Rachelle Ingrid S.

Fiala Material Science Equipment Report

4 ChE-A January 4, 2011

Differential Scanning Calorimeter (DSC)

Every element, compound, mixture or material has its own thermal characteristics, heat
capacity, specific heat and enthalpy to name a few.
When a material is subjected to heat its temperature will increase by an amount determined by
its specific heat. As the temperature of the material is increased it can lead to chemical or physical
processes in the sample such ah melting and is accompanied by changes in the latent heat of fusion,
heat of reaction and enthalpy changes. The detection of these changes is the basis of thermal analysis.
Thermal analysis has a wide range of techniques, one of which is Differential Scanning Calorimetry or
DSC. [1]

What is DSC?

DSC measures temperatures and heat flows associated with thermal transitions in a material. It
is a thermoanalytical technique involving a sample material and a reference material. It measures the
difference in the amount of heat required to increase the temperature of a sample and reference as a
function of temperature. Throughout an experiment the temperature of the sample and the reference is
nearly the same and is maintained. The temperature program for a DSC analysis is designed such that
the sample holder temperature increases linearly as a function of time. Over a range of temperatures to
be scanned, the heat capacity of a reference sample should be well-defined. [1]

The most widely used thermoanalytical technique is DSC. It is used for the characterization of
polymers, organic materials, metals ceramics and composites. The DSC measurement is basically a
function of differential heat flow with temperature for compounds that exhibit thermal transitions,
thermal transitions such as melting, crystallization and glass transition. Such measurements provide
quantitative and qualitative information about physical and chemical changes that involve endothermic
or exothermic processes. [1]
 Studying phase transitions, such as melting, glass transitions or exothermic decompositions, is
the main application of DSC. With great sensitivity, a DSC detects these transitions involving energy
changes or heat capacity changes. [1]

E.S. Watson and M.J. O'Neill developed this technique back in the 1960’s. DSC was commercially
introduced at the 1963 Pittsburgh Conference on Analytical Chemistry and Applied Spectroscopy. [1]
Figure 1 shows an example of a Differential Scanning Calorimeter.

Figure 1.TA Instruments Q500 Differential Scanning Calorimeter

Types of DSC

There are two types of Differential Scanning Calorimeters namely, the heat flux DSC and the
power compensation DSC. A differential method of measurement is used by both types of DSC.
Differential method of measurement is a method of measurement in which the measurand is compared
with a quantity of the same kind, of known value only slightly different from the value of the measurand,
and in which the difference between the two values is measured. [2]

Heat Flux DSC

This type of DCS belongs to the class of heat-exchanging calorimeters. A defined
exchange of the heat to be measured with the environment takes place via a thermal resistance is found
in heat flux DSCs. The measurement signal is the temperature difference. It describes the intensity of the
exchange and is proportional to the heat flow rate φ. [2]

Power Compensation DSC

This type of DSC belongs to the class of heat-compensating calorimeters. Almost all of
the heat to be measured is compensated with electric energy by increasing or decreasing an adjustable
Joule’s heat. [2]

Theoretical Fundamentals of Differential Scanning Calorimeters

Heat Flux DSC

The Zeroth Approximation
Steady-state heat flow rates, only the thermal resistance between furnace and
sample is taken into account (no interaction between sample and reference sample), no heat capacities
are taken into accounts, sample temperature equal to measured temperature, no heat exchange
between the surroundings, are the simplifications made in the model of the zeroth application. [2]

The First Appoximation

Non-steady state processes in the sample are also permitted. Manifestations of
which are “peaks” of the measured curve. This means that the change in temperature is not constant in
time. [2]

Higher Order Approximations

It involves the indirect measurement of the temperatures of the sample and of
the reference sample with reference sample assumed to be homogenous. A thermal resistance between
the temperature measurement points and the respective sample is present. Depending on the design of
the measuring system, the resistance is made up of several parts differing in amount and originating in
the transition layers between samples, bottom of the crucible and support; there are further resistances
between support and temperature sensor. When the sample temperature changes, the temperature
measurement point reacts after some delay. [2]
Detection of Phase Transitions

When a sample undergoes a physical transformation such as phase transitions, heat will more or
less flow to it than the reference so that both are maintained at the same temperature. This is the
fundamental principle of Differential Scanning Calorimetry. The amount of flowing to the sample
depends on whether the process is exothermic or endothermic. If a solid sample melts into liquid, it will
require more heat flowing to the sample to increase its temperature at the same rate as the reference
because of the absorption of heat as it undergoes the endothermic phase transition from solid to liquid.
If a sample unergoes an exothermic process, less heat is required to raise the sample temperature. The
observed difference in heat flow between the sample and reference enables the Differential Scanning
Calorimeter to measure the amount of heat absorbed or released during transitions. [1]

Result of DSC Experiment

The result of a DSC experiment is a curve normally called as DSC curve. It is a curve of heat flux
versus temperature or time. DSC curve is used to calculate enthalpies of transitions. Calculation is done
by integrating the peak corresponding to a given transition. Enthalpy of transiton can be expressed
through the equation
∆ H =KA
where ∆ H is the enthalpy of transition, K is the calorimetric constant and A is the are under the curve.
The determination of the calorimetric constant is determined by analyzing a well-characterized sample
with known enthalpies of transition and differs from instrument to instrument. [1] Figure 2 shows an
example of a DSC curve.

Figure 2.DSC curve of lauric acid recorded at 0.2 8C/min scanning rate
Applications of DSC
Through the use of DSC one can determine many characteristic of a sample. The DSC gives
observations on the crystallization and melting characteristics of a material. It can also give observations
on glass transition temperatures. Oxidation and other chemical reactions can also be studied through
the use of a Differential Scanning Calorimeter. [1]

Liquid Crystals
In liquid crystals, a liquid in a liquid crystalline state, DSC makes it possible to observe
the small e Using DSC, it is possible to observe the small energy changes that occur as matter transitions
from a solid to a liquid crystal and from a liquid crystal to an isotropic liquid. [1]

Oxidative Stability
In oxidative stability, DSC is used to study the stability and oxidation of samples. It
involves a special test that is done isothermally, the sample being brought to a desired test temperature
under an inert atmosphere. Oxygen is added to the system. If there is an observed deviation in the
baseline, oxidation occurs. This analysis is used to determine the stability and optimum storage
conditions for materials or compounds. [1]

Drug Analysis
In drug analysis, DSC serves as a tool for studying curing process which allows the fine
tuning of polymer properties. After the glass transition, a positive peak in the DSC curve appears which
means the cross-linking of polymer molecules in the curing process is exothermic. [1]

In pharmaceuticals, well-characterized drug compounds are important for defining

process parameters. Characterization of drug compounds can be done with the use of DSC. [1]

General Chemical Analysis

In general chemical analysis, the evaluation of freezing-point depression of a substance
is used to determine purity when analyzed in DSC. The temperature range over which a mixture of
compounds melts is dependent on their relative amounts. A less pure compound will exhibit a
broadened melting peak that begins at lower temperature than a pure compound. [1]
 Food Science
In determining water dynamics in food science, DSC is used together with other thermal
analytical techniques. Changes in texture may be correlated to changes in water distribution. The effects
of curing on confectionery products can also be analyzed with the use of DSC. [1]

Polymers

Examination of the Composition of polymers is done with the use of DSC. The
percentage crystallinity of a polymer can also be found using DSC. It can be found from the
crystallisation peak from the DSC graph since the heat of fusion can be calculated from the area under
an absorption peak. Impurities in polymers can be determined by examining thermograms for
anomalous peaks, and plasticisers can be detected at their characteristic boiling points. [1]

Metals
Though there are low quantity of literatures to support that DSC can be of use in
characterizing metals it is known that it is possible to use DSC to find solidus and liquidus temperature of
a metal alloy, but the widest application is, by now, the study of precipitations. [1]

References:
[1] SAM, D. s. (n.d.). Retrieved December 30, 2010, from scribd.com:
http://www.scribd.com/doc/15006289/Differential-scanning-calo-SAM

[2] Höhne, G., Hemminger, W., & Flammersheim, H.-J. (1996). Differential Scanning Calorimetry . Berlin:
Springer-Verlag. p 7,8,14,22,24,28-29