ME427 Advanced Material

Characterization
What is X-Ray?
We can define X-Rays or X-radiation as a form of electromagnetic radiation. They are powerful waves of
electromagnetic energy. Most of them have a wavelength ranging from 0.01 to 10 nano metre, corresponding
to frequencies in the range 3 × 1019 Hz to 3×1016 Hz and energies in the range 100 eV to 100 keV.
German physicist Wilhelm Rontgen is typically credited for the discovery of X-Rays in 1895
The X-Rays properties are given below:
•They have a shorter wavelength of the electromagnetic spectrum.
•Requires high voltage to produce X-Rays.
•They are used to capture the human skeleton defects.
•They travel in a straight line and do not carry an electric charge with them.
•They are capable of travelling in a vacuum.
X-Ray Diffraction Methods:-
X-ray diffraction methods are the most effective methods for determining the crystal
structure of materials.

Diffraction methods can identify chemical compounds from their crystalline structure, not
from their compositions of chemical elements.
This means that the different compounds (or phases) that have the same composition can
be identified.

Diffraction methods include X-ray diffraction, electron diffraction, and neutron diffraction.

X-ray diffraction by crystals was discovered in 1912, and since then it has been the most
extensively studied and used technique for materials characterization
Monochromatic X-rays, also known as monochromatic X-ray radiation, refer to a type of X-ray radiation in which the X-rays
are of a single, specific energy level or wavelength. In contrast, conventional X-ray sources often produce a broad spectrum of
X-ray energies, which can range from low to high energy levels. Monochromatic X-rays are generated using specialized
techniques and equipment to select and produce X-rays of a very specific energy range.
Monochromatic X-ray radiation has several applications, including:
1.Medical Imaging: Monochromatic X-rays can be used in medical imaging to provide clearer images with enhanced contrast.
2.Material Analysis
3.Non-Destructive Testing
4.Reseaech
Thermionic emission is a phenomenon in which electrons are emitted from the surface of a material when it is heated to a
sufficiently high temperature. This emission of electrons occurs due to the thermal energy gained by the electrons in the
material, allowing them to overcome the electrostatic forces holding them within the material's structure. One common
application of thermionic emission is in thermionic vacuum tubes, also known as electron tubes or vacuum tubes.

•Characteristic radiation is produced through specific energy-level transitions in the atomic structure of the target material,
resulting in X-rays with distinct energy levels specific to the element being used.
•Continuous radiation (bremsstrahlung) is produced when high-energy electrons are deflected or decelerated by atomic
nuclei, resulting in a continuous spectrum of X-ray energies covering a range of values.
Both characteristic and continuous X-ray emissions play essential roles in various applications of X-rays, from medical imaging
to materials analysis and research.
Unlike characteristic radiation, which produces distinct energy lines, continuous radiation produces a broad spectrum of X-ray
energies. The maximum energy of the continuous X-ray spectrum depends on the energy of the incident electrons and the
strength of the electromagnetic field around the atomic nuclei. The continuous X-ray spectrum is used in medical imaging and
other applications where a broad range of X-ray energies is required.
Generation of X-Rays:-
X-rays are generated by accelerating electrons to high energies and then allowing these electrons to collide with a target
material. The interactions between the high-energy electrons and the target material result in the production of X-ray
photons. The process typically takes place in a device called an X-ray tube. Here's how X-rays are generated:
The wavelength of X-ray radiation (λ) is related to the acceleration voltage of electrons (V) as shown in the following
equation:- 1.X-ray Tube Components:
1. Cathode: The cathode is a heated filament that emits electrons through a process
called thermionic emission when it's heated to a high temperature. The emitted
electrons form an electron cloud around the cathode.
2. Anode: The anode is a metal target material placed a short distance away from
the cathode. The anode serves as the target for the accelerated electrons and is
typically made of a material with high atomic number (like tungsten) to efficiently
produce X-rays.
2. Electron Acceleration:
When a voltage is applied between the cathode and the anode, it creates an electric
field that accelerates the emitted electrons towards the anode. The electrons gain kinetic
energy as they accelerate.
3.Electron-Target Interaction:
As the high-energy electrons from the cathode strike the anode, they interact with the atoms of the target material. There are two main
mechanisms through which X-rays are generated: Continuous and Characteristic Radiation
4.X-ray Emission:
The X-ray photons produced in the interactions emerge from the anode in all directions. Some of these X-rays will pass through the body or
object being examined and reach a detector on the other side.
5.Detection and Image Formation:
The X-ray detector, which can be photographic film, scintillation detectors, or solid-state detectors, captures the X-ray photons that pass
through the body or object. The intensity of the X-rays reaching the detector is converted into an electrical signal, which is then processed to
create a visual representation of the internal structures, forming an X-ray image.
How X-Ray is getting observed?
X-rays are a form of electromagnetic radiation with higher energy and shorter wavelengths than visible
light. They cannot be observed directly with the naked eye because they lie outside the visible spectrum.
However, there are specialized instruments and techniques that allow us to observe and detect X-rays.
The primary methods for observing X-rays include:
1.X-ray Detectors: X-ray detectors are devices designed to detect and measure the intensity of X-rays.
There are several types of X-ray detectors, each with its own principles of operation. Some common
types include:
1. Photographic Film: In the early days of X-ray imaging, photographic film was used to capture X-
ray images. When X-rays pass through the body or an object, they can expose the film just like
visible light does, creating a shadow image of the internal structures.
2. In summary, X-rays are observed using detectors and imaging techniques designed to convert the
X-ray energy into visible signals or digital data that can be processed and interpreted. This allows
us to visualize the internal structures of objects, diagnose medical conditions, and study high-
energy phenomena in space.
Miller Indices
• Miller indices are a system used to describe the orientation and crystallographic planes within a crystal lattice. They are a
set of three integers that represent the reciprocals of the intercepts of a crystal plane with the three axes of the crystal's
coordinate system. Miller indices provide a concise and standardized way to describe the orientation of crystallographic
planes and directions.
• Here's how Miller indices are determined and used:
1. Intercepts: Consider a crystal plane that intersects the x-axis at a distance of a, the y-axis at a distance of b, and the z-axis
at a distance of c. The reciprocals of these intercepts are denoted as h, k, and l, respectively.
2. Miller Indices Notation: The Miller indices notation is represented by enclosing the integers h, k, and l within parentheses
or square brackets, without any commas. If the plane is parallel to an axis (i.e., no intercept on that axis), the
corresponding index is denoted as "∞" or "0."
3. Reducing to Smallest Integers: Miller indices are typically represented using the smallest set of integers that maintain the
same relative ratios. For example, if a plane intersects the x-axis at 2/3 of its length, the Miller index for that direction
would be (3, 0, 0) rather than (2, 0, 0).
4. Direction Indices: Besides plane indices, Miller indices are also used to describe crystallographic directions. To describe a
direction, the intercepts along the three axes are used as indices. For instance, if a direction crosses the x-axis at a
distance of a/2, the y-axis at 2b, and the z-axis at 3c, the direction's Miller indices would be (1/2, 2, 3).
• Miller indices are valuable in crystallography for various reasons:
• They provide a compact and standardized way to communicate crystallographic orientations and relationships.
• They aid in understanding the arrangement of atoms within crystals and how different planes and directions relate to one
another.
• They are crucial for analyzing crystal growth, symmetry, and material properties in fields like materials science,
mineralogy, and solid-state physics.
• Overall, Miller indices are a fundamental tool in crystallography, facilitating the clear communication of crystal lattice
orientations and aiding in the interpretation of crystal structures.
 How the Miller Indices direction found in terms of Vector and Plane?
Miller indices can also be related to vectors and planes in the crystal lattice. The Miller indices of a direction
and a plane in a crystal lattice can be determined in the following ways:
1.Direction Indices and Vectors:
The Miller indices of a direction correspond to the direction of a vector within the crystal lattice. Each index
is related to the ratios of the components of the vector along the crystallographic axes. Here's how to find
the vector corresponding to a given set of direction indices (h k l):
The vector is given by: [u, v, w] = (h, k, l)
For example, if the direction indices are (2, -1, 3), the corresponding vector would be [2, -1, 3].
Plane Indices and Normal Vectors:
The Miller indices of a plane correspond to a normal vector to that plane in the crystal lattice. To find the
normal vector corresponding to a given set of plane indices (hkl):
1. Determine the reciprocals of the indices: (1/h, 1/k, 1/l)
2. The components of the normal vector are: [u, v, w] = (1/h, 1/k, 1/l)
If the plane indices are (1, 2, -3), the corresponding normal vector would be [1, 1/2, -1/3
Absorption of X-Rays:-

X-ray absorption is a process in which X-ray photons are absorbed by matter, leading to the transfer of energy from the X-ray
photons to the atoms or molecules within the material.

When X-rays pass through a substance, they can interact with the electrons in the atoms, causing the electrons to move to
higher energy levels or even be ejected from their orbits. This absorption process has several important implications and
applications: Medical Imaging, Material Analysis.

The absorption of X-rays depends on various factors, including the energy of the X-rays, the atomic number of the material's
elements, the density of the material, and the path length of the X-rays through the material. Different elements and
materials have unique absorption characteristics, leading to their specific interactions with X-rays.

X-ray absorption by materials is a function of the linear absorption coefficient (μ) and mass density (ρ). The X-ray intensity (I)
passing through an absorption layer with thickness x is expressed by the following equation.

This equation is also called Bears Law:-

Equation (2.2) expresses the exponential in terms of (μ/ρ), which is called the mass absorption coefficient. It is independent
of the physical state of the solid or liquid. The mass absorption coefficient varies with chemical element; an element of
higher atomic number has a higher μ/ρ value than an element of lower atomic number. The mass absorption coefficient
generally decreases with decreasing wavelength of X-ray radiation.
The feature of the absorption edge can be used for X-ray radiation filtering. The X-ray filtering mechanism is illustrated
in Figure 2.5. We may select a filter material of which the absorption edge is located at a wavelength slightly shorter
than that of Kα radiation. The filter material can effectively absorb Kβ and continuous X-rays with wavelengths shorter
than the absorption edge, as shown in Figure

Filtering mechanism of X-ray radiation. Spectra of X-ray radiation are compared:

(a) before and (b) after filtering. The dotted line indicates the sharp increase of
absorption at a slightly shorter wavelength than the Kα radiation that enables a
nickel filter to generate single-wavelength radiation.
Bragg’s Law

Equation (2.5) does not directly provide the Miller indices of

crystallographic planes. We need to convert (h^2 + k^2 + l^2) to
(hkl) or {hkl}. This should not be difficult for low-index planes of
cubic systems. For example, when (h^2 + k^2 + l^2) is equal to 1,
the plane index must be {001}; when it is equal to 2, the index
must be {110}.
A crystal lattice may be defined as a solid composed of atoms,
ions or molecules arranged in a pattern periodic in three
dimensions.
Reciprocal Lattice
Ewald Sphere
The Ewald sphere is an imaginary sphere with a radius of λ^-1
in reciprocal space. The center of the Ewald sphere is located at
a crystal to be examined. The incident beam is represented by a
line that passes through a crystal at the sphere center and
targets the origin of the reciprocal lattice located on the surface
of the sphere (CO). The diffraction beam is represented by line
connect the sphere center and a lattice point of the reciprocal
lattice (CB). The angle between lines CO and CB should be
twice that of θ defined. Changing the diffraction angle (2θ) can
be represented by rotation of the reciprocal lattice around its
origin, point O in Figure 2.10. The Bragg conditions are satisfied
when a lattice point touches the Ewald sphere surface. It can be
proved that these geometric relationships represented in the
Ewald sphere are equivalent to Bragg’s Law, using Figure 2.10
as an example.
Diffraction Intensity
Diffraction intensity refers to the distribution of light or other waves as they interact with obstacles or apertures and
undergo a phenomenon called diffraction. Diffraction is the bending or spreading of waves as they encounter obstacles or
pass through small openings. This phenomenon occurs with all types of waves, including light, sound, water waves, and
more.
The diffraction intensity relies on collective scattering by all the atoms in the crystal. In an atom, the X-ray is scattered by
electrons, not the nucleus of the atom. An electron scatters the incident X-ray beam to all directions in space.
The scattering intensity is a function of the angle between the incident beam and the scattering direction (2θ). The X-ray
intensity of electron scattering can be calculated by the following equation.

Io is the intensity of the incident beam, r is the distance from the electron to the detector, and K is a constant related to
atom properties. The last term in the equation shows the angular effect on intensity, called the polarization factor. The
incident X-ray is unpolarized, but the scattering process polarizes it.
The atomic scattering factor (f ) is
used to quantify the scattering
intensity of an atom.
f = amplitude of the wave scattered
by one atom/ amplitude of the wave
scatter by one electron eq(2.10)
The atomic scattering factor is a
function of scattering direction and X-
ray wavelength, as shown in Figure
2.13b for copper atom.
X-Ray Diffractometry XRD, the most widely used X-ray diffraction technique is used for examining the crystal structure of
powder samples. The XRD instrument is called an X-ray diffractometer. In the diffractometer, an X-ray beam of a single
wavelength is used to examine polycrystalline specimens. Diffractometry enables us to identify the crystal structure and
quality by analyzing then comparing the spectrum with a database containing over 60 000 diffraction spectra of known
crystalline substances.
The basic function of a diffractometer is to detect X-ray diffraction from materials and to record the diffraction
intensity in a range of the diffraction angle (2θ). Figure 2.15 shows the geometrical arrangement of the X-ray source,
specimen, and detector. An X-ray tube passes through special slits that collimate the X-ray beam. These Soller slits are
commonly used in the diffractometer. They are made from a set of closely spaced thin metal plates to prevent beam
divergence in the direction perpendicular to the figure plane.
Modern diffractometers commonly use a monochromator made from a graphite crystal that is designed to diffract a
single wavelength based on Bragg’s Law.
The Bragg–Brentano arrangement
Diffractometers can have various types of geometric arrangements to enable collection of X-ray data. The majority of
commercially available diffractometers use the Bragg–Brentano arrangement, in which the X-ray incident beam is fixed, but
a sample stage rotates around the axis perpendicular to the figure plane of Figure 2.15 in order to change the incident
angle. Atoms are oriented in a random manner so it is moving. However, it is not suitable for thin samples such as thin films
and coating layers.
THIN-FILM
The technique of thin-film XRD uses a special optical arrangement for detecting the crystal structure of thin films and
coatings on a substrate.
The incident beam is directed to the specimen at a small glancing angle (usually < 1◦ ) and the glancing angle is fixed during
operation and only the detector rotates to obtain the diffraction signals, as illustrated in Figure 2.16.
Thin-film XRD requires a parallel incident beam, not a divergent beam as in regular diffractometry.
Also, a monochromator is placed in the optical path between the X-ray tube and the specimen, not between the specimen
and the detector.
The small glancing angle of the incident beam ensures that sufficient diffraction signals come from a thin film or a coating
layer instead of the substrate.
System Aberrations
In ideal conditions, an X-ray beam focuses on a specimen and the intensity of diffraction from the specimen is
detected accurately at the 2θ angle.
The focusing arrangement in a diffractometer, however, cannot ensure true focusing due to features of the X-ray
source and specimen. Thus, errors due to para focusing always exist.
The errors of para focusing are referred to as:
• axial divergence error;
• flat-specimen error; and
• specimen-transparency error.
Errors due to para
focusing can be illustrated using the Bragg–Brentano arrangement of the diffractometer.
Residual Stress:-
Any factor that changes the lattice parameters of crystalline specimens can also
distort their X-ray diffraction spectra. For example, residual stress in solid
specimens may shift the diffraction peak position in a spectrum.
Residual stress generates strain in crystalline materials by stretching or
compressing bonds between atoms. Thus, the spacing of crystallographic planes
changes due to residual stress.
Peak shifts in spectra occur when there is residual stress in a sample, as illustrated
in Figure 2.22.
In fact, X-ray diffraction is an effective tool to examine residual stress in solids.

Figure 2.22 Effects of residual stress and strain on diffraction

peak position and shape: (a) no strain; (b) uniform strain; and
(c) nonuniform strain.
Weight Fraction:-
The intensity of the diffraction peaks of a particular crystalline
phase in a phase mixture depends on the weight fraction of the
particular phase in the mixture. Thus, we may obtain weight
fraction information by measuring the intensities of peaks
assigned to a particular phase. Generally, we may express the
relationship as the following

where the peak intensity of phase i in a mixture is proportional

to the phase weight fraction (Ci ), and inversely proportional to
the linear absorption coefficient of the mixture (μm). K is a
constant