BACKGROUND

XRD (X-Ray Diffraction) is a non-destructive technique to characterize crystalline

materials. It provides information on structures, phases, preferred crystal orientations
(texture), and other structural parameter. XRD analysis is done by shooting a focused
X-Ray beam at the sample at a specific angle of incident, which results a diffraction
pattern which can be compared to diffraction pattern database. Every crystalline
substance gives a pattern. The same substance always gives the same pattern and in
a mixture of substances each produces its pattern independently of the others. XRD
analysis can be applied to inorganic samples such as salts, minerals, metals, etc and
organic samples (biological molecules) such as vitamins, drugs, proteins, and also
nucleic acids such as DNA.
HOW DOES IT WORK?

1. XRD analysis, a focused X-Ray beam is shot at the sample at a specific angle of
incidence.
2. The X-Rays deflect or "diffract" in various ways depending on the crystal
structure (inter-atomic distances) of the sample. The locations (angles) and
intensities of the diffracted X-Rays are measured.
3. Crystalline substances have an ordered three-dimensional arrangement with a
particular spacing of atoms.
4. When x rays strike the atoms within the crystal, the atoms absorb and reemit
the energy from the x rays in the form of spherical wave fronts emanating from
each atom. The waves travelling outward from each atom interact with other
waves in the processes known as constructive and destructive interference

which results a diffraction pattern. The patterns are controlled by the spacing of
atoms within the matrix and are unique to that substance.
Every compound has a unique diffraction pattern. In order to identify a
substance, the diffraction pattern of the sample is compared to a library
database of known patterns.

Instrument component

Part of XRD Machine

An XRD Machine consist of :
1.
2.
3.
4.
5.

Source ( X ray tube)

Primary Optics ( Lead Screen)
Sample Holder
Secondary Optics ( Optional)
Detectors ( Photographic plate)

1. Source
The source come from the X- ray Tube.
What does the source produce?
The source produces X- ray that will be used for analyzing the sample.
What is an X ray Tube?
An X ray tube is usually made from evacuated ceramic or glass vessel. A x
ray tube contain a tungsten filament which is located in the cathode. From the
cathode, electron are emitted. The x ray tube also contain an anode where
these electrons are accelerated with a potential of several ten thousand volt.

Component of an X ray tube

Cathode
- conduct the high voltage current
-

focus the emitted electrons

Filaments
-

Very tightly wound coil wire

When an electric current is passed through the filament, it heats up to
such an extent that some of the electrons have enough (thermal
vibrational) energy to break free of the attractive (electrostatic) forces
holding them inside the filament.

amount of electrons that are emitted from the filament = amount of

electrons flowing inside the filament (i.e., the current).

Anode
-

positive end of the x-ray tube, target for stream of electron that are
emitted by the cathode

The anode assembly is important as the source of the x-rays, as the

primary conductor of heat out of the tube and as an integral part of the
high voltage circuit.

The process
accelerated electrons hit inner shell electrons from atoms of the target metal
material, remove them and leave holes behind. These holes are quickly filled
from higher level electrons of the same atom. On falling down to the lower
energy level the atoms emit characteristic radiation ( X ray) with sharply
defined frequencies associated with the difference between the atomic energy
levels of the target atoms.
2. Primary Optic
Function
controls the beam produced by the X-ray source, and manipulates it into forms
more useful for diffraction experiments

Components of Primary Optics

Soller Slit
reduce the axial divergence of the X- Ray beam to less than 6 = to
collimate the X ray Beam

The divergence slit

It reduces the height divergence (beam spread) and increases the

resolution of the output.

Monochromator
Prevent the passing of other lights ( in nm) except for the chosen

wavelength
3. Sample holder
Function
Place to put the sample.
The best result is obtained when the sample is a rotating sample holder.
In the sample holder, the most common error that might occurred is due
to overfilled or underfilled of the sample in the sample holder. This will
cause error on the result.
4. Detectors
The detectors based on the image above is the photographic plate.

Function
allows the diffracted X-rays to be detected
Mechanism
The photographic plate is sensitive to light, this happened since there is
coating of emulsion of silver salts. When the x- rays emits its beam, the
photographic plate will absorbs it beams and undergo chemicals changes
which can capture the diffracted X ray patterns

INTERPRETATION OF XRD DATA

Data of XRD is in the form of Diffraction Pattern

The data obtained from XRD are in the form of DIFFRACTION PATTERN,

which is also shown in the X-Ray detector.

How the data is obtained?
o When X-Ray is passed through a crystal, it will bent at various
angles/diffracted
o It is because the electromagnetic radiation will strike the lattice
atom of the crystal in the lattice plane
o As a result, the electromagnetic radiation is diffracted off sets of
planes from where the X-Rays attack and interact with the lattice
atom of the crystal in the lattice plane
The set of planes itself is defined by the shape/geometry of
the unit cell (smallest component of the crystal)
o The result of the diffracted X-rays is shown as diffraction pattern in
the detector, which we use to determine what kind of crystal
present in our sample.

What happen during XRD analysis?

Diffraction pattern obtained from

XRD

What happen when X-ray attack the

lattice atom of the crystal plane?

IN ORDER FOR THE DIFFRACTION PATTERN TO BE ANALYZED WE

SHOULD UNDERSTAND MORE AOBUT THE DIFFRACTED LIGHT
How diffraction happen? - Inside of Crystals

The regular arrangement atom molecules of the crystal can be described

by using framework-like model called crystal lattice. Each intersection of
the lines will represent the position of the actual arrangement of atoms in
a crystal.

During XRD analysis the X-ray will attack the atom in the crystal lattice
and then diffracted off set of planes that are present inside the unit cell
(smallest constituent that make up the crystal lattice or repeating unit of
crystal lattice).

Condition for light to be reflected

There should be a constructive interference between the waves

Constructive interference occurs when the reflection of light satisfy the

Bragg equation
How constructive interference occurs?
During analysis, same wavelength of X-ray will attack different atom in

different planes of the crystal.

However some X-ray will attack atom that is located in the planes that
is deeper into the atomic plane.

Therefore for the same wavelength of the X-ray to attack the atom
located in a deeper atomic plane and thus reflected, it needs to travel

extra 2dsin
If the extra distance is equal to the wavelength of two waves they will

constructively interfere when exit both the crystal

The result of the waves when they exit the crystal is seen as one
whole wave.

Direction of diffraction depends on the orientation of planes in the

crystal

In general the direction where the light are reflected depends on the
orientation of planes inside the unit cell. Different orientation of planes

will make the X-Ray to be diffracted in various directions.

The set of planes of planes in crystal are labeled according considering
how the plane (or indeed any parallel plane) intersects the main

crystallographic axes of the solid.

In mathematical terms the set of planes is labeled in the form of Miller

Indices
Which is a set of numbers that show the intercepts of the planes in
crystal and thus may be used to uniquely identify the plane or surface.
o It is because different miller indices represent planes with different
orientation.

The result of the difference in the

direction of diffraction from different planes result different in the
location of the dots in the diffraction pattern

This would mean that each dots in the

diffraction

pattern

will

represent

the

planes in the crystal from where the x-ray is diffracted.

Analysis of Diffraction Pattern

The analysis of Diffraction Pattern primarily involves the calculation of d
spacing between the crystal lattice planes of atoms that produce the
constructive interference by using Bragg Equation.
How?

Wavelength is known

Measurement is made at angle 2

where

constructive

interference

occur

Solving Bragg's Equation gives the dspacing between the crystal lattice
planes of atoms that produce the
constructive interference

The d-spacing interplanar spacing (d-spacing) of a crystal is used for

identification and characterization purposes in X-ray diffraction (XRD). It is
because the d spacing of the atom is unique to each type of crystal although
the diffraction may come from the same planes of crystal with the same miller
indices.

Example: comparison between d spacing value of aluminum and copper

Applications of XRD
The main function of XRD application are:
To identify the unknown crystalline materials
To determine the charcteriation of crystalline materials
To measure the samplepurity.
There are 4 example of XRD application in real life:

Pharmaceutical insustry
o X-ray diffraction (XRD)

can

be

used

to

unambiguously

characterize the composition of pharmaceuticals. An XRD-pattern

is a direct result of the crystal structures, which are present in the

pharmaceutical under study. As such, the parameters typically

associated with crystal structure can be simply accessed. For
example, once an active drug has been isolated, an indexed Xray powder diffraction pattern is required to analyse the crystal
structure, secure a patent and protect the companys investment.
o For multi-component formulations, the actual percentages of the
active ingredients in the final dosage form can be accurately
analysed.

Forensic Sccience
o XRD is used mainly in analysis. Examples of contact traces are paint flakes,
hair, glass fragments, stains of any description and loose powdered
materials. Identification and comparison of trace quantities of material can
help in the conviction or exoneration of a person suspected of involvement in
a crime.

Geological Application
o XRD is the key tool in mineral exploration. Mineralogists have
been amongst the foremost to develop and promote the new field
of X-ray crystallography after its discovery. Thus, the advent of
XRD has literally revolutionized the geological sciences to such a
degree that they have become unthinkable without this tool.
Nowadays,
mineralogical

any

geological

studies

would

group
be

actively
lost

involved

without

XRD

in
to

unambiguously characterise the individual crystal structures.

Each mineral type is defined by a characteristic crystal structure,
which will give a unique x-ray diffraction pattern, allowing rapid
identification of minerals present within a rock or soil sample. The
XRD data can be analysed to determine the proportion of the
different minerals present

Microelectics Industry
o As the microelectronics industry uses silicon and gallium arsenide
single crystal substrates in integrated circuit production, there is a
need to fully characterise these materials using the XRD. XRD
topography can easily detect and image the presence of defects
within a crystal, making it a powerful non-destructive evaluation

tool for characterising industrially important single crystal

specimens.

Glass industry
o While glasses are X-ray amorphous and do not themselves give X-ray
diffraction patterns, there are still manifold uses of XRD in the glass industry.
They include identification of crystalline particles which cause tiny faults in
bulk

glass,

and

measurements

texture, crystallite size and crystallinity

of

crystalline

coatings

for