DSC (Differential Scanning Calorimetry)

• Differential scanning calorimetry (DSC) is one of the thermal analysis techniques where
differences in heat flow between a specimen and reference are measured against the
temperature or time while the specimen is continuously heated under controlled conditions.
• Function of calorimeter is to measure the heat content which comes in and out of the
sample.
• DSC give both quantitative as well as qualitative information regarding the physical and
chemical changes which involves endothermic and exothermic processes or variations in heat
capacity of the sample.
Principle
❖ To maintain the sample and reference at equal temperature during the physical transformations
of the sample (like phase transitions), either more or lesser amount of heat is required to be
applied on it then that required for the reference sample or an empty sample pan. This heat
required depends on the nature of the transformation process, that is, whether it is
exothermic or endothermic. For instance, at a constant heating rate, when a solid sample
changes to liquid, more heat is required to be applied to the sample for increasing its temperature.
This happens because heat is absorbed by the sample while it changes state from solid to liquid.
However, if there is exothermic process in the sample (for instance, crystallization), less amount
of heat is needed to increase the temperature of the sample. Thus, by calculating the heat flow
differences between the reference and sample, DSC technique can determine the amount of
heat released or absorbed during a transition process.
 Types of DSC
Power Compensated DSC:
❖ Both reference and sample are heated separately under different furnace. Difference of temperature between reference and
sample is maintained at zero i.e. both are at the same temperature and the difference of energy between reference and sample
is recorded as a function of sample temperature.
❖ Two independent heating unit are employed for power compensation DSC. To rapidly heat, cool or maintaining equilibrium,
small heating unit is required. The heating unit needs to be integrated with a relatively larger temperature controlled heat
sink. For continuously monitoring the temperature of the material in reference and sample holders,platinum resistance
thermometeris used. The increasing the temperature, suitable power is applied to the reference and sample heaters. This
power required to maintain equal temperature of reference and sample is recorded by the power compensated DSC as a
function of temperature.
❖ Power compensated DSC has lower sensitivities than the heat flux DSC, however power compensated DSC are faster than
their heat flux counterparts. Thus, power compensated DSC are often used in studying kinetics wherein very fast
equilibrium to a desired temperature is reached. These instruments also have higher resolution than the heat flux DSC.
The calibration constant in power compensated DSC, which converts peak area into joules, is an electrical conversion
factor.
2. Heat Compensated DSC: Here, both the reference and sample are heated under the same furnace. The
difference between the temperatures of the reference and sample is recorded and converted into a power difference
and plotted against time or temperature. The main cell assembly of DSC is enclosed within a heated silver block
cylinder, from which heat is transmitted onto the specimen by a constant disc connected to the cylinder. The
reference and sample pan are kept on two raised platforms in the system. The underside of both the platforms is
connected to the constant disc via connecting wires and chromel (alloy of nickel and chromium) disks, thereby
forming a thermocouple which is used to measure the temperature difference between the two platforms. In
addition to this, the individual temperatures of the two platforms can be measured by the junction of alumel wires
linking the platforms to the chromel disks. Another separate thermocouple is integrated with the silver block which
acts as a temperature controller for programmed heating cycles. Inert gas can be introduced within the cell at
constant flow rate of ~40nm/min. Unlike the power compensated DSC, the calibration constant (which converts
peak area into joule) in heat flux DSC is a thermal factor.
Total heat flow dH/dt in heat flux DSC is:
dH/dt = Cp dT/dt + f (T,t)
Where, H is enthalpy in J/mol
f (T,t ) is kinetic response of the specimen in J/mol
Cp=specific heat capacity in JK-1mol-1.
Therefore, total heat flow is equal to the sum of the two terms; where one term is related to the kinetic response
and the other is related to the heat capacity
Modulated DSC: The cell and heating arrangement are analogous to those used in heat flux
DSC. A separation of overlapping events in the DSC scans is the main advantage of this
technique . In modulated DSC, a linear heating ramp usually is overlapped with a sinusoidal
function described by an amplitude and frequency to create a sine wave shaped temperature
which varies with time.
Fourier transformation can be used to break the DSC signal in two parts: reversible and
reflecting events, as:
T= T0 = bt+B sin(wt) dq/dt=C [b+Bw cos(wt)] +f(t,T)+K sin (wt)
here,
T represents the temperature,t is time,C is specific heat, f (t,T) is the average underling
kinetic function obtained by subtracting the effect of sine wave modulation, and w is
frequency
[b+Bw cos (wt)]= is the calculated quantity dT/dt or Curve reversing.
K= kinetic response amplitude of the sine wave modulation.
MDSC technique is a valued extension of conventional DSC. Applications of this DSC
includes study of the energy of relaxation and precise determination of glass transition
temperature.
Hyper DSC: New type of power compensating DSC gives high resolution for melting
analysis and detection of glass transition temperature (Tg) in medications or
crystallisation of metals. This DSC can perform accurate measurements of heat flow
with very high linear controlled rates (till 500 K/min) mainly during cooling, i.e., at
relatively higher rates than conventional power compensated DSC which works below
10 K per minute. These devices benefit by avoiding unwanted transformation like solid
– solid transformation, offer greater sensitivity at higher rates, etc. Hyper DSC is
extensively used in pharmaceutical industries at varying temperatures where very high
heating rates are required to eliminate various undesirable reactions etc.

Pressure DSC: This technique is used to characterize samples at specific environment

conditions upto 10MPa as a function of time or temperature. It is often employed in
evaluation of catalysts, studying pressure sensitive reactions, and resolution of
overlapping transitions.
Instrumentation
1. Detector: In case of detector thermocouple is used to measure the temperature change
while the sample heated under controlled environment. For the case of low temperature
copper- constantan or cromel alumel thermocouple is used and for the case of corrosive
atmosphere or high temperature pt/13%rh thermocouple is used.
2. Sample Container: Sample container is designed in such a a way that it can be used
under high pressure and thermal environment. For high temperature case platinum or
ceramic is used for sample holder and for low temperature case aluminium is used.
3. Reference material: Generally reference material is made up of calcined alumina
Al2O3 or carborundum, silicon carbide.
4. Temperature controller: Temperature controller is used to maintain the temperature of
the reference and sample at the desired value.
5. Furnace: One block of furnace is required in case of heat compensated DSC and two
block of furnace is required in case of power compensated DSC.
 Exothermic ( for crystals)

Endothermic ( for amorphorous)

DSC curve of polymer

Factors affecting DSC curve
1. Instrumental factors: These include parameters such as – Furnace heating rate, furnace
atmosphere, recording speed, geometry of sample holders, location of sensors, sensitivity of the
recording system and material of the sample container.
2. Sample characteristics: Parameters including type and weight of sample, particle size, solubility of
evolved gases in the sample, heat of reaction and thermal conductivity.
Applications of DSC
DSC can be used in studying heat of melting, crystallization, percentage of crytallinity, heat
capacities, thermal stabilities, purities, oxidative stabilities, food science, drug analysis, and liquid
crystals.