CHAPTER 1

INTRODUCTION
The polymer can be defined as a large number of molecules constructed from many
smaller structural units called monomers, covalently bonded together in any conceivable
pattern. In certain cases, it is more accurate to call the structural or repeat unit a monomer
residue because atoms are eliminated from the simple monomeric unit during some
polymerization process. The physical and chemical properties of polymer depend to the
overall size of the polymer chain and on the inter- and intra-molecular forces that hold the
polymer together. They do not posses any segmental motions at low temperatures which
is below their glass transition temperature, Tg and are normally insulators.

A polymer will become ionically conducting when inorganic salts are inferred in them.
The polymer will act as host while the inorganic salts dissociate to provide mobile
species. The degree of the dissociation salts is dependent to the salt concentration.
(Wright et al., 1973).Polymer electrolyte is the polymer that has an ability to allow ions
to move in their matrix. This term may refer to the materials (polymers) with solventfree system where the ionically conducting phase is formed by dissolving salts in a high
molecular weight polar polymer matrix and the ionic conductivity is responsibly occurred
in the amorphous region. From the previous studies, (Berthier et al, 1989,) the ionic
mobility is inversely proportional to the crystallinity of the polymer and hence the
conductivity will increase with increasing of amorphousity of the polymer.

1.1 Problem Statement

1. Solid Polymer Electrolytes and Gel polymer Electrolytes have low conductivity
for applications in electrochemical devices such as super capacitors and batteries
2. High internal resistance for use in electrochemical devices
3. Poor electrodeelectrolyte contact

1.2 Objectives
1. To enhance the ionic conductivity up to 10-2 S/cm
2. To improve electrode-electrolyte contact

1.3 Limitation of the works

In this work, PMMA-grafted natural rubber (MG30) was doped with lithium salt to
prepare gel polymer electrolytes (GPEs). Plasticizers propylene carbonate (PC) and
ethylene carbonate (EC) were introduced to enhance the conductivity to the highest
conducting polymer salt complex composition. Several methods were employed to
characterize the physical and electrical properties of the prepared samples including FTIR
spectroscopy, ac impedance spectroscopy, dc polarization, and linear sweep voltammetry.

1.4 Scope of Study

1. To study the physical characterization of the sample by using the FTIR, DSC,
XRD, and polarized microscope
2. To study the electrical characterization of the sample by using impedance
spectroscopy, Lithium transfer number ad LSV.

CHAPTER 2
LITERATURE REVIEW
2.1

INTRODUCTION

Polymer gel electrolytes is one of the category of polymer electrolytes in which the
solvent is retained in the electrolyte and these show high value of conductivity
approaching 102 S/cm at room temperature. These electrolytes belong to solventsalt
polymer hybrid system in which the salt solution is immobilized by the addition of a
suitable polymer matrix (Feuillade and Perche 1975;Tsuchida et al 1983; Abraham and
Alamgir 1990). The solvent provides the conducting medium whereas polymer provides
mechanical stability to these electrolytes (Webber 1991; Sekhon et al 1998).

The study of polymer electrolytes was initiated by Fentonet al.in 1973, but their
technological significance was only appreciated later after the publications by Armand et
al.To date, several types of polymer electrolytes such as poly(ethylene oxide) (PEO),
poly(acrylonitrile), poly(methyl methacrylate) (PMMA), poly(vinyl chloride), and
poly(vinylidene fluoride) have been developed and characterized.

These have been prepared and characterized as solid polymer electrolytes (SPEs) and
gelled polymer electrolytes (GPEs) systems. SPEs are lightweight and show good thin
film-forming ability, processing ease, flexibility, and elasticity, but they suffer low ionic
conductivity at room temperature.

GPEs seem to be an attractive alternative to SPEs as they possess higher ambient ionic
conductivities (~103 S cm1) and good dimensional stability. The major drawbacks of
GPEs are their insufficient strength to be used as electrode separators and their creep
under pressure. Grafted polymers have been reported to have an ability to improve the
mechanical properties of GPEs, increase adhesion to the electrode, increase solvent
intake, change solubility characteristics, and enhance conductivity. Nasef and Saidi
explored the effect of adding grafted styrene onto poly(vinylidene fluoride) and found it
to be a successful method in increasing the ionic conductivity and reducing the inherent
crystallinity of the host polymer. Idris and Glasse has explored the potential application
of epoxy natural rubber, ENR25, and PMMA-grafted ENR50 as an electrolyte for lithium
ion battery, but their conductivity is far from adequate for practical room temperature
applications.

2.2 GENERAL PROPERTIES

The polymer electrolytes have occupied an important role in solid-state ionic due to their
unique properties (Chandra and Chandra, 1994) which includes;
a) Ease to prepare in thin film form: this means that it can be fabricated with large
surface area giving high power levels
b) Ability to accommodate a wide range of doping composition of inorganic salts
c) Provide good electrode-electrolyte contact.
d) High ionic conductivity.
e) Flexibility/mould ability. The flexible nature of materials allows space-efficient
cell designs of variable dimensions to be constructed. This property is important
in accommodating volume changes in the cells during cycling so that physical
degradation of the interfacial contacts does not take place.

2.3

Polymer Electrolytes

According to A. Manuel Stephan, (2005), polymer electrolyte may generally be defined

as a membrane that possesses transport properties comparable with that of common liquid
ionic solutions. This means that polymer consists of inorganic salts dissolved in polymer
matrix which enables ionic conduction in a bulk. The mobile species comes from the
inorganic salts dissociated into cation and anion which contributes to the conductivity.

Many types of monovalent, divalent and trivalent salts have been dissolved in polymer
(Armand, 1987) which that exhibit ion conductivity polymers. Two classes of materials
have been primarily used as polymer electrolyte: solvent-free membranes, formed by
blending a thermoplastic polymer with the lithium salt and gel membranes formed by
thermoplastic polymers trapping the liquid solution of the electrolyte. Typically, the
solvent-free membrane is based on poly (ethylene oxide) and still suffers from poor
conductivity at ambient temperature (J.R. Nair et al, 2007). A number of polymers are
electrically conductive or can be made to be conductive by doping with an electron donor
or acceptor. Polymeric gel electrolytes (polymer solvent salt systems) are of current
interest due to their suitability for solid state ionic devices.

They have a high value of conductivity (~10 -3 S cm-1) along with good adhesive
properties, high transmission in the visible region and liquid like behaviour in the
operational range temperature, (S.S Sekhon et al.,2000). Among the earliest measurement
of ionic conducting in polymer-salt complexes were carried out by Wright (1975).
However, only in the late 1970s, when Armand et al (1972) proposed that these polymer
electrolytes could be applied to solid-state battery did the research take off.

2.4

Criteria of Polymer Electrolytes

The polymer should have several characteristics to acts as a successful polymer host. This
criterion (Ratner, 1987 and Gray, 1991) has been laid down as a guide for the selection of
polymer materials that can be use in the electrolytes systems. These characteristics
include;
a) The availability of the atoms or groups of atoms in the polymer

that have

sufficient electron donating power to form cathode coordinate bonds with the
cations from doping salts. The polymer is able to solvate the salt through
interaction with the cation of the salt. This is afforded by the availability of lone
pair electrons of N, O, S, Cl groups in the polymer.
b) Segmental motion of the polymer chain can occur easily. To ensure the
effectiveness of salvation of cation, the polymer chain should be flexible and
provide favorable salvation entropy
c) The polymer also should have low glass transition temperature to ensure low
cohesive energy density.
d) The lattice energy of dopant salt is important in the formation of polymer-salt
complex. The lattice energy of the salt should be low for which salt with larger
anions is most suitable. For example of large anions includes I-, ClO4-, and SCN-.

There are four representatives polymeric systems include of PEO, PAN, PVdF, and
PMMA based polymer electrolytes. PMMA as a host polymer was first reported by Iijima
et al., (1985) and Bohnke et al (1993). Wixwat et al., (1990) reported the properties of
agel polymer madeby PMMA-PEG-LiClO 4. Appetechi et al., (1995) studied the kinetics
and the stability of lithium electrode in PMMA-based gel electrolytes. Sekhon et al.,
(1998) reported that the transport properties of lithium electrolytes gelled with PMMA.

10

2.4

Classification of Polymer Electrolytes

Polymer electrolytes are determined largely by the local mobility of the polymer
segments (Ratner et al), but the best values are typically 1001000 times lower
than those of conventional liquid electrolytes at a given temperature. This
reduction may be compensated, to some extent, by forming the electrolytes into
thin films, typically 100 m thick, but for high-power applications, higher intrinsic
conductivities are required. Therefore, a number of new forms of polymer
electrolyte have been developed. Although in practice a continuum of types exists,
it is sometimes useful to consider dividing these polymer electrolytes into 5
classes:

Class 1: Amorphous macromolecule-salt complexes, typically based on polyether hosts.

Class 1 polymer electrolytes are sometimes referred to as solvent-free or dry systems. To
prevent crystallization and improve mechanical stability, sophisticated polymer synthesis
is often used to develop architectures based on, for example, random and block
copolymers, comb-branched copolymers, networks, interpenetrating networks, or liquidcrystal-based systems. Particular attention has been paid to the synthesis of single ionic
conductors, in which the anion is linked to the polymer backbone (Ratner et al.). In such
systems, hence in a lithium battery, concentration polarization is prevented.

11

Class 2: Plasticized systems, in which small amounts of low-molar-mass polar

liquids are added to Class 1 polymer electrolytes.
A plasticizer is a low-molar-mass material that may be added to increase polymer
segmental motion and flexibility and thereby improve the ionic conductivity of salts
dissolved in the system. Addition of suitable organic solvents can increase conductivity
by a factor of almost 100. Any slight degradation of mechanical properties can be offset
by subsequent cross-linking of the system. Since the plasticizing molecules also interact
with (and indeed may preferentially solvate) the ions, coordinating macromolecules such
as the polyethers may be replaced by more inert polymers such as poly(vinylidene difluoride) (PVdF), polyacrylonitrile (PAN), poly(methyl methacrylate) (PMMA), or
PVdF hexafluoropene copolymers.

Class 3: Gel electrolytes, formed by incorporating a nonaqueous electrolytes solution

within an inactive structural polymer matrix.
Among all kinds of polymer electrolyte, gel polymer electrolyte (GPE), in which liquid
electrolyte is immobilized in a polymer matrix, has been attractive for developing Li-ion
batteries due to its combined advantage of liquid electrolyte (high ionic conductivity) and
solid electrolyte (free of leaking), (Zheng Tian et al, 2006). Gel polymer electrolytes are
formed by addition of a suitable amount of organic solvent of low molecular weight (also
known as plasticizer) to an ionically conducting polymer electrolyte.

12

This class of polymer electrolytes has ionic conductivities ranging between 10 -4 to 10-3 S
cm-1 at temperature 20C.(Refer to table for ionic conductivity values of gel polymer
electrolytes). The conductivity of these electrolytes critically depends upon to the
viscosity and the dielectric constant of the plasticizer. The degree of salt dissociation
increase when plasticizers with high dielectric constant are used. The mobility of the ions
increases when the viscosity of the plasticizer is lower (Southall et al, 1996). There are
some examples of plasticizing solvents are ethylene carbonate, propylene carbonate and
other organic solvents such as dimethyl formamide, diethyl phthalate, diethyl carbonate,
methylene carbonate, dimethyl carbonate and -butyrolactone.

Table show the ionic conductivities of some polymer gel electrolytes:

Polymer System
PEO-LiClO4-DOP
PVdF-LiN(CF3SO2)2-EC-PC

Conductivity (S cm-1)
10-5
2.2 x 10-3

References
(Michael et al, 1997)
(Jiang et al,1997)

PVC-LiTFSI-DBP-DOP

10-4

(Sukeshini et al,1997)

PVC-PMMA-LiCF3SO3-PC

10-3

(Rhoo et al, 1997)

13

Class 4: Polymer in salt or rubbery electrolytes, in which high-molar-mass

polymers are dissolved in low-temperature molten salt mixtures.
Rubbery electrolytes were discovered by Angell and co-workers; they combine
the advantages of vitreous solid electrolytes, in which the cationic motion is decoupled
from the matrix, with those of simple polymer electrolyte amorphous phases. The salt or
salt mixture must have a low glass-transition temperature Tg , so that a rubbery material,
rather than a glass, is formed when the polymer is dissolved in the fused salt.
Unfortunately, most salts that have, or contribute to, a suitably low Tg tend to be very
chemically reactive or thermally unstable.

Class 5: Composites, based on the addition of either nanoparticulate ceramics or dualphase block copolymers.
In composite polymer electrolytes, electrochemically inert particulate fillers are
incorporated into the polymer matrix. The fillers used are high surface area inorganic
solids incorporated into a dry solid polymer system or gel polymer system. Composite
solid polymer electrolytes have potential advantages over conventional solid polymer
complexes; for example, they exhibit better mechanical strength, higher ionic
conductivity, and better lithium anode and electrolyte interfacial stability (Seok Kim et
al., 2007).

14

The table below lists some of the examples of composites polymer electrolytes system.
Polymer System
Li3N/(PEO)12/LiCF3SO3

Conductivity (S cm-1)
5.0 x 10-7

PMMA/LiBF4/DBP/ZrO3

4.6 x 10-5

(PEO)10LiClO4/-LiAlO2

5.0 x 10-7

LiI/PEO/PMMA/DBP/ZrO3

1.4 x 10-4

2.6

References
(Abraham and Alamgir,
1990)

Models of Ionic Conduction In Polymer Electrolytes

15

The ionic conduction in polymer electrolytes is due to the mobility of anionic or cationic
ions that act as the conducting species. The polymer will act as an immobile solvent for
the ionic salts. Ion conducting polymers have attracted great attention due to their
potential applications. As in all polymer-salt complexes, conductivity is attributed to both
anions and cations. The mobility of the each ion is quit comparable (Henri, 1982). The
ionic mobility in ionic conduction is influence by the property of amorphous phase and
ion association, ion-polymer interaction and local relaxations of the polymer. It is a
movement of positive and negative charge ions, which is hop from lattice site to lattice
site under the influence of an electrical field.

According to Tsunemi et al., (1982), the ionic conduction in polymer was caused by the
diffusion of carrier ions through their free volume. Therefore, ionic conductor should be
obtained by dispersing carrier ions in polymer domain at molecular level, (Tsunemi et al.,
1983). Saito et al.,(2000) state that ionic conductivity is given by = ieinii where ei is
charge of species, ni is charge carrier concentration and i is their mobility. The mobility is
proportional to the Nernst-Einstein equation.The ionic conductivity of polymer-salt
complexes is affected by the used in the complex. For example, lithium salts with large
anions such as CF3SO3, (CF3SO2)N, BF4, and ClO4 exhibit higher conductivity than salts
with smaller anions like as Br- and Cl-.

16

The higher conductivity is caused by higher percentage of salt that dissociate in the
complex (due to low ion-ion interaction) and plasticizing effect of the anions (it migrates,
or at least limit the phase charges of the polymer by which the polymer becomes
crystalline). Furthermore, the plasticizing effect of the anion may reduce the glass
transition temperature, Tg of the polymer which may be turn increase the ionic
conductivity of the electrolyte (Nagasubramaniam et al., 1995). Interpreting the
conduction phenomena is a difficult task. This is made worse when multiple ions are
formed in the polymer electrolytes (Qurtarone et al., 1998). However, there are several
models was found which can quite accurately explain this phenomenon. One of the useful
models is macroscopic approaches. In macroscopic approaches, the conductivity in
polymer electrolytes is generally fitted in term of Arrhenius equation and the VogelTamman- Flucher (VTF) equation.

17

2.7

MG rubber

MG rubber is a modified natural rubber which is made by polymerizing metacrylate

monomer in latex so that polymer chains become attached to the rubber molecule. Three
grades of Heveaplus Mg are commercially available; MG30 based is based on a nominal
30% of methyl metacrylate content, MG 40 is based on 40% nd Mg 49 is based on
49%.Heveaplus Mg rubber giving compounds of high tensile modulus, hardness,good
electrical properties and fine finish. It also acts as a adhesive for bondibg PVC to NR.
According to Bevan and Bloomfield(1963), there is a substantial increase in bond
strength obtained between NR and PVC once level of poly(metyl metacrylate) is excess
of 35%.

Rezaifard and others have done studies on evaluation

of MG 30 and MG 50 s

toughening agents for epoxy resin. Previous researches have also show by adding rubber
material as impact modifiers will decrease the modulus and yield stress of the plastic
rubber blend. Filter is one of the most important additives used in this research that is
precipitated calcium carbonate (PCC) with diameter 1m,PCC was added into
formulation sample to overcome the problem of the modulus reduction.

18

Figure 2.7.1 : monomer of MG

2.8

Poly (methyl methacrylate), PMMA

19

Poly (methyl methacrylate), PMMA is a one of polymer that has good physical
characteristics such as rigid, hard, transparent, good weather resistance and good scratch
resistance. It is a polymeric materials that also posses many desirable properties such as
light weight, high light transmittance, chemical resistance, resistance to weathering
corrosion and good insulating properties. Due to the good properties, PMMA is being
useful polymer in manufacturing applications. It has an amorphous morphology and the
Tg is 120 C. PMMA is a vinyl polymer made by free radical vinyl polymerization from
monomer of methyl methacrylate.

It structure contains of C=O which in acrylics functional group that bears the lone pairs
electrons. PMMA has a polar functional group in its polymer chain that exhibits a high
affinity for lithium ions and plasticizing organic solvents. Therefore, it displays one of
the essential characteristics of a potential polymer electrolyte material. The oxygen atom
from its carbonyl group is expected to form a coordinate bond with the lithium ions from
the doping salts. In the previous study, PMMA used as a polymer host material in the
development of a polymer based electrolyte. It was found that, in its gel form, it has
given high ionic conductivity at sub-ambient temperature and good solvent retention
ability, (Famiza Latif et al 2006

20

To date, there are many research about PMMA-based gel electrolytes have be done and
they have received much attention and have been tested in electrochemical devices. These
systems have exhibited high ionic conductivity at room temperature and have better
interfacial properties towards the lithium electrodes when compared to a PAN based gel.
Following these studies, several systems based on PMMA has been applied to other
applications such as in electrochromic devices. Due to its good optical properties, PMMA
has become a good candidate for non-linear optical applications in communications
technology.

The most serious drawback of plasticized gel-based PMMA system is its poor mechanical
property and to date this remains unsolved. Mechanical properties can only be improved
by modifying the polymersolvent ratio. However, these will adversely affect the
conductivity of the material. Another serious problem is facing PMMA/PC systems in
which, the presence of PC can easily corrode the lithium metal anode in an
electrochemical cell. High ionic conductivity of 104 S cm1 can only be reached at about
100 C. Blending the polymer with another polymer can circumvent problems associated
with poor mechanical properties.

21

Furthermore, the blending approach can form a freestanding PMMA-based electrolyte

film and therefore provide good mechanical properties. PMMA is being used in gel
electrolytes due to its high transmission in the visible region. It is use for applications in
electro-chromic windows.

Figure 2.8.1: Structure of PMMA.

22

CHAPTER 3
EXPERIMENTAL METHOD

3.1 Sample Preparation

MG30 was obtained from the Rubber Research Institute of Malaysia and lithium
trifluoromethanesulfonate (LiCF3SO3 or LiTf), obtained from Aldrich, was dried for 48h
under vacuum at 110 C. PC from Aldrich was distilled over a molecular sieve type 4A
before use and EC also from Aldrich was used without further purification. All gel
electrolytes were prepared by the solution cast technique. FTIR spectroscopy was carried
out using the PerkinElmer Spectrum One spectrometer in the frequency range of 650 to
4,000 cm1 with a resolution of 2 cm1. The ionic conductivity of gel electrolytes was
measured by complex ac impedance method using HIOKI 3532-50 LCR Hi Tester, which
was interfaced to a computer in the frequency range of 100 Hz to 500 kHz at
temperatures between 30 to 110 C.

The gel electrolyte was sandwiched between two stainless steel (SUS 316) self-designed
blocking electrodes and was then placed into an oven coupled with a temperature
controller. For each temperature step, the sample was rested for 15 min before the
impedance was recorded. Linear sweep voltammetry was performed using the Auto-Lab
Potentiostat/Galvanostat. The sample was mounted on a cell and lithium metal was used
as the counter and reference electrodes at a scanning rate of 1.0 mV/s.

23

Direct current polarization was carried out by sandwiching the gel films between
symmetrical lithium metal electrodes and the measurement was performed as described
in the BruceVincent method. The GPE was sandwiched between two unblocking
electrodes in an argon-filled MBRAUN glove box (O2<0.1 ppm; H2O<0.1 ppm).

24

3.2 Fourier Transform Infrared Spectroscopy

Infrared (IR) spectroscopy is a technique use to identify certain molecular species in a

sample through the interaction of infrared radiation with the various modes of the
molecules of the species leading to absorption of the infrared radiation (George et al.,
1987). According to Rajendran et al., (2002a), IR spectroscopy has been used to
characterize the polymer structure chain and has led the way in interpreting the reactions
of multifunctional monomers including rearrangements and isomerizations. The IR spctra
of these materials vary according to their compositions and may be able to show the
occurrence of the complexation and interaction between the various constituents. In the
present study, IR spectroscopy is used to establish the interactions between polymer and
salt which it will change the vibrational modes of the atom or molecules in the material
(Rajendran et al., 2002b).Fourier Transform Infrared Spectroscopy (FTIR) has been
extensively developed over the two past decades and provides a number of advantages.

Radiation containing all IR wavelengths is split into two beams; one beam is a fixed
length, and the other beam is a variable length (moveable mirror). There are several
advantages of FTIR compared to other techniques. Since a monochromator is not used,
the entire radiation range is passed through the sample simultaneously and much time is
saved. FTIR instruments are also characterized by high resolution (0.001 cm-1).

25

Moreover since the data undergo analog- to- digital conversion, IR results are easily
manipulated whereas results of several scans are combined to verge out random
absorption artifacts and excellent spectra from very small sample can be obtained.

As with any computer aided spectrometer, spectra of pure samples or solvents (stored in
computer) can be subtracted from mixtures. Flexibility in spectral printout is also
available; for example, spectra linear in either wave number or wavelength can be
obtained from the same data set. A theoretical advantage of Fourier Transform
instruments is that their optics provides a much larger energy throughput (one or two
order magnitude) than do dispersive instrument, which are limited in throughput by the
necessity of narrow slit widths.

The potential gain here, however, may be partially offset by the lower sensitivity of the
fast- response detector required for the interferometric measurements. Finally, it should
be noted that the interferometer is free from the problem of stray radiation because each
infrared frequency is, in effect, chopped at a different frequency.These infrared
absorption bands identify molecular components and structures. Absorptions bands in the
range of 4000cm-1 1500 cm-1 wave numbers are typically due to functional groups
such as OH, C=O, N-H, CH3 and others.

26

The region between 1500 cm-1 4000 cm-1 wave numbers is referred to as the
fingerprint region. Absorption bands in this region are generally due to intra- molecular
phenomena, and are highly specific for each material. The specificity of these bands
allows computerized data searches to be performed against reference libraries to identify
a material ( Koeing et al., 1991).In the present work, FTIR spectroscopy will carry out to
identify the effect of interaction between MG 30 with the plasticizers.

27

3.3 Impedance spectroscopy

Alternating current methods represent the most popular approach in determining the
electrical properties of polymer electrolytes. This is because a very simple cell
incorporating inert blocking electrodes may be used to determine the bulk impedance of
the electrolyte (MacDiamid, 1987).

In impedance spectroscopy, a sinusoidal voltage was applied to the cell under

investigation and the sinusoidal current passing through the cell is determined. This
experiment involves measuring the impedance as a function of frequency of the applied
signal over a wide frequency range. This is because the impedance is precisely frequency
dependent. A typical experiment consists of determining the complex impedance of a cell
as a function of the signal frequency and presenting the result in the form of a complex
impedance plot, Z (). The results can also be represented in the complex admittance
Y (), complex permittivity () and complex dielectric modulus M () formalism
where:
Z () = Z + jZ
Y() = 1/Z() = jCo
M() = 1/ = jCoZ()

28

Where,
= 2f (angular frequency)
Co = vacuum capacitance of the empty cell,
Z = Zcos, Z = Zsin and
J = (-1)
Any of these four basic response quantities can be donated by a general term called
immitance, I () = I + jI.

Impedance spectroscopy will use to measure the electrical properties of polymer

electrolytes. In this work, the measurement will be done by using a HIOKI 3530-50 LCT
Hi Tester that has been interfaced to a computer. The frequency range will be used
from100 Hz to 5 MHz. the electrode area and the thickness of each film will measure
using a micrometer screw gauge. The conductivity will be obtained for a different
temperature from room temperature up to 378 K.

29

3.4 Differential Scanning Calorimetry (DSC)

Differential scanning calometry is a technique used to study what happens to polymers

when heat is applied and to observe the thermal transitions of a polymer. The thermal
transitions are the changes the take place when heating the polymer. The melting of a
crystalline polymer is example of such transitions temperature. The glass transition is also
thermal transition.

In the most popular DSC design, two pans sit on a pair of identically positioned platforms
connected to a furnace by a common heat flow path. In one pan, the polymer sample is
placed and the other one is the reference pan which is left empty(Figure 3.5). All the
scanning progress is monitored and controlled by the computer which turns on the
furnace and tells it to heat the two pans at a specific rate, usually something like 10 C per
minute. The computer makes sure that the heating rate stays exactly the same throughout
the experiment. However, more importantly, it makes sure that the two separate pans heat
at the same rate as each other. A plot as the temperature increases will be obtained.

30

Figure 3.4.1: Differential Scanning Calorimetry (DSC)

31