Submitted to: Dr.

Shazia Noreen
Submitted by: Maria Yasmin
Roll no. : 88
Section : Physical Chemistry
Course title : Polymer Chemistry
Course Code : Chem-
 Thermal analysis of polymers

Table of contents

Sr. no. Topic Page no.

1. Introduction…………………………………………………………………………………... 1
2. Classification of polymers………………………………………………………………. 1
 Thermosets
 Thermoplasts
3. Techniques of thermal analysis……………………………………………………… 4
 Laser flash method
 Dilatometry and thermo mechanical analysis
 Thermo gravimetric Analysis
 Differential Scanning colorimeter
 Dynamic mechanical analysis
 Dielectric Thermal analysis
 Thermo optic analysis
 Evolved gas analysis
 Differential thermal analysis
4. References……………………………………………………………………………………… 13

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 Thermal analysis of polymers

“Characterization of polymers by thermal analysis”

Introduction:

A polymer ( Greek poly-, "many" + -mer, "part") is a large molecule, or macromolecule, composed of many
repeated subunits. Due to their broad range of properties both synthetic and natural polymers play essential
roles in everyday life. Polymers range from familiar synthetic plastics such as polystyrene to natural
biopolymers such as DNA and proteins that are fundamental to biological structure and function. Polymers,
both natural and synthetic, are created via polymerization of many small molecules, known as monomers.

Thermal analysis is a branch of materials science where the properties of materials are studied as they change
with temperature. Thermal Analysis is important to a wide variety of industries, including polymers,
composites, pharmaceuticals, foods, petroleum, inorganic and organic chemicals, and many others. These
instruments typically measure heat flow, weight loss, dimension change, or mechanical properties as a function
of temperature. Properties characterized include melting, crystallization, glass transitions, cross-linking,
oxidation, decomposition, volatilization, coefficient of thermal expansion, and modulus. These experiments
allow the user to examine end-use performance, composition, processing, stability, and molecular structure and
mobility.

Basic principle of thermal analysis:

 Sample hold compartment. Sensors to detect/ measure property of the sample and the temperature
An enclosure within which the experimental parameters (temperature, speed, environment) may be
controlled.
 A computer to control data collection and processing.

Classification of polymers on the basis of thermal response:

The primary physical difference is that thermoplastics can be remelted back into a liquid, whereas thermoset
plastics always remain in a permanent solid state. Think of thermoplastics as butter – butter can be melted and
cooled multiple times to form various shapes. Thermoset is similar to bread in that once the final state is
achieved, any additional heat would lead to charring.

 Thermosets:

Thermoset plastics contain polymers that cross-link together during the curing process to form an irreversible
chemical bond. The cross-linking process eliminates the risk of the product remelting when heat is applied,
making thermosets ideal for high-heat applications such as electronics and appliances.
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 Thermal analysis of polymers
Features & Benefits
Thermoset plastics significantly improve the material’s mechanical properties, providing enhances chemical
resistance, heat resistance and structural integrity. Thermoset plastics are often used for sealed products due to
their resistance to deformation.
Pros
 More resistant to high temperatures than thermoplastics
 Highly flexible design
 Thick to thin wall capabilities
 Excellent aesthetic appearance
 High levels of dimensional stability
 Cost-effective
Cons
 Cannot be recycled
 More difficult to surface finish
 Cannot be remolded or reshaped

 Thermoplastics

Thermoplastics pellets soften when heated and become more fluid as additional heat is applied. The curing
process is completely reversible as no chemical bonding takes place. This characteristic allows thermoplastics
to be remolded and recycled without negatively affecting the material’s physical properties.

Features & Benefits

There are multiple thermoplastic resins that offer various performance benefits, but most materials commonly
offer high strength, shrink-resistance and easy bendability. Depending on the resin, thermoplastics can serve
low-stress applications such as plastic bags or high-stress mechanical parts.

Pros
 Highly recyclable
 High-impact resistance
 Remolding/reshaping capabilities
 Chemical resistant
 Hard crystalline or rubbery surface options
 Eco-friendly manufacturing

Cons
 Generally more expensive than thermoset
 Can melt if heated
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 Thermal analysis of polymers

“Techniques of thermal analysis”

Here are some techniques which are commonly used for the thermal analysis of polymers.

1. Laser Flash Method (LFA)

The laser flash method was developed by Parker et al. in 1961. In a vertical setup a light source (e.g. laser,
flashlamp) heats the sample from the bottom side and a detector on top detects the time-dependent temperature
rise. For measuring the thermal diffusivity, which is strongly temperature-dependent, at different temperatures
the sample can be placed in a furnace at constant temperature.

Perfect conditions are

 homogenous material,
 a homogenous energy input on the front side
 a time-dependent short pulse – in form of a Dirac delta function
Several improvements on the models have been made. In 1963 Cowan takes radiation and convection on the
surface into account. Cape and Lehman consider transient heat transfer, finite pulse effects and also heat losses
in the same year. Blumm and Opfermann improved the Cape-Lehman-Model with high order solutions of radial
transient heat transfer and facial heat loss, non-linear regression routine in case of high heat losses and an
advanced, patented pulse length correction
The laser flash analysis or laser flash method is used to measure thermal
diffusivity of a variety of different materials. An energy pulse heats one side of
a plane-parallel sample and the resulting time dependent temperature rise on the
backside due to the energy input is detected. The higher the thermal diffusivity
of the sample, the faster the energy reaches the backside. A state-of-the-art laser
flash apparatus (LFA) to measure thermal diffusivity over a broad temperature
range, is shown on the right hand side. In a one-dimensional, adiabatic case the
thermal diffusivity is calculated from this temperature rise as follows:

a = 0.1388 ⋅ d 2t1/2
Where
a is the thermal diffusivity in cm²/s
d is the thickness of the sample in cm
t1/2 is the time to the half maximum in s

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 Thermal analysis of polymers
2. Dilatometry and Thermomechanical Analysis

Dilatometry is a thermo-analytical method for measuring the shrinkage or expansion of materials over a
controlled temperature regime. Our dilatometer has the capability to accurately measure the thermal expansion
of materials at temperatures between ambient and 1000ºC in air or under an atmosphere.

DIL Measurement Information • Linear thermal expansion • Determination of coefficient of thermal expansion
• Sintering temperatures • Softening points • Phase transitions

ε=1/r*(dr/dT)

ε – thermal expansion coefficient r- sample length

Dilatometry deals with the determination of length or volume as a function of temperature. Thermomechanical
analysis (TMA) is the term applied to dilatometry carried out under tension or load. Historically, dilatometry
and TMA date back to ancient metrology. Obvious length
measurements are made through side-by-side comparison with a
standard; obvious volume measurement is through comparison
with the content of a standard vessel. The highest precision in
length measurement is achieved by interferometry, which allows,
for example, the maintenance of the standard meter to a precision
within 1 part in 108. Volume determination with pycnometers,
volumetric flasks, cylinders, burettes and pipettes is difficult to
push beyond 0.01%.

A schematic drawing of a typical TMA apparatus is shown. The

length measurement is performed via a linear-variable differential
transformer (LVDT). A change in the position of the core, which
floats frictionlessly within the transformer coil, results in a linear
change in output voltage. A force is applied to the sample by
balancing flotation and weight. Measurement is possible in the
compression, tension and bending modes. Typical heating rates
range from 0.1 to 40 K min−1. Temperature ranges from 100 to
1000 K are common, but high-temperature TMA to 2500 K is
available. Sample sizes are usually of the gram and centimeter
magnitudes.

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 Thermal analysis of polymers
A typical TMA of a drawn fiber, such as a polyester (poly(ethylene terephthalate)), is shown schematically in
Fig. 11. Below the glass-transition temperature Tg the TMA curve shows normal, almost linear expansion. At
Tg, the fiber shrinks owing to relaxation of the only partially crystallized molecules. This trend is reversed as
some low-temperature crystallization stabilizes the fiber. Close to the melting temperature Tm the fiber expands
limitlessly owing to flow. Details of manufacturing and performance variables can thus be quickly evaluated by
TMA. Expansivities, shrinkage, glass and melting transitions are most easily measurable by TMA.

Two extensions of TMA are pressure–volume–temperature determinations and dynamic mechanical analysis.
The former lead to the equilibrium functions of state and are available for many substances up to the gigapascal
range, revealing many high-pressure and high-temperature crystal forms. The latter involves time-dependent
stress–strain determination at various temperatures and is basic to the analysis of mechanical properties
(elasticity and viscoelasticity).

Common Applications:
Determine softening point (Tg) of polymers
Measure coefficient of thermal expansion (CTE) of polymers, composites, ceramics, inorganics and metals
Characterize CTE differences of polymer in glassy state (below Tg) and in rubbery state (above Tg)
Study effects of physical aging, crosslinking or post-cure on the Tg of thermoplastics or thermosetting
polymers
Determine dimensional stability of parts at operating temperature and loading
Characterize shrinkage of oriented films
Force ramp or step force to evaluate changing load on dimension change
Isostrain: measure the force required to maintain constant strain while material is heated
Strengths:
Small sample size
Low force range
Force alteration: linear and stepwise
Programmable temperature: (1) sequential heating and cooling cycles, (2) isothermal
Limitations:
Requires parallel faces and uniform thickness for expansion
Reasonably flat samples for penetration

3. Thermogravimetric Analysis (TGA or TG)

Thermogravimetric analysis is an experimental method whereby changes in mass are used to detect and
measure the chemical or physical processes that occur upon heating a sample. represents common TGA results
and demonstrates how they are commonly used in interpreting results from DSC analysis.

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 Thermal analysis of polymers

Although several variations in design exist, the simple design of TGA instruments includes a highly precise
analytical balance to which the sample pan is attached. The sample pan is typically suspended within a heater,
which is under computer control. The control of the balance and sample atmospheres again varies but in basic
instruments, they share a controlled atmosphere usually of nitrogen gas. Instruments are also available that
allow the user to provide one atmosphere for the balance and another for the sample/heater area and control the
pressure as well. Most instruments also have the ability to use isothermal or dynamic heating and cooling cycles
and some can also be programmed to hold a specific temperature once a change in mass is detected then
maintain that temperature until there is no further change and resume the heating program. TGA results like
DSC can vary greatly depending on sample and experimental conditions which can make it very difficult to
compare the work of one researcher to another.

In addition to supporting other thermal analysis techniques, TGA is extremely useful in studying various kinetic
processes of solids and liquids as long as the processes involve the loss of mass. This is achieved with the
accuracy of the balances used as well as the precise control of heating/cooling rates and atmospheric conditions.

Evolved Gas Analyzer options for TG-EGA include:

Fourier Transform Infrared Spectrophotometer (FTIR) – identification of chemical family, and, in some
cases, specific compound Mass Analyzer – chemical residuals are specifically assigned, but sometimes have
other possible answers The FTIR spectra of evolved gas species from 400°C – 600°C were collected. Intense
evolution of CO, H2O, CO2 and C6H5OH can be seen above 580°C.

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 Thermal analysis of polymers

4. Differential scanning colorimeter

DSC is a thermoanalytical technique in which the difference in the amount of heat required to increase the
temperature of a sample and reference is measured as a function of temperature. Both the sample and reference
are maintained at nearly the same temperature throughout the experiment. Generally, the temperature program
for a DSC analysis is designed such that the sample holder temperature increases linearly as a function of time.
The reference sample should have a well-defined heat capacity over the range of temperatures to be scanned.
The term DSC was coined to describe this instrument, which measures energy directly and allows precise
measurements of heat capacity. Types of DSC:

 Power-compensated DSC, keeps power supply constant

 Heat-flux DSC, keeps heat flux constant

hf-DSC
DSC is a technique where the heat flow rate difference into a sample and reference material is measured. One is
heat-flux DSC (hf-DSC), initially referred to as Quantitative DTA but now it is commonly referred to as a DSC
method. This development was an improvement over DTA in that it allowed for a measurement in the changes
in heat flow as opposed to temperature only. This was done by the addition of a second series of thermocouples
to measure temperatures of the furnace and a heat sensitive plate. During a phase change, the heat emitted or
absorbed by the sample would alter the heat flux through the heat sensitive plate. By measuring the heat
capacity of the heat sensitive plate as a function of temperature during the manufacturing process, an estimate of
the enthalpy of transition can be made from the incremental temperature fluctuations.

Modulated Temperature – DSC (MT-DSC)

A sample in which glass transitions need to be studied will contain material that is only partially amorphous or
may be in complex mixtures of materials that are crystalline or amorphous. This can result in glass transitions
occurring in a temperature range that is relatively close to other endothermic or exothermic transitions, which
due to their larger signal can “cover up” the Cp increase indicative of the glass transition.

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 Thermal analysis of polymers

Where Q = amount of heat evolved, Cp = heat capacity, T = absolute temperature, t = time, and f(t,T) is a
function of time and temperature that governs the response associated with the physical or chemical
transformation. While this can be accomplished with either pc- or hf-DSC instruments, recent improvements in
the sensitivities and more accurate temperature control for both types of instruments have also contributed to
making MT-DSC a valuable and accepted technique.

DSC-curve:
The result of a DSC experiment is a curve of heat flux versus
temperature or versus time. There are two different conventions:
exothermic reactions in the sample shown with a positive or negative
peak, depending on the kind of technology used in the experiment.
This curve can be used to calculate enthalpies of transitions. This is
done by integrating the peak corresponding to a given transition. It can
be shown that the enthalpy of transition can be expressed using the
following equation:
ΔH = KA
where ΔH is the enthalpy of transition,
K is the calorimetric constant, and A is the area under the curve. The
calorimetric constant will vary from instrument to instrument, and can
be determined by analyzing a well-characterized sample with known
enthalpies of transition.
5. Dynamic mechanical analysis:

Dynamic mechanical analysis (abbreviated DMA, also known as dynamic mechanical spectroscopy) is a
technique used to study and characterize materials. It is most useful for studying the viscoelastic behavior of
polymers. A sinusoidal stress is applied and the strain in the material is measured, allowing one to determine the
complex modulus. The temperature of the sample or the frequency of the stress are often varied, leading to
variations in the complex modulus; this approach can be used to locate the glass transition temperature of the
material, as well as to identify transitions corresponding to other molecular motions.

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 Thermal analysis of polymers

The instrumentation of a DMA consists of a displacement sensor such as a linear variable differential
transformer, which measures a change in voltage as a result of the instrument probe moving through a magnetic
core, a temperature control system or furnace, a drive motor (a linear motor for probe loading which provides
load for the applied force), a drive shaft support and guidance system to act as a guide for the force from the
motor to the sample, and sample clamps in order to hold the sample being tested. Depending on what is being
measured, samples will be prepared and handled differently. A general schematic of the primary components of
a DMA instrument.

Types of analyzers
There are two main types of DMA analyzers used currently: forced
resonance analyzers and free resonance analyzers. Free resonance
analyzers measure the free oscillations of damping of the sample
being tested by suspending and swinging the sample. A restriction
to free resonance analyzers is that it is limited to rod or rectangular
shaped samples, but samples that can be woven/braided are also
applicable. Forced resonance analyzers are the more common type
of analyzers available in instrumentation today. These types of
analyzers force the sample to oscillate at a certain frequency and
are reliable for performing a temperature sweep.
Analyzers are made for both stress (force) and strain (displacement) control. In strain control, the probe is
displaced and the resulting stress of the sample is measured by implementing a force balance transducer, which
utilizes different shafts. The advantages of strain control include a better short time response for materials of
low viscosity and experiments of stress relaxation are done with relative ease. In stress control, a set force is
applied to the same and several other experimental conditions (temperature, frequency, or time) can be varied.
Stress control is typically less expensive than strain control because only one shaft is needed, but this also
makes it harder to use.
6. Dielectric thermal analysis

Dielectric thermal analysis (DETA), or dielectric analysis (DEA), is a materials science technique similar to
dynamic mechanical analysis except that an oscillating electrical field is used instead of a mechanical force. For
investigation of the curing behavior of thermosetting resin systems, composite materials, adhesives and paints.
The great advantage of DEA is that it can be employed not only on a laboratory scale, but also in process.
In a typical test, the sample is placed in contact with two electrodes (the dielectric sensor) and a sinusoidal
voltage (the excitation) is applied to one electrode. The resulting sinusoidal current (the response) is measured
at the second electrode. The response signal is attenuated in amplitude and shifted in phase in relation to the
mobility of the ions and alignment of the dipoles. Dipoles in the material will attempt to align with the electric
field and ions (present as impurities) will move toward the electrode of opposite polarity. The dielectric
properties of permittivity ε' and loss factor ε" are then calculated from this measured amplitude and phase
change.
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 Thermal analysis of polymers

7. Thermo-Optic Analysis
Thermo-optic analysis involves predicting the changes in optical performance due to the refractive index
changes caused by changes in temperature in transmissive optics. Temperature profile predictions from a
thermal finite element model and thermo-optic material properties and is able to make thermo-optic
predictions using two methods: the OPD integration method and the user defined gradient index method.

 OPD Integration Method:

The first method of thermo-optic analysis is to perform integration through the finite element model to
compute optical path difference (OPD) along integration paths. These integrations result in OPD maps that
may be placed on the optical surfaces of the optical analysis model through a macro file .

 User Defined Gradient Index Method:

The second method of thermo-optic analysis is user defined gradient index lens capability in the optical
analysis. In this technique device generates a three-dimensional representation of the disturbed refractive
index profile to be used in conjunction with a dynamic link library provided with Sig Fit to allow the optical
analysis to obtain the index of refraction anywhere in each lens. This method has greater accuracy compared
to the OPD integration method but is significantly more computationally intensive.
8. Evolved gas analysis

Evolved gas analysis (EGA) is a method used to study the gas evolved from a heated sample that undergoes
decomposition or desorption. It is either possible just to detect evolved gases using evolved gas detection
(EGD) or to analyze explicitly which gases evolved using evolved gas analysis (EGA). Therefor different

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 Thermal analysis of polymers
analytical methods can be employed such as mass spectrometry, Fourier transform spectroscopy, gas
chromatography, or optical in-situ evolved gas analysis.
By coupling the thermal analysis instrument, e. g. TGA (thermogravimetry) or DSC (differential scanning
calorimetry), with a fast Quadrupole Mass Spectrometer (QMS) the detection of gas separation and
identification of the separated components are possible in exact time correlation with the other thermal analysis
signals. DSC/TGA-QMS or TGA-QMS yields information on the composition (mass numbers of elements and
molecules) of the evolved gases. It allows fast and easy interpretation of atomic/inorganic vapors and standard
gases like H2, H2O, CO2, etc. Fragmentation, interpretation of organic molecules is sometimes difficult.

The combination with an FTIR (Fourier transform infrared spectrometer) has become popular, especially in the
polymer producing, chemical and pharmaceutical industry. DSC/TGA-FTIR or TGA-FTIR yields information
on the composition (absorption bands) of the evolved gases (bonding conditions). The advantage is an easy
interpretation (spectra data bases) of organic vapors without fragmentation. Symmetrical molecules can not be
detected.
Strengths:

Simultaneous thermogravimetric analysis (TGA) and characterization of evolved chemical residuals.

Small sample size.
Analysis of solids and liquids with minimal sample preparation.
Detection of multiple mass loss thermal events from physical and chemical changes of materials.
Limitations:

TGA-FTIR does not detect non-polar molecules, such as H2, N2, O2 TGA-FTIR spectral identification of
product gases may be limited to chemical family or class.
Secondary gas-phase reactions can complicate identification of product gases.
9. Differential thermal analysis
Differential thermal analysis (or DTA) is a thermoanalytic technique that is similar to differential scanning
calorimeter. A DTA consists of a sample holder, thermocouples, sample containers and a ceramic or metallic
block; a furnace; a temperature programmer; and a recording system. The key feature is the existence of two
thermocouples connected to a voltmeter. One thermocouple is placed in an inert material such as Al2O3, while
the other is placed in a sample of the material under study. As the temperature is increased, there will be a brief
deflection of the voltmeter if the sample is undergoing a phase transition. This occurs because the input of heat
will raise the temperature of the inert substance, but be incorporated as latent heat in the material changing
phase.

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 Thermal analysis of polymers

In DTA, the material under study and an inert reference are made to undergo identical thermal cycles, (i.e.,
same cooling or heating programme) while recording any temperature difference between sample and reference.
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. Thus, a
DTA curve provides data on the transformations that have occurred, such as glass transitions, crystallization,
melting and sublimation. The area under a DTA peak is the enthalpy change and is not affected by the heat
capacity of the sample.

 Endothermic means heat goes into the sample.

 Exothermic means heat moves out of the sample.

Conclusion:

Thermal analysis techniques have played, and continue to play, a prominent role in the characterization and
development of polymer blends and copolymers of various architectures. Thermal analysis technique that
delivers extremely sensitive measurements of heat change can be applied on a broad scale with pharmaceutical
development. The increasing use of the combined techniques is providing more specific information, and thus
facilities more rapid interpretation of the experimental curves obtained.

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 Thermal analysis of polymers

References:

 Cheng, S.Z.D., Li, C.Y., Calhoun, B.H., Zhu, L., Zhou, W.W., Thermal analysis: the next two decades.
Thermochim. Acta 355 (2000): 59-68.
 Sestak, J. Thermophysical properties of solids. In: Svehla, G. ed. Comprehensive Analytical Chemistry:
Volume XII, Thermal Analysis Part D. New York, NY: Elsevier Science Publishing; 1984: ISBN 0-444-
99653.
 Recommendations for Names and Definitions in Thermal Analysis and Calorimetry. ICTAC
website.http://www.ictac.org/ICTACNews/articles/dec98/ind98030.pdf. Accessed January, 2010.
 J. Sestak, Thermophysical properties of solids (Academia, Prague, 1984)
 G. Höhne, W. Hemminger, H.-J.Flammersheim, Differential Scanning Calorimetry (Springer, Berlin,
1996)
 Roger Stout, “Linear Superposition Speeds Thermal Modeling”, Part 2, pp28-33,
 Power Electronics Technology, February 2007 5. T. Hopkins, et al, “Designing with Thermal
Impedance”, SGS-Thompson Application Note AN261/0189, reprinted from Semitherm Proceeding
1988
 E. Moukhina, J. Therm Anal. Calorim. (2012) 109: 1203-1214
 REBECA-3D, http://www.rebeca3d.com
 Roehr, Bill and Bryce Shiner, “Transient Thermal Resistance - General Data and Its Use,” AN569 in
Motorola Power Applications Manual, 1990.

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