on the spread out film is termed S, S is related to the radius of the powder camera R:
S = 4RƟ
In the powder method, the intensity of the reflected beam can also be recorded in a
diffractometer, which uses a counter in place of the film to measure intensities. The counter
moves along the periphery of the cylinder and records the reflected intensities against 2Ɵ.
Peaks in the diffractometer recording correspond to positions where the Bragg condition is
satisfied.

STRUCTURE DETERMINATION:
The procedure for determining the structure of monoatomic cubic crystals is outlined below.
( h 2+ k 2 + l 2)
sin2 Ɵ= λ2
4 a2
Ɵ-values can be determined from a powder pattern using
S = 4RƟ

Since monochromatic radiation is used in the powder technique, the value of λ is known.
Then, the unknowns in EQUATION are the Miller indices of the reflecting planes that
correspond to the measured angles of reflection. We have extinction rule to help us with.

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GRAPH:
We plotted the graph using given set of data. The graph is plotted between Intensity and 2Ɵ.

Tracing from diffractometer

17000
16000
15000
14000
13000
12000
11000
10000
9000
intensity

8000
7000
6000
5000
4000
3000
2000
1000
0
15 20 25 30 35 40 45 50 55 60 65 70 75 80 85

Angle (in degrees)

Fig: Intensity v/s 2Ɵ

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 ANALYSIS OF GRAPH:

PEAK 2Ɵ Intensity
1 28.4969 15974
2 47.3782 8406
3 56.1624 4500
4 69.1613 1140
5 76.383 1706
Table: graph analysis

CALCULATIONS:

Pea 2Ɵ Intensity Ɵ Ɵ Sin Ɵ Sin^2( Ɵ Ratio Round Planes

k ) off ratio
1 28.496 15974 14.248 0.24868 0.24613 0.06058 1 3 111
9 4
2 47.378 8406 23.689 0.41345 0.40177 0.16142 2.66468 8 220
2 1
3 56.162 4500 28.081 0.49011 0.47072 0.22158 3.65773 11 311
4 2
4 69.161 1140 34.580 0.60355 0.56757 0.32213 5.3176 16 400
3 7
5 76.383 1706 38.191 0.66657 0.61829 0.38228 6.31058 19 331
5

**THIS IMPLIES THAT GIVEN SPECIMEN HAS FCC STRUCTURE.

Now taking λ = 1.54 A˚. We will use 2 d sinƟ = nλ

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And d = nλ / 2sinƟ
Now n=1, wavelength we have assumed and Ɵ we take for the max angle. This gives:
d = 3.13 A˚

Now,
a
d=
√ h +k 2+l2
2

Now a =3.13 x √ 3
a = 5.42132 A˚
Approximately, a=5.42 A˚

THIS IMPLIES THAT THE GIVEN SPECIMEN IS SILICON (Si) [a=5.4309 A˚]

RESULT:

Structure FCC
Interplanar Spacing, d 3.13 A˚

Lattice Parameter, a 5.42 A˚

Specimen Silicon (Si)

CONCLUSION:

The specimen has been identified as Silicon (Si) sample using data as obtained from powder
method using X-Ray Diffraction Method.

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 REFERENCES

1. Material Science by V.Raghavan

2. http://chemed.chem.purdue.edu/genchem/topicreview/bp/ch13/u
nitcell.php

3. https://serc.carleton.edu/research_education/geochemsheets/tech
niques/XRD.html

4. https://ecee.colorado.edu/~bart/book/bravais.htm

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