GROUP ASSIGNMENT

SKA3013 ANALYTICAL CHEMISTRY

GROUP A

SEMESTER 2 SESSION 2019/2020

“Thermal Analysis”
Application of Thermal Analysis Techniques in Polymers

LECTURER:
DR MAZLINA MUSA
GROUP MEMBERS
NAME STUDENT ID
TAN JUN HONG D20181083121
MAC PARSCELLA IVY AK AMONG D20181083126
SITI HUMAIRAH BT HAMZAH D20181083139
LAU LEE LEE D20181083140
FATIN AFRINA BT MOHD ZAHARI D20181083142
Main title: Thermal analysis
Group title: Application of
thermal analysis in polymers
TABLE CONTENT

No. Contents Page(s)

1.0 Introduction

2.0 Objective

3.0 Methodology
3.1 Preparation of free films
3.2 Thermal mechanical analysis experiment
3.3 Differential scanning calorimetry experiment

4.0 Result and discussion

4.1 Thermal mechanical analysis experiment
4.2 Differential scanning calorimetry experiment

5. Conclusion

6. References
1.0 INTRODUCTION

1.1 Thermogravimetry (TG)

Thermogravimetric analysis (TGA) or thermogravimetry (TG) is a technique

where the mass of a polymer is measured as a function of temperature or time while
the sample is subjected to a controlled temperature program in a controlled
atmosphere. Temperature ranges for commercial TGAs are typically ambient to 1000
° C or more, a sufficient upper limit for polymer applications. A purge gas flowing
through the balance creates an atmosphere that can be inert, such as nitrogen,
argon, or helium. With polymers, a reducing atmosphere is rarely needed. The
moisture content of the purge gas can vary from dry to saturated. Polymers generally
exhibit mass loss, although mass gain may be observed prior to degradation at slow
heating rates in an oxidizing atmosphere. Mass loss may be categorized as volatile
components such as absorbed moisture, residual solvents, or low molecular mass.
Additives or oligomers that generally evaporate between ambient at around 300 ° C.
For the reaction products, such as water and formaldehyde from the cure of phenolic
and amino resins, which generally form between 100 ° C and 250 ° C. Furthermore,
the generation of volatile degradation products resulting from chain scission that
generally required temperatures above 200 ° C but not more than 800 ° C. All of
these mass loss processes may be characterized by TGA to yield information such
as composition, extent of cure, and thermal stability. The kinetics of these processes
may also be determined to model and predict cure, thermal stability, and aging due to
thermal and thermooxidative processes.
Thermogravimetric analysis provides a quantitative measurement of the mass
change, but it does not indicate the nature of the material lost. Hence, it is often used
in a combined manner with evolved gas analysis (EGA) measurements on the same
sample. EGA determines the specific nature of the changes in the gas phase and
may be done in a qualitative or quantitative manner. There are several modes of
operation. Gas samples can be trapped and analyzed periodically either during or at
the end of the experiment. More common and more useful is to monitor the
atmosphere and correlate its chemical nature with the observed mass change in a
near. This is simultaneous mode, with negligible delay between mass loss in the TGA
and gas detection by EGA. The resolution of the chemical analysis with the
temperature and time of the TGA measurement will depend on a number of factors,
importantly the heating rate, the required analysis or scan time of the EGA
measurement, and the delay caused by the transfer time between the TGA source
and the EGA detector. The latter is a function of the atmosphere’s flow rate and the

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length of the path prior to analysis. The temperature (typically 200 to 230°C, high
enough to prevent condensation but not so high as to promote degradation) and
nature of the transfer path can influence the results through condensation or reaction
of the products.
Any technique for gas analysis can be applied to EGA. The most frequently
used methods are mass spectroscopy (MS) and Fourier transform infrared
spectroscopy (FTIR). Many instrument manufacturers provide the ability to interface
their TGAs with MS or FTIR. Temporal resolution between the TGA and the MS or
FTIR detector is an important feature, for example, in distinguishing absorbed water
from water as a reaction product and in assigning a decomposition product to a
specific mass loss. Each method has its experimental requirements, limitations, and
advantages. Mass spectroscopy is a very sensitive technique that identifies volatile
species by their mass to charge ratio, referred to as m/z . The evolution of the sum of
all m/z species can be plotted and compared with the derivative TGA plot to ensure
temporal resolution between the TGA and the mass spectrometer. The evolution of a
specific m/z, associated with species such as water or formaldehyde, can show the
distinct evolution of these compounds.
The most common ionization is by 70 eV electron impact (EI), which operates
under high vacuum. Because the ion source filaments are sensitive to oxygen, TGA
is normally restricted to pyrolysis in an inert atmosphere. EI tends to fragment larger
molecules that are formed during thermal degradation, creating ambiguity in the
precise identification of the degradation products. However, the fragmentation
patterns can be an aid in identifying the class of degradation product, such as
saturated hydrocarbons, polyethers, or carbonyl. Mass spectrometers that employ
atmospheric pressure chemical ionization (APCI) simplify interfacing to ambient
pressure TGA and allow analysis of processes that occur in air, but they are more
expensive than EI mass spectrometers.
Many polymers evolve relatively simple gases on heating, such as water,
ammonia, acetic acid, hydrogen chloride, and oxides of carbon, nitrogen, and
sulphur. These gases are easily identified in the purge gas by FTIR, since they have
characteristic absorption frequencies and band contours. More complex products are
not always totally identifiable, but the observed group frequencies are often enough
to define the class of product. An evolution profile for the entire gas stream can be
compared with the DTG plot to ensure temporal resolution between the TGA and the
FTIR.
Specific gas profiles such as water, CO2, or even the carbonyl group can also
be plotted. FTIR gas analysis is an ambient pressure process that can accommodate

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both reactive and inert atmospheres within the TGA. An option to maintaining the
FTIR gas cell at elevated temperature to prevent condensation is to purposely trap
the higher molecular mass condensable products, which tend to foul the gas cell and
complicate the IR spectra, on a membrane for subsequent analysis while allowing the
gaseous products to be analyzed in real time. At 1989, Lewis et al. used a fiber to
reinforce composite as both the sample and the membrane and were able to
measure diffusion of volatile degradation products through the sample. Thus, the
selection of an EGA detector is based on the specific experimental conditions and
goals.
Besides the common texts on thermal analysis, the pulsed gas techniques
make quantitative measurements more reliable. Energetic information supplied
through DTA or DSC also complements the information from TGA. They not only
provide information on the enthalpy of the process but also detect transitions and
reactions that do not result in a change in mass of the system. Simultaneous
TGA/DTA or TGA/DSC has several advantages over separate experimentation. In
addition to a savings in time and some costs, the primary advantages are concerned
with the alleviation of potential ambiguities in the interpretation of the results that
might arise from differences in samples, atmospheric conditions, temperature, and
other variables. The combination of the calorimeter and quartz crystal microbalance
is a more recent novel application of such measurements.

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1.2 What is polymer?

The polymers, we hear about it a lot, is very vital and one cannot imagine the
life without it. Polymers are a large class of materials, consist of many small
molecules named monomers that are linked together to form long chains and are
used in a lot of products and goods that we use in daily life. Polymers are large
molecules, macromolecule comprised of many repeating units. These units are
joined together to form really long chains and their broad range of properties, both
synthetic and natural polymers play essential and ubiquitous roles in everyday life.
Polymers can be natural, such as starch, cellulose from the composition of plants
and nucleic acids from the animal. Polymers can also be synthetic by the factory,
such as Nylon, Polystyrene, and Polyethylene.

Polymers with both natural and synthetic, are created via polymerization of
many small molecules, known as monomers. Polymers consequently large molecular
mass, relative to small molecule compounds, and forming an unique physical
properties including toughness, viscoelasticity, and a tendency to form glasses and
semicrystalline structures rather than crystals. Polymer characterization can establish
the molecular structure, mass, and morphology of synthetic and natural polymeric
materials. These are comprised of concurrent structures, or chains, of covalently-
bonded macromolecules. The thermodynamic and mechanical properties of these
structures vary depending upon their chemical and biological composition, however
they typically emerge as high-versatility materials with a range of interdisciplinary
applications. The natural polymers include materials such as wool and rubber, while
synthetic polymers are primarily comprised of plastics such as polythene and
polystyrene.

Nowadays, polymers are widely used advanced materials, which are found
almost in every material used in our daily life. The properties of polymers make it
become more important and use the applications of polymer in different dominions of

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 sciences, technologies and industry, from basic uses to biopolymers and therapeutic
polymers.

1.3 Thermal mechanical Analysis(TMA)

1.4 Dynamic Mechanical Analysis (DMA)

Polymers are viscoelastic materials, whose mechanical behaviour exhibits

characteristics of both solids and liquids. Thermal analysts are frequently called on to
measure the mechanical properties of polymers for a number of purposes. Of the
different methods for viscoelastic property characterization, dynamic mechanical
techniques are the most popular, since they are readily adapted for studies of both
polymeric solids and liquids. They are often referred to collectively as dynamic
mechanical analysis (DMA). Thermal analysts often refer to the DMA measurements
on liquids as rheology measurements. Dynamic mechanical analysis involves
imposing a small cyclic strain on a sample and measuring the resulting stress
response, or equivalently, imposing a cyclic stress on a sample and measuring the
resultant strain response. In most commercial DMA instruments strain is the
controlled input, while the resulting stress is measured. DMA is used both to study
molecular relaxation processes in polymers and to determine inherent mechanical or
flow properties as a function of time and temperature.

Since DMA is a technique for viscoelastic characterization, understanding the

basics of DMA is facilitated by first considering the behavior of ideal elastic solids and
ideal viscous liquids, which are briefly described below, followed by discussion of the
characterization of viscoelastic behavior and the role of DMA in relation to other test
methods. Following this, a major portion of this chapter is concerned with the
interpretation of DMA data, citing numerous examples of what DMA data look like
and how the data can be used effectively to solve important problems in polymer
applications. Finally, some of the key factors that influence viscoelastic properties are

5
 described, along with other important issues in conducting DMA measurements and
determining accurate data.

Viscoelastic transitions or relaxations in amorphous polymers include Tg and

several secondary transitions resulting from relaxation processes that are observed
at temperatures below Tg. The secondary transitions are not observed in DSC
experiments because the associated Cp changes are too small, and there are no
heat associated with these transitions. In semicrystalline polymers there often is an
additional secondary relaxation between Tm and Tg. These relaxations are of
continuing scientific interest and engineering importance. They are intimately
associated with the stiffness of engineering thermoplastics, impact toughness,
diffusion rates of low - molecular - weight vapors and liquids, and the effectiveness of
plasticization, among others. The three points of greatest interest in relation to
characterizing relaxation processes are (1) determining in what phase they originate,
(2) describing the molecular processes underlying them, and (3) relating relaxation
behavior to engineering properties and practical applications. DMA has proved most
useful in helping to address these issues as noted in the review by Chartoff (1997).
For constant, the frequency of experiments on amorphous polymers, the highest
temperature relaxation is the glass transition, also referred to as α, while secondary β
and γ relaxations are commonly observed. There also may be a δ process. In this
case all the relaxations are associated with the amorphous phase. The γ and δ
relaxations are below -100°C. These relaxations would be missed if the only cooling
device available were a mechanical chiller that would cool to only − 100 ° C. For
semicrystalline polymers in the temperature range between Tm and liquid nitrogen
temperature [ − 196 ° C (77 K)], at least three relaxation processes are often found.
The high - temperature αc process, when present, is a secondary relaxation related
to the crystalline fraction. The β process in semicrystalline polymers that have an αc
process represents the glass transition, which is related to the amorphous phase.

This is different from the case of amorphous polymers, where the α relaxation is the glass
transition. The low temperature γ process is generally considered to originate in the
amorphous phase but may also have an important component associated with the crystalline
phase. There also may be a δ process or even in certain instances lower temperature ε and
ζ relaxations as for Nylon 6, which are associated with the amorphous phase.

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1.5 TMA and DSC in determining the glass transition temperatures of polymer

In this report the film forming polymers Kollicoat® SR and Kollicoat® IR were analyzed
regarding their glass transition temperatures by using heat flux DSC and TMA operating in
penetration mode. Furthermore, the compatibility of both polymers was characterized by
determining the glass transition temperatures of Kollicoat® SR/IR films. Therefore, the total
amount of film forming polymer as a sum of Kollicoat® SR and Kollicoat® IR as well as the
total amount of plastcizer triacetin remained the same in both film formulations. Solely the
Kollicoat® SR/IR ratio was varied to study the influence of PEG-PVA on the glass transition
temperature.

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2.0 OBJECTIVES

i) To determine the glass transition temperature (Tg) of polymer films through

thermal mechanical analysis (TMA).
ii) To determine the glass transition temperature (Tg) of polymer films through
differential scanning calorimetry(DSC).

8
3.0 METHODOLOGY

3.1 Preparation of free films

The polymer films were first prepared for thermal mechanical analysis experiment and
differential scanning calorimetry experiment. Pure Kollicoat® IR films were prepared by
mixing 60.0 g PEG-PVA with 140.0 ml distilled water to obtain a polymer solution of 30 %
(m/m). Kollicoat® SR 30 D was used as received and it was only blended before casting the
films. Polymer dispersions with different Kollicoat® SR/IR ratios were prepared according to
Table 1. They were prepared by adding triacetin, Kollicoat® IR and Kollicoat® SR 30 D to 60
ml distilled water and subsequent blending. Mixing was always carried out for 3 min using an
Ultra Turrax at 18.000 rpm. PVP was diluted in 35 ml distilled water. After adding talc and
titanium dioxide to the PVP solution, the suspension was dispersed. Then the pigment
suspension was incorporated into the polymer suspension and mixed again.

Components (g) SR/IR:9/1 SR/IR:8/2

Kollicoat® SR 30 D 87.0 84.6
Kollicoat® IR 2.6 5.0
Triacetin 1.4 1.4
Kollidon® 30 1.0 1.0
Titanium dioxide 1.0 1.0
Talc 7.0 7.0
Distilled water 95.0 95.0
Table 1: Composition of Kollicoat® SR/ Kollicoat® IR

9
Amounts of 20 ml polymer dispersions were cast onto teflon coated plates and subsequently
dried to obtain a constant weight in a heater at 60 °C for 12 hours. Polymer films were
removed from the teflon plates and then stored at 20 °C and 60 % relative humidity for 3
days. The thickness of the films was determined using a manual micrometer at 15 random
positions of the film. The mean standard deviation did not exceed 3.5 % of the average
thickness, which exhibited values as shown in Table 2.

Film Kollicoat® IR Kollicoat® SR SR/IR:9/1 SR/IR:8/2

Film thickness 143 ± 3 μm 150 ± 5 μm 148 ± 5 μm 142 ± 4 μm
Table 2: Film thickness of free films casted on Teflon plates

3.2 Thermal mechanical analysis experiment

TMA experiment was carried out by heating the samples with a heating rate of 5 K/min within
a range of 0 °C to 100 °C. Nitrogen was used as a washing gas with a rate of 50 ml/min. The
glass transition temperature was determined by the change of the slope of the obtained
curves. Experiments were performed in duplicate.

3.3 Differential scanning calorimetry experiment

DSC measurement was operating with a heating rate of 10 K/min within a range of 0 °C to
100 °C. After an equilibration phase, the samples were first heated, afterwards cooled down
to 0 °C and then heated again following the same regimen like before. Nitrogen was used as
a flushing gas with a flow rate of 10 ml/min. The weight of the free film samples used for the
DSC measurements varied from 4.5 to 7.8 mg. The samples were placed into aluminium
pans with a pierced lid. Then the data of the second heating curve was analyzed. This was
to determine the glass transition temperature Tg. DSC experiments were carried out in
triplicate.

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4.0 RESULT AND DISCUSSION

4.1 Thermal Mechanical Analysis Experiments

Fabricated polymers, plastics, fibers, and films are a group of materials used
in our daily lives. Applications include simple food containers, kitchenware coatings,
medical devices, materials for controlled drug delivery, blood storage bags, and
sutures, as well as plastic devices such as composite parts for automobiles and
aerospace devices. This list can be easily expanded to areas of specific polymer
applications. In all these areas, understanding of process, structure and property
relationships are of primary importance because of their effect on end to use
performance. For instance, a multilayer food package can keep food fresh for a
longer period of time, because it acts as a barrier against oxygen permeation. A
multicomponent which is multilayer tire can serve under extreme mechanical and
temperature conditions without delaminating.

Unlike metals and ceramics, polymers are viscoelastic. The properties have
both viscous and elastic components, which control the mechanical response as a
function of time and temperature. Therefore, the accurate characterization of
polymeric materials is extremely important for prediction of performance and service
lifetime. Among the thermal characterization techniques described in this book,
thermal mechanical analysis (TMA) has its own distinct advantages, as will be shown
in this chapter. Thermal mechanical analysis measures changes in sample length or
volume as a function of temperature or time under load at atmospheric pressure. The
load is usually static or variable. This technique is also referred to as
thermodilatometry (TD), if sample dimensions are measured under negligible load.
TMA is an especially useful thermal analysis technique, because measurements can

11
be carried out on actual manufactured parts of a variety of shapes, provided they are
small enough to fi t in the TMA apparatus.

TMA experiments are generally carried out under static load with a variety of
probes for measurement of sample dimensions in compression, tension, or flexure.
The most important TMA measurements include determination of the coefficient of
linear thermal expansion (CLTE, α) and the glass transition temperature, Tg. But
several other measurements can be made by applying special modes and various
attachments. These include stress relaxation, creep, tensile properties of films and
fibers, flexural properties, dimensional stability (reversible and irreversible
dimensional change), parallel plate rheometry, and volume dilatometry. This is to
explain the basis of the TMA techniques and their application to polymeric materials
and shaped plastic products. Thermal mechanical analysis measures the change in
sample length in compression or tension under constant or variable force as a
function of temperature or time. For thermal expansion measurements, the applied
force must be negligible, just enough to keep the probe in contact with the sample.
Some confusion exists about the terminology. Thermodilatometry (TD) and
thermomechanical analysis (TMA) are essentially identical techniques. According to
ASTM E473, the International Union of Pure and Applied Chemistry (IUPAC, 1989 )
and the International Confederation for Thermal Analysis and Calorimetry (ICTAC,
1980), “ thermodilatometry is a technique in which a dimension of a substance under
negligible load is measured as a function of temperature while the substance is
subjected to a controlled temperature program in a specified atmosphere. Linear TD
and volume TD are distinguished on the basis of the dimension measured. ” On the
other hand, TMA is a technique in which the deformation of a substance under
nonoscillatory (static) load is measured as a function of temperature or time while the
substance is subjected to a controlled temperature program in a specified
atmosphere.

Thus, a researcher who uses an instrument that was marketed as a

“thermomechanical analyzer” puts a minimum load on the probe to measure the
coefficient of thermal expansion essentially carries out a dilatometry measurement.
Nevertheless, the vast majority of publications talk about TMA even when the load on
the sample is negligible. Although this is incorrect in principle, in publications the
word dilatometry is often used only for measurements in which the volume change of
the sample is measured in some liquid, as in a mercury dilatometer. Polymers are
viscoelastic materials, whose mechanical behavior exhibits characteristics of both
solids and liquids.

12
 The timescale and temperature of observation are critical to the relative
degree of solid like and liquid like behaviour exhibited by viscoelastic materials.
Generally, they will behave more solid like at lower temperatures or over shorter
timescales, but more liquid like at higher temperatures or longer timescales. As will
be described later in this chapter, TMA can be used to measure the viscoelastic
phenomenon of creep and, in some cases, stress relaxation. But it should be pointed
out that whenever a load is imposed on a polymeric material, the material will
respond in a viscoelastic fashion; specifically, its penetration or elongation will exhibit
time dependence. When the load is small, the temperature is low and/or the time is
short, these effects (such as penetration of the probe into the polymer and creep) will
be negligible. But when the load is large, the temperature is high, and/or the time is
long, these effects may be significant and may in fact be necessary to observe the
desired effect.

Thermal Mechanical Analysis (TMA) is used to measure coefficient of thermal

expansion of polymers. Polymers typically expand as temperature is increased. The
glass transition temperatures can be determined from thermal mechanical analysis
experiments. When an amorphous polymer is heated, the temperature at which the
polymer structure turns “viscous liquid or rubbery" is called the glass transition
temperature, Tg. It is also defined as a temperature at which amorphous polymer
takes on characteristic glassy-state properties like brittleness, stiffness and rigidity. If
a material goes through a glass transition temperature during a thermal mechanical
analysis test, the curve shape changes significantly and glass transition temperature
can be calculated by using an onset technique. Amorphous polymers would typically
not utilize the thermal mechanical analysis approach because the material would
soften to the point where the probe penetrates into the sample. The factor that
affected the glass transition temperature (Tg) is heating rate. Thermal Mechanical
Analysis curves are characterized by two inflection points, whereas the first indicates
the glass transition temperature. At the glass transition temperature of the polymer,
the mobility of the polymer chains will move more freely and thus the free volume of
the sample increases, leading to a penetration of the measuring sensor into the
sample. Therefore, the onset in TMA thermograms indicates the glass transition
temperature of the polymer (Figure 4.1).

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Figure 4.1 : TMA curves of Kollicoat® SR and Kollicoat® IR free films.

4.2 Differential Scanning Calorimetry Experiments

Differential scanning calorimetry (DSC) is the most popular thermal analysis

technique, the “workhorse” of thermal analysis. This is a relatively new technique. Its
name has existed since 1963, when Perkin Elmer marketed their first differential
scanning calorimetry (DSC). The term DSC simply implies that during a linear
temperature ramp, quantitative calorimetric information can be obtained on the
sample. DSC is a technique in which the heat flow rate difference into a substance
and a reference is measured as a function of temperature, while the sample is
subjected to a controlled temperature program.

The expression “DSC” refers to two similar but somewhat different thermal
analysis techniques. It is a common feature of these techniques that the various
characteristic temperatures, the heat capacity, the melting and crystallization
temperatures, and the heat of fusion, as well as the various thermal parameters of

14
chemical reactions, can be determined at constant heating or cooling rates. It is
important to note that the acronym DSC has two meanings which are an abbreviation
of the technique and the measuring device.

Since the 1960s the application of differential scanning calorimetry grew

considerably, and today the number of publications that report DSC must amount to
more than 100,000 annually. One of these techniques that brought into science the
name DSC, called today power compensation DSC , was created by Gray and O’Neil
at the Perkin Elmer Corporation in 1963. The other technique grew out of differential
thermal analysis (DTA), and is called heat flux DSC. Differential thermal analysis
itself originates from the works of Le Chatelier (1887), Roberts Austen (1899), and
Kurnakov (1904). It needs to be emphasized that both of these techniques give
similar results, but of course, they both have their advantages and disadvantages.
The major applications of the DSC technique are in the polymer and pharmaceutical
fields, but inorganic and organic chemistry have also benefited significantly from the
existence of DSC.

Among the applications of DSC, we need to mention the easy and fast
determination of the glass transition temperature, the heat capacity jump at the glass
transition, melting and crystallization temperatures, heat of fusion, heat of reactions,
very fast purity determination, fast heat capacity measurements, characterization of
thermosets, and measurements of liquid crystal transitions. Kinetic evaluation of
chemical reactions, such as cure, thermal and thermooxidative degradation is often
possible. Also, the kinetics of polymer crystallization can be evaluated. Lately, among
the newest users of DSC, we can list the food industry and biotechnology.
Sometimes, specific DSC instruments are developed for these consumers. DSC is
extremely useful when only a limited amount of sample is available, since only
milligram quantities are needed for the measurements. As time goes by, newer
techniques are introduced within DSC itself, like pressure DSC, fast scan DSC, and
more recently modulated temperature DSC (MTDSC). Also, with development of
powerful mechanical cooling accessories, low temperature measurements are
common nowadays. DSC helps to follow processing conditions, since it is relatively
easy to fingerprint the thermal and mechanical history of polymers. Although
computerization, enormously accelerated the development of DSC, this has its own
negatives. For example, many operators tend to use the software without first
understanding the basic principles of the measurements. Nevertheless, newer and
more powerful software products have been were marketed that increased the
productivity of the thermal analyst by significantly reducing the time for calculation of

15
experimental results, and sometimes, interpretation of the data. It is unfortunate that
few of these software applications are available to the research personnel for
modification and thus for use in special conditions.

Nowadays, differential scanning calorimetry (DSC) is a routine technique. The

DSC instrument can be found virtually in every chemical characterization laboratory,
since the instruments are relatively inexpensive. Unfortunately, this has its drawback.
It is a popular misconception that if we recorded a DSC peak, we did our job. We
would like to prove, from one side, that this is not true, but from the other side that
despite this, DSC is still a simple and easily applied technique. Our goal is to present
a simple but consistent picture of the present state of this measuring technique.

Referring to the differential scanning calorimetry curves, the glass transition

temperature is apparent as an endothermic step. From the Figure 4.2, the glass
transition temperature is determined as the intersection point of the baseline and the
tangent of the gradient differential scanning calorimetry curve. As differential
scanning calorimetry (DSC) curves often exhibit a gradient baseline, the correct
determination of the glass transition temperature is possibly interrupted. Hence, for
the comparison of the results obtained by DSC and TMA, the midpoint of the steps in
the DSC curves are used for the determination of the glass transition temperature
(Figure 4.2). The midpoint of the steps in the DSC curves which also represents the
inflection point of the curve.

Glass transition temperature is typically calculated by using a half-height

technique in the transition region. The heating rate and sample heat history are a
couple of factors that may affect the test result. Depending on the equipment
capability, differential scanning calorimetry can be used for a wide range of
thermoplastic and thermoset polymers. For materials that have broad glass transition
temperature, differential scanning calorimetry may not be sensitive enough to show a
large enough transition for calculation purposes.

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Figure 4.2 : DSC curves of Kollicoat® IR and Kollicoat® SR free films.

The glass transition temperatures obtained by both methods are compared in Table
4.3. The glass transition temperatures is one of the most important properties of any epoxy
and is the temperature region where the polymer transitions from a hard, glassy material to a
soft, rubbery material. The determination of glass transition temperature (Tg) values of
polymers often tend to vary depending on the technique used. TMA provides a large amount
of valuable information on solids and other materials that is difficult to obtain by other
analytical techniques. Values determined by TMA tend to be higher than those acquired by
DSC. This phenomenon has already been described in the literature, whereas values
determined by TMA exceed DSC values by 6 °C in average. Thus, a comparison of Tg
obtained by different methods are still difficult. TMA offers a higher degree of sensitivity
compared to DSC for the detection of the glass transition temperature of polymers.

Polymeric film Tg determined by TMA Tg determined by DSC

Kollicoat® IR 41.6°C 37.4°C
Kollicoat® SR 30 D 47.9°C 40.6°C
Table 4.3: Glass transition temperatures of Kollicoat® IR and Kollicoat® SR 30 D films
determined by TMA and DSC.

Free films with a Kollicoat® SR/ Kollicoat® IR ratio of 9:1 exhibited a glass transition
temperature of 27.4 °C, which was lower compared to pure free films. The decrease in Tg

17
value was expected due to the addition of the plasticizer triacetin (Figure 4.3). The increase
in PEG-PVA content because the decreased of glass transition temperature to a value of
25.8 °C. Since the plasticizer PEG is covalently bound to the film forming polymer,
Kollicoat® IR acts as a polymeric plasticizer. Hence, PEG-PVA improves film coat properties
such as mechanical strength and facilitates the film formation. The coat properties at lower
temperatures acts as the further lowering of the glass transition temperature. The
appearance of only one glass transition temperature of the polymer films with different
Kollicoat® SR/Kollicoat® IR ratios indicates the compatibility of both polymers.

Figure 4.3: DSC measurements of SR/IR:9:1 and SR/IR:8/2 films.

5.0 CONCLUSION

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The glass transition temperature Tg of the polymer can be determined by thermal analysis
such as thermal mechanical analysis (TMA) and differential scanning calorimetry (DSC). In
this experiment, TMA and DSC allowed the glass transition temperature Tg determination of
pure Kollicoat® IR and Kollicoat® SR films as well as of polymer films with different
Kollicoat® SR/IR ratios. The condition of film coats during the dissolution process is
expressed by the glass transition temperatures of the swollen polymer films. Lower T g values
of polymer films are related to a higher probability of being exceeded by the physiological
temperature. Thus, an increased mobility of the polymer chains will contribute to a higher
permeability of the film coat facilitating drug release. It was shown, that both coating
formulations are effectively plasticized by the addition of triacetin and Kollicoat® IR acting as
a polymeric plasticizer.

6.0 REFERENCES

19
 Hardy, C. S. O. (1986). An overview of thermal analysis of polymers. Asean
Journal On Science and Technology, 3(1), 36-54. Retrieved from
https://www.researchgate.net/publication/322079857_An_Overview_of_Thermal_Ana
lysis_of_Polymers

Joseph D.M & R.Bruce Prime. (2009). Thermal Analysis Of Polymers. A John
Wiley & Sons, Inc., Publication.

Kimberly Lawson. (2016). Thermal Analysis In Polymers. Retrieved from

https://www.azom.com/article.aspx?ArticleID=12883

Mettler Toledo. (2013). Thermal Analysis Of Polymers. Retrieved from

https://www.mt.com/dam/LabDiv/guidesglen/tapolymer/TA_Polymers_Selected_Apps
_EN.pdf

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