Differential scanning
calorimetry (DSC)
DTA and DSC Comparison
• DTA measures the differential temperature change between
the specimen and reference for the same amount of heat
input. DSC measures the differential heat input required to
increase the temperature of both the specimen and the
reference.
• DTA evaluates how applied temperature affects a material's
temperature. It determines endo- and exothermic event
temperatures, and shows phase transitions.
• DSC compares heat flow, and determines the heat flow of a
material as a function of time and temperature. It also allows
for the determination of caloric values such as the heat of
fusion or heat of crystallization
DTA and DSC Comparison
Differential scanning calorimetry or DSC is a thermoanalytical
technique in which the difference in the amount of heat required to increase
the temperature of a sample and reference are measured as a function of
temperature.
DTA DSC
• Differential scanning calorimetry (DSC) is a thermo-
analytical technique, it measures the difference in the
amount of heat required to increase the temperature of
a sample and reference is measured as a function of
temperature.
• When the sample undergoes a physical transformation
such as phase transitions, more (or less) heat will need to
flow to it than the reference to maintain both at the
same temperature.
• In DSC, the sample and the reference are also
subjected to a continuously increasing or decreasing
temperature.
• In the scanning operation (DSC) the sample and the
reference show different temperature independent
heat capacities.
• Heat (dQ/dt) is added to the sample or to the
reference as necessary to maintain the two identical
temperatures.
• This noticeable difference results in the appearance of an
upper or lower peak, depending on whether the
transformation is exothermic or endothermic.
• A solid sample melting to a liquid will require more heat
flowing to the sample to increase its temperature at the
same rate as the reference, and is an example of an
endothermic process.
• If a liquid crystallizes into a solid during a cooling scan,
more heat would have to be removed compared to the
reference and is an example of an exothermic process.
• Bottom: (b) measured
curve. m is the
measured heat flux. bl
is the heat flux
corresponding to the
base line and t is time.
Sample Reference
T1 T2
Pt thermopile Pt thermopile
Low mass
1 gram heater heater
N2 flow
W
What DSC Can You tell you?
• Qualitative analysis
• minerals, clays, polymers
• Sample purity
• Melting points
• Heat capacity, cp
• Glass transition temperature, Tg
• Crystallization temperature, Tc
• Phase transitions including proteins
Glass Transition, Tg
Thermogram
• Step in thermogram
• Transition from disordered
solid to ordered glassy
• Observed in glassy solids,
dH/dt, mJ/s
Glass transition
e.g., amorphous polymers
Tg
Temperature, K
Crystallization, Tc
Thermogram
• Sharp positive peak.
• Disordered to ordered
transition. Crystallization
• Material can crystallize!
dH/dt, mJ/s
• Observed in glassy solids,
e.g., crystalline or semi-
crystalline polymers. Tc
• Tc, crystallization
temperature.
Temperature, K
Melting Temperature, Tm
Thermogram
Negative peak on
thermogram
Ordered to disordered
transition Melting
dH/dt, mJ/s
Tm, melting temperature
NB: melting happens to
Tm
crystalline polymers;
glassing happens to
amorphous polymers
Temperature, K
Protein Analysis –
Secondary Structure
Protein – Secondary Structure
DSC Thermogram Profile
Oxidation
Heat Flow -> exothermic
Crystallisation Cross-Linking
(Cure)
Glass
Transition
Melting
Temperature
6
Instrumentation
Furnace
Types of Pans
Sample Preparation
• 5-10 mg of sample is sufficient.
• Pan should be tightly closed using lids and
compression pressure.
How to get ∆H
dH Cp = Sample Heat Capacity
= DSC heat flow signal
dt = Sample Specific Heat x Sample Weight
dH dT
= Cp + f (T, t)
dt dt
dT
= Heating Rate f (T, t) = Heat flow that is function of time
dt at an absolute temperatu re (kinetic)
• The area of a DSC peak can be used to estimate the
enthalpy of transition, ∆H.
Structure analysis
Melt-crystallization exotherms
% Crystallinity
Polymer Miscibility
PVC-EVACO
Curing
Curing
Effect of additives Vs
Secondary structure
Induced structural transitions
random, α-helix to β sheet
Tm
decompose
Effect of additives Vs Secondary structure
0.2
bimodal to unimodal transition
155°C
134°C
0.0
× ×
×
-0.2
50 100 150 200
β-sheet
Effect of additives Vs Secondary structure
0.1
0.0
-0.1
-0.2
-0.3
Melting ∆H increasing upon addition of
additives as β content increases
-0.4
150 200 250 300
Program for Oxidative Stability
Interpretation of
Oxidative Stability
Modulated DSC
• Compensate the conventional DSC limitations.
• Separate reversible and non-reversible phase
transformations.
• Sinusoidal heating or cooling rate applied.
• simultaneous measurement of the sample's heat capacity
• Temperature never decreases during the modulation
Typical M-DSC
Thermodynamic Miscibility and Thermal and Mechanical Properties of Poly(ethylene-co-vinyl acetate-co-
carbon monoxide)/Poly(vinyl chloride) Blends
Effect of heating rate
Exo
Heat flow (mW)
Endo
Temperature (0 C)
Polymer characterization
exo
Polymer A
Polymer B
endo
Blend of A+B
