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Materials Characterization
Dr. Mohsin Ali Raza
Institute of Metallurgy and Materials
Engineering
University of the Punjab, Lahore
Dr. Mohsin Ali Raza
Course content
Properties and production of x-rays, absorption of x-rays, use of filters,
synchrotron radiation source, x-ray safety, crystallography, reciprocal
lattice, Bragg’s law, Diffraction methods, x-ray diffraction, Ewald sphere,
Debye-Scherrer technique, powder diffraction, indexing planes,
diffractometer, experimental consideration during diffraction, intensity
calculations, structure factor calculations, application of x-ray diffraction
(Scherrer equation, size and strain analysis), wet analysis, electron
microscopy (SEM & TEM),electron diffraction, AFM, EDX, XRF,
spectroscopic techniques (FTIR, UV), thermal characterization of
materials: TGA, DSC, DTA, non-destructive testing.
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Books
• 1. “Elements of X-ray Diffraction-4th Edition”, B. D.
Cullity, Addison-Wesley Publishing Co. Inc. 2014.
• 2. “Interpretation of X-ray Powder Diffraction Patterns”,
H. Lipson, H. Steeple, Macmillan London, 1970.
• 3. “Essentials of Crystallography-2nd Edition”, D. Mckie,
Christine Mckie, Blackwell Scientific Publications
Oxford, 1986.
• 4. “Crystallography” R. Steadman, Van Nostrand
Reinhold Company Ltd. New York, 1983.
• 5. “X-ray diffraction and Crystallography” by Y. Waseda,
E. Matsubara and K. Shinoda, Springer-Verlag,
Germany, 2011.
Dr. Mohsin Ali Raza
Classification of Materials Characterisation Techniques
• Structural analysis tools (X-ray diffraction, Phase identification, indexing and
lattice parameter determination, Analytical line profile fitting using various
models, Neutron diffraction; Reflection High energy electron Diffraction
(RHEED), Low energy Electron Diffraction (LEED)
• Microscopy techniques (Optical microscopy, SEM, TEM, AFM, STM)
• Thermal analysis Tools (Differential thermal analysis (DTA), Differential
Scanning Calorimetry (DSC), Thermo-gravimetric analysis (TGA), DMA,
Rheometer)
• Electrical characterisation (Electrical resistivity in bulk and thin films, Hall
effect, Magnetoresistance, Impedance spectroscopy)
• Magnetic characterisation (Magnetic property measurements, Magnetic
hysteresis loops, time and temperature dependent magnetization
measurement)
• Optical/Spectroscopic Characterisation Techniques (Absorption,
transmission, reflection, Fourier transform infrared spectroscopy (FTIR),
Photoluminescence, Raman, X-ray photoelectron spectroscopy (XPS)
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Properties of X-Rays
• Discovered in 1895 by Rontgen
• Invisible
• Electromagnetic waves
• Travel in straight line and affect photographic film
• Can pass through human body, wood, metal and other
opaque objects and can shine fluorescent screens.
• Radiography (reveal internal details of order of 0.01 mm
(10 µm).
• Discovery of x-ray diffraction by crystals
proved the wave nature of x-rays leading
to new method for determination of internal
structure of crystals (0.001 µm = 1 nm)
Dr. Mohsin Ali Raza
x-Rays are Electromagnetic Radiations
X-rays have wavelength in the range of 0.01-10 nm and
energies in the range of 120 eV to 120 keV
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x-Rays are Electromagnetic Radiations
Wavelength of visible light = 6000 Å = 600 nm
Wavelength of x-rays for medical applications = 0.0124-0.124 nm
Wavelength of x-rays for crystal structure determination/diffraction = 0.5-2.5 Å
= 0.05-0.25 nm
Dr. Mohsin Ali Raza
x-Rays are Electromagnetic Radiations
z
Fig. Electric and magnetic fields associated with a monochromatic beam/wave moving
in the x-direction
Wave is called plane polarized, if electric field stays in xy-plane
Wave is called unpolarised, if electric field (E) and magnetic field (H)
both assume all directions in yz-plane
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Variation of Electric Field for a Plane Polarised Wave
Amplitude (A)
+E
Fig. The E variation with t at
fixed value of x or with x at
Time (t) or fixed value of t
-E distance (x)
λ Dr. Mohsin Ali Raza
Variation of Electric Field for a Plane Polarised Wave
A sinusoidal variation of E represents periodicity of wave
𝑥
𝐸 = 𝐴 sin 2𝜋 − 𝜈𝑡
𝜆
Where, A = Amplitude of the wave
λ = Wavelength
ν = frequency
The relationship of frequency and wavelength is given as
𝑐
𝜆=
𝜈
c = Velocity of light = 3 x 108 m/s
Intensity : X-rays carries energy and the rate of flow of this energy through unit area
perpendicular to direction of motion of the wave is called intensity I, measured by
counting number of photons incident on a detector or by measuring degree of blackening
of photographic film exposed to x-ray beam.
𝑰 ∝ 𝑨𝟐
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Electromagnetic Radiations as waves or particles
Classical Theory
An electromagnetic radiations due to its sinusoidal variation of electric field
which can be positive or negative (oscillating charge about mean position) are
considered as waves.
Quantum Theory
An electromagnetic radiations can be considered as a stream of particles called
quanta or photons.
The energy of each photon is hν , where h is Planck’s constant ( 6.63 x 10-34
joule.se)
X-rays have dual wave-particle character and their link can be obtained by
𝒄
𝑬 = 𝒉𝝂 = 𝒉
𝝀
Dr. Mohsin Ali Raza
Production of x-rays
X-rays are produced when high speed electrons with sufficient kinetic
energy hit metal target
Rapid deceleration of any electrically charged particle can produce x-rays
W filament
Mo
Most of KE is lost as
heat and less than 1%
energy is transformed
into x-rays
The kinetic energy (joules) of the electrons on impact is given by
𝟏
𝑲. 𝑬 = 𝒆𝑽 = 𝒎𝒗𝟐
𝟐
e is charge on electron (1.6 x10-19 coulomb) and V is voltage across the electrodes, m
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is mass of electron (9.11 x 10-31 kg), v is velocity in m/s just before impact
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The Continuous Spectrum
X-rays coming from target are mixture of different wavelengths, and this
variation is dependent on the tube voltage.
Polychromatic, continuous
or white radiation consists of
Characteristic x-
rays of many wavelengths
rays were
(Bremsstrahlung)
discovered by
W.H.Bragg
The area under the curve
is the total x-ray energy
emitted per second.
Fig. X-ray spectrum of molybdenum as a function of applied voltage
Dr. Mohsin Ali Raza
The Continuous Spectrum
Decelerating electrons emits energy but not all electrons decelerates in
one impact while other deflects and loses their fraction of total energy
Electrons stopping in one impact produce photons of maximum energy i.e., x-
rays of minimum wavelength and transfer all their energy into photon energy
𝑒𝑉 = ℎ𝜈𝑚𝑎𝑥
𝑐 ℎ𝑐
𝜆𝑆𝑊𝐿 = 𝜆𝑚𝑖𝑛 = =
𝜈𝑚𝑎𝑥 𝑒𝑉
Short wavelength limit as function
of applied voltage 12.40 × 103
𝜆𝑆𝑊𝐿 =
𝑉
The total x-ray intensity is given by
𝑰𝒄𝒐𝒏𝒕.𝒔𝒑𝒆𝒄𝒕𝒓𝒖𝒎 = 𝑨𝒊𝒁𝑽𝒎
(Z atomic number of target , i tube current (number of electrons per second striking
the target, A proportionality constantDr.and mAliisRazaa constant with value about 2)
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The Continuous Spectrum
Find the shortest wavelength that is present in X-rays produced at an
accelerating potential of 50 KV. Calculate the corresponding frequency also.
12.40 𝑉.𝑚
𝜆𝑆𝑊𝐿 = 50×103 𝑉
𝑐
𝜈=
𝜆𝑚𝑖𝑛
Dr. Mohsin Ali Raza
Nomenclature for Principle x-ray emission Lines
Characteristic x-rays
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Energy Level Diagram Showing the Allowed Transitions
Energy difference of x-ray
photon is equal to energy
difference between the levels
concerned
E1-E2= hν
In the case of Kα1
hνα1= Wk- WLIII
ℎ𝜈𝐾𝛼1 = ℎ𝜈𝐾 − ℎ𝜈𝐿𝐼𝐼𝐼
WLIII
Wk
1 1 1
=
𝜆𝐾𝛼1 𝜆𝜅 − 𝜆𝐿𝐼𝐼𝐼
Eα2= Wk- WLII
hνα2= Wk- WLII
Energy level diagram showing transitions responsible for
Dr. Mohsin Ali Raza
K and L emission lines
Energy Level Diagram Showing the Allowed Transitions
If K, L, M energy levels for platinum lie roughly at 78, 12 and 3 KeV, respectively.
Calculate the approximate wavelength of the Kα and Kβ lines.
Principal Quantum number
ℎ𝜈𝐾𝛼 = EL-EK = -12-(-78) =66 KeV Energy in eV
E=0 n=
ℎ𝜈𝐾𝛽 = EM-EK = -3-(-78) =75 KeV
E=-3 n=3 , M Shell
Kβ
E=-12 n=2 , L Shell
Kα
E=-78
Dr. Mohsin Ali Raza n=1, K Shell
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The Characteristic Spectrum
Spectrum of Mo at 35 kV
Kα = 0.071nm
Kβ = 0.0632 nm
• Voltage necessary to excite K characteristic radiation is more than 20 kV for Mo.
• Increase in voltage above the critical voltage increases the intensities of the
characteristic lines relative to continuous spectrum but does not change their
wavelengths.
• Kα is always stronger than Kβ (5/1) as there are more chances of electron falling
Dr. Mohsin Ali Raza
from L shell into K due to small distance.
The Characteristic Spectrum
Dependence of Intensity of Kline
𝐼𝐾𝑙𝑖𝑛𝑒 = 𝐵𝑖(𝑉 − 𝑉𝐾 )𝑛
Where B is proportionality constant, Vk the excitation voltage, i tube
current, and n a constant with a value of about 1.5)
• Kα line has the highest intensity in the spectrum (90 times higher than
adjacent wavelengths).
• Sharp Kα line has made x-ray diffraction possible (as this will be like a
monochromatic radiation)
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Absorption of x-rays
Interaction of x-rays with matter results in partial transmission and partial absorption
(Photoelectric effect and Compton effect)
Intensity I of an x-ray beam decreases as it passes through any homogeneous
medium and is proportional to the distance traversed x. This is given by
𝒅𝑰
− = 𝝁𝒅𝒙
𝑰
Where the proportionality constant µ is called the linear absorption coefficient
(attenuation)and is dependent on the substance considered, its density and the
wavelength of the x-rays.
𝑰𝒙 = 𝑰𝒐 𝒆−𝝁𝒙 (where Io= intensity of x-ray beam and Ix= intensity of transmitted
beam after passing through a thickness x)
• Mass absorption coefficient
(Characteristic of the
𝝁 material)
−( )𝝆𝒙
𝑰𝒙 = 𝑰𝒐 𝒆 𝝆
𝝁
can be calculated for solutions or compounds by taking weighted average of the mass
𝝆
𝜇 𝜇 𝜇
absorption coefficients of constituent elements asRaza= 𝑤1
Dr. Mohsin Ali + 𝑤2 +⋯
𝜌 𝜌 𝜌
Example
Find the thickness of water required to
reduce the intensity of 100 keV x rays by
a factor of 1000.
From Figure, µ = 0.035 cm. We want the
value of Δx that gives I = 10-3 Io;
10-3 = exp( - 0.035Δx) or 0.035 Δx = ln
1000
Δx = (6.9078/0.035) cm = 197.4 cm ~ 2 m
It is worth noting that the relative
absorption of bone to water is
approximately 150. That is, bone is 150
times more opaque to x rays than is
water. Lead is about 75 times more
opaque than bone.
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