oxidation

functionavailable sample
DSCtemperature involve
in flows
be qualitative energy
Calorimetry
Both(DSC)
Differential and
ThermogravimetryIncharacterization
provides It (TG) polymer
2. arThermal
[Link]
e LHERMALpolymers.
branched
(vi) polymers
curve
considered DTA heat
TG swollen
()(iv) 62
andcapacity associated change
the Diferential
enables Thermogravimetry
endothermic technique
processes of from is techniques as deformation
temperature. is
difference a a and quantitative analysis
METHODs
a
shown as
technique
reference the function
DTA the during quantitative in Thermal
transitionGlass with a stoichiometry mass thermal
can refined is
Fig. intechnique. (heat substance. are a OF and
Fig. betweenbeIn material inthetransitions Analysis information changes (TG) of
group annealing
17: Crystallisation studied whichabsorbed) linked analysisCHARACTERIZATION
polymers, versiondegradation
information
temperature/time.
Typical 17. and
a DTA/DSC of as of
is a together techniques
Temperature with sample temperature In of
recorded in (DTA)/DMerential
a a of
DSC or
(DTA)/Differential reaction on
Melting glass DSC DTA exothermic the function polymersINTRODUCTION
the processes
curve and the and
ofaboutmeasures
and
help
transition, polymers.
as materials. to
Cross-linking
Oxidation energy it are of The in OF
of reference difference
a gives a physical be PoLYMERs
a (cure) of function taking time which
most
polymer (heat concerned the followed To
Degradation
DTA/DSC
practically
necessary Such a PoLYMER
crystallization, evolved)temperature
and place
orseanning common
material of
AT= Scanning temperature property
measurements
chemical directly.
techniques. temperature. wvith with ScENCt
(T,-T) process calorimery thermal
to all ol
is the measurement
change a
establish
recorded change are the AND
meltinginformations changes
A between or measured nethods
polymer TECHNOLogy
DSC changes provide and
typical in (DSC)
and aszero can that hea of mas
a a
 PoLYMERS
63
The amount of heat needed to maintain zero
temperature difference between the
samples and the reference represents heat absorbed
The area under the curve gives directly the heat or evolved during the process.
process. (energy) change involved in the
There are three types of DSCtechnigques but the first twO are
used. more frequently
(i) Heat flux DSC
(ii) Power compensated DSC
(ii)) Modulated DSC
Heat Flux DSC
In heat flux DSC the difference in heat flux between the
sample and the inert
reference is monitored as a function of temperature.
The DSCplot consists of the rate of heat flow into or out of the
sample as a
function of temperature or time.
The area under the DSC curve yields directly the enthalpy change involved in
the transformations.

Power Compensated DSC

In power compensated DSC the heat (energy) changes accompanying any chemical
reaction or the phase transformation taking place in the sample are compensated in
the reference by means of a heater so that the temperature difference between the
sample and the reference is always maintained zero.
DTA-DSC curves showing various thermal processes appearing during heating
of different polymers are given in Fig. 18.
132°C

178°C
>Endothermic
Endothermic
dAQ/dt
Exothermic

Poly(oxymethylene)
Poly(ethylene)
7-77°C Poly(vinyl chloride
Exothermic
105°C Poly(styrene)
-59°C
4°C
Poly(ester)-poly(ure thane
148°C
47C
Natural rubber
67°C
-24°C

50 50 100 150 200

-100
Temperature (°C)

Fig. 18: DTA-DSCcurves of some common polymer

 PoLYMER S SCIENCE AND TECHNOLOG
INTRODUCTION To
64
TECHNIQUES IN PoLYMER RESEARCH
APPLICATION OF DTA-DSC
techniques are commonly used to measure
DTA-DSC
(i) glass transition temperature (T)
(ii) melting points (Tm)
(ii) decomposition temperatures (T) measurement of the
direct
DTA-DSC methods can also be applied in the
energy
absorbed or evolved in studies of
() heats of fusion
(ii)heats of vaporization
(iii) heats of crystallization
combustion)
(iv) heats of reaction (including polymerization, oxidation and
(v) heats of decomposition (dehydration)
(vi) heats of solution
(vi) heats of adsorption (desorption)
(viii) specific heats
(ix) activation energies
() entropies of transition
(xi) solid state transition energies.

CHARACTERIZATION OF PoLYMERS ON THE BASIS OF THEIR MoLECULAR WEIGHTS