Unit III: Spectrometric & Thermo-
gravimetric Methods
Thermal Method of Analysis: Elementary discussions
of TGA, DTA & DSC.
Chromatographic Methods of Separation, Gas
Chromatography, HPLC & Potentiometric methods
Spectrophotometer : Infrared, Ultra-Violet and
Visible spectrophotometer, NMR and Raman
Spectroscopy and their application
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DSC: Differential Scanning Calorimetery
Differential Scanning Calorimetery (DSC) is the most
widely used technique for analytical investigation of
Substances / materials.
It measures the differences in energy inputs into a
substance and a reference material as they are
subjected to a controlled temperature program,
because practically all physical and chemical
processes involves changes in enthalpy or specific heat
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DSC Instrument and its block diagram
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Sample & Reference pans are
heated by two independent
furnaces embedded in a
temperature-controlled heat
sink.
DSC Measures the difference in
Energy Inputs into a substance
and a reference material as
they are subjected to control
temperature program.
GEOMETERY and SIZE of
Sample & Reference Cells are
important because the Heat
Flow depends on geometry and
Thermal Diffusivities.
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DSC sample preparation
procedures are as follows:
Weigh your sample to the nearest 0.1 mg with the analytical
balance & Record the weight.
2. Use forceps to place sample in the bottom half of an
aluminum DSC pan.
3. Use forceps to place the aluminum pan lid on top of your
sample.
4. Use forceps to load the aluminum pan and sample into the
sample encapsulating press Align the sample pan in the
encapsulating press, and press down on the handle to seal the
aluminum pan.
5. Crimp an empty aluminum pan and lid. You will use the
empty pan as a reference sample.
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DSC Procedure
Standard procedure to perform DSC.
1. THREE RUNS are performed for each sample analysis.
2. 1st Heat sample at a rate of 10ºC min–1 from ambient to
300ºC above the melting point or to temperatures high enough to
remove previous thermal history.
3. Hold temperature for 10 minutes.
4. Cool to at least 50ºC below the peak crystallization
temperature at a rate of 10ºC min–1.
5. Repeat the process as 2nd Heating cycle at the rate of 10ºC
min–1.
6. Scan thermal transition from temperature 1 to temperature 2
and in the subsequent cycles performed.
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A schematic of a DSC Thermogram
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DSC-Analysiss
Parameters Analyzed:
Rate of change of Enthalpy,
Tm is taken at maximum of endothermic peak from the second heating cycle.
TC is taken as the maximum of exothermic peak from the cooling cycle.
The degree of crystallinity was calculated via the total enthalpy method, according to
the equation
Δ Hm
Xc = -------------------
Δ Hm+
Where
Δ Hm+ is the specific melting enthalpy for 100% crystalline LDPE value taken as
Δ Hm+ = 276 J/g [24].
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Heat capacity
Melting
Melting occurs when your material changes phase from a
solid to a liquid. When a material starts to melt, its
intermolecular bonds absorb energy and begin to loosen and
break.
Since melting involves absorption of energy, it is an
endothermic process and appears on the DSC curve as a
large, temporary decrease in heat flow.
Once the material has completely melted, the heat flow
returns to its original baseline value. The melting
temperature is generally measured at the onset point of the
melting curve.
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Melting Study
The determination of melting point of polymers is required to find out the processing
temperature of the semi crystalline polymeric material
Basically melting destroys the crystalline nature of polymers. Polymer melt over a range of
temperature in which onset of melting endotherm is often quoted as melting temperature.
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Glass transition temperature Tg
Glass transition temperature (Tg) is also an important
characteristic of noncrystalline and semicrystalline
materials, but Tg is a particularly significant property of
many common polymers.
Glassy State Polymer Rubber State Polymer
At a temp. below Tg, amorphous and semicrystalline
polymers tend to be hard and brittle because the polymer
chains are locked in a tangled, coiled position.
Above Tg, the polymeric chains are able to more easily
rotate and slip past each other, and the polymer becomes
softer and more ductile.
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Glass transition temperature Tg
Generally the glass transition point depends on the
Processing of the material and
Material’s natural characteristics such as structure,
bonding, and molecular weight.
Since it takes energy to break these bonds, the glass
transition appears on a DSC curve as an endothermic
process. In DSC, the Tg can be found by a permanent
decrease in baseline heat flow, and Tg is usually taken as
the inflection point in the curve
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The crystallization temperature (Tc)
The crystallization temperature (Tc) is another important
transition that occurs in some polymeric materials.
At the crystallization temperature, the polymer loses its random
chain arrangement, intermolecular bonds form, and the polymer
molecules become more ordered.
Formation of bonds during crystallization is an exothermic
process, so an increase in heat flow (a peak on the DSC curve)
accompanies the crystallization process.
Generally, the Tc is found by finding the onset point of the
crystallization curve.
Note that many amorphous polymers never undergo
crystallization.
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Applications of DSC
• Melting study
• Crystallization study
• Glass transition temperature study
• Crystallinity study
• Oxidative stability study
• Blend analysis
• Curing study.
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