High Performance

polymers
Unit 1
 Difference
HPPs generally characterized by

➔ Tensile strength and modulus

➔ Resistance to heat and flame
➔ Resistance to chemical environment

Conventional/ commodity polymers High performance polymers

Volume driven Technically driven

Price oriented Application oriented

Large scale production Small batch production

 High Performance polymers
❏ Polymers and polymer processing well established technologies at the heart of
manufacturing.
❏ In many advanced applications, metals are opted because conventional polymers
either cannot deliver the required mechanical performance or are thermally
vulnerable.
❏ HPPs could overcome these obstacles and are the lightweight replacements for
metals
❏ HPPs can function at elevated temperature and have excellent solvent, chemical
resistance
❏ Exhibit excellent mechanical properties in comparison to general purpose
polymers. Examples: polyamides, polycarbonates, polysulfones etc.
❏ In the beginning era stabilities were in the range of 400°C to 500°C in air. But
Within past years the development of these polymers for thermal properties up to
600°C in air were realized. For ex poly(quinoxaline)s
 properties
HPPs are defined as materials

● Thermally stable
● stable to radiation and chemical reagents. resistant to oxidative degradation
at elevated temperature
● resistant to thermolytic process
● resistant to ionising radiation, corrosion, abrasion and stress-fatigue,
● have low toxicity, are lightweight,
● because of their linear molecular structures, they are mechanically tough.
● Examples include fluoropolymers, such as PTFE, polyimides, polyphenylene
sulfide (PPS), aromatic polysulfones (PSU) etc.
High cost
Drawback High processing temperature
and melt viscosity
 Structural requirement for high temperature resistance of
polymers
Thermal resistance: resistance to thermal degradation for acceptable periods
during their service live

Chemical resistance: resistant to chemical attacks, inert in nature at both

ambient and elevated temperature

thermal resistance arise from aromatic or ladder like structure which offer very
high melting point or Absence of melting transition

composed of aromatic and heterocyclic moiety linked by flexible bridging groups

 Structural requirement for high temperature resistance of polymers
Requirement

presence of high strength in the primary Bond of polymer backbone

presence of aromatic ring structure

presence of functional group such as sulfone, amide linkage, imide linkage, CF2 groups

halogen containing polymers mainly fluorine containing

presence of higher Secondary attraction (dipole dipole interaction), resins of ladder structure
(polymer containing series of ring structure linked to each neighboring rings by at least two bonds
are known ladder polymers)

heat resistance up to 650° C combined with perfect adhesion

durability under extreme temperature, long lasting corrosion protection, UV weathering resistance
 polyamides
Known as polyamide due to the presence of

Lorem
polyamides
Ipsum

Lorem
Aliphatic
Ipsum Lorem
Aromatic
Ipsum

Nylon 6, Nylon 6,6 Nomex, kevlar

Aromatic polyamide in comparison to aliphatic polyamide offers outstanding resistance to high

temperature and high tensile strength for use as fire retardant and can be useful as protective armor or
weight i.e. resistance to bullet piercing. That is bullet proof jackets are made from aromatic polyamides
Factors influencing heat resistance property
rigid intra-chain structure,

primary bond strength,

secondary bonding forces,

molecular weight and molecular weight distribution

resonance stabilization

stable end groups on the molecules

Primary bond strength
significant factor which influences heat resistance.

Bond dissociation energy of C-C is 350 KJ/mol, C=C is 610 KJ/mol and of aromatic systems it is even
higher.

As a result aromatic and heterocyclic rings are extensively used in the thermally stable polymers.

The key requirements for high temperature resistant polymers are higher softening point and resistance
to thermal oxidation.

The higher bond strength in inorganic polymers offer potential for good high resistance property.

Carbon-fluorine bonds have greater bond strength than carbon-hydrogen or carbon-carbon bonds;
therefore fluoro polymers are extremely resistant to oxidative degradation. They also have superb
resistance to chemical and solvent attack.
Secondary or Van der Waals bonding
offers additional strength and thermal stability to the polymer.

Dipole-dipole interactions and hydrogen bonding contribute towards molecular stability and affect the
cohesive energy density, which impacts on the stiffness, Tg, melting point and solubility.

Resonance stabilization, mechanism of bond cleavage, rigid intra-chain structure, molecular symmetry
(structural regularity), branching and cross-linking also affect the properties of a polymer.

Physical properties of polymer are also influenced by atomic interaction between chain atoms

The substitution of aromatic or heterocyclic ring in the polymer backbone leads to rigid structure.

The p-oriented aromatic polymers have lower solubility and processability compared to that of
m-oriented aromatic polymers.
Stability and processability of polymers
The chemical structure that makes a polymer thermally stable also makes it
difficult to form into useful items because of limited solubility and moldability

The high rigidity and regularity of the backbone of certain high performance
polymers results in high melting points, high crystallinity, low solubility and
strong chain-chain interaction.

How can we overcome it

Heat resistance and thermal stability of polymers
Ability of polymers to retain their useful properties at elevated temperature

Sets and upper limit to the temperature region in which polymeric material can
support mechanical load without undergoing change in shape

Loss of heat resistance consequence of physical processes such as transition of

glassy polymers to high elastic state or melting of crystalline polymers

Thermal stability sets upper limit to working temperature in case where stability
of polymers is governed by chemical resistance i.e. resistance to reaction that
leads to the degradation of polymers in inert or oxidizing media

Thermal stability is of great importance in processing and shaping of articles

 Determination of Heat resistance of polymers

❏ TG measurement widely used for evaluation of heat resistance of polymers

❏ Thermal decomposition of polymers accompanied by weight change

❏ TGA/DTA/DSC can be used for evaluation of heat resistance and thermal

stability of polymers
 Thermal Analysis
❑ Branch of materials science where properties of materials are studied with respect
to temperature while the temperature of sample in specified atmosphere is
programmed.
❑ provide qualitative or quantitative analytical information about material
❑ Upon heating a material undergoes certain physical and chemical changes
✔ Physical changes include phase changes such as melting, vaporization,
crystallization, etc.
✔ Chemical changes include chemical reactions to formation new products,
oxidation, decomposition, dehydration, chemisorption etc.
❑ These physical and chemical changes takes place over a wide range of temperature
 Why we need to study
Thermal Analysis
❑ Materials are used over a wide range of temperature conditions i.e. from extreme cold to
extreme hot conditions, in corrosive environment, variable humidity, and under load
(stress).

❑ therefore it is of extreme importance to characterize materials and their behavior over a

wide range of temperature to find out type of materials that are suitable for specific uses
and to determine the temperature range that they can withstand without undergoing
changes.

❑ This sort of information can be used to predict safe operating conditions i.e. the average
expected lifetime of materials when exposed to variable temperature conditions.
Rate of degradation of material if measured accurately helps in predicting properties of material
Classification
 What Properties Are Measured?

Property Technique Abbreviation

Mass Thermogravimetry TGA

Difference in Temp Differential Thermal Analysis DTA

Rate of flow of heat Differential Scanning Calorimetry DSC

Thermogravimetric Analysis (TGA)
 Thermogravimetric Analysis
(TGA)

❑The measured weight loss curve gives A B

Weight loss (%)

Horizontal portion
information on: (no change in weight)

✔ changes in sample composition

✔ thermal stability Curve BC
✔ kinetic parameters for chemical (represents change in weight)
C D
reactions in the sample
Temperature ( °C)
❑ If one wants to know the stoichiometry of the compound than the molecular weight of the
component being burnt off can be ascertained based on the weight percent lost and total
molecular weight of material
❑ In case of non stoichiometric material the curves can interpreted by measuring decomposition
temperature of different components
 Derivative thermogravimetry

❖ First derivative of mass change vs temperature curve

❖DTG curve presents information in more visually accessible form
❖Area under DTG curve is directly proportional to the mass change
 Mass change mechanism

All of these are kinetic processes i.e. there is a rate at which they occur
 Instrumentation
Modern instrumentation used for thermal analysis consist of following parts
 Block Diagram of TGA

Thermocouple Amplifier X-Y recorder

Ice Bath Thermobalance

Thermocouple located
immediately below sample Sample Environment
container used to measure control Equipment
Furnace
furnace temperature
Modern Thermobalance fully
Microprocessor computer controlled allows variety of
Sample crucible placed in
heating, cooling & isothermal
quartz or Pyrex house controlled modes and enables user to change
glassing located within the
furnace
power source sample atmospheric conditions
automatically
 Characteristic of Good Thermobalance

Should have facilities for the provision of variable heating rates to permit
heating in variety of controlled atmosphere and for heating in vacuum
Factors affecting Thermogravimetric Results
 Heating rate

❖When a substance is heated at a faster rate, the

rate and temperature of decomposition will be fast heating rate
higher than that obtained at a slower rate of low resolution
heating.
❖Eg.: for a 10% decomposition of polystyrene the
temperatures are 375 °C for a heating rate of 1°
C/min and 394 °C for a heating rate of 5°C/min mid heating rate
better resolution
❖At slower heating rate number of steps obtained
will be more, gives better information and
detection of intermediate compound by slow heating rate
thermogravimetry is very much dependent on good resolution
heating rate employed
 Furnace atmosphere

❖Nature of surrounding atmosphere have profound effect on temperature of decomposition stage

❖function of atmosphere is to remove gaseous products evolved during thermogravimetry in order to
ensure the nature of surrounding gas remains as constant as possible throughout experiment
❖By controlling the atmosphere with O2, N2 it may be possible to encourage or suppress oxidation
reactions thus controlling to some extent nature of thermal events.
Static air: Air from surrounding (atmosphere) flows through the
furnace
Dynamic air: compressed air from cylinder is passed through furnace at
measure flow rate
N2 (inert environment): oxygen free nitrogen gas used as an inert
environment

❖ For example decomposition of CaCO3 occur at much higher

temperature if CO2 rather than N2 gas is employed as surrounding
atmosphere
 Crucible geometry

❖Geometry of crucible can alter the shape of thermogravimetric curve

❖ sample holder ranges from flat plates to deep crucibles of various capacities
❖Materials used in their construction varies from glass, alumina, and ceramic
compositions to various metals and metallic alloys
❖ A flat plate shape crucible is preferred because the diffusion of evolved gases is easier
with flat shape i.e. rapid exchange of gases takes place between sample and the
surrounding atmosphere
❖Sample to be studied is placed in sample holder or crucible i.e. attached to the
weighing arm of microbalance

❖ crucible must have temperature at least 100K greater than temperature

range of experiment and must transfer heat uniformly to sample
 Sample characteristics

❖Weight, particle size, mode of preparation governs thermogravimetric results

❖Large volume of sample can often create deviation from linearity particularly in case of fast exothermic
reaction. A large volume of sample in crucible can impede the diffusion of evolved gases through the
bulk of solid crystals. For example evolution of CO during decomposition of CaC 2O4 to CaCO3.

❖Particle size: with particle size of smaller dimension the decomposition takes place at lower temperature
in comparison to greater particle size.

❖Previous history of the sample: For example TG studies shows that Mg(OH)2 prepared by precipitation
reaction has different temperature of decomposition that that of naturally occurring material. This
factor shows that one must be confirm about the source or method of formation of the sample

❖Compactness of sample: A compressed sample will decompose at higher temperature than loose sample.
 Interpretation of TGA Curves
TGA curves obtained may be classified into various types
Type (i) curve: sample doesn’t undergo any decomposition i.e. sample is stable
over the wide temperature range considered (no loss of volatile products).
Type (ii) curve: rapid initial mass-loss characteristic of desorption or drying.
Type (iii) curve: represent decomposition of the sample in a single stage. The
curve may be used to define the limits of stability of the reactant, to determine
the stoichiometry of the reaction.
Type (iv) curves: represent multi-stage decomposition with relatively stable
intermediates.
Type (v) curve: represent multi-stage decomposition, stable intermediates are
not formed and little information on all. It is important to check the effect of
heating rate on the resolution of such curves. At lower heating rates, type (v) may
resemble type (iv) curves more closely, while at high heating rates reverse may
happen leading to the loss of detail of the complex decomposition

Type (vi) curves: represent gain in mass as a result of reaction of the sample with the surrounding atmosphere. A typical example would be the oxidation of a metal
sample.

Type (vii) curves: are not often encountered. The product of an oxidation reaction decomposes again at higher temperatures 2 Ag + O2 🡪 Ag2O 🡪 2 Ag + O2
Applications
 Analysis of Inorganic and Organic Mixtures

● Consider a Binary mixture of two compounds AB and CD

having characteristic TG Curves different from each other as
shown in Fig. 1
● Decomposition of pure compound AB and CD occur at T1,
and temperature T2.
● TG curve of mixture AB and CD together is shown in Fig 2.
● For mixture plateaus (corresponding to the regions of
constant mass) commence at about the same temperature as Fig 1
in the TG Curves for the pure compounds.
● mass loss overall up to T1 is x mg and from T1 to T2 it is an
additional y mg.
● By measuring these two quantities x and y from the TG
curves we can determine the relative quantities of AB and CD
in the original binary mixture. Fig 2
 Study of polymers

✔ versatile application in polymer analysis

✔thermal stability of polymers
❖ The main conclusion drawn by TGA are: thermal stability, compositional analysis, and degradation
kinetics.
❖ The TG curve provides information about the decomposition of various polymers, which may be used
for identification purposes also assessment of thermal stability (each kind of polymer has particular
characteristic pattern)
❖ The basic route by which a polymer degrades can be categorized according to following mechanism:
✔main chain scission
✔side chain scission
✔elimination
✔depolymerisation
✔cross-linking
 Study of polymers

❖ TGA of Polyvinyl Chloride (PVC), High Density

Polyethylene (HDPE), Poly Methyl Methacrylate (PMMA),
Polytetrafluoroethylen (PTFE) and Polystyrene (PS) are
shown in fig.
❖ thermal stability of PVC is lower (250°C)and decomposition
takes place in two steps while PMMA, LDPE and PTFE start
degrading at higher temperatures 400 °C , 450 °C and 550 °C
respectively and in single steps.

❖ Qualitatively, the higher the decomposition temperature, the

more positive is the ∆G value at room temperature and the
greater the stability.
❖ This can predict the relative stability of the polymers.
 Thermal stability of PANI

✔Thermal stability up to 300°C

✔From the DTG traces, the presence of five-step

mass loss (for the ordered PANI) was noticed.

✔ due to the departure of moisture from the

sample.

✔Removal of the acid dopant and evolution of

other thermolabile components (such as small TGA and DTG of PANI synthesized using H2O2
and VOSO4H2O
oligomers)
Nagarajan etal., Adsorption Science & Technology 2017
✔And degradation of polymer took place
 Differential Thermal Analysis (DTA)

❖ term differential emphasize

important feature of the
technique
❖ Difference in temperature of
sample and reference is measured
ΔT= TS-TR
S - Sample
R- Reference
 Differential Thermal Analysis (DTA)

❖ technique for recording difference in temperature between sample and reference material
against either time or temperature as the two specimens are subjected to identical temperature
regimes in an environment heated or cooled at controlled rate
❖ In DTA both the test sample and inert reference material (usually αAl2O3) undergoes
controlled heating or cooling program which is usually linear w.r.t time
❖There is zero temperature difference between sample and reference when sample does not
undergo physical or chemical change
❖But if any reaction takes place than a temperature difference ΔT exist between sample and
reference
❖Thus in an endothermic process e.g when sample melts or dehydrates, sample is at lower
temperature than reference material. This condition is only transitory because on completion
of reaction the sample will again show zero temperature difference compare with reference
 Features of DTA Apparatus

❖ Sample holder assembly:

✔consist of thermocouple for each sample and reference surrounded by a block to ensure an even
heat distribution
✔Sample is contained in small crucibles made up of materials such as silica, alumina, platinum
etc.
✔Thermocouple should not be placed in direct contact with sample to avoid contamination and
degradation

❖Furnace and temperature programmer

✔Essential requirement of furnace is that it should provide a stable and efficiently large hot zone
and must be able to respond rapidly to commands from temperature program
✔Temperature programmer is essential in order to obtain constant heating rate.
 Block Diagram of DTA

Amplifier X-Y recorder

Thermocouple 1 Thermocouple 2 Amplifier

Ice Box
Reference Sample Environment
Furnace control Equipment

Microprocessor controlled
power source
 Representation of DTA

✔Plot is made of ΔT against temperature or time if

heating or cooling is linear w.r.t time
✔ An idealized DTA curve is shown in figure
✔ shape and size of peak gives a large amount of
information about nature of test sample
✔Sharp endothermic peak signifies change in
crystallinity or fusion process while broad
endothermic peaks arise from dehydration reactions
✔ physical changes usually result as endothermic curves
whereas chemical reactions particularly those of an
oxidative nature are predominantly exothermic
Factors affecting DTA Curve
 Factors affecting DTA Curve

❖Let us assume that the samples of

different masses are heated at different
heating rates.

❖The peak temperature affected by

heating rate and sample mass, i.e., with
increasing heating rate, the peak
position shifts to higher temperature.
Schematic of DTA curves obtained at different heating rates and
❖However, the onset of peak is not different masses.
affected by any margin.
 Characterization of polymers

❖ Illustrate various types of transitions that may be encountered during heating of a polymer
 Qualitative analysis of polymer mixtures

❖Fig shows DTA of a mixture of polymers

❖Each peak give characteristic melting point of one of the polymers
❖PTFE has an additional low temperature peak due to crystalline transition

HIPPE – High pressure low density polyethylene

LPPE-Low pressure high density polyethylene
PP- polypropylene
POM- polyoxy methylene
 TG/DTA

❖For many problems, it is advantageous to use both DTA and TG, because DTA events can be classified into
those which do or do not involve mass change.

❖For example: At the temperature range 500 to 700°C there is a mass change in TG curve, which corresponds to
dehydration of Al4(Si4O10)(OH)8, and this dehydration shows up on DTA curve as an endotherm.
❖At 950 to 980°C, a second DTA effects occurs but this effect not occurs on the TG curve, because this event
corresponds to recrystallization of the dehydrated kaolin. This recrystallization process is exothermic.

❖TG-DTA modes can be used to determine the following:-

✔Melting points
✔Glass transition temperatures
✔Crystallinity
✔Moisture/ volatile content
✔Thermal and oxidative stability
✔Purity
✔Transformation temperatures TG & DTA curves for Al4(Si4O10)(OH)8
 Differential Scanning Calorimetry (DSC)

❖ One of the most common thermo-analytical technique

❖ developed by E.S. Watson and M.J. O'Neill in the year 1962 and got commercialized in 1963 at the Pittsburgh
Conference on Analytical Chemistry and Applied Spectroscopy .

❖ DSC provides useful information about the thermal transitions (transitions associated with the change in
temperature ) occurring in a sample.

❖ very informative tool for studying the phase changes taking place in an amorphous material as a function of
temperature.

❖Basic phase changes occurring in an amorphous material upon heating are:

✔Glass transition: reversible phase change involving change in the structure of an amorphous material i.e. from a
relatively hard state (glassy) to a rubbery state. Temperature at which glass transition occurs is known as Tg

✔Crystallization: irreversible phase change involves the ordering of the disordered structure through nucleation and
growth processes, thereby forming crystalline structure.
 Differential Scanning Calorimetry (DSC)

✔ Melting: phase change in which the crystalline lattice breaks into a disordered state (solid to
liquid transition → “fusion”).
✔single step endothermic process, unlike crystallization which is a two-step, exothermic process
(nucleation and growth).
❖ In DSC energy necessary to establish a zero temperature difference between the sample and
reference material is measured as a function of temperature or time
❖ thus when endothermic transition occurs the energy absorbed by the sample is compensated
by an increased energy input to the sample in order to maintain a zero temperature difference
❖Since this energy input is equivalent in magnitude to the energy absorbed in transition direct
calorimetric measurement of energy of transition is obtained from this balancing energy
 Differential Scanning Calorimetry (DSC)
✔In DSC plot the abscissa indicates the transition
temperature and peak area measures the total
energy transfer to or from the sample.
❖Thus DSC measures amount of heat required to
raise the temperature of sample, w.r.t reference, as
a function of temperature i.e. provides
information about the exothermic and
endothermic processes occurring in sample by
measuring the amount of heat absorbed or
released during heating or cooling of the sample
❖provides information about the glass transition
temperature, crystallization and melting
temperatures, heat of phase changes such as
fusion and melting, heat capacity, etc.
 Differential Scanning Calorimetry (DSC)

b o ut
us a o f
s
Tell kind
the tion e
re a c p l a c
i n g
tak

DSC curve for polyethylene terephthalate

 Instrumentation

❖ consist of identical components to that of DTA except that it contains individual heaters located as close as possible
to the sample and reference vessels

❖A metallic disc (made of constantan alloy) is the primary means of heat transfer to and from the sample and
reference

❖Sample contained in a metal pan and the reference an empty pan sits on raised platform in constantan disc.

❖As heat is transferred through the disc the differential heat flow to the sample and reference is measured by
thermocouple formed by the junction of constantan disc and chromel wafers which cover the underside of platform

❖These thermocouples are connected in series and measures differential heat flow

❖Chromel and alumel wires attached to the chromel wafers form thermocouple which directly measures sample
temperature

❖Purge gas is admitted to the sample character through an orifice in the heating block
 Block Diagram

Amplifier X-Y recorder

Ice
Thermocouple 1 Thermocouple 2 Amplifier
Box
Transducer
Environment
control Reference Sample Secondary
Equipment Furnace power
applied to
Secondary sample or
Microprocessor controlled power reference
power source source to make
ΔT=0
 Effect of heating rate on DSC curve

❖ effect of heating rate on fusion

of indium is shown in fig
❖Broader and deeper peak at high
heating rate
❖Efficacy of extrapolated onset
temperature compare to peak
temperature is evident
 Effect of sample weight on DSC curve

❖ sample weight also affects the thermal

properties significantly. Figure shows
the typical DSC curves taken at a
constant heating rate for different mass
of the samples.
❖It could be clearly seen that the onset of
melting, peak point of melting and
enthalpy undergo small variations
when the sample mass is changed.
 Glass Transition

✔downward shift in the baseline with increase in

temperature (or time)
✔ This shift in baseline does not occur instantly,
rather it takes place over a temperature range.
✔ Due to this the determination of the Tg
becomes difficult and generally it is taken out to
be in the middle of the transition.
✔ It is an endothermic transition, i.e., it absorbs
heat.
✔Hence the heat capacity of the material
increases during glass transition
 Differential Scanning Calorimetry (DSC)

Crystallization:
✔ exothermic event, in which the material releases heat and forms a
low energy (stable) ordered structure.
✔enthalpy of crystallization can be obtained by calculating the area
under the peak, and dividing it by the heating rate.
✔ Further the percentage crystallinity at a particular degree of
conversion can also be calculated.
✔Along with the enthalpy of crystallization and the crystallization
temperature, DSC can be used to determine whether the amorphous
material crystallizes in a single step or it takes multiple steps to
crystallize.
Melting: As heating of a material is continued beyond crystallization,
eventually it melts. Melting is an endothermic process that
transforms a solid material into liquid.
 advantages

✔The advantages of DSC technique can be summarized as

✔It is a fast technique, i.e., it takes a small time to perform one run
✔Different kind of samples such as solid, liquid, powders, thin films can be tested in a
variety of environments (air, vacuum, inert gas, etc
✔A wide range of temperature can be used to analyze the phase transitions in a material,
and quantitative analysis of these transitions can be done easily using softwares.
✔ The applicability of DSC can be extended to a wide variety of materials that includes the
pharmaceutical and drug industry, polymers, liquid crystals, and food science.
✔DSC can also be used to determine the oxidative stability of a material.
 Difference

DTA DSC
Temperature of sample is compared with that of a Heat energy is supplied at varying rate to the sample or
reference material as both are heated at uniform rate reference so as to keep their temperature identical

A DTA output plots T = (TR – TS) vs temperature of the A DSC output plots heat energy supplied to the sample
furnace (T0) (or reference) vs identical temperature of two

Provides calorimetric accuracy in temperature range of Provides calorimetric accuracy in temperature range of
-190 °C to 1600 °C -170 °C to 750 °C
Area under peak in ordinary DTA is complex function of Area under peak can be directly related to enthalpy
sample geometry, heat capacity and heat losses change occurring

No secondary power source is required secondary power source is required for supplying heat
to either sample or reference to keep temperature of
sample or reference identical