Differential Thermal Analysis and Differential Scanning Calorimetry

DTA and DSC are the most widely used TA techniques.

Both techniques have the objective to examine thermal events in a sample by heating or
cooling without mass exchange with its surroundings.

The thermal events examined by DTA and DSC include

-solid-phase transformation
-glass transition
-crystallization and
-melting.

‘‘Differential’’ emphasizes that analysis is based on differences between sample material and
a reference material in which the examined thermal events do not occur.
Working Principles

Differential Thermal Analysis

 A DTA instrument is designed to measure temperature differences between the

sample and reference.

 A sample and reference are symmetrically placed in a furnace.

 The temperature difference between the sample and reference are measured by two
thermocouples.

 The reference should be made from a material that satisfies the following conditions: -it
does not undergo thermal events over the operation temperature range, -it does not react
with any component in the instrument, and
-it has similar thermal conductivity and heat capacity to the sample being examined.
 Figure 10.3 DTA curve for a polymer sample under a constant
Figure 10.2 Differential thermal analysis (DTA) heating rate.
instrumentation. VTs and VTr are the thermocouple voltages
for measuring sample and reference temperatures,
respectively.

 The temperature difference between sample and reference ( T) should be zero when no
thermal event occurs in the sample, because of similar thermal conductivity and heat
capacity between the sample and reference.

 When a thermal event occurs in the sample, nonzero T will be generated and it will be
negative if the thermal event is endothermic (absorbing heat) or positive if the thermal even
is exothermic (releasing heat).
Differential Scanning Calorimetry

A DSC instrument is designed to measure the heat-flow difference between sample

and reference.

There are two widely used DSC systems:

-the heat flux DSC and
-the power-compensated DSC

Figure 10.4 Differential scanning calorimetry (DSC) instrumentation design: (a) heat flux DSC and (b) power compensation
DSC. A, furnace; B, separate heaters; and C, sample and reference holders.

Heat flux DSC

The heat flux DSC is also called ‘‘quantitative DTA’’ because it measures the temperature
difference directly and then converts it to a heat-flow difference.
Power-compensated DSC
The power-compensated DSC directly measures the enthalpy change of a sample during a
thermal event.

In power-compensated DSC, there are two separate chambers to contain the sample and
reference. Each chamber has its own individual heating element to control temperature.

Figure 10.5 Schematic DSC curves for a polymeric sample. Tg, glass-transition
temperature.

The instrument always maintains a thermal null state (del T = 0). When a thermal event
occurs in the sample, the power to the heating element has to change in order to
maintain the sample temperature the same as that of the reference.
The heat flow has a unit of energy per unit time per unit mass, usually in units of Wg -1.

Commonly, heat flow into a sample is indicated as an upward feature of the DSC curve while
in a DTA curve, an endothermic event is indicated as a downward feature.

The DSC curves are commonly recorded over a temperature range by heating or cooling a
sample with a constant rate, similar to DTA curves.

Deference between DTA and DSC :

-DTA is a qualitative technique because measured temperature differences do not
provide any quantitative data for energy. DSC is a quantitative technique because
measured heat flow provides enthalpy changes in the sample during a thermal event.
-DTA can operate over a wider temperature range than DSC. The DTA can
reach a temperature of greater than 1500◦C, while the power-compensated DSC is
restricted to a maximum temperature of about 750◦C. This DTA feature is
important for examining materials with high melting temperature such as ceramics
and some metals.
Temperature-Modulated Differential Scanning Calorimetry

In conventional DSC measurements, the enthalpy change of thermal events in the

sample is measured at a constant heating rate. This means the sample temperature
change with time as written as follows

To is the starting temperature, t is time, and β is the heating rate.

In TMDSC which the heating rate is modulated by superimposing a cyclic heating rate on the
constant rate; for example, a sinusoidal temperature modulation is superimposed on the
temperature profile

B is the amplitude of temperature modulation that is commonly in the range of ±1 to ±10 K and
ω = 2π p−1, in which p is the modulation period that is commonly in the range 10–100 s.
At any moment of a DSC experiment, the heat flow can be expressed as a differential equation

Reversing thermal Nonreversing

events thermal events

CP is the sample heat capacity. f (T,t) is also referred as to the kinetic component of heat flow.

The main advantage of TMDSC is its ability to separate the reversing and nonreversing
thermal events.
-Reversing thermal events include glass transition and fusion (melting).
-Nonreversing thermal events include oxidation, curing, relaxation,
and cold crystallization (glass–crystal transition below the melting temperature).

(b) temperature modulated DSC (TMDSC)

Poly(acrylonitrile–butadienestyrene) (PET–ABS) blends: (a) first heating curves with β = 2 K min−1, p = 60 s, and B =
conventional DSC first and second heating curves with ±1 K. Tg, glass-transition temperature.
heating and cooling rate of 10 K min−1
Experimental Aspects
Sample Requirements
-Samples for DTA or DSC should be in the form of dense powders or small disks.
-Film, sheets, and membranes are often cut into disks fitting into the sample pans.
-Large shear forces during cutting samples should be avoided.
-Low-mass samples are also preferred.
-Lower limit of sample size relates to the nature of the sample materials. For
composites and polymer blends, large sample size of about 10 mg may be required.

DTA is usually operated in a high-temperature range. Platinum and gold crucibles

are commonly used as sample and reference holders.

DSC is usually operated in a low-temperature range (<5000C), and thus aluminum pans are
commonly used as sample and reference holders. The pans often need to be sealed to avoid
sample mass change due to evaporation.
Baseline Determination
Thermal-event measurement from a DTA or DSC curve relies on determining the deviation of
the experimental curve from the curve baseline.

There are two baselines: the instrument baseline (also called the zero line) and the 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. In practice, however, the baseline may be curved and/or display a high level
of noise.

Accuracy of enthalpy-change measurement relies on

correctly constructing the sample baseline from the
curve. Construction of the sample baseline from the
measured curve may not be straightforward.
Figure 10.9 Examples of sample baseline
interpolation for different types of differential
thermal analysis (DTA) and DSC curves.
Effects of Scanning Rate
DTA and DSC experiments are commonly run through a temperature range with
a constant heating or cooling rate. This rate should be reported with the DTA and
DSC results for reasons that are described here. 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.
-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.

Figure 10.10 Scanning rate effects on DSC curves of a poly(ethylene terephthalate) (PET) sample: (a)
heating and (b) cooling. I, 10 K min−1; II, 20 K min−1; and III, 40 K min−1.
The scanning rate effects are even more obvious in cooling than in heating. 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.

A slower rate can make a measurement more accurate, a fast heating rate often
makes thermal event peaks more obvious in the curve. The scanning rate of DTA
and DSC instruments commonly varies from 0.1 to 40 ◦C min−1.

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.

The scanning rate should be reported with the DTA and DSC results.