DSC (Differential Scanning Calorimetry)

Differential scanning calorimetry (DSC) is one of the thermalanalysis techniques. In case of DSC,
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. Throughout the experiment both
reference and sample are maintained at nearly constant temperature. Usually for DSC analysis
temperature program for sample holder is designed in such a way that its temperature increases
linearly with time. For DSC analysis only few mg material is required. It is the most used thermal
technique due to its speed, availability and simplicity. DSC technique is used for quantitative analysis.
These measurements 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

Various types of DSC are:

1. Power Compensated DSC:In case of 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.
Basic diagram of power compensated DSC is shown in Figure 1.
 Figure 1Schematics of a typical power compensated DSC equipment.

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 constantan 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 constantan 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 heta 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.Figure 2 shows heat compensated DSC.
 Heating block Alumel wire

Figure 2 Heat compensated DSC.

3. Modulated DSC: In case of modulated DSC,the cell and heating arrangement are analogous
to those used in heat flux DSC. This is a relatively recent technique and was proposed in
1993. 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
functiondescribed 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.

4. 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 extensivelyused in pharmaceutical industries at
 varying temperatures where very high heating rates are required to eliminate various
undesirable reactions etc.

5. Pressure DSC:This technique is used to characterize samples atspecific 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

Figure 3 shows the block diagram of DSC instrument

GasControl Furnace

Sample Reference

Furnace
Detectors controller

Data
Micro-volt acquisition
amplifier

Figure 3: BLOCK DIAGRAM OF DSC.

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.

DSC Thermogram

DSC curve isemployed to determine the enthalpy of transitions by integrating the peak area for given
transitions.Thetransition enthalpy is found as follows:

ΔH=KA

here,K is the calorimetric constant

A is the area under the peak and

ΔH is the enthalpy of transition

The area of a peak scales directly with the heat absorbed (endothermic) or evolved (exothermic)
during a reaction, and the peak’s height varies directly with the reactionrate. Transitions involve glass
transition temperature, melting temperature, crystallization temperature. DSC curve also used to
calculate the specific heat capacity of the material using equation:

Specific heat capacity (Cp) = Absolute value of heat flow/ Heating rate

Where Absolute value of heat flow = Heat supplied per unit time

And Heating rate = Temperature increase per unit time

Therefore Cp = q/t /ΔT/t

Cp = q/ΔT.

Lets consider the case of polymer , initially on heating it absorbs heat and curve look like flat after
absorbing certain amount of heat its temperature starts to rise and its heat capacity increase on further
heating plot will go downward and polymer reach to its glass transition(second order as there is no
latent heat involved) temperature with further increase it comes to its crystallization(first order latent
heat involve) temperature and give off certain amount of heat and reaches to the state of ordered
arrangement on further heating it absorbs heat and reaches to its melting(first order) temperature.
Figure 10 shows DSC curve.
 Figure 10: 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.

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