D IFFER EN TIA L TH ER M A L

A N A LY S IS

Principle
Differential thermal analysis (DTA) is a technique

in which the temperature of the substance under

investigation is compared with the temperature
of a thermally inert material such as -alumina
and is recorded with furnace temperature as the
substance is heated or cooled at a
predetermined uniform rate.
When a physical change takes place in the
sample, heat is absorbed or generated. For
example, when a metal carbonate decomposes,
CO2 is evolved. This is an endothermic reaction;
heat is absorbed and the sample temperature
decreases. The sample is now at a lower
temperature than the reference. The temperature

 A differential

thermogram consists of
a record of the
difference in sample
and reference
temperature(T) plotted
as a function of time t,
sample temperature(Ts),
reference
temperature(Tr) or
furnace temperature(Tf).

When no reaction occurs in the

sample material, the
temperature of the sample
remains similar to that of
reference substance. This is
because both are being heated
exactly under identical condition
i.e. temperature difference T
(TsT) will be zero for no
reaction. As reaction starts, the
sample becomes either hot or
cool
depending upon whether the
reaction is exothermic or
endothermic. A peak develops
on the curve for the

 During TG, pure fusion

reactions, crystalline
transition, glass
transition and
crystallization and
solid state reactions
with no volatile
product would not be
indicated because they
provide no change in
mass of the specimen

 Analysis of a polymer

shows several features

due to physical and
chemical changes,
including:
glass transition: glassy,

amorphous polymer
becomes flexible
crystallization of

amorphous polymer into

microcrystals is
exothermic.
oxidation peak would be

absent in N2 atmosphere
Copyright@RGH

5/18/16

Instrum entation
A typical DTA apparatus consists of the
following components.
1} Furnace
2} Sample holder
3} temperature controller and recorder
4} thermocouple
5} Cooling device
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5/18/16

D IFFER EN TIA L S C A N N IN G
C A LO R IM ETR Y

 DSC is a thermal method in which the

difference in the amount of heat required

to increases or decreased the temperature
of a sample and reference are measured
as a function of temperature.
The basic difference between DTA and DSC
DSC- calorimetric method, energy differences

measured.
DTA- temperature differences measured.

P rinciple:
Whenthesampleundergoesaphysicaltransformationsuchas

phasetransitions,moreorlessheatwillneedtoflowtoitthanthe
referencetomaintainbothatthesametemperature,dependson
whethertheprocessisexothermicorendothermic.

Eg!Asolidsamplemeltstoaliquiditwillrequiredmoreheat

flowingtothesampletoincreasesitstemperatureatthesame
rateasthereference.

Thisisduetotheabsorptionofheatbythesampleasit

undergoestheendothermicphasetransitionfromsolidtoliquid.

Eg!!Sampleundergoesexothermicprocesses(suchas

crystalization)lessheatisrequiredtoraisethesample
temperature.

Byobservingthedifferenceinheatflowbetweenthesampleand

reference,differentialscanningcalorimetersareabletomeasure
theamountofheatabsorbedorreleasedduringsuchtransitions.
Copyright@RGH

5/18/16

11

 Basically, there are two types of

DSC;
Power compensated DSC:

Sample and reference heated by separate

heaters to keep same temperature, as T is
changed linearly
Heat flux DSC:

Difference in heat flow into sample and

and reference is measured with (linear)
change in sample temperature.

Pow er Com pensated D SC

Platinum sensors

Sample heater

Reference heater

Instrument has 2 small,

independent furnaces,
one for sample and one
for reference,
embedded in a large
temperature-controlled
heat sink . The sample
and reference holders
have Pt resistance
thermometers for T
measurements

H eat Flux D SC
sampleandreferenceareconnectedby
alow-resistanceheatflowpath
AlorPtpansplacedonconstantandisc
Sensors:
chromel-constantanarea
thermocouples(differentialheat
flow)
chromel-alumelthermocouples
(sampletemperature
temperaturecontroller

the temperature difference between

the sample and reference is converted
to differential thermal power, dq/dt,
which is supplied to the heaters to
maintain the temperature of the
sample and reference at the program
value