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DIFFERENTIAL THERMAL ANALYSIS (DTA)

AND
DIFFERENTIAL SCANNING CALORIMETRY (DSC)

The Differential Thermal Analysis (DTA) and Differential Scanning


Calorimetry (DSC) have always used to study the same phenomena.

Differential Thermal Analysis (DTA) is a thermal technique where the


sample temperature is compared with the temperature of a reference
(an inert material) and the temperature difference is recorded as a
function of the sample, reference or furnace temperature while the
sample is being heated or cooled at a constant rate.

The temperature change is detected by a differential method as shown


in Figure 6.1.

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Figure 6.1 The basic concept of DTA system

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• The DTA method is very useful for the characterization of materials that will
undergo physical or chemical changes by the heat effect without the mass
change.

• The temperature change of the sample is due to either an endothermic or


exothermic reaction or enthalpy change.

• The related processes include:


 a phase change
 fusion
 melting
 crystal structural inversion
 destruction of the crystal lattice
 boiling
 sublimation
 evaporation
 dehydration reaction
 other reactions.

• The phase change, dehydration, reduction and some of the decomposition


processes produce endothermic effect, while crystallization, oxidation and
some of the decomposition reactions give exothermic effects.

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Comparison between the thermal method and the differential thermal
analysis are shown in Figure 6.2

The Normal Thermal Method: The Differential Thermal Method:


 In curves (a) and (b) the  In curve (c) the difference between the sample
temperature is measured as a temperature and that of the reference (Ts – Tr) is
function of the furnace measured as a function of the system
temperature or time, while the temperature, T.
sample is continuously heated at a
constant rate of temperature  At Ti, the curve deviates from horizontal and
increase. forms an upward peak (exothermic) or
downward peak (endothermic).
 No enthalpy change is indicated by
the curve (a), but an endothermic  The final reaction temperature Tf, does not occur
and exothermic enthalpy change is at the top of the peak, but lies on the higher
indicated by the curves in (b). temperature side of the relevant peak. It’s exact
Subsequently no deviation in curve position depends on the instrumental system
(a), but there are deviation in used.
curves (b): the change in Ti is due
to exothermic or endothermic  Therefore, in a differential thermal method, a
change. very small temperature change can be detected
easily and the peak area is proportional to the
 These changes subside at Tf and enthalpy change (H) and the sample mass.
the sample temperature returns to
that of the furnace temperature.

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DTA curve is a plot of the temperature difference (T = Ts - Tr) versus the temperature
(T). Endothermic process is shown as a downward peak, while exothermic process
is shown as an upward peak (Figure 6.3)

Four types of transitions


detected by DTA method: Figure 6.3

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;

III a broad endothermic curve


due to a decomposition or
dissociation process;

IV an exothermic curve due to


the crystalline phase
change.

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Temperature Sensor in DTA
Two approaches in the temperature sensing system of DTA (Figure 6.4):

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

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Differential Scanning Calorimetry (DSC)
DSC is a technique in which the difference in the heat flow (power) to the sample (container) and the
reference (container) is detected versus time or temperature while the sample is continuously heated
in a certain atmosphere

Two Types of DSC:


i) Power Compensated DSC: the sample and the reference are heated separately by
using different heaters and the temperature difference between the sample and the
reference is maintained zero while the electrical power needed to maintain that both
temperatures are the same (P = d(Q/dt) is measured (Figure 6.5)

The heat absorbed by the sample per unit time is


compensated accurately by the difference in the
electrical power (P) supplied to the heaters

P = dq / dt =  . (CS – CR)


The peak area is, therefore, directly
proportional to the value of H. In the power
compensated DSC the calibration constant
needed to convert the peak area into joule is
the electrical conversion factor.
Figure 6.5

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The Effect of High Temperature Power Compensated DSC

• Most DSC systems are designed to measure heat capacity and H at


temperatures of less than 700 oC. At higher temperatures, radiation (which
increases with the temperature rise) becomes more significant.

• Most DTA systems work on the principle of heat conductivity at lower


temperatures where the heat radiation is low. At higher temperatures the heat
transition from its source to the sample takes place at faster rate and if the
thermocouple is placed below the sample holder, the system becomes less
sensitive.

The Effect of the Sample Size


When a sample undergoes a reaction, there is a temperature gradient in the
sample. In order to obtain a meaningful calorimetric data, the sample size should
be minimum to reduce the heat gradient in the sample. However, if the sample
consists of different materials it is usually difficult to obtain a sufficiently small but
representative sample.

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ii) Heat Flux DSC: the sample and the reference are heated using the same
heat source and the temperature difference T is measured (Figure 6.6). The
signal is converted into the power difference P and this value is plotted versus
temperature or time

The DSC curve is a plot of P versus


temperature (or time). Since an endothermic
process involves absorption of more heat by the
sample than the reference, the process is
indicated by the upward peak.

In a heat flux DSC system the


thermocouple is placed under the
sample and the reference containers
(Figure 6.8 (a)-(e)). The base line
variation is due to a change in the heat
capacity of the sample and it is not
influenced by other properties of the
sample. The DSC system can be used
for the determination of heat capacity
of the material. However, since the
base line variation is influenced by the
physical properties of the sample
container material, the instrument
needs to be calibrated using a Figure 6.6 Heat flux DSC (Source: Haines F 3.4)
standard material.
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The area under the peak is directly proportional to the heat of reaction:

H = K ∫T dt = K . (peak area)

The calibration constant K is a thermal factor (varies with temperature) that is


used to convert the peak area into joule.

THE INSTRUMENTATION SYSTEM OF DSC/DTA


The main components of the DTA/DSC system is shown in Figure 6.7.

The main components ot the DTA/DSC system:

 The DTA/DSC detector and amplifier


 The furnace and temperature sensor
 Computer and temperature programmer
 Recorder, plotter or any data collection device

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The DTA/DSC Detector
 In the DCS/DTA method, a thermocouple is used to detect the temperature change while the sample
being heated under controlled conditions.
 For a low temperature process, a copper–constantan or cromel-alumel thermocouple may be used,
while heating at high temperature or under corrosive atmosphere the Pt-Pt/13%Rh thermocouple is
used.
 The choice of thermocouple that can be used for a DSC/DTA system is shown in Figure 6.8.

The Sample Container


 Various materials may be used to make the sample plate and crucible, but most of the sample
container for use at lower temperatures (less than the melting point of Al: 660 oC), are made from
aluminum.
 Platinum or ceramic may be used as the materials for the sample holder when the experiments
involve heating at higher temperatures. However, the thermal conductivity difference must be taken
into account in making a choice of the sample holder to be used.

 A DTA/DSC experiment normally uses between 10 – 20 mg of sample.


 A sample container may also be specially designed for use in high pressure thermal experiment. For
example in the pressure DSC (PDSC) technique, the sample container can should be able to stand
up to 70 atm pressure. Hence, reactions that produce gas at high temperature can be studied.
 For example in the stability study of accelerated oxidative experiment by using a PDSC to a cooking
oil under high oxygen pressure or under catalytic reduction of organic compound by using hydrogen.

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Reference Materials

 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.

 Sometimes the sample is diluted with the reference material.

 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.

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THEORY OF DTA/DSC

The shape and size of the DTA/DSC curve are influenced by:

 The environment of the sample and the reference


 The reaction control mechanism
 The characteristics of the sample and the reference material

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.

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 During the melting process,
completion of the reaction is
indicated by the tip of the
peak.
Active area
 Curve A indicates the curve
that is obtained experimentally
returns gradually to the
baseline (curve A)

 Theoretically, the curve (peak)


should return immediately to
the baseline (curve B)

Figure 6.9: The normal DTA or DSC curve for a melting material

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Figure 6.10 A change in the temperature detected by the thermocouple
before and after the thermal reaction which is due to a change in the
thermal conductivity of the sample material (Source: Haines F 3.7)

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Two types of DTA Theory

The First Type Theory: thermal analogue of Ohm’s law


dq/dt = (Ta - Tb)/Rab
where dq/dt = the heat flow between a and b
Rab = the thermal resistant

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

Assuming a fast heat transfer, the theory is true if:

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
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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.
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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.

 Under such conditions, determination of the constant A would be difficult.

 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.

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 Since the tip of the DTA peak might  For example: a mixture of silica and potassium
not really represent the reaction sulphate show two peaks:
process difficulty could arise if two
close consecutive reactions i) due to the structural inversion of silica at
573 oC
produce two overlapping peaks or
completely combined peak. ii) due to the crystal transition of potassium
sulphate at 583 oC.
 The ability to separate such
overlapping peaks indicate the
resolution of the instrument.

 Most DTA theory assume that:


a) during the thermal reaction, the physical properties of the material does not change
and it does not depend on temperature,
a) the baseline is the same before and after the reaction.

 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.

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The baseline change of the DTA/DSC
curve will affect:  If the baseline is changed, estimation of the
peak area may be carried out by first drawing a
calculation of the area under the DTA straight line across the peak from where the
peak peak leaves the baseline to the point where the
the magnitude of error in the area peak meets the baseline again (Figure 6.11(a))
calculation which depends on the peak  The result is that the measured peak area
size: the smaller the peak the larger the tends to become larger
error
 Two baselines approach may also be used as
the actual determination of the baseline shown in Figure 6.11(b).

(a)
(b)

Figure 6.11 Estimation of the


area under the DTA/DSC curve by
constructing a baseline before and
after the reaction as shown by the
dotted lines

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CALIBRATION
 The instrument temperature must be properly calibrated in order to obtain accurate data.
 For the DSC system, sensitivity of the calorimetry need to be calibrated.
 Some of the reference materials recommended by the ICTAC (International Confederation for
Thermal Analysis and Calorimetry) for the calibration of DTA/DSC system is given in Table 6.1.

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

Where HS = the fusion enthalpy of indium (28.71 J/g)


mS = mass of the indium sample (g)
AS = peak area (cm2)
K = calorimetric sensitivity (J/cm2)

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Calibration for a wide operational temperature
range using various materials allows
determination of relationship between K and
temperature.

Example: pure indium sample 6.68 mg gives a


peak with area of 21.94 cm2. Calculate the value
of K at 156 oC.

Answer: K = (28.70 x 6.68 x 10-3) / 21.94


= 8.74 x 10-3 J / cm2
Note !
The DTA or DSC curve depends on the conditions of the sample
and the instrument:
• Heating Rate
• Sample (chemical properties, purity, origin)
• Sample mass (volume, packing, distribution, dissociation)
• Crucible (material, geometry)
• Atmosphere (gas, static, flowing)

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)

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