Crystallography

CO- For a given X-ray diffraction (XRD) pattern for an elemental cubic
material, students will be able to index the XRD peaks, determine the
crystal structure and lattice parameter.

Unit Outcomes
1) For given intercepts on crystal axes, students will be able to
determine the Miller indices for the crystal plane and direction.
2) For a given crystallographic plane, students will be able to
determine the intercepts on crystal axes.
3) Students will be able to draw the given crystal plane and
direction.
4) For a given XRD pattern for an elemental cubic material,
students will be able to determine the crystal structure and
lattice parameter.
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 Crystallography Classification of Engineering
Materials
Materials can be classified in three groups according to their
nature: 1. Metals and alloys
2. Ceramics and glasses
3. Organic polymers
Level of structure
The magnification and the resolution of the physical aid used to
study the structure of materials is the measure of the level of
observation. Depending on the level, we can classify the structure
of materials as – Macrostructure, Microstructure, Substructure,
Crystal Structure, Electronic Structure and Nuclear Structure.
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 2) Tetragonal
Crystallography a = b ≠ c α = β = γ = 90 °
3) Orthorhombic
Bravais Lattices
Crystal System β

1) Cubic α
c
γ
a
a = b = c α = β = γ = 90 °

a ≠ b ≠ c α = β = γ = 90 °
b
4) Rhombohedral
a = b = c α = β = γ ≠ 90 °
5) Hexagonal
a = b ≠ c α = β = 90 ° γ = 120 °
6) Monoclinic: a ≠ b ≠ c α = β = 90 ° ≠ γ 7) Triclinic:
a ≠ b ≠ c α ≠ β ≠ γ ≠ 90 °
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 Axes nomenclature3/71

Crystallography Crystal Directions and Planes

Crystallographic planes and directions are specified with respect to
these axes in terms of Miller indices.

☞ To Find out Miller Indices of a Crystallographic Plane:

Step1 Find the intercepts of the plane ��
along the axes a, b, c ��
��
 ��
��
��
Step 2 Take reciprocals of the intercepts ��
��
��
��
��
��
Step 3 Convert into small integers in the Take LCM
same ratio

Step 4 Enclose in parenthesis (A B C)

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 Crystallography
Rules for Miller Indices
☞ Determine the intercepts (a,b,c) of the planes along the
crystallographic axes, in terms of unit cell dimensions. ☞
Consider the reciprocal of the intercepts measured. ☞ Clear the
fractions, and reduce them to the lowest terms in the same ratio
by considering the LCM.
☞ If a hkl plane has a negative intercept, the negative number is
denoted by a bar ( ̅) above the number.
☞ If the crystal plane is parallel to an axis, its intercept is zero and
they will meet each other at infinity.
☞ The three indices are enclosed in parenthesis, hkl and known
as the hkl indices. A family of planes is represented by {hkl}
and this is the Miller index notation.

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Crystallography General Principles of Miller

Indices
☞ If a Miller index is zero, then it indicates that the given plane is
parallel to that axis.
☞ The smaller a Miller index is, it will be more nearly parallel to
the plane of the axis.
☞ The larger a Miller index, it will be more nearly perpendicular to
the plane of that axis.
☞ Multiplying or dividing a Miller index by a constant has no
effect on the orientation of the plane.
☞ By changing the signs of the indices 3 planes, we obtain a
plane located at the same distance on the other side of the
origin.
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Crystallography
Examples
1. Determine the Miller Indices of Simple Cubic Unit Cell Plane
having intercepts 1,∞,∞ on the three axes

Step 1: Take the reciprocal of the intercepts

�� �� ��
�� ∞ ∞

Step 2: Take LCM of these fractions to reduce them into the

smallest set of integers.
100

Step3: Miller indices of the Plane is

 (100)
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Crystallography
2. Determine the Miller Indices for the Plane having intercepts 1,∞,1
in a cubic lattice
Ans: (101)

3. Determine the Miller Indices for the Plane having intercepts

½,1,∞ in a cubic lattice
Ans: (210)

4. Determine the Miller Indices for the Plane having intercepts

−1,∞,½

������: (�� ��2)

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Crystallography

Problem1:
A plane makes intercepts 2, 3 and 4 Å on 3-axes on a
orthorhombic crystal with a : b : c = 4 : 3 : 2. Determine the
Miller indices of the plane.

Answer?

Problem2
In an orthorhombic unit cell, a : b : c = 1 : 2 : 3. The
 magnitude of a is 2 Å. What are the intercepts in Å of a plane
of Miller indices (230)?

Answer?
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Crystallography
Ex 1: Draw a plane (111) in a cubic lattice01/02/2024
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Crystallography
Ex 2: Draw a plane (210) in a cubic lattice01/02/2024
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Crystallography
Ex 2: Draw a plane (003) in a cubic lattice01/02/2024
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Crystallography

Figure?
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Crystallography
 Some useful relations
1. [uvw] is normal to (hkl) when u = h; v = k; w = l. i.e., [111] is normal to (111).

2. [uvw] is parallel to (hkl), i.e., [uvw] lies in (hkl), when hu + kv + lw = 0. is a

direction in the plane (111)

3. Two planes (h1k1l1) and (h2k2l2) are normal if h1h2 + k1k2 + l1l2 = 0 4. Two
directions [u1v1w1] and [u2v2w2] are normal if u1u2 + v1v2 + w1w2 = 0

Crystallography

01/02/2024 Some useful relations

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5. Angle between two planes (h1k1l1) and (h2k2l2) are given by
hhkkll
θ= ++
 cos
h k l h k l 121212

2 2 2 1/ 2 2 2 2 1/ 2
()()
++++1
1 1 2 2 2

6. In a cubic crystal, the interplanar spacing is given by the following relation

a
hkl
d ++
=
{}
hkl
222

7. When the Miller indices contain more than one digit, the indices must be
separated by commas for clarity, e.g., (3, 10, 15)
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Crystallography
Miller indices of a direction
1) Choose a point on the direction as the origin
2) Choose a coordinate system with axes parallel to the unit cell
edges
3) Find the coordinates of another point on the direction in terms of
a, b, c
4) Put in square bracket [uvw] [100]

☞ Miller indices of direction

represent only the
orientation of the line
 corresponding to the
direction and not its
position or sense
☞ All parallel directions have
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the same Miller Indices
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Crystallography
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OA=1/2 a+1/2 b+1c

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��
��, ��, ��
��

[������]

Crystallography
Family of a direction
〈uvw〉 = [uvw] and all other directions related to the [uvw] by the
symmetry of the crystal

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Crystallography
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Crystallography
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Crystallography Hexagonal Close-Packed (hcp) System

In hcp system, it is convenient to use a four-digit notation,
hkil, called the Miller-Bravais indices. These indices are
based on four axes;
# the three axes a1, a2, a3are 120° apart in the basal plane,
and the vertical c axis is normal to the basal plane.
# Third index is related to the first two by the relation
i = - (h +k).

BC

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Basal plane, ABCDE – (0001)

Crystallography
G D Prism plane,
A FE
 −
FEJH— (1010)
a1=

a2=
a3
a3=
a2
HJ
Pyramidal plane,
GJH— Directions—
a1
vector:
1) Projection method
2) Vector method

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There are two methods for drawing

Crystallography Drawing of HCP Crystallographic

 Directions

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Crystallography Draw in a HC unit cell

 direction is represented by vector from point O to S.
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Crystallography
Determination of HCP Crystallographic Directions
Start with 2D
Covert to 4 digit notations
[uvw] [UVTW]

Vectorically, a1 + a2 + a3 = 0
ua1 + va2 + wa3 = Ua1 + Va2 + Ta3 + Wc
= Ua1 + Va2 – T(a1+ a2) + Wc
= (U—T)a1 + (V—T)a2 + Wc
Comparing above, we have
u = U—T
v = V—T
w=W

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Crystallography

There are two equations and three unknowns Hence,

another equation is introduced U + V + W = 0 Solving
equations
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Crystallography
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 Crystallography
Determine the Miller-Bravais Indices for the given vector (Green)
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3—axes in 2D
Crystallography
X—axis
Y—axis

Z—axis

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Miller Bravais Notation

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 Crystallography What are X-rays?
☞ X-rays are electromagnetic radiations with same nature of light but
of very shorter wavelengths.
☞ X-rays used in diffraction studies have wavelengths in the range
of 0.5—2.5 Ǻ
Properties of X-rays
☞ X-rays travel in straight lines at the speed of light
☞ X-rays (uncharged and neutral particles can not be deflected by
electric or magnetic fields.
☞ They affect photographic films.
☞ Can produce fluorescence and photographic emissions.
☞ Can penetrate matters.
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 Crystallography

Generation of X-rays
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Crystallography
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Crystallography
 ☞ When a filament (cathode) is heated by current, many electrons are
emitted by thermionic emission.
☞ These electrons are accelerated in vacuum by high-electric field in
the range 20-60 kV towards a metal target.
☞ When the high-speed electrons strike the target metal, K.E is
transformed into heat and X-ray radiation

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 Crystallography

Continuous radiation:
☞ Most of the K.E. of the
electrons
is converted into heat
energy of
electromagnetic radiation.
☞ Only less than 1% of
energy is
converted into x-rays.
☞ The radiation consists of
continuous range of
wavelengths
and is called white radiation
The minimum wavelength in the continuous spectrum is inversely
proportional to the applied voltage, which accelerates the electrons
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Crystallography
Characteristics radiation
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Crystallography
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Crystallography Use of Filters

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Crystallography

X-ray Diffraction (XRD)

☞ X-ray diffraction – one of the best methods of determining a
crystal structure.
☞ An intense beam of X-ray strikes the crystal of study ☞ In general,
crystal diffracts the X-ray beam differently depending on its structure
and orientation.
☞ The diffraction pattern consists of reflections of different
 intensities which can be used to determine the structure of the
crystal.
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Crystallography
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Crystallography
 ☞ A beam of X-rays directed at a crystal interacts with the electrons
of the atoms that constitute 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
that of 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 oscillation
electrons of all the atoms.
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Crystallography
☞ The emissions will be in phase and reinforce one another
only in certain specific directions, which depends on the
direction of 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 the different sources.
☞ The Bragg Law is the easiest way to visualise the diffraction
effects produced by the 3D grating of the atoms of a crystal.
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Crystallography
The Bragg,s Law of XRD
Assumptions:
1) The interaction between electrons of the atoms and the X rays
is visualised as a process of reflection of X-rays by the
atomic planes.
2) The atomic planes are also assumed to be semi
transparent

The Bragg condition for constructive diffraction can be written

as nλ = 2dhkl sinθ
where n is an integer. For first order reflection n = 1, for second order
reflection n = 2 and so on.

dhkl is the interplaner distance and θ is the incidence angle

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Crystallography
The two rays reflected from two planes will reinforce each other, only
when this path difference is equal to an integral multiple of the
wavelength.
When Bragg’s law is satisfied, the reflected beams are in phase and
interfere constructively

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Crystallography 01/02/2024
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Crystallogra
phy
 2dsinθ
=2nλ

Path
(hkl) (hkl) (hkl)
difference
1
between Ray1 θ
and Ray2 =
θ
ABC 2 dhkl
=dsinθ + dsinθ A C
=2dsinθ Path B
3
difference
F
between Ray1 D
d sinθ
and Ray3 = 2× E

This implies that if Ray1 and Ray 2 interfere constructively, Ray 1 and Ray3
will also interfere constructively and so forth
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 Crystallography

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 Crystallography

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Crystallography
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Crystallography
Maximum and minimum value of λ
This depends on the interplaner spacing
☞ For the typical value of interplanar spacing of 2 Å, the upper
limit for λ for obtaining first order reflection as 4 Å. There will
be no reflection if λ is greater than 4 Å.
☞ Reduction of values of λ results reflection set of planes
having interplanar spacing less than 2 Å as well as an
increasing number of higher order reflections.
☞ Very small wavelength of the order of 1 Å is not necessarily
an advantage, as it tends to produce other effects such as
knocking off electrons from the atoms of the crystals and
getting absorbed in the process.
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Crystallography
Should we use higher order reflection?
A second order reflection from (100) planes must satisfy the
following Bragg condition:
2λ = 2d100 sinθ λ = d100 sinθ
Similarly, a first order reflection from (200) planes will give the
following condition
λ = 2d200 sinθ
The above two equations are identical. As these two equations
are identical, the two reflections will superimpose on each
other and can not be distinguished. Similarly, the third order
reflection from the (100) planes will superimpose on the first
order reflection from (300) planes.
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Crystallography
In view of such superimposition, there is no need to consider
the variations in n separately; instead n is taken to be unity for
all reflections from parallel set of planes such as (100), (200),
(300), etc.
PROBLEM: Determine the interplanar spacing and the Miller indices of
the reflecting planes, a = 3.16 Å, λ =1.54 Å. Peak position of XRD
peaks are given below:
Peak 2θ (in degree)
1 40.6
2 58.4
3 73.4
4 87.2

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Crystallography
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Crystallography
The powder method of XRD (Debye-Scherrer Camera)
A monochromatic x-ray beam, usually Kαradiation is incident
on randomly oriented powder crystals.
A very small amount of powdered material is sealed into a fine
capillary tube made from glass that does not diffract x-rays.
The camera consists of a cylindrical cassette with a strip of
photographic film placed around the periphery of the cassette.
The specimen is positioned at the centre of the cylindrical
cassette.
The powder diffracts the x-rays in accordance with Bragg law
to produce cones of diffracted beams.
01/02/2024 πR
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Crystallography Film

Specimen

Incident X-ray Exit x-rayray 4θ

S

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Entry hole Exit hole

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Crystallography
The angle between a reflected line lying on the surface of the cone
and the exit beam is 2θ. Therefore the included angle at the apex of
the cone is twice this value is 4θ. When the Bragg angle is 45°, the
cone opens out into circle and reflection at this angle will make a
straight line intersection on the film strip at the midpoint between the
incident and the exit points. When the Bragg angle is greater than
45°, back reflection is obtained, i.e., reflected cones are directed
towards the incident beam.
S

πR=W
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Spread out Film

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Crystallography
S, which is related to the radius of the powder camera R
 by S =4Rθ
For easy conversion of the distance S measured in mm to Bragg angle in
degrees, the camera radius is often chosen to be 57.3 mm, as 1 rad =
57.3°.
In powder method, the intensity of the reflected beam can also be recorded
in a diffractometer which uses a counter in the place of the film to measure
intensities.

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Crystallography
Determination of Crystal Structure (Indexing of XRD
Peaks) We Know

1/d2 = (h2 + k2 + l2) / a2

Combining Bragg’s law with the above equation
yields 1/d2 = (h2 + k2 + l2) / a2 =4 sin2θ
/λ2
or, sin2θ = (λ2/4a2)(h2 + k2 + l2)
or, Sin2θ ∝ (h2 + k2 + l2)
i.e., as θ increases, planes with higher Miller indices will diffract.
Hence for two different planes and dividing, we get Sin2θ1 /
Sin2θ2 ∝ (h12 + k12 + l12) / (h22 + k22 + l22)
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 Crystallography
In the cubic system, the first reflection in the diffraction pattern is due
to diffraction from the planes with Miller indices (100) for simple cubic,
(110) for BCC and (111) for FCC lattice. Therefore, h2 + k2 + l2= 1, 2 or
3 respectively.
Since the ratio of sin2θ values scales with the ratio of h2 + k2 + l2
values for different planes, and since h, k, l are always integers, h2 +
k2 + l2 values can be obtained by dividing the sin2θ values of different
reflections by the smallest one (i.e., sin2θ of the first reflection) and
multiplying the ratios thus obtained by an appropriate integer.
These subsequent integers represents the h2 + k2 + l2 values and
hence corresponding h, k, l values can be easily identified.
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Crystallography
The Bravais lattice can be identified by noting the systematic
presence (or absence) of reflections in the diffraction pattern.

Thus, h2 + k2 + l2 values for the different cubic lattices follow the

sequence: (Extinction Rule)
Simple 1, 2, 3, 4, 5, 6, 8, 9 --------------
 BCC 2, 4, 6, 8, 10, 12, 14, 16, --------
FCC 3, 4, 8, 11, 12, 16, 19, -----------
DC 3, 8, 11, 16, 19, 24, --------
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Crystallography
 S θ ���� ���� P×1 P×2 P×3
(mm) (=S/4) ���� ���� ��
(deg) �� =������
��
��
��������
��������
``

h2 + k2 + l2 hkl a (Å/nm)

Only one
value of a

Sometimes, values of θ will given directly . In that case, the first

column will not be required
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Crystallography

Problem:
From a Powder camera of diameter 114.6 mm, using x-ray beam of
wavelength 1.54 Å, the following S values in mm were recorded 86,
100, 148, 180, 188, 232, 272
Determine the Miller indices of the reflecting planes and the lattice
parameter. What is the structure of the material?
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Crystallography

aa
dhkl =
= 222
19 ++
331

We know that λ = 2dhkl sinθ

Or a = 3.62 Å

The Crystal structure is FCC with a=3.62 Å

Sinθ vs. θ curve

Determine lattice parameter at the highest Bragg angle

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Crystallography
To find out chemical composition of an alloy
A XRD experiment was performed with Cu kα radiation, using a diffractometer
on a Cu-Ni alloy (FCC solid solution); the first Bragg reflection was observed
at , θB = 22.1°. What is the composition of the alloy?
Given: λ =1.54 Ǻ, θ111 = 22.1°

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 Crystallography

Joint Committee of Powder Diffraction Standards (JCPDS)

The crystal structure, the lattice parameter and dhkl for a metal
are fixed.
dhkl values of first five diffracting planes of a metal are
characteristics of the metal.
Knowing dhkl values from the XRD pattern and comparing with
JCPDS data, the structure and the metal is identified.
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Crystallography
X-ray diffraction from (100) in a bcc crystal
(100) planes contain the corner atoms and the effective number of atoms is
one. The midway (200) plane between two (100) planes contains the
central atom. The reflection from (200) will be out of phase exactly by half
of the wavelength (λ/2) with the reflection from (100). As the effective
number of atoms in (100) and (200) are equal, the intensity of the reflected
beams from these two planes are also equal. Hence the phase difference
of λ/2 results in the cancellation of the reflection from each of the plane.
Hence there is no first order reflection from a(100) in bcc crystal.
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Crystallography

Planes in 2D
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Crystallography

Home work: (Sessional) DOS: tomorrow

1) In a certain Debye Scherrer experiment on a cubic sample
following S values were recorded:
 76, 90, 132, 156, 166, 194, 226
Determine the Miller indices of the reflecting planes and the lattice
parameter. Take λ = 1.54 Ǻ and camera radius R = 57.3 mm. What
is the structure of the material?
2) A XRD experiment was performed with Cr kα radiation,
using a diffractometer on a cubic crystal; only two Bragg
reflections were observed at 34.6° and 65.51°. What is the
crystal structure and the lattice parameter? Show that these
are the only two reflections possible.
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