Properties and Applications of Nano Materials (Nano Composites)

Braggs X Ray diffraction Spectrometer

Principle: The Crystalline atoms cause a beam of X-rays to diffract into many specific directions. By
knowing the angle of diffraction θ, the interplanar spacing d can be obtained using the Brag’s Law

2d sin θ = n λ

Here λ is the wavelength of the X-rays.

Construction: X-rays from an X-ray tube are collimated into a narrow beam by two slits S1 & S2.
Now the beam is allowed to incident at a glancing angle on the sample (crystal), which is mounted
on the turntable of the spectrometer. The position of the crystal can be red from the circular scale
C. Most of the incident beam passes straight through the crystal. Some X-rays scattered by atoms
in different crystal planes. The reflected X-ray beam enters an ionization chamber carried by the
spectrometer arm. This arm is capable of rotation about the same axis as the turntable. When the
turntable rotates through an angle θ, the arm is designed to rotate an angle 2θ. Thus the X-ray
beam always enters the ionization chamber. The ionization current produced by the reflected
beam is measured by a sensitive electrometer E (or recorded on a photographic plate).
Working: The single crystal under investigation is
mounted on the turntable such that the glancing
angle θ= 0o. The ionization chamber is adjusted to
receive the X-rays. Then the crystal is moved in
small angles and the corresponding deflection
obtained in the electrometer is noted down. A graph
of glancing angle verses intensity of diffracted x-
rays is plotted.

It is seen from the graph that intensity of ionization

current increases abruptly for certain values of
glancing angle. This occurs whenever Bragg’s equation is satisfied. i.e., for 2d sin θ = n λ.

Here, d is the interplanar distance (the distance between any two consecutive atomic planes), θ is
the glancing angle, λ is the X-ray wavelength, n is the order of the reflection.

Thus by knowing n, λ and θ one can obtain the interplanar distances in the crystal by using
“Braggs Spectrometer”.

Application of X-ray diffraction spectrometer

1. It is used in determination of structure of the crystal materials.

2. It is used in determination of the orientation of the single crystal.
3. It is used to differentiate between crystalline and amorphous materials.
4. It is used in determination of the texture of poly-grained materials.

Crystal size determination by Scherrer equation

The formula given by Paul Scherrer relates the size of sub-micrometer crystallites in a solid to the
broadening of peak in a diffraction pattern. The Scherrer equation is written as

D=

Here, D is the size of the crystalline domain, K is a dimensionless shape factor, λ is the X-ray
wavelength, is the full width of half maximum of the intensity peak and θ is the peak position
Bragg angle.

Clear diffraction peaks are only observed when the sample possesses adequate long range order.
Diffraction lines from perfect crystals are very narrow. For crystallite sizes below 100 nm, line
broadening occurs due to incomplete destructive interference of scattered x-rays. X-ray line
broadening provides a quick, but not always reliable estimate of the particle size.
 Atomic Force Microscopy (AFM)

Principle: A laser beam is focussed on the back of a cantilever that moves up and down on
surface of the specimen. The deflection of the beam is captured. This beam gives the topography
of the surface.

Construction: In AFM, a sharp tip is mounted on a very flexible cantilever. A laser beam source,
photo diode detector system is the main feature of AFM. In AFM, a piezoelectric tube (PZT)
measures the deflection of the cantilever. For getting the image of the sample an image display
system is used. A sample holder is used to mount the sample.

Working: When the tip is brought into proximity of a sample surface, forces between the tip and
the sample lead to a deflection of the cantilever according to Hooke’s Law. The sample-tip
interactions may be due to Van der Waals force, electrostatic force, magnetic and chemical force.
The deflection of the cantilever is characterized by sensing the reflected laser light from the
backside of the cantilever with the position sensitive photodiode. For generating the image the tip
passes back and forth in a straight line across the sample. The tip-sample force is held constant by
adjusting the vertical position of the tip. A topographic image is build up by the computer by
recording the vertical position of the tip.

Applications of AFM

1. The AFM is useful for obtaining three dimensional topographic information of insulating
and conducting surfaces.
2. The AFM is used to detect clusters of atoms and molecules, individual macromolecules and
biological species (Cells, DNA and Proteins).
3. The AFM can be used to measure physical properties including elasticity, adhesion,
hardness, friction and chemical fluctuations of the sample.
 X-ray Photoelectron Microscopy (XPS)

Principle: Surface analysis by XPS is accomplished by irradiating sample with monochromatic

soft x-rays and analysing energy of the detected electrons. These photons have limited penetrating
power in a solid. This causes emission of photoelectrons from the surface atoms. The kinetic
energy of the emitted electrons is given by

K.E =hυ – B.E – ϕ

Here, hυ is the energy of the photon; B.E is the binding energy of the electron and ϕ is the
photoelectric work function.

Construction: An XPS consists of an x-ray source, sample holder, energy analyser and detector.
The common source used is an Al target x-ray source. The sample is placed in a sample holder.
The energy of the photoelectrons is identified by applying electrostatic and magnetic fields. To
avoid the contamination by air and water vapours the entire setup is laced in an ultra-high vacuum
chamber.

Working: The sample is illuminated by low energy x-ray photons. Due to this atoms on the
surface emit photoelectrons. The process is described as follows.

1. The bound electrons absorb a photon and converts part of the energy to kinetic energy.
2. While leaving the atom, some energy is consumed in overcoming the attraction of nucleus.
3. At this time outer orbitals readjust and deliver extra energy to outgoing electrons.
4. Then the XPS spectrum is obtained by determining the K.E and number of electrons
escaping from the upper surface of the sample.

Applications of XPS

1. XPS is employed to study metal alloys, semiconductors, Polymers, glasses, ceramics etc.
2. XPS can be employed for identification of active sites.
3. XPS can be employed for analyzing dust on the sample.
4. XPS can be used for the determination of oxidation state of the element.
 Scanning electron Microscopy (SEM)
SEM is an improved model of an electron microscope. SEM is used to study the three dimensional
image of the specimen.
Principle: When the accelerated primary electrons strike the sample, it produces secondary
electrons. These secondary electrons are collected by a positively charged electron detector which
in turn gives a 3-d image of the sample.
Construction:

SEM consists of an electron gun to produce high energy electron beam. A magnetic condensing lens is
used to condense the electron beam. A scanning coil is arranged in-between magnetic condensing lenses
and the sample. The electron detector (scintillator) is used to collect the secondary electrons and convert
them into electrical signals. These signals can be fed to CRO through video amplifier.

Working: Stream of electrons is produced by the electron gun and these primary electrons are
accelerated by the grid and anode. These accelerated electrons are made to incident on the sample
through condensing lenses and scanning coil.

These high energy incident electrons on falling over the sample produce low energy secondary electrons.
The collection of secondary electrons is done by applying a very high voltage to the collector. Thus
collected electrons produce scintillations on photo-multiplier tube (detector) and are converted into
electrical signals. These signals are amplified by the video amplifier and fed to the CRO.

By similar procedure the electron beam scans the sample from left to right and again left to right (similar
to we read a book) . The whole picture of the sample is obtained on the CRO tube.

Applications of SEM:

1. SEM is used to examine the structure of very large specimens in a three dimensional view.
2. SEM has various applications over fields such as Biology, industries, engineering, Physics, Chemistry
etc.
Transmission Electron Microscope (TEM)
In scanning electron microscope the resolution of the image is
limited only up to 10-20 nm. This will not help in understanding
the internal features of a sample of the size of the order say 0.2
nm. For these purposes the transmission electron microscope is
used.

Principle: Electrons are made to pass through the specimen and

the image is formed in the fluorescent screen, either by using
transmitted beam (bright field image) or by using the diffracted
beam (Dark field image).

Construction: TEM consists of an electron gun to produce

electrons. Magnetic condensing lenses condense the electrons
and thus adjust the size of the electron beam that falls on the
sample. The sample is placed in-between the condensing lens and
the objective lens as shown in the figure. The magnetic objective
lens blocks the high angle diffracted beams. The aperture is used to eliminate the diffracted beam and
thus it increases the contrast of the image.
The magnetic projector lens is placed above the fluorescent screen in order to achieve higher
magnification. The image can be recorded by using a fluorescent screen.

Working: Stream of electrons from the electron gun is made to fall on the specimen using the magnetic
condensing lens. Based on the angle of incidence, the beam is partly transmitted and partly diffracted.
Both transmitted and diffracted beams are recombined at the Ewald sphere to form the image. The
combined image is called Phase contrast image.
In order to increase the intensity and contrast of the image the diffracted beam must be eliminated. To
eliminate the diffracted beam, the resultant beam is passed through the magnetic lenses and the
aperture. The aperture is adjusted in such a way that the diffracted beam is eliminated. Thus the final
image obtained due to the transmitted beam alone is passed through the projector lens for further
magnification.

This magnified image is recorded in the fluorescent screen. Thus obtained high contrast image is called
“Bright field image”.

Applications of TEM
1. TEM is used to find the internal structure of the nanomaterials.
2. TEM is used to find 2-D image of very small biological cells, virus, bacteria etc.
3. Used in thin film technology, metallurgy, bio-chemistry, micro-biology.
4. Used to study the composition of paints, papers, fibers, composite materials, alloys etc.