Identification and quantification of phases

in microstructure by X-ray diffraction

S.R. Meka
Assistant Professor
Metallurgical and materials engineering department
Indian Institute of Technology Roorkee
Email: [email protected]

Contents of this lecture are largely based on the information from the following two text books on X-ray diffraction
1. B.D. Cullity and S.R.Stock, elements of X-ray diffraction, 3rd edition, peasrson new international edition, 2014.
2. C. Suryanarayana and M. Grant Norton, X-ray diffraction-a practical approach, Plenum publishing corporation, 1998
 X-ray diffraction in materials characterization
discovery of x-rays by Wilhelm Rontgen in 1895; first use in radiography
discovery of XRD by crystals in 1912 by Max von Laue
crystal structure determination by XRD in 1913 by W.H. Bragg and his son W.L. Bragg
X-rays: electromagnetic radiation (200 eV- 1 MeV)

eV is the amount of energy an electron picks up when it moves between

a potential (voltage) difference of 1 volt. 1 eV = 1.602 X 10-19 J

- The useful range of wavelengths for x-ray diffraction studies is

between 0.05 and 0.25 nm.
- Interatomic spacings in crystals are typically about 0.2 nm
X-ray diffraction production of X-rays
Principle: bombarding a metal target with electron beam
X-ray spectrum of Mo

only a small percentage (less than 1 %) of the electron beam is

converted to x-rays; the rest gets dissipated as heat in metal anode.
X-ray diffraction production of X-rays
X-ray spectrum of Mo Continuous radiation:
electrons losing their energy in a series of collisions with
the atoms that make up the target

A:constant, i: tube current, Z: atomic no., V: voltage, m is about 2

X-ray diffraction production of X-rays
X-ray spectrum of Mo
Short Wavelength Limit (SWL):
an electron loses all its energy in a single collision with a
target atom, generating an x-ray photon with the maximum
energy or the shortest wavelength is produced.

With increasing accelerating voltage SWL moves to lower

values
X-ray diffraction production of X-rays
X-ray spectrum of Mo Characteristic radiation:
If the incident electron has sufficient energy to eject an inner-shell
electron, the atom will be left in an excited state with a hole in the
electron shell. When this hole is filled by an electron from an outer
shell, an x-ray photon with an energy equal to the difference in the
electron energy levels is produced. The energy of such x-ray
photon is characteristic of the target metal. Characteristic X-rays
are most useful in x-ray diffraction work.
 X-ray diffraction production of X-rays; characteristic radiation
X-ray spectrum of Mo @ V= 35 kV
K
Kα
K𝛼

K𝛼

L
intensity(a.u)

• The characteristic lines are classified as

K, L, M,etc.
• except K shell, other shells contain sub
shells
Kβ M • Change of accelerating V does not
change the values of characteristic
wavelengths.
• The intensity (I) of a characteristic line
depends on both the applied V and the
tube current i

Wavelength (nm)
B:constant, i: tube current, 𝑉 : critical excitation V of K line, V: voltage, n is about 1.5
 X-ray diffraction production of X-rays; monochromatic radiation
X-ray spectrum of Mo @ V= 35 kV For most x -ray diffraction studies monochromatic beam
(x-rays of a single wavelength) is required
Kα • Using a filter to remove unwanted 𝜆s from the spectrum
• Using a crystal monochromator; usually single crystal of graphite
before filtration after filtration
Kα
K𝛼
intensity(a.u)

Kα

K𝛼 Kβ
Kβ

Kβ

𝜆 (angstroms) 𝜆 (angstroms)

Comparison of the spectra of Cu radiation before and after passage through a

Wavelength (nm) nickel filter (schematic).The dashed line is the mass absorption coefficient of nickel
(picture from text book “elements of X-ray diffraction” by B.D. Cullity and S.R. Stock.
X-ray diffraction production of X-rays; monochromatic radiation

- In general the so-called monochromatic Kα radiation still consists of Kα1 and Kα2 wavelengths

- Intensity of Kα1 is twice that of Kα2

- Weighted Average the wavelength of the unresolved Kα line is taken as the weighted average
of the wavelengths of its components Kα1 and Kα2 . The wavelength of the unresolved Mo Kα
line is thus
X-ray diffraction production of X-rays; Moseley’s Law

Characteristic wavelength of any

particular line decreases with increase
in atomic number of the emitter

and are constants

λ of α1 ≈ λ of α1
X-ray diffraction scattering of X-rays by an atom
x-rays incident on the atom, makes the electrons in the atom to oscillate about their mean positions.
- Electron oscillation involves acceleration (during which electron absorbs X-ray) and deceleration (during which
electron emit X-ray).
- This process of absorption and reemission of electromagnetic radiation is known as scattering.
- Elastic and inelastic scattering; energy is lost or not during interaction of X-ray with electrons

Two x-ray waves (1 and 2) incident on atom;

- Wave 1 and 2 gets scattered in forward direction by electrons at A
and B, respectively.
- Both the forward scattered waves will be in phase at wavefront XX’
1 as the path difference is zero
- If we add these two forward scattered waves across wavefront XX'
(i.e., we sum their amplitudes), we obtain a wave with the same
2 wavelength as incident wave but twice the amplitude.
- The scattered waves on wave front YY’, other than those scattered in
forward direction, will not be in phase when the path difference (AD-
CB) is not an integral multiple of 𝜆.
X-ray diffraction scattering of X-rays by an atom
atomic scattering factor, f, quantifies how efficient an atom is
scattering X-rays in a given direction

• for scattering in the forward direction (i.e., the scattering angle, θ = 0°) f
= Z (the atomic number) since the waves scattered by all the electrons in fCu
the atom are in phase and the amplitudes sum up.

• as θ increase, the waves become more and more out of phase because f
they travel different path lengths and, therefore, the f decreases.
fAl
• f also depends on the 𝜆 of the incident x-rays. For a fixed value of θ, f is
smaller for shorter-wavelength radiation.
fO
• f is generally plotted against (sin θ)/𝜆 to take into account the variation
of f with both θ and 𝜆. 𝑠𝑖𝑛𝜃
(𝑛𝑚 )
𝛾
X-ray diffraction scattering of X-rays by a crystal
Interaction of X-ray beam with a crystal consists of several closed spaced atoms

The scattered waves from each atom interfere. If the interfering waves are in phase, then constructive interference
occurs. If the waves are 1800 out of phase, then destructive interference occurs

A diffracted beam is a beam composed of a large number of superimposed scattered waves

Scattering is the process whereby the incident radiation is absorbed and then reemitted in different directions

Interference is the superposition of two or more of these scattered waves, producing a resultant wave that is the
sum of the overlapping wave contributions

Diffraction is constructive interference of more than one scattered waves

X-ray diffraction scattering of X-rays by an atom
Illustration of the superposition of two monochromatic waves “1” and 2” having different amplitudes.
resultant wave is “3” and its maximum intensity is indicated with red dashed line

3
3
2 2 1
1 1

“1” and 2” in phase “1” and 2” having phase difference “1” and 2” out off phase
Lattices and Crystal structures Types of solids based on atomic order
Single crystal Polycrystal Amorphous

Crystals possess long-range order due to arrangement of atoms in a regular ordered pattern in three dimensions

In a single crystal the periodic atomic arrangement extends throughout the entire volume of the material

A polycrystalline material consists of many small single-crystal regions (called grains) separated by grain boundaries.
The grains on either side of the grain boundary are misoriented with respect to each other. The grains in a
polycrystalline material can have different shapes and sizes.

In amorphous materials, such as glasses and many polymers, the atoms are not arranged in a regular periodic manner
Lattices and Crystal structures POINT LATTICES AND THE UNIT CELL
three-dimensional arrangement of points in space with every point having identical surroundings is called a
point lattice, i.e., every point in point-lattice will have exactly the same number and arrangement of neighbours.

Unit Cell is the smallest unit of point lattice which when stacked in three dimensions reproduces the point lattice.

the interrelationship between the lengths (a, b, c) of its sides and the interaxial angles (α, β, λ) defines the unit cell
the lengths (a, b, c) and the interaxial angles (α, β, λ) are called the lattice parameters

point lattice unit cell

Lattices and Crystal structures CRYSTAL SYSTEMS AND BRAVAIS LATTICES
Only a total of 7 unit-cell shapes are possible which meet the requirement of able to reproduce the point lattice upon
stacking in 3 dimensions and these are known as the seven crystal systems
All crystals in nature belong to anyone of these 7 crystal systems. quasi crystals are exception

If we put a lattice point at the corner of each unit cell of the

seven crystal systems, we obtain seven different point
lattices. However, other arrangements of points also satisfy
the requirement of a point lattice; i.e., each point has
identical surroundings. Auguste Bravais, in 1848,
demonstrated that there are 14 possible point lattices and no
more which are known as Bravais Lattices
Lattices and Crystal structures CRYSTAL SYSTEMS AND BRAVAIS LATTICES

• P stands for a primitive or simple cell, where there is a lattice

point at each comer.
• F refers to a face-centered cell, where a lattice point is
centered on each face, in addition to the comers of the unit cell.
• I is used for body-centered cells, where a lattice point is in the
center of the cell-in the interior of the cell-in addition to the comers
of the unit cell.
• A, B, and C refer to base-centered cells where lattice points
are centered on opposite faces of the cell, in addition to the comers
of cell
CRYSTAL STRUCTURES-one atom of same kind per lattice point
What is the difference between a lattice point and an atom?
A lattice point represents equivalent positions in a Bravais lattice. In a real crystal a lattice point may be occupied by
one atom or by a group of atoms. In the latter case the atoms are in a fixed relationship with respect to each lattice
point. In both cases, the number, composition, and arrangement of atoms is the same for each lattice point. The
arrangement of atoms at lattice points is known as the basis.

lattice points tell us nothing about the chemistry or bonding within the crystal; for that we need
to include the identity of the atoms and their positions

The relationship between Bravais lattices and actual crystal structures involves the basis.
We can express this relationship as Bravais lattice + basis → Crystal structure

cubic P lattice + 1 atom → SC structure

(α-Po; 1 atom/ cell))
BCC (cubic I) lattice + 1 atom → BCC structure
(W, Mo, Na, α-Fe; 2 atoms/cell)

FCC (cubic F) lattice + 1 atom → FCC structure

(Al, Cu, Au, γ-Fe; 4 atoms/cell)
CRYSTAL STRUCTURES-two atoms of same kind per lattice point
Hexagonal P lattice + 2 atoms → HCP structure (Ti, Zn; 2 atoms/cell)

FCC (cubic F) lattice + 2 atoms → DC structure (Si and Ge; 8 atoms/cell)

CRYSTAL STRUCTURES- two different atoms per lattice point
• Cesium chloride (CsCI) cubic P lattice + 2 atoms → CsCl structure (NiAl, CsBr ; 2 atoms/cell)
• Sodium chloride (NaCl, or rocksalt)
• Zinc blende (ZnS, or sphalerite)
• Wurtzite (ZnS)

FCC (cubic F) lattice + 2 atoms → NaCl structure

CRYSTAL STRUCTURES
Miller indices (hkl) describes uniquely the different crystal planes in a lattice.
Miller indices (hkl) describes uniquely the different crystal planes in a lattice.

Procedure to identify the miller indices of a crystal lattice plane

1. Identify the points at which the plane intersects the a, b, and c axes. The intercept is measured in terms of
fractions or multiples of the lattice parameters. If the plane moves through the origin, then the origin must be
moved.

2. Take reciprocals of the intercepts. This is done because if the plane never intersects one of the axes the
intercept will be at infinity. We don't want to have infinity in the indices so we take redprocals.

3. Clear the fractions. We only want whole numbers in the indices, but don't reduce the numbers to the lowest
integers.

4. Enclose the resulting numbers in parentheses (h k l). Negative numbers are written with a bar over the number,
and pronounced, for example, as bar one.
Parentheses ( ) are used for a specific plane, and braces { } are used for a family of planes. The six planes
in the {l O O} family of planes for a cubic unit cell are (l 0 0), (0 1 0), (0 0 1), (T O O), (o T o), and (O O T).
Miller indices (hkl)
Miller indices (hkl) Interplanar spacing “d”
(h k l) and (nh nk nl)

For cubic crystals

Direction indices [u v w] Interplanar spacing “d”
DIFFRACTION FROM CRYSTALLINE MATERIALS- BRAGG'S LAW
an atom can scatter x-rays, and if many atoms are together then the scattered waves from all the atoms can interfere.
If the scattered waves are in phase (coherent), they interfere in a constructive way and we get diffracted beams in
specific directions. These directions are governed by the wavelength of the incident radiation and the nature of the
crystalline sample.

criterion for the existence of the diffracted wave:

the scattered x-rays should all be in phase across a
wavefront BB'. i.e. the path difference between wavefronts AA'
and BB' for the rays shown must be equal to n λ

𝑑′ - spacing between planes (hkl)

𝑑 - spacing between planes (nhnknl)
Bragg’s law
n is known as the order of reflection and is the path difference, in terms of number of wavelengths, between
waves scattered by adjacent planes of atoms
DIFFRACTION FROM CRYSTALLINE MATERIALS- Structure factor F
F describes the effect of the crystal structure on the intensity of the diffracted beam
Thus, for certain structures some reflections will be absent
Base centered body centered from the diffraction pattern. They are known as forbidden
orthorhombic orthorhombic reflections-they are forbidden by the structure factor. The
intensity of the beam diffracted by all the atoms in the unit
cell in a given direction predicted by Bragg's law is
proportional to F 2.

( )

Diffraction from (001) planes u v w represent the position of atoms

001 planes diffract

001 planes cannot diffract

Diffraction of X-rays by crystals vs. reflection of visible light by mirror

1. The diffraction of monochromatic x-rays takes place only at those particular angles of incidence which satisfy
Bragg’s law. The reflection of visible light takes place at any angle of incidence.

2. The diffracted beam from a crystal is built up of rays scattered by all the atoms of the crystal which lie in the path
of the incident beam. The reflection of visible light takes place in a thin surface layer only.

3. The reflection of visible light by a good mirror is almost 100 percent efficient. The intensity of a diffracted x-ray
beam is extremely small compared to that of the incident beam.
Laue’s diffraction conditions
For to be diffraction vector all 3 Laue
conditions must be simultaneously satisfied

2′
2′ 2 𝛽
1′
𝛽 𝛽
2 𝛼
𝛼 𝛼
1′ 𝛽 1 𝛽
1
𝒐

The must satisfy; The must satisfy; The must satisfy;

P.D = 2 2’ - 1 1’ = P.D = 2 2’ - 1 1’ = P.D = 2 2’ - 1 1’ =
Laue’s diffraction conditions
For to be diffraction vector all 3 Laue conditions must be simultaneously satisfied

Zero-order diffraction cone

2′

2 𝛼
𝛼 𝛼
1′
1
𝒐

P.D = 2 2’ - 1 1’ =
Laue’s diffraction conditions
Incidence angle 𝛼 and diffraction
angle 𝛼 is measured, anticlockwise
from the line connecting scattering
centres and the corresponding
incidence/diffraction vector

minus 1st order diffraction cone

1st order diffraction cone

P.D = 2 2’ - 1 1’ = P.D = 2 2’ + 1 1’ =
Laue’s diffraction conditions

Zero-order diffraction cone 1st order diffraction cone minus 1st order diffraction cone
Laue’s diffraction conditions
Laue’s diffraction conditions diffraction by 2D lattice
Laue’s diffraction conditions diffraction by 2D lattice
Laue’s diffraction conditions diffraction by 3D lattice
Laue’s diffraction conditions

Along this direction all 3 Laue

conditions are satisfied,
simultaneously; all 3 Laue cones
intersect. This is the diffraction
vector.
Laue’s diffraction conditions
(321) Plane – Diffraction happens when
x-ray beam make an angle (with the
plane) such that the third order cone
about OA, second order cone about OB
and the first order cone about OC
intersect in a common line to satisfy
Laue condition of diffraction..
 Reciprocal lattice vs direct lattice
𝟏
𝟐 𝟑
𝟐
𝟑 𝟏 𝟏 𝟐 b – reciprocal lattice vectors
𝟑
𝟏 𝟐 𝟑 𝟏 𝟐 𝟑 𝟏 𝟐 𝟑 a – direct lattice vectors

𝟏 𝟐 𝟏 𝟐 3 3 unit vector
𝟏 𝟐

𝟑
𝟑 𝟑 𝟏 𝟐

𝟐
𝟑 3

𝟏
𝟑 3

bi is the reciprocal lattice vector normal to the direct-lattice plane containing two direct-lattice
vectors aj (j≠i). Magnitude of bi is inverse of the interplanar spacing of the direct-lattice planes
normal to bi.
𝒊 𝒋 𝒊 𝒋
 Reciprocal lattice vs direct lattice

𝒃𝟐
1
𝒂𝟐
Å
4
(010)

010 020 030 040

4Å

(100)
2Å

110 210

𝟏
𝟑 2Å 4Å 𝟑 100 200 300 400 𝟏

direct cubic-lattice reciprocal cubic-lattice

 Reciprocal lattice vs direct lattice
hexagonal crystal
direct lattice reciprocal lattice

• the reciprocal lattice vectors hb1+kb2+lb3 are normal to the direct lattice planes hkl.
• the non-cubic direct-lattice vectors pa1+qa2+ra3 are not normal to the planes having p, q, r
as intercept-lengths along lattice vectors a1, a2, a3, respectively.
Primitive direct-lattice vector Reciprocal lattice vs direct lattice
OA = pa1 + qa2 + ra3 p, q and r must be integers to represent a lattice point
S and So are unit vectors representing incident and diffracted beams, respectively
Path difference (P.D.)= uA + Av = Om + On
-So
P.D.= So . OA + (-S . OA) = - OA . (S - So )
S-So 1
S So Phase difference (φ; in radians)

θ O 𝒐 scattering vector, H
θ

2
So -S 𝟏 𝟐 𝟑 𝟏 𝟐 𝟑
𝒂𝒊 𝒃𝒋 = 0 for 𝑖 ≠ 𝑗
𝒂𝒊 𝒃𝒋 = 1 for 𝑖 = 𝑗
A
primitive lattice p, q and r are integers and h, k and l of any reciprocal lattice are integers. for all h, k, l values of primitive lattice
ℎ 𝑝 + 𝑘 𝑞 + 𝑙 𝑟 is an integer which satisfies the necessary condition of diffraction for all hkl planes of primitive lattice.
direct lattice vs reciprocal lattice and Ewald sphere
direct lattice reciprocal lattice (RL)
λ=1.54Å

1 Å-1
0.5Å-1
1Å

000 100

2Å
𝒐 scattering vector, H
Bragg’s Law
Figures shown in this ppt are copied from text book titled Elements of X-ray diffraction (3rd edition) by Cullity and Stock
 reciprocal lattice
Ewald sphere and limiting sphere
0.5Å-1

020
Ewald sphere limiting sphere

Ways to satisfy diffraction condition, i.e., Bragg’s law

b2
310

𝑺𝒐 𝑺
𝜆 𝜆

100 300
origin
b3
b1

Figures shown in this ppt are copied from text book titled Elements of X-ray diffraction (3rd edition) by Cullity and Stock
Diffraction methods: Laue
Laue-transmision Laue-back reflection
Laue method visualization with
stereographic projection

Reference sphere with the crystal at the center

Figures shown in this ppt are copied from text book titled Elements of X-ray diffraction (3rd edition) by Cullity and Stock
Diffraction methods: Laue
RL with Ewald spheres direct lattice
120 reflection

Figures shown in this ppt are copied from text book titled Elements of X-ray diffraction (3rd edition) by Cullity and Stock
Diffraction methods: Rotating-(single) Crystal

Cylindrical film

mono-
chromatic
X-ray beam

Figures shown in this ppt are copied from text book titled Elements of X-ray diffraction (3rd edition) by Cullity and Stock
Diffraction methods: Rotating-(single) Crystal

Figures shown in this ppt are copied from text book titled Elements of X-ray diffraction (3rd edition) by Cullity and Stock
Diffraction methods: powder

Figures shown in this ppt are copied from text book titled Elements of X-ray diffraction (3rd edition) by Cullity and Stock
Diffraction methods: powder

Figures shown in this ppt are copied from text book titled Elements of X-ray diffraction (3rd edition) by Cullity and Stock
Diffraction methods: powder

Figures shown in this ppt are copied from text book titled Elements of X-ray diffraction (3rd edition) by Cullity and Stock
Diffraction methods: powder

Figures shown in this ppt are copied from text book titled Elements of X-ray diffraction (3rd edition) by Cullity and Stock
Diffraction methods: powder

Figures shown in this ppt are copied from text book titled Elements of X-ray diffraction (3rd edition) by Cullity and Stock
X-ray diffraction vs. electron diffraction
RL

Ewald sphere for

Cu-Kα (λ= 1.54 Å)

Ewald sphere for

100 KeV electron
beam (λ= 0.037 Å)
Intensity of diffracted beams: Thomson scattering and polarization factor
JJ Thompson: expression for intensity of scattered beam by e-

X-ray beam from tube is unpolarised; its E vector

will be in random direction in the yz plane

E can be resolved into 2 plane polarized Ez E

components along z and y
For random orientation of E, Ez=Ey r
p
𝟐 𝟐 𝟐
𝒚 𝒛
2θ O Ey y
𝟐 𝟐 𝟐
𝒚 𝒛
𝟐

x
𝑶𝒚 𝑶𝒛 𝟎
Intensity of diffracted beams: Thomson scattering and polarization factor
JJ Thompson: expression for intensity of scattered beam by e-

𝑶𝒚 𝑶𝒛 𝟎

𝑷 𝑷 𝑷
𝑬𝒀 𝑬𝒁
Ez E

𝑷
𝒐
𝟐
𝑷𝑶𝒀 𝒐
𝟐
𝑷𝑶𝒁 r
𝟐 𝟐 p
2θ O Ey y
𝑷 𝟐
𝒐 𝟐 𝒐 𝟐

𝟐
𝑷
Polarization factor x
𝒐 𝟐
Intensity of diffracted beams: incoherent Compton scattering
A.H. Compton: interaction of X-ray with loosely bound or free e-s
The accelerated e- gets knocked off from its position and travels with certain K.E.
The incident X-ray lose its part of energy and changes its direction as the interaction is elastic

This can be understood considering the particle nature of X-ray only

before impact after impact

No fixed phase relation between incident and scattered radiation-incoherent scattering

Can not lead to diffraction effects-only increases the undesirable background intensity
I increases with decreasing atomic number-i.e., with increase in the fraction of loosely bound electrons
Interaction of X-ray with sample
X-ray diffraction scattering of X-rays by an atom
x-rays incident on the atom, makes the electrons in the atom to oscillate about their mean positions.
- Electron oscillation involves acceleration (during which electron absorbs X-ray) and deceleration (during which
electron emit X-ray).
- This process of absorption and reemission of electromagnetic radiation is known as scattering.
- Elastic and inelastic scattering; energy is lost or not during interaction of X-ray with electrons

Two x-ray waves (1 and 2) incident on atom;

- Wave 1 and 2 gets scattered in forward direction by electrons at A
and B, respectively.
- Both the forward scattered waves will be in phase at wavefront XX’
1 as the path difference is zero
- If we add these two forward scattered waves across wavefront XX'
(i.e., we sum their amplitudes), we obtain a wave with the same
2 wavelength as incident wave but twice the amplitude.
- The scattered waves on wave front YY’, other than those scattered in
forward direction, will not be in phase when the path difference (AD-
CB) is not an integral multiple of 𝜆.
X-ray diffraction scattering of X-rays by an atom
atomic scattering factor, f, quantifies how efficient an atom is Thomson-
scattering the X-rays in a given direction
Amplitude of wave scattered by an atom
𝑓( ) =
Amplitude of wave scattered by one 𝑒

• for scattering in the forward direction (i.e., the scattering angle, 2θ = 0°)
f = Z (the atomic number) since the waves scattered by all the electrons fCu
in the atom are in phase and the amplitudes sum up.

• as θ increase, the waves become more and more out of phase because f
they travel with larger path-length difference and, therefore, the f
decreases. fAl

• f also depends on the 𝜆 of the incident x-rays. For a fixed value of θ, f is

smaller for shorter-wavelength radiation. fO
• f is generally plotted against (sin θ)/𝜆 to take into account the variation 𝑠𝑖𝑛𝜃
of f with both θ and 𝜆. 𝛾
(𝑛𝑚 )
X-ray diffraction scattering of X-rays by unit cell

(ℎ00)

𝑎
origin 𝑑 =
ℎ

In 3D, for a general hkl plane satisfying bragg condition, 𝜙

between the waves scattered by atoms at B and A(origin)

𝑢, 𝑣, 𝑤 are the fractional coordinates of atom B along x,y, z directions, respectively

X-ray diffraction scattering of X-rays by unit cell
In 3D, for a general hkl plane satisfying
bragg condition, between the waves
scattered by atoms at B and A(origin)

• The scattered rays from A and B along the

diffraction direction of hkl plane may also 𝑧
𝑥
have different amplitude if the atoms sitting 𝑦
at A and B are different. This effect can be
taken care by using the corresponding f.
• Effective intensity of diffracted beam in a given
direction of unit cell for a given hkl plane in diffraction
condition needs addition of waves scattered in that
direction by different atoms of unit cell.
X-ray diffraction scattering of X-rays by unit cell
resultant sine wave-3

two sine waves of

different A and

Addition of monochromatic sine waves of different amplitudes and phases

X-ray diffraction scattering of X-rays by unit cell
A of wave is the magnitude of vector and the of the wave is given as inclination angle of
vector with reference axis. Resultant wave can be obtained by geometrical addition.

Vector addition of monochromatic waves

X-ray diffraction scattering of X-rays by unit cell
• Using complex numbers to represent vectors
imaginary axis
• Wave vector in a complex plane having A (length)
and (angle with real axis)
• Analytical expression for vector is the sum of
horizontal and vertical components (ON+OM)

real axis

wave as vector in a complex plane

X-ray diffraction scattering of X-rays by unit cell

Expression for scattered wave in the diffraction direction of a given hkl

𝒔𝒊𝒏𝜽
𝝀 𝟏
𝟐𝝅𝒊 𝒉𝒖𝟏 𝒌𝒗𝟏 𝒍𝒘𝟏
𝟐
𝟐𝝅𝒊 𝒉𝒖𝟐 𝒌𝒗𝟐 𝒍𝒘𝟐
𝟑
𝟐𝝅𝒊 𝒉𝒖𝟑 𝒌𝒗𝟑 𝒍𝒘𝟑 …….

N-no. of atoms in unit cell

X-ray diffraction scattering of X-rays by unit cell

for all integer values of n

(for all even values of n)

(for all odd values of n)

X-ray diffraction Calculation of F for SC unit cell
𝑵
𝟐𝝅𝒊 𝒉𝒖𝒏 𝒌𝒗𝒏 𝒍𝒘𝒏
𝒏
𝟏

SC unit cell N=1 at (u v w)= (0 0 0)

𝟐 𝟐 𝟐 is independent of h k l

one atom of the same kind per unit cell

all hkl
X-ray diffraction Calculation of F for BCC unit cell
𝑵
𝟐𝝅𝒊 𝒉𝒖𝒏 𝒌𝒗𝒏 𝒍𝒘𝒏 BCC unit cell
𝒏
𝟏
N=2 at (0 0 0) and ( ½ ½ ½)
𝟎 𝝅𝒊 𝒉 𝒌 𝒍

𝝅𝒊 𝒉 𝒌 𝒍

when h+k+l is even 𝟐 𝟐

when h+k+l is odd 𝟐

two atoms of the same kind per unit cell

110, 200, 211, 220….
100, 111, 210….
X-ray diffraction Calculation of F for base centred unit cell
𝑵 Base centred unit cell;
𝟐𝝅𝒊 𝒉𝒖𝒏 𝒌𝒗𝒏 𝒍𝒘𝒏 centered on C face
𝒏
𝟏

N=2 at (0 0 0) and ( ½ ½ 0)

𝟎 𝝅𝒊 𝒉 𝒌

𝝅𝒊 𝒉 𝒌

when h and k are unmixed 𝟐 𝟐

when h and k are mixed 𝟐

two atoms of the same kind per unit cell
001, 110, 111, 112, 021, 022, 023….
210, 211, 011, 012, 013, 230….
X-ray diffraction Calculation of F for FCC unit cell
𝑵
𝟐𝝅𝒊 𝒉𝒖𝒏 𝒌𝒗𝒏 𝒍𝒘𝒏
𝒏 FCC unit cell
𝟏

N=4 at (0 0 0), (0 ½ ½) ( ½ ½ 0) and ( ½ 0 ½)

𝟎 𝝅𝒊 𝒌 𝒍 𝝅𝒊 𝒉 𝒌 𝝅𝒊 𝒉 𝒍

𝝅𝒊 𝒌 𝒍 𝝅𝒊 𝒉 𝒌 𝝅𝒊 𝒉 𝒍

when h k l are unmixed 𝟐 𝟐

4 atoms of the same kind per unit cell

when h k l are mixed 𝟐

111, 200, 220, 311…

100, 110, 210… F is independent of shape and size of the unit cell!
X-ray diffraction Calculation of F for NaCl structure
X-ray diffraction Calculation of F for NaCl structure
N=8 4 Na at (0 0 0), (0 ½ ½) ( ½ ½ 0) and ( ½ 0 ½)

4 Cl at (½ ½ ½), (0 0 ½) ( 0 ½ 0) and ( ½ 0 0)

𝝅𝒊 𝒌 𝒍 𝝅𝒊 𝒉 𝒌 𝝅𝒊 𝒉 𝒍 𝝅𝒊 𝒉 𝒌 𝒍 𝝅𝒊 𝒍 𝝅𝒊 𝒌 𝝅𝒊 𝒉
𝑵𝒂 𝑪𝒍

𝝅𝒊 𝒌 𝒍 𝝅𝒊 𝒉 𝒌 𝝅𝒊 𝒉 𝒍 𝝅𝒊 𝒉 𝒌 𝒍 𝝅𝒊 ( 𝒉 𝒌) 𝝅𝒊( 𝒉 𝒍) 𝝅𝒊( 𝒌 𝒍)
𝑵𝒂 𝑪𝒍

𝝅𝒊 𝒉 𝒌 𝒍 𝝅𝒊 𝒌 𝒍 𝝅𝒊 𝒉 𝒌 𝝅𝒊 𝒉 𝒍
𝑵𝒂 𝑪𝒍

𝑵𝒂 𝑪𝒍
𝝅𝒊 𝒉 𝒌 𝒍 when h k l are unmixed

𝑵𝒂 𝑪𝒍 𝑵𝒂 𝑪𝒍
h k l must be unmixed
𝑵𝒂 𝑪𝒍 𝑵𝒂 𝑪𝒍
X-ray diffraction Calculation of F for NaCl structure
𝝅𝒊 𝒉 𝒌 𝒍 𝝅𝒊 𝒌 𝒍 𝝅𝒊 𝒉 𝒌 𝝅𝒊 𝒉 𝒍
𝑵𝒂 𝑪𝒍

𝑵𝒂 𝑪𝒍
𝝅𝒊 𝒉 𝒌 𝒍
when h k l are unmixed

𝑵𝒂 𝑪𝒍 𝑵𝒂 𝑪𝒍
h k l must be unmixed
𝑵𝒂 𝑪𝒍 𝑵𝒂 𝑪𝒍

when h k l are mixed 𝟐

111, 200, 220, 311…

100, 110, 210…
X-ray diffraction Calculation of F for diamond cubic structure of Carbon

Total 8 C atoms per unit cell

at 000 + face centering translations

(0 0 0), (0 ½ ½) ( ½ ½ 0) and ( ½ 0 ½)

at ¼ ¼ ¼ + face centering translations

(¼ ¼ ¼ ), (¼ ¾ ¾ ) ( ¾ ¾ ¼ ) and ( ¾ ¼ ¾ )

𝒉 𝒌 𝒍 𝒉 𝟑𝒌 𝟑𝒍 𝟑𝒉 𝟑𝒌 𝒍 𝟑𝒉 𝒌 𝟑𝒍
𝝅𝒊 𝒌 𝒍 𝝅𝒊 𝒉 𝒌 𝝅𝒊 𝒉 𝒍 𝝅𝒊 𝝅𝒊 𝝅𝒊 𝝅𝒊
𝑭 = 𝒇𝑪 𝟏 + 𝒆 +𝒆 +𝒆 + 𝒇𝑪 𝒆 𝟐 +𝒆 𝟐 +𝒆 𝟐 +𝒆 𝟐

𝒉 𝒌 𝒍
𝝅𝒊 𝒌 𝒍 𝝅𝒊 𝒉 𝒌 𝝅𝒊 𝒉 𝒍 𝝅𝒊
𝑭 = 𝒇𝑪 𝟏 + 𝒆 +𝒆 +𝒆 + 𝒇𝑪 𝒆 𝟐 𝟏 + 𝒆𝝅𝒊 𝒌 𝒍
+ 𝒆𝝅𝒊 𝒉 𝒌
+ 𝒆𝝅𝒊 𝒉 𝒍

𝒉 𝒌 𝒍
𝝅𝒊
𝑭 = 𝒇𝑪 + 𝒇𝑪 𝒆 𝟐 𝟏 + 𝒆𝝅𝒊 𝒌 𝒍
+ 𝒆𝝅𝒊 𝒉 𝒌
+ 𝒆𝝅𝒊 𝒉 𝒍
 calculation of F for diamond cubic structure of C
3 cases for unmixed indices

(i) even multiple of 2:

𝟐 𝟐
𝑪

(ii) odd multiple of 2:

(ii) are odd:

n is odd; sum of 3 odd numbers
n is odd; cos 𝑛 = 0

𝜋 +1 (for n = 1, 5, 9,13 … )
𝟐 𝟐 sin 𝑛 =
𝑪 2 −1 (for n = 3, 7, 11, 15 … )
𝒉𝟐 + 𝒌𝟐 Diamond FCC
+ 𝒍𝟐
𝒉𝒌𝒍
cubic 𝑭𝟐 𝑭𝟐 F for diamond cubic structure of C
1 100 0 0 𝟐 for mixed indices
2 110 0 0
3 111 32𝑓 16𝑓 3 cases for unmixed indices
4 200 0 16𝑓
(i) even multiple of 2:
5 210 0 0 𝟐 𝟐
𝑪
6 211 0 0
7 (ii) odd multiple of 2:
8 220 64𝑓 16𝑓 𝟐
9 3 0 0/2 2 1 0 0
10 310 0 0 (ii) are odd:
11 311 32𝑓 16𝑓
𝟐 𝟐
12 222 0 16𝑓 𝑪

13 320 0 0
14 321 0 0
15
16 400 64𝑓 16𝑓
17 4 1 0/3 2 2 0 0
 Powder diffraction- relative I calculation
Factors influencing rel. I

1. Polarization factor: I of X-ray beam scattered by single e- is a function of θ;

2. Structure factor F

3. Multiplicity factor P

4. Lorentz factor

5. Absorption factor

6. Temperature factor
 Powder diffraction relative I calculation : Multiplicity factor
The probability that a particular set of hkl planes satisfying Bragg’s condition
depends on the number of planes in the crystal having same d-spacing.

In a cubic crystal all 100-type planes will have same d-spacing

number of planes of 100 type will be 6: (100), (010), (001), (-100), (0-10) and (00-1)

In a cubic crystal all 111-type planes will have same d-spacing

number of planes of 111-type will be 8 (111), (11-1), (1-11), (1-1-1) and the corresponding negative poles

𝐼 8 4
Provided all other factors influencing I are same for 100 and 111, then 𝐼
= =
6 3

Values of P for different hkl in cubic system

 Powder diffraction relative I calculation : Lorentz factor I
Trigonometric functions vary non-linearly as a function of ;
this introduces the dependence for

2𝜃
𝜽𝟐
𝜃
𝚫𝜽 = 𝜽𝟏 − 𝜽𝑩
𝜃
𝜽𝟏
𝜽𝑩 − 𝜽𝟐 = 𝚫𝜽

𝒎𝒂𝒙 𝑩
𝒊𝒏𝒕𝒆𝒈𝒓𝒂𝒕𝒆𝒅 𝒎𝒂𝒙
 Powder diffraction relative I calculation : Lorentz factor I

path difference for rays scattered

by either side end atoms
This sets the condition for
maximum ∆θ contributing I at 2θB
Powder diffraction relative I calculation : Lorentz factor I

.
(Scherrer equation)
Powder diffraction relative I calculation : Lorentz factor II
 Powder diffraction relative I calculation : Lorentz factor III
Intensity of entire diffraction cones are not measured in the usual one dimensional detectors.
i.e., unit length of every diffraction cone is measured.

Length of diffraction line (after unfolding the cone) is .

per unit length of diffraction line .

Powder diffraction relative I calculation : effective Lorentz factor

𝟐
𝑩
𝟐
𝑩 𝑩
 Powder diffraction relative I calculation : absorption factor

Incident X-ray Transmitted X-ray

Sample
Intensity 𝒐 Intensity 𝒕

f intensity is proportional to the fractional increase in thickness of

sample along the travel direction of X-ray
𝑰𝒕 𝒕
𝝁𝒕
𝒕 𝒐
𝑰𝒐 𝟎

-linear absorption coefficient of sample

(unit; length-1)
𝝁
material for a given material, i.e., independent of physical state
𝝆
 Powder diffraction relative I calculation : absorption factor
𝝁𝒕
𝒕 𝒐
𝝁
( 𝝆)𝝆𝒕
𝒕 𝒐 unit;

𝟏 𝟏
nickel 𝟏 𝟏

Discontinuities at absorption edges

Powder diffraction
relative I calculation : Absorption factor (A) Hull/Debye-Scherrer Camera
depends on geometry of diffraction-method
2𝜃2𝜃 = 180°

2𝜃

Incident X-ray transmitted X-ray

forward diffracted absorption length AB+BC Strongly absorbing specimen

backward diffracted absorption length DE+EF
some of the pictures are copied from http://pd.chem.ucl.ac.uk/pdnn/inst1/optics2.htm
Powder diffraction
relative I calculation : Absorption factor (A) Diffractometer
is independent of ; Flat plate sample
does not influence .

http://www.directindustry.com/prod/pa
http://www.cnndt.com/en/xray/Diffractometer/31A720161215926.html nalytical/product-25274-84402.html
Powder diffraction
relative I calculation : Absorption factor (A) Diffractometer
• θ smaller- area irradiated is large and the penetration depth of x-ray is small
• θ larger- irradiated area is small, but the penetration depth is relatively large.
irradiated volume is constant and is independent of θ

𝒐 (ergs/cm2/s), is 1cm 2 in cross section

𝑫 (ergs/s), diffracted I by thin film

𝑫 𝒐
𝝁(𝑨𝑩) 𝝁(𝑩𝑪)
(ergs/s)

by unit volume of specimen

Powder diffraction
relative I calculation : Absorption factor (A) Diffractometer
𝑙 cos 90 − 𝛾 = 1
𝑫 𝒐
𝝁(𝑨𝑩) 𝝁(𝑩𝑪) (ergs/s) 1
𝑙=
𝝁(𝑨𝑩 𝑩𝑪) (ergs/s) 𝑠𝑖𝑛𝛾
𝑫 𝒐

𝟏 𝟏
𝒐 𝝁𝒙 𝒔𝒊𝒏𝜸
𝒔𝒊𝒏𝜷
𝑫

In case of focusing diffractometer

𝒐 𝟐𝝁𝒙
𝒔𝒊𝒏𝜽
𝑫

Integrating for infinitely thick specimen, i.e., x = 0 to x =

𝒐 flat specimen making equal angles with the incident and diffracted beams and the
𝑫
specimen fills the incident beam at all angles and is effectively of infinite thickness
Powder diffraction
relative I calculation : Absorption factor (A) Diffractometer
for infinitely thick specimen 𝑑𝐼 (@𝑥 = 𝑜)
𝑑𝐼 (@𝑥 = 𝑡)
𝒐 𝟐𝝁𝒙 x=0
𝒔𝒊𝒏𝜽
𝑫

x=t
Infinite thickness “t” is the thickness of flat sample producing diffracted I from a thin layer on its back side
which is 1/1000 times the diffracted I from a thin layer on front surface
𝒐
𝑫
𝟐𝝁𝒕
𝑫 𝒐 𝒔𝒊𝒏𝜽

𝟐𝝁𝒕
𝒔𝒊𝒏𝜽

For a given material and for a chosen of X-ray, penetration depth (t) increases sinusoidal until the
maximum possible diffraction angle of 90o
Powder diffraction
relative I calculation : Absorption factor (A) Diffractometer: penetration depth
For a given material and for a chosen of X-ray, penetration depth (t) increases
sinusoidal until the maximum possible diffraction angle of 90o
of Ni = 8.9 g/cc (Cu-Kα) = 1.542 (Cu-Kα) =

𝜇
as a function of 𝝀 for nickel
𝜌
Penetration depth (𝜇𝑚)

θ(°)
 Penetration depth calculation
of Fe = 7.86 g/cc
(Cu-Kα) =

(Fe-Kα) =
Penetration depth (𝜇𝑚)

Fe-Kα

Cu-Kα 𝜇
(𝑐𝑚 /𝑔)
𝜌

θ(°)
Powder diffraction
relative I calculation : Temperature factor
Thermal vibration of atoms occurs even at room T and the amplitude of vibration increases with T
In Al at room T: 0.17 avg. displacement of atom
mean distance between e-s increases; decreases with increase in θ

With increase in T:
• Lattice expands leading to decrease in θ of peaks
• Integrated I of diffraction lines decreases and the background I increases
At constant T:
• The integrated I of diffraction lines decreases with increase in θ; influences the relative intensity

Schematic illustration of T effect

Powder diffraction
relative I calculation : Temperature factor
Thermal vibration of atoms occurs even at room T and the amplitude of vibration increases with T
At constant T:
• The integrated I of diffraction lines decreases with increase in θ; influences the relative intensity

• Exact calculation of T factor and A factor is difficult Calculated T factor values

for Iron at room T
The T effect and the A effect in cylindrical specimens of
Hull/Debye–Scherrer method depend on angle in opposite
ways; A decreases with increase in θ and opposite effect
for . The two effects do not exactly cancel one
another at all angles; however, if the comparison of line
intensities is restricted to lines not differing too greatly in
values, the absorption and temperature effects can be
safely ignored in the Hull/Debye–Scherrer method.

• Mean amplitude of atomic vibration

At a given T: u decreases as material gets stiffer (Al and W)
Powder diffraction
relative integrated I calculation
Hull/Debye-Scherrer camera

This can be assumed to be 1 for adjacent reflections

Diffractometer

Above equations cannot be used in case of

• Preferred orientation; crystallographic texture
Derived Lorentz factor and multiplicity factors are invalid. To eliminate grind a powder from solid
sample
• Extinction- decrease of the integrated intensity of the diffracted beam as the crystal becomes
more perfect is called extinction
Equations
. derived for ideally imperfect crystal samples used kinematical theory; mosaic structure has
higher diffracting power than perfect crystal
 Diffractometers and Measurements
X-ray spectrometer: An instrument for measuring x-ray spectra by means of a single crystal of known structure
and orientation using diffraction phenomenon.

X-ray diffractometer: An instrument for studying crystalline (and noncrystalline) materials by measurements of the
way in which they diffract (scatter) x-rays of known wavelength.
 Diffractometers and Measurements
X-ray spectrometer: An instrument for measuring x-ray spectra by means of a single crystal of known structure
and orientation using diffraction phenomenon.

X-ray diffractometer: An instrument for studying crystalline (and noncrystalline) materials by measurements of the
way in which they diffract (scatter) x-rays of known wavelength.
 Diffractometers and Measurements

Rigaku θ-2θ diffractometer. The x-ray tube is at the left, and the inset phtograph
shows the radiation enclosure and PC controlling the diffractometer motions
 Diffractometers and Measurements

• Continuous scan
• Step scan

Rigaku diffractometer. Here more possibilities exists to tilt/rotate the sample with respect to
specimen surface normal; suitable for texture and residual stress measurements
 Diffractometers and Measurements

Diffraction pattern of NaCl powder. Copper K radiation, monochromator, variable divergence slit diffractometer. The vertical
axis shows the square root of the number of counts.
 Diffractometers vs. Powder Camera

Diffractometer: not all diffraction peaks will be recorded at one instant so variation in incident beam I
alters the relative Is. Must to have voltage and current stabilizers
Powder Camera: all diffraction peaks will be recorded in one instant so change in incident beam I will
not alter relative Is
 Diffractometer; sampling for diffraction
Polycrystalline solid samples generally contain crystallographic texture which must be kept in mind
in utilizing the relative intensities of peaks for determining crystal structure and/or phase fractions.
Spinning and rocking the sample improves the powder nature of sample
Wires: several small cut lengths must be bonded onto a substrate like glass.
powder
Sieve
pressure

Powders:

Pressed from back side to get a flat surface on the other end where measurements can be made.

Powder particle size less than 10μm are optimal and the surface roughness should be as less as possible;
for too rough surfaces lower angle reflections suffer much larger absorption than higher angle reflections
 Diffractometer; focusing geometry for flat specimen
Diffractometer circle

detector
lower 2θ higher 2θ

• Focusing circle centres on specimen normal and passes through F and S and its size decreases with
increase in 2θ; this focusing enhances the I of weak reflections especially at lower 2θ.
• Flat specimen in focusing geometry broadens the peaks and shifts the peak maximum to lower angles.
This can be minimized by minimizing the divergence in incident beam
• Perfect focusing requires curved specimen with the radius of curvature equal to the radius of
diffractometer circle
 Diffractometer; focusing geometry for flat specimen
X-ray sources can not work as perfect thin line sources; all rays in beam will be parallel to the plane of
the diffractometer circle. This scattering can be minimized using a Soller slit.

Entrance

exit

• Entrance and exit slits control the divergence on the plane of the diffractometer circle. For forward
diffraction a small divergence angle of 1o would be sufficient whereas for backward diffraction region
3-4o divergence would enhance the irradiated area to give measurable I especially for weak reflections.
• Soller slit controls/minimizes the divergence on planes not parallel to the plane of diffractometer circle.
Diffractometer; focusing geometry for flat specimen

• Diffracted beam is made to pass through another Soller slit

and receiving slit F before reaching the detector.
• Increased width of F increases the maximum I at the expense of
resolution but it will not alter the integrated Is of peaks

For good quality diffractograms;

1. line source, specimen surface, and receiving-slit axis are all parallel,
2. the specimen surface coincides with the diffractometer axis, and
3. the line source and receiving slit both lie on the diffractometer circle.
 Diffractometer; peak position determination

Average of the
Peak maximum
inflection points

2θ at which
Midpoint of half
Integrated I to left
maximum
equal to that of
intensities
right, AL=AR

Other methods:
• Centroid of the peak (center of mass)
• Parabolic-fit:Fitting top 15% intensity to a parabola and the axis of the parabola is assumed to be the peak
center. widely used in macrostrain measurement
Diffractometer; peak position determination by 3 point parabolic fit

Simpler method: three measured points on the line

profile around the maximum intensity maximum
which are separated by the same angular interval c,
are sufficient to find the peak position complying
with parabolic-fit. The central point should be near
the maximum and the other two have intensities of
about 85 percent of the maximum. Once the
intensity differences
and are found, the
center of the peak is given by;
peak position determination for macrostrain measurements by parabolic-fit
– correction for absorption and L-P to broad peaks

𝜓 𝑖𝑠 𝑎𝑛𝑔𝑙𝑒 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 𝑑𝑖𝑓𝑓𝑟𝑎𝑐𝑡𝑖𝑛𝑔 𝑝𝑙𝑎𝑛𝑒 𝑛𝑜𝑟𝑚𝑎𝑙 𝑎𝑛𝑑 𝑠𝑝𝑒𝑚𝑒𝑛 𝑠𝑢𝑟𝑓𝑎𝑐𝑒 𝑛𝑜𝑟𝑚𝑎𝑙

Both factors introduce asymmetric peak shape thus needs to be corrected for precise
peak position measurement. combining the two into one leads to LPA factor;

Measured intensities at every 2θ position of the peak must be divided by LPA factor to correct for
LPA so the peaks become more symmetric to apply the parabolic-fit to determine the peak position
Phase diagram determination; composition of binary solid solutions
Binary solid solution:
Phase diagram determination; C content in Fe-C austenite and Fe-C martensite
Phase diagram determination; solvus line determination
Solvus line can be found by
1. Parametric method
2. Disappearance of 2nd phase method; lever rule

Amounts of phases in 2 phase field:

Powder diffraction:
Quantitative phase analysis; powder diffraction
Diffractometer:

Ihkl is integrated intensity per unit length of diffraction line (joules sec-1 m-1), I0 intensity of incident beam
(joules sec-1 m-2), A is cross-sectional area of incident beam (m2), λ is wavelength of incident beam (m), r
is radius of diffractometer circle (m), , e is charge on electron (C), m is mass of electron (kg), v is volume
of unit cell (m3), Fhkl is structure factor for reflection hkl, p is multiplicity factor, 𝟐𝑴 is temperature
𝟏
factor, and is linear absorption coefficient (m-1).
𝟐𝝁

In case of multiphase mixture (e.g. :

(volume fraction of )

𝜶
𝒎
𝝁𝒎 − 𝒍𝒊𝒏𝒆𝒂𝒓 𝒂𝒃𝒔𝒐𝒓𝒑𝒕𝒊𝒐𝒏 𝒄𝒐𝒆𝒇𝒇𝒊𝒄𝒊𝒆𝒏𝒕 𝒐𝒇 𝒎𝒊𝒙𝒕𝒖𝒓𝒆
Quantitative phase analysis; powder diffraction
In case of multiphase mixture (e.g. :

𝜶
𝒎
values independent of 𝐶

The three methods of analysis based on chosen reference:

(1) external standard method (a line from pure ),
(2) direct comparison method (a line from another phase in the mixture), and
(3) internal standard method (a line from a foreign material mixed with the specimen)
Quantitative phase analysis; direct comparison method
Determining the amount of retained austenite in steel c :

𝜸
𝒎

R-depends on the crystal structure and

𝜸 𝒊𝒏 ( ) composition of phase
K- is independent of phase and
dependent on only instrument
𝒊𝒏 ( )

𝜸 𝒊𝒏 ( )
+ =1
𝒊𝒏 ( )
Quantitative phase analysis; direct comparison method

For pure Fe @ 20oC

One should know/calculate;
- Well resolved peaks of austenite and
martensite
- Lattice parameters of austenite and
martensite both having same C content
- Bragg angles for the chosen reflections for
the chosen wavelength
- Structure factors for chosen hkl reflections
of austenite and martensite
- T factors for chosen reflections
- LP factor and p for chosen austenite and
martensite reflections
Stereographic projections; poles of planes
represents planes of a crystal by their normals all starting from one point at the centre of a reference
sphere and all these normals intersect the surface of reference sphere in a set of points which are
called “poles”. After that all the poles can be projected on to a projection plane which is tangent to the
reference sphere in such a way that we preserve the angles between poles. The poles represent
orientation of the planes (i.e., orientation of crystal) by their positions on the reference sphere. Plane
may also be represented by its trace on reference sphere making a great circle on the reference sphere.
Stereographic projections; poles and traces of planes

great circle passing

through the poles

great circles: all the circles

whose centre coincides with
the centre of reference sphere

small circles: all the circles whose

centre does not coincide with the
centre of reference sphere
Traces of planes
great circles
Stereographic projections; small and great circles

small circles- latitude lines

excluding equator

great circles-longitude lines

Stereographic projection; projecting poles on 2D surface Projection
plane
• projection plane should be normal to chosen diameter (BCA) of
reference sphere. Other end of line connecting the centre of N’
sphere and the projection plane serves as projection point (B). Reference
• All the poles on the reference hemisphere touching the projection sphere
p’ N
plane gets projected within the basic circle. Poles on the remaining p
hemisphere can be projected by interchanging the positions of
projection plane and point of projection. W B B-point of
W’
• Every plane-normal passes through the centre of reference sphere. projection
C
Because of this the poles which are not getting projected within A
the basic circle can be represented by their negative poles; If 100 E
E’
pole is getting projected outside the basic circle, then 100 can be
definitely within the basic circle. S
• When a pole goes out of basic circle, this can be represented by its
negative pole in the basic circle. Negative pole location can be
found by moving pole back on the small circle by the same extent
of degree it has travelled on it (to go out of basic circle)and its pole
S’ Basic circle
will be indicated on opposite quadrant of basic circle as an
inversion point through centre of basic circle,; i.e., the negative
pole will be on line connecting the positive pole and centre of basic
circle, at equi-angular distant from centre.
Stereographic projection; projecting poles on 2D surface Projection
plane

N’

• All the great circles gets projected as longitude lines; all the great Reference
circles pass through diametrically apposite points on basic circle. N sphere
the angular length of projected great circles on basic circle is 180o
• All the small circles having their normal, normal to projection plane
B
get projected as latitude lines W’ W B-point of
• Angle between poles can be measured only on great circles or C projection
equator. Measured angle son small circles will be always larger A E
than the actual angles
E’
• Wulff net is useful as a scale to measure the angles between poles.
S

S’ Basic circle
Stereographic projection; Wulff net construction Wulff net; as a result of stereographic
N
projection of ruled globe
Ruled globe N

W E W E

S S
Reference sphere having great circles passing through N and
S poles and small circles having their centres on N-S axis. All
small circles and great circles are marked with 10o interval
Stereographic projection; measuring angles between planes/poles

E
D
20o
F
C
A 60o B
 N measuring angles
between planes/poles
not on great circle
B

Initial positions of poles on

W E projection

positions of poles after

rotating the projection to
bring them on great circle
of wulffnet

S
finding traces/longitudes of planes/poles
N
α
B
A

90o
W 90o E

S
Stereographic projection; rotation of poles about N-S axis by 60o in clockwise direction

• Rotation about N-S axis, makes the poles (A1 and B1)
to rotate on corresponding small circles.
B2
• Angle between poles A1 and A2 will be less than 60o!
A1 60o A2

B1

B’1
Stereographic projection; rotation of pole A1 about an axis B1 by 40o in clockwise direction
N
• By rotation of projection bring B1 to
equator as B2. A1 goes to A2
A2 A3 • Move B2 by 30o along equator to bring it to
A1
40o center of projection as B3. move A2 by
same 30o along its small circle to bring it to
A5 A4 A3.
B4 • Now rotate A3 about B3 by 40o in clockwise
W E direction which brings A3 to A4.
• Move A4 and also B3 on their latitude lines
(i.e., small circles) by 30o which brings them
B1 to A5 and B4, respectively.
• Now rotate back the projection to its initial
position which brings B4 to the original
position of B1 and A5 to A6.
• After rotation of A1 about B1 by 40o in
clockwise direction A1 moves to A6.
S
Standard projections for cubic crystals

001

𝟎𝟏𝟏 𝟎𝟏𝟏
𝟏𝟎𝟏
𝟏𝟏𝟏 𝟏𝟏𝟏

𝟎𝟏𝟎 100 010

𝟏𝟏𝟎 𝟏𝟏𝟎

𝟏𝟏𝟏 𝟏𝟏𝟏
𝟏𝟎𝟏
𝟎𝟏𝟏 𝟎𝟏𝟏

𝟎𝟎𝟏

Standard (001) projection of cubic crystal

Standard (100) projection of cubic crystal
-different rotation operators have been indicated
Standard projections for cubic crystals
Standard projections for cubic crystals

001 001

𝟎𝟏𝟏 𝟎𝟏𝟏
𝟏𝟎𝟏 𝟎𝟏𝟏
𝟏𝟎𝟏 𝟏𝟏𝟏 𝟏𝟏𝟏
𝟏𝟏𝟏 𝟏𝟏𝟏 𝟎𝟏𝟏 𝟏𝟏𝟏

𝟎𝟏𝟎 100 010

𝟏𝟏𝟎 𝟏𝟏𝟎 𝟏𝟏𝟎 10𝟎 𝟏𝟏𝟎 𝟎𝟏𝟎 𝟏𝟏𝟎

𝟏𝟏𝟏 𝟏𝟏𝟏
𝟏𝟏𝟏
𝟏𝟏𝟏 𝟏𝟏𝟏
𝟏𝟎𝟏 𝟎𝟏𝟏 𝟏𝟎𝟏 𝟎𝟏𝟏
𝟎𝟏𝟏 𝟎𝟏𝟏

𝟎𝟎𝟏 𝟎𝟎𝟏

Standard (100) projection of cubic crystal Standard (110) projection of cubic crystal
Standard projections for cubic crystals
001

𝟏𝟎𝟏 𝟎𝟏𝟏
𝟏𝟏𝟏 𝟏𝟏𝟏
𝟏𝟏𝟏

𝟏𝟏𝟎 10𝟎 𝟏𝟏𝟎 𝟎𝟏𝟎 𝟏𝟏𝟎

𝟏𝟏𝟏
𝟏𝟏𝟏 𝟏𝟏𝟏
𝟎𝟏𝟏 𝟎𝟏𝟏

𝟎𝟎𝟏

Standard (110) projection of cubic crystal

Standard projections for cubic crystals

Standard (110) projection of cubic crystal

Standard (001) projection of cubic crystal
Standard projections ; finding hkl of a given pole
Standard projections ; finding hkl of a given pole
Angle between two planes of a cubic crystal