Thermal Analysis 2

Course Conducted By
Fatema-Tuz-Zahra
Department of MSE
KUET
 Baseline Determination
There are two baselines: Instrument baselines (zero baseline) and sample baseline.
• The instrument baseline is the curve recorded without the sample over the
instrument’s operational temperature range. Ideally, the instrument baseline is a
straight line over a temperature range.
• However, the baseline may be curved and/or display a high level of noise. For
example, the instrument may be contaminated with trace amounts of residue
from a previous experiment.
• Decomposition or sublimation of such a residue will distort the instrument
baseline. The instrument baseline will also be affected if the flow rate of purge
gas in the instrument is not constant or if the purge gas contains a large amount
of water vapor.
• Thus, we should always check the instrument baseline by first running the
instrument without a sample.
➢The sample baseline of an experimental curve, as illustrated in Figure
is the line that connects the curve before and after a peak, as if no peak
had developed.
➢Accuracy of enthalpy-change measurement relies on correctly
constructing the sample baseline.
Baseline Determination
 Effect of Scanning Rate
➢The rate of scanning through a
temperature range affects the
thermal-event measurement.
➢More specifically, the scanning rate
can change the curve shape and
characteristic temperature
indicated in a curve.
➢Figure 10.10a reveals that the
peak area of PET melting increases
with increasing heating rate. Figure
10.10b reveals that the
crystallization temperature of PET
decreases and peak width
increases with increasing cooling
rate.
➢The rate effects on the curves simply reflect the fact that thermal events
are kinetic processes.
➢The processes of material change, such as melting, require time for heat
transfer and atom or molecule diffusion.
➢Increase of the scanning rate will result in an increase of the
temperature gradient in the sample and the instrument, thus making it
difficult for the sample to reach equilibrium.
➢The scanning rate of DTA and DSC instruments commonly varies from 0.1
to 40 ◦C/min.
➢The programmed scanning rate may not represent the true rate of sample
heating or cooling, because of the possible temperature gradient between
sample and thermocouple.
➢Scanning-rate effects are difficult to eliminate, particularly for polymeric
samples.
Measuring Transition Temperatures
Applications of DTA & DSC

❑Measurement of Temperature and Enthalpy Change

❑Determination of Heat Capacity
❑Determination of Phase Transformation and Phase Diagrams
Measurement of Enthalpy Change

• The enthalpy change of phase transformation can be directly measured

from the corresponding peak area of a DSC curve. The DSC is
𝑑𝐻
commonly plotted as per mass unit versus temperature. The total
𝑑𝑡
enthalpy change ∆H should be proportional to the peak area (𝐴𝑝 ).

• where 𝐾𝐶 is a calibration factor that includes contributions from the

experimental conditions and the thermal conductivity of the system.
We can obtain 𝐾𝐶 by measuring the peak area of the standard samples,
for which we know enthalpy change, such as those listed in Table 10.3.
• For the power-compensated DSC, 𝐾𝐶 is virtually independent of temperature.
• For the heat flux DSC, 𝐾𝐶 becomes temperature dependent and has to be
determined at a temperature close to that of the peak to be measured. The 𝐴𝑝
measurement relies on interpolation of the sample baseline
Determination of Phase Transformation and
Phase Diagrams
• DTA and DSC curves are sensitive to the first-order transition, which exhibits an
enthalpy change.
• First-order transitions include melting and solid-state phase transformations.
The curve peaks of DTA and DSC readily reveal solid-state phase
transformations over a temperature range.
Determination of Heat Capacity
The principle of heat capacity measurement is based on proportionality of the
DSC response to the heat capacity. By definition, the heat capacity of
materials under constant pressure is the following.

The displacement between the baseline and sample line (h) should be
proportional to sample heat capacity.

The proportional factors are determined by the heating rate (β) and by the
calibration factor (B).
• Sapphire is commonly used as
the standard with known heat
capacity.
• Figure 10.13b illustrates DSC
curves with an empty sample
holder (pan), with a sample, and
with a standard sample recorded
on the same chart.
• The heat capacity of the sample
can be calculated with the heat
capacity of the standard (𝐶𝑃𝑠 )
and displacements measured
from:
 Application to polymers
• Polymeric materials are more sensitive to temperature than metals and
ceramics.
• A large number of polymers exhibit physical and chemical property changes with
changes in temperature
• Besides determining the temperatures of glass transition, crystallization, and
melting, we can also determine special properties of polymers such as
crystallinity, curing status, polymer content, and stability.
• A large number of polymeric materials have both amorphous and crystalline
structures. The melting temperature is that of a crystalline solid to liquid
transformation.
• We can estimate the crystallinity of polymer (Xc) by comparing its melting ∆H
with that of its fully crystalline counterpart (∆𝐻100 ).
• However, it is not commonly used because 100% pure crystalline samples for
most polymers are not available. One alternative approach is to use the fusion
enthalpy, the latent heat of melting, of chemical repeated units (∆𝐻𝑢 ) to
replace ∆𝐻100 in the calculations.
• ∆𝐻𝑢 can be calculated using the Flory relationship for the depression of the
equilibrium melting temperature of a homopolymer due to the presence of
low molecular mass diluents.
• The ∆𝐻𝑢 values of some polymers are available in the literature.
• A DSC curve can reveal the curing status of thermosetting polymers. When a
polymer is going through a curing process, its DSC curve will show a broad
peak at the curing temperature, as shown in the curve of the first scan. When
crosslinking is complete, the curing peak disappears and is replaced by a
feature of glass transition.
• DSC curves can also be used to
identify individual polymers in a
polymer mixture. This is a rather
unique capability of DSC or DTA.

• A DSC curve can also reveal the

thermal stability of polymers.