Thermal Properties

of
Polymer
Organized Presented
By By
Anila Anwar
Dr. Chanchal Roy 1018032716
 Table of Content:
Polymer and Thermal Property
Thermal Characterization or Analysis
Thermal Technique
1. TGA
2. DSC
3. DTA
Comparison of Thermal Technique
Conclusion
 Thermal Property of Polymer:
Polymers are large macromolecules consisting of repeating structural
units. The morphology of most polymers is semi-crystalline.

Thermal properties are those properties of a material which is related

to its conductivity of heat, electricity and deformation of mechanical
or chemical.
 Thermal Property of Polymer:

• Molecules can vibrate

slightly but are not able
Lower to move significantly.
Temperature • Brittle, hard and rigid.
• Glassy State.

• Chains are able to

Higher wiggle around.
Temperature • Soft and flexible.
• Rubbery state.
 Thermal Characterization or Analysis:
• The term thermal analysis (TA) is frequently used to describe analytical experimental
techniques which investigate the behavior of a sample as a function of temperature.

THERMAL TECHNIQUE PROPERTY USES

Thermogravimetry (TG) Mass Decomposition, oxidation reactions

Temperature
Differential Thermal Analysis (DTA) Phase change reactions
difference

Differential Scanning Calorimetry (DSC) Heat flow Heat capacity, phase change reactions

Thermo-mechanical Analysis (TMA) Deformations Softening, Expansion

Dynamic mechanical Analysis (DMA) Deformations Phase changes

Di-electrical Thermal Analysis (DETA) Electrical Phase changes
Thermal Technique

TGA DSC DTA

TGA:

Thermo-gravimetric analysis
(TGA) is an experimental
technique in which the weight
of a sample is measured as a
function of sample
temperature or time.

The TG curve is a plot of the mass

against time or temperature, with
the mass loss on the ordinate
plotted downward and mass gains
plotted upward relative to a
baseline.
 TGA

Most of the TGA curves show weight loss. They are

typically caused by
1) Chemical reaction (decomposition and loss of
water of crystallization, combustion, reduction of
metal oxide).
2) Physical transition (evaporation, sublimation,
desorption, drying).

Occasionally a gain in weight is observed. This can

result from
1) Chemical reaction (reaction with gaseous
substances in the purge gas O2 , CO2 with the
formation of nonvolatile or hardly volatile
compounds
2) Physical transition (adsorption of gaseous
substances on sample such as active charcoal).
 TGA and DTGA
This TGA plot shows the decomposition of
calcium oxalate monohydrate, CaC2O4 . H2O, in
air at a heating rate of 10 K/min. The
decomposition occurs in three mass-loss steps
(Green curve) with the release of water (12.3%),
carbon monoxide (18.9%) and carbon
dioxide(29.93%).

Alternatively, data can be presented as a

derivative thermo-gravimetric (DTG) curve,
which is a plot of the rate of change of mass with
respect to time or temperature against time or
temperature. The DTG mass losses should also
be plotted downward and the gains upward.

The corresponding 1st derivative of the TGA

curve (dotted line, DTGA) provides the
decomposition rate and is helpful for evaluating
the mass-loss steps accurately
 Application of TGA
TGA can be used to evaluate the thermal stability of a material. In a
desired temperature range, if a species is thermally stable, there will
be no observed mass change.
TGA also gives the upper use temperature of a material. Beyond this
temperature the material will begin to degrade.
TGA is used in the analysis of ceramics and thermally stable
polymers.
It is especially useful for the study of polymeric materials, including
thermoplastics, thermosets, elastomers, composites, films, fibers,
coatings and paints.
 Differential Scanning Calorimetry (DSC)
• Differential scanning calorimetry is a technique that is used to study the thermal
transition of a polymer. Thermal transitions are the changes that take place when a
polymer is heated. The melting of a crystalline polymer and the glass transition (Tg) are
examples of thermal transitions.
 Differential Scanning Calorimetry (DSC)
 The device that is used to measure Tg and other thermal transitions (such as the melting and
crystallization temperatures) is shown in the Figure.
 This device consists of two pans. In one pan, the polymer sample is loaded. The other pan is the
reference pan and is normally left empty. These two pans are located on top of a heater.
 The computer assembly will turn on the heaters and the heating rates (q/t) of the two pans are
accurately controlled (about 10 C per minute). The computer programs the heating rate to stay
exactly the same through out the experiment. It is also important to note that the two separate
pans, with their heaters are heated at the same rate as each other.
 The presence of polymer material in the sample pan results in an uptake of more heat in order to
keep the temperature of the sample pan increasing at the same rate as the reference pan. This
means that the heater underneath the sample pan will provide more heat energy than the heater
under the reference pan. The DSC experiment is all about the measurement of HOW MUCH heat
that the sample pan heater has to put out as compared to the reference pan heater. In DSC
experiments the data of temperature increase (T) are plotted against the difference in heat
output of the two heaters at a given temperature.
 Differential Scanning Calorimetry (DSC)

 The computer will provide plots of the difference in heat output

of the two heaters against temperature. This means that the
above plot is the heat absorbed by the polymer against
temperature.
Heat / time = q/ t = heat flow
Temperature increase/ time = ΔT/t = heating rate
 When we divide the heat flow q/t by the rate of heating ΔT/t.
We obtain:
(q/t)/( ΔT/t) = q/ΔT = Cp = Heat Capacity
 The amount of heat it takes to get a certain temperature
increase in a material is called heat capacity, or Cp. Heat
capacity is obtained by dividing the heat supplied by the
temperature increase. Therefore DSC plot gives Cp.
 A typical DSC plot of a polymer:
 It is important to recognize
that not all polymers will
show Tc and Tm. Tm and Tc
will only show up for
polymers that can form
crystals.

 Completely amorphous .
polymers exhibit only Tg.

 Polymers with both

crystalline and amorphous
domains, will show all the
features as shown in Fig.
 Application of DSC:
Inorganic materials, salts and complexes has been measured to study their
physical properties, chemical changes and qualitative thermal behavior.

One special use of DSC for physical changes is the determination of purity.

Glass transition temperatures and melting points are useful for qualitative
estimation of materials, although thermal methods alone cannot be used for
identification(Previous Fig).
 DIFFERENTIAL THERMAL ANALYSIS (DTA)
Differential Thermal Analysis (DTA) measures the temperatures and temperature
differences (between sample and reference) associated with transitions in
materials as a function of time and temperature in a controlled atmosphere.
This differential temperature is then plotted against time, or against temperature
(DTA curve or thermogram).
Changes in the sample, either exothermic or endothermic, can be detected
relative to the inert reference.
A DTA curve provides data on the transformations that have occurred, such as
glass transitions, crystallization, melting and sublimation.
 DTA : Applications
In the study of polymeric materials:
1. Physical changes and thermal transitions
2. Chemical reactions like:
Dehydration,
Degradation and curing, etc.
 Comparison

 Thermal  Differential  Deferential

DSC
DTA
TGA

Gravimetric Thermal Analysis. Scanning

Analysis.  Can be used to Calorimetry
 Can determine study the melting  Can determine
the thermal point, phase transition,
degradation polymorphism, melting point,
pathway of the thermal stability reaction kinetics ,
molecule and of the compound Eutectic temp.
weight lose.  Sample Can be  Sample is always
 Sample Can be solid substance. liquid.
solid substance.
 Conclusion:
TGA, DTA and DSC are thermal analysis techniques. These techniques are
used to analyze the behavior of a particular substance when the
temperature is changed. These techniques are also applicable for certain
chemical reactions in order to find the relationship between reactions and
the temperature. The main difference between TGA, DTA and DSC is the
method of measuring the changes in samples that are caused by heat.
Thank You