ASSIGNMNT - 2

CERD-616 - Bio-Fuels Development and Applications

Working Principle of Equipment / Methods for Structural, Chemical and

Thermal Characterization

Group – Solid Biomass

Submission date: 16-01-2021

Submitted to: Dr. Mohsin Ali Kazmi
 Structural Characterization
Nuclear Magnetic Resonance (NMR):

For the analysis of the molecular structure of a material, Nuclear Magnetic

Resonance (NMR) instrument has used which observe / measure the interaction of
nuclear spins in a powerful magnetic field.
Electron Microscopes and X-rays diffraction instruments can also be used for the
analysis of molecular structures at atomic level. However, due to non-destructive
process and less sample preparation, NMR have a big advantage over other
methods / instruments.
For the improvement / development of in the field of Chemistry, Biology, Food,
Organic EL, Battery films etc. Nuclear Magnetic Resonance (NMR) has become a
vital analysis tool in leading-edge science and technology fields.

Principles of Nuclear Magnetic Resonance (NMR)

When a nucleus (such as H or C) is placed in a strong magnetic field that possesses
a magnetic moment and it will begin to precess, like a spinning top as shown in
below figure.
What we can learn from NMR spectra
1. Composition of atomic groups within the molecule.
2. Information about adjacent atoms.
3. Information on molecular dynamics.
4. “Quantitative information, e.g. atomic ratios within a molecule that can be
helpful in determining the molecular structure, and proportions of different
compounds in a mixture.”

Normally, there are two types of Nuclear Magnetic Resonance spectrometers,

Fourier-Transform (FT-NMR) and Continuous-wave (CW). FT-NMR instruments are
more accurate as compare to CW-NMR spectrometers. However, CW-NMR still
widely used in industries due to the lower maintenance and operating costs.
CW-NMR instruments have water based cooling system and magnets in FT-NMR
spectrometers are cooled with liquid helium.
Scanning electron microscope (SEM):
Scanning Electron Microscope (SEM) is used a high energy electron focused beam
to generate different signals for the structure analysis of solid specimens. Electron
focused beam signals can reveal information about the specimens i.e. Chemical
Composition, External Morphology and orientation of material / crystalline structure.
In conventional SEM, imaged areas ranging in a scanning mode is from
approximately 1 cm to 5 microns (magnification ranging from 20X to approximately
30,000X). However, SEM is capable to performing the analysis at a selected point on
the specimen. This approach is especially useful in determining the chemical
compositions, crystal orientations, semi-quantitatively or qualitatively and crystalline
structure.

Fundamental Principles of Scanning Electron Microscopy (SEM):

Scanning Electron Microscope carries a significate amount of kinetic energy when
electrons accelerated. After the incident electrons are decelerated in the solid
sample, then this kinetic energy degenerates and a variety of signals has been
generated.
Generated signals include photons, secondary electrons, deflected backscattered
electrons, backscattered electrons, heat and visible light.
1) Backscattered electrons and secondary electrons are generally used for
sample imaging.
2) For showing topography and morphology on samples, secondary electrons
are the most valuable.
3) Backscattered electrons are most valuable for illustrating contrasts in
composition in multiphase samples
Essential components of all SEMs include the following:
1. Electron Source ("Gun")
2. Electron Lenses
3. Sample Stage
4. Detectors for all signals of interest
5. Display / Data output devices
6. Infrastructure Requirements:
a. Power Supply
b. Vacuum System
c. Cooling system
d. Vibration-free floor
e. Room free of ambient magnetic and electric fields
Transmission Electron Microscopy:
The most powerful microscope in material sciences is transmission electron
microscope. Same like SEM a high energy beam of electrons is shone through a
very thin specimen. We can observe the features like grain boundaries and crystal
structures etc.
As the basic principal of TEM and light microscope is almost same but in TEM beam
of electrons are used instead of light because the wavelength of electrons is much
smaller than the wavelength of the light. Due to optimal resolution attainability and
many orders of magnitude, TEM reveal the finest details of internal structure (even
as small as an individual atom).
Working Principle of Transmission Electron Microscope:

“In a transmission electron microscope, an electron gun, fires a beam of electrons.

The gun accelerates the electrons to extremely high speeds using electromagnetic
coils and voltages of up to several million volts.”

“The electron beam is focused into a thin, small beam by a condenser lens, which
has a high aperture that eliminates high angle electrons. When electrons reached at
highest speed, they zoom through the ultra-thin sample and parts of the beam are
transmitted depending on the transparency of the sample.”

“Objective lens focus the portion of the beam that is emitted from the sample into an
image. Another component of the TEM is the vacuum system, which is essential to
ensure electrons do not collide with gas atoms.”

“A low vacuum is first achieved using an either a rotary pump or diaphragm pumps
which enable a low enough pressure for the operation of a diffusion pump, which
then achieves vacuum level that is high enough for operations. High voltage TEMS
require particularly high vacuum levels.”

“The image produced by the TEM, called a micrograph, is seen through projection
onto a screen that is phosphorescent. When irradiated by the electron beam, this
screen emits photons. A film camera positioned underneath the screen can be used
to capture the image or digital capture may be achieved with a charge-coupled
device (CCD) camera.”
Fourier Transform Infrared Spectroscopy (FTIR):
“FTIR stands for Fourier transform infrared, the preferred method of infrared
spectroscopy. When IR radiation is passed through a sample, some radiation is
absorbed by the sample and some passes through (is transmitted). The resulting
signal at the detector is a spectrum representing a molecular ‘fingerprint’ of the
sample. The usefulness of infrared spectroscopy arises because different chemical
structures (molecules) produce different spectral fingerprints.”

“Fourier Transform Infrared Spectroscopy, also known as FTIR Analysis or FTIR

Spectroscopy, is an analytical technique used to identify organic, polymeric, and, in
some cases, inorganic materials. The FTIR analysis method uses infrared light to
scan test samples and observe chemical properties. In short, Fourier Transform
converts the detector output to an interpretable spectrum and FTIR generates
spectra with patterns that provide structural insights.”

Working Principle of FTIR:

“The FTIR uses interferometry to record information about a material placed in the IR
beam. The Fourier Transform results in spectra that analysts can use to identify or
quantify the material.”

 “An FTIR spectrum arises from interferograms being ‘decoded’ into

recognizable spectra”
 “Patterns in spectra help identify the sample, since molecules exhibit specific
IR fingerprints”

“The FTIR instrument sends infrared radiation of about 10,000 to 100 cm -1 through a
sample, with some radiation absorbed and some passed through. The absorbed
radiation is converted into rotational and/or vibrational energy by the sample
molecules. The resulting signal at the detector presents as a spectrum, typically from
4000 cm-1 to 400cm-1, representing a molecular fingerprint of the sample. Each
molecule or chemical structure will produce a unique spectral fingerprint that making
FTIR analysis a great tool for chemical identification.”
 Chemical Characterization
Elemental Analyzer:
“Elemental analysis is an experiment that determines the amount (typically a weight
percent) of an element in a compound. A CHN/O Analyzer is a scientific instrument
which can determine the elemental composition of a sample. The name derives from
the three primary elements measured by the device: carbon (C), hydrogen (H) and
nitrogen (N) and oxygen (O). Sulfur (S) can also be measured.”
Basic Principle:

“The capsule is injected into a high temperature (1000°C) furnace and combusted in
pure oxygen under static conditions. At the end of the combustion period, a dynamic
burst of oxygen is added to ensure total combustion of all inorganic and organic
substances. The resulting combustion products pass through specialized reagents to
produce carbon dioxide (CO2), water (H2O) and Nitrogen (N2) and oxides of nitrogen.
These reagents also remove other interferences including halogens, sulfur and
phosphorus. The gases are then passed over copper to scrub excess oxygen and
reduce oxides of nitrogen to elemental nitrogen. After scrubbing, the gases enter a
mixing volume chamber to ensure a homogeneous mixture at constant temperature
and pressure. The mixture then passes through a series of high-precision thermal
conductivity detectors, each containing a pair of thermal conductivity cells. Between
the first two cells is a water trap. The differential signal between the cells is
proportional to the water concentration, which is a function of the amount of
hydrogen in the original sample. Between the next two cells is a carbon dioxide trap
for measuring carbon. Finally, nitrogen is measured against a helium.
 Thermal Characterization
Flash point & Fire Point:
Flash point testing is a procedure designed to determine whether a sampled mixture
of Vapour and air is flammable. It can also determine the temperature at which
flammability occurs in a sample.
The lowest temperature at which its Vapours ignite from an ignition source is the
flash point of a material.
Flash point analysis is important for testing various products, including lubricants and
petroleum-based materials.
Testing of Flash Point:
The major uses of flash point testing are:
 Assessing safety hazards of liquids and semi-solids, including their
flammability
 Classifying these materials according to these results.
There are two main methods for carrying out the flash point test:
1. open cup
2. closed cup.
Each of these methods may be more appropriate for different applications. Certain
products or regulations may specify one method or the other.
The type of product you are testing should be within the scope of the testing method
you choose.
Within the two broad open cup and closed cup classes of flash point testing, there
are several different techniques.
Open Cup Flash Point Measurement:
The open cup method for flash point testing uses a vessel, or container, that is
exposed to the outside air.
Once the sample material is placed in the vessel, you then gradually raise its
temperature, and pass an ignition source over it, until it flashes and ignites at a
certain point.
This is the sample’s flash point.
The most common open cup method is the Cleveland open cup (COC). Other
methods include Tag and Setaflash.
Initially, the open cup method for flash testing was developed to assess potential
hazards when there were spillages of liquids.
As a method, the open cup test is less precise than closed cup, because vapours are
free to escape into the atmosphere, and may be affected by local conditions.
Flash point results from this method may also read higher at temperatures above
ambient because of the reduced concentration of vapours compared to closed cup
methods.
Closed Cup Flash Point Measurement:
In the closed cup method, you conduct the test using a vessel, which is sealed off
from the outside atmosphere.
You then heat both the vessel and sample, which replicates the effect of accidently
introducing an ignition source into a sealed container, such as a gas tank or other
storage vessel.
This close approximation of real-life conditions, and the precise nature of the testing,
makes the closed cup method ideal for product specifications and regulations.
Closed cup testing will generally produce lower flash points because the contained
heat is more likely to make the sample material flammable at an earlier stage.
This delivery of lower results tends to make closed cup methods preferred for
industry standards.
It is the common method for testing the fire and flash points of all petroleum products
that have a flash point above 79°C.
There are four main closed cup flash point testing methods: Pensky Martens, Abel,
Tag and Setaflash.
Thermal gravimetric analysis:
Thermal analysis (TA) as a group of techniques that monitor changes of physical or
chemical properties of a sample with time as it is subjected to a temperature
program. In other words, TGA is a technique in which, upon heating a material, its
weight increases or decreases.
Thermogravimetric analyzers (TGA) monitor and record sample mass, time, and
temperature. The temperature program may include heating, cooling, isothermal
holds, or a combination of them. The analyzer consists of a precise micro balance
connected to a sample pan inside a furnace with a temperature programmer and
controller.

Working Principle of TGA:

A TGA analysis is performed by gradually raising the temperature of a sample in a
furnace as its weight is measured on an analytical balance that remains outside of
the furnace. In TGA, mass loss is observed if a thermal event involves loss of a
volatile component. Chemical reactions, such as combustion, involve mass losses,
whereas physical changes, such as melting etc. The weight of the sample is plotted
against temperature or time to illustrate thermal transitions in the material, such as
loss of solvent and plasticizers in polymers, water of hydration in inorganic materials,
and finally, decomposition of the material.