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DIFFERENTIAL SCANNING CALORIMETRY (DSC)
Exothermic
I second order transition,
where a change in the
horizontal line is detected
(e.g. glass transition);
Endothermic
II a sharp endothermic curve
due to the fusion or melting
process;
1. Classic DTA: the thermocouple is immersed into the sample and the reference materials
2. Heat flux DTA: the thermocouple is placed outside the sample and the reference
materials
Figure 6.4
DTA and DSC are defined as the differential techniques because the behaviour
of the sample is compared with the behaviour of a reference.
All thermal properties that could be involved in the thermal analysis experiment
must be taken into account.
For example, emissivity of the sample might change when the sample changed
phase, or react or change in colour.
Among the commonly used materials for the reference are calcined alumina
Al2O3 or carborundum, SiC.
In this case, the sample does not react with the reference material
Dilution of the sample with the reference material will normally improves the
base line and the the shape of the DTA peak.
The shape and size of the DTA/DSC curve are influenced by:
Figure 6.9 shows the normal DTA or DSC curve( curve B) for a melting material
(theoretically curve A).
Sometimes the curve does not return to the original baseline but becomes higher
or lower as shown in Figure 6.10. This is due to a change in the thermal
condictivity of the sample material.
Figure 6.9: The normal DTA or DSC curve for a melting material
This theory does not take into The theory assumes that there is no
account the reaction mechanism temperature gradient among the various
and its role in the development components of the instrument, although
of a peak thermogram. in reality thermal gradient exists among
the thermal instrument components
a) A uniform temperature of the sample holder (only true for a liquid, and not for a
solid material)
b) Heat transfer only by conduction
c) The heat transfer constant must be the same for both the sample and reference
holders
d) The heat capacities of the tested materials are the same
Lecture 6 DTA & DSC 01 16
The Second Type Theory: The Relationship Between T
and The Sample Temperature
This theory takes into account various Therefore, the plot of ln(T) vs time
relationship between the temperature beyond the point E of the curve A will be
difference T and the sample linear.
temperature at certain times in order to The “active area” is the area that begins
obtain the activation energy and the from the point where the curve starts to
order of the reaction. the point E of the curve.
The theory, however, does not take into The relationship between the active area
account the effect of heat transfer and the reaction heat is shown by the
following equation:
There exists a relationship between the
“active area” of the DTA peak thermogram
Heat = A (“active area”)
and the quantity of heat involved.
where A = slope of the plot ln(T) vs time
The active area of the DTA/DSC curve
evolved from the thermal reaction process, The theory assumes that the physical
while the other areas are produced as the properties of the sample and the reference
T returns to the baseline after the do not change during the thermal
reaction has completed (point E in Figure experiment
6.9).
Therefore, the curve region after the point
The shape of the curve (curve B) is E is influenced by the instrumental system
exponential due to the influence of natural used.
heating or cooling process and it depends
on the arrangement of the sample holder.
Lecture 6 DTA & DSC 01 17
For melting, crystal change and zero order reactions:
The active region of the DTA curve (related to the reaction) ends near the tip of the
DTA peak
A portion of the DTA curve exponentially returns to the baseline which is influenced by
the instrumental parameters
Therefore, the end of the reaction and the A factor can be precisely determined.
For reactions other than melting, the T position before the curve returns to the
baseline when the reaction has been completed will depend on the type of the
reaction.
However, if the reaction is controlled by a different type mechanism, the reaction ends up
while the T gets near to the baseline.
The DTA curve that ends up at high temperature might contain a mixture of reaction
mechanisms and the final portion of the curve is exponential, hence, differ from one device
to another.
However, most DTA/DSC curves do not have the same baseline before and after
the reaction because physical changes always occur during the thermal reaction.
(a)
(b)
The DSC thermogram of the melting process of pure indium metal (99.999%) is
shown in Figure 6.12.
The melting point 156.6 oC is obtained by determining the intersection point Te.
The area marked under the peak, AS in the Figure is used for the determination of
calorimetry sensitivity constant, K:
K = HS . mS / AS
Figure 6.12 DSC peak for indium melting process which shows the determination of
intersection point Te (6 mg, 10 K/min, nitrogen) (Source: Haines: F 3.11)