Defining Polymers: Little to Big

Behavior of polymers represents a continuation of the

behavior of smaller molecules at the limit of very high
molecular weight. For example:
General formula

Introduction to Physical Polymer Science by Sperling 6

Defining Polymers: Little to Big
Properties increase dramatically with increasing the number
of repeat units, also called monomers.

A typical polymer contains tens of thousand monomers.

Therefore, polymers are also classified as macromolecules.

Introduction to Physical Polymer Science by Sperling 9

• Some polymers are flexible. Others are very stiff.

• Just think of the many types of plastics: The material in a flexible soda bottle is
very different from that in a rigid pipe made from polyvinyl chloride (PVC).

• Sometimes materials scientists add other things to their polymers to make

them flexible. They’re called plasticizers.

• These take up space between individual polymer chains. Think of them as

acting like a molecular-scale lubricant. They let the individual chains slide
across each other more easily.

• Polymers don’t have a definite length.

• They usually don’t form crystals, either.

• Finally, they usually don’t have a definite melting point, at which they
immediately switch from a solid into a pool of liquid. Instead, plastics and
other materials made from polymers tend to soften gradually as they heat up.

https://www.snexplores.org/article/explainer-what-are-polymers
11
Defining Polymers: Applications
A vast number of applications are linked with polymers
used in our life:
1. In aircraft, aerospace, automotive, buildings, and
sports goods
2. Printed circuit board substrates
3. 3D printed plastics
4. Packaging materials
5. Bulletproof materials
6. Organic polymer flocculants for water purification
7. Green chemicals: Polymers and biopolymers
8. Polymeric biomolecules
12
Defining Polymers: Applications
Sports Goods

https://www.arkema.com/en/products/solutions/sports-equipment/

http://www.worldofchemicals.c
http://www.bpf.co.uk/pvc-and-additives.aspx

om/446/chemistry-
articles/chemical-makeup-of-
sports-equipments.html

16
Classification: Natural Vs Synthetic
Natural Polymers
Macromolecules found in nature.
e.g. DNA, RNA, Wood, Potatoes,
Proteins, etc.
What is this material coming out
from the tree?

Synthetic Polymers
These polymers are derived from
petroleum, and further
polymerized.
e.g. PE, Nylone, PS, etc.

20
Classification: Thermal Behavior
Based on thermal properties, two major classifications:
Thermoplastics
Polymers which can be heat-softened in order to
process into a desired form.
Thermosets
Polymer in which individual chains are chemically
crosslinked by covalent bonds during
polymerization or by subsequent steps after
polymerization. Once formed, they cannot be
melted, they degrade upon heating.

21
Classification: Chain Size
Based on the number of monomer units, chain size is
defined.
Dimers: Containing only two monomers
Trimers: Containing three monomers
Tetramers: containing four monomers
Oligomers: containing 5-100 monomer units. It is
in between a polymer and monomer.
Macromolecule: Containing 1000s of monomer
units.

22
Classification: Structural Arrangement
These are usually the copolymers with different
structural arrangements.
Random Copolymers
Alternating Copolymers
Block Copolymers
Graft Copolymers

26
Applications of biopolymers including pharmacy, medicine, biomedical,
packaging, food, cosmetic, and agriculture.
Mehrpouya and Vahabi, 2023 34
Plastics can also be separated into thermoplastics
and thermosets.
A thermoplastic material is a high-molecular-weight
polymer that is not cross-linked.
It can exist in either a linear or a branched structure.
Upon heating, thermoplastics soften and melt, which
allows them to be shaped using plastics processing
equipment.

Handbook of Plastics Technologies: The Complete Guide to Properties and

Performance, 1st Edition By Charles A. Harper
5
A thermoset has all of the chains tied together with
covalent bonds in a three dimensional network (cross-
linked).
Thermoset materials will not flow once cross-linked,
but a thermoplastic material can be reprocessed
simply by heating it to the appropriate temperature.
The different types of structures are shown in Fig.
1.3.

Handbook of Plastics Technologies: The Complete Guide to Properties and

Performance, 1st Edition By Charles A. Harper
6
Figure 1.3 Linear, branched, and cross-linked polymer
structures.

Handbook of Plastics Technologies: The Complete Guide to Properties and

Performance, 1st Edition By Charles A. Harper
7
Polymer science and polymerization methods toward hybrid materials
https://doi.org/10.1016/b978-0-12-813294-4.00004-2 8
Defining Polymers: Classification
Let’s refer back to our main classification
of polymers from last lecture Processing

Natur. Vs Chain size

Synth.
Amorp. Vs Structure
Classification
Cryst.
Structural
Polymerization arrangement
Mechanism
Branching

Tacticity
13
Mechanism: Addition Polymerization
Chain Initiation
Initiation starts by the attack on the monomer molecule by
a free radical, a cation, or an anion; accordingly, the chain
polymerization is called free radical, cationic, or anionic
polymerization.
Free radical
A reactive substance having an unpaired electron is usually
formed by the decomposition of a relatively unstable
material called initiator.
Common example: Benzoyl peroxide

17
Mechanism: Addition Polymerization
Chain Initiation (cont’d)

Chain Propagation
Subsequently, monomer radicals attack on further
monomers and start forming a long chain.

18
Mechanism: Condensation Polymerization

The monomers that are involved in condensation

polymerization are not the same as those in addition
polymerization.
Condensation polymerization monomers have two
main characteristics:
1. Instead of double bonds, these monomers have
functional groups (alcohol, amine, carboxylic acid
groups)
2. Each monomer has at least two reactive sites, which
usually means two functional groups

22
Polymerization and Functionality
Condensation polymerization may occur only if the
monomers involved in the reaction have the proper
functionalities.
Definition of Degree of Functionality
The degree of functionality of a molecule is the number
of sites it has for bonding to other molecules under the
given conditions of the polymerization reaction.
• A monomer with functionality 2 is called bifunctional
monomer. It can link to two other molecules
• Styrene has functionality of 2.
• Minimum requirement for polymerization is 2.
35
Polymer Structure
Polymer chains have three basic properties.
1. The molecular weight and molecular weight distribution
of the molecules
2. Chain conformation in space: The term conformation
refers to the different arrangements of atoms and
substituents of polymer chains brought about by
rotations about single bonds. Examples include fully
extended planar zigzag, helical, folded chain, and
random coils.
3. Chain Configuration: It refers to the organization of
atoms along the chain. Sometimes, term “microstructure”
is used instead of configuration. Configuration involves
isomerism.
47
Isomerism: Structural Isomerism
We just label the C-atoms of the monomer in order:

Now let’s break one of the bonds in one of the double bonds and
leave the C-atoms still attached by a single bong. This leaves on
“unshared” electron on each of the C-atoms involved.

Now let’s do the same for the other double bond:

Obviously, we can now connect the middle dots to make a new

double bond, leaving unshared electrons “hanging-out” on C-atoms
1 and 4.

59
Isomerism: Structural Isomerism
Two such units can become attached through their C-atoms,
1 and 4:

This can be repeated, building up a chain with 1,4 linkages.

Of course, this step-by-step breaking and reforming of
bonds is not what happens in a real reaction. This example
is just to demonstrate where 1,4 part of the nomenclature
comes from.
It should also now be clear that we can add units by just
“breaking” (i.e. reacting) one of the double bongs (1,2
and 3,4) and incorporating those units into the chain.

60
Isomerism: Structural Isomerism
The various possibilities for the
polymerization of isoprene are
shown. There is still one thing we
haven’t explained however. There
are two types of 1,4 units, cis
and trans .
As in organic chemistry, it refers
to the arrangement of carbon
toms around the double bond.
• cis – carbon-carbon chain
extensions of the same
side
• trans – carbon-carbon
chain extensions of
opposite sides
61
Molecular Forces in Polymers
The structure that polymer chains take in the various
states of matter but particularly in their solid form,
depends on a number of different factors:
1. Bonding and the forces between the chains
2. Polymer conformations- ordered or
disordered
3. Stacking or arrangement of chains into
crystalline domains
4. The morphology of polymer crystals.
Let’s start with the first factor for now, and we will
come back to other three later in the course.
62
Molecular Forces in Polymers
Bonded Forces
When we talk about bonding forces, we are speaking
strictly about intramolecular forces, that is strong
covalent bonds:

In this case, we looking at a simple polymer backbone.

The bond lengths, d, and the bond angles, ϴ, do not
vary by very much.
Typically:

63
Molecular Forces in Polymers
4. Coulombic Interactions
These forces are a result of interactions between charges either
present on the polymer chain itself or in solution. Networks
formed by these interactions are often referred to as ionomers.
e.g. Poly(acryl amide) crosslinked with metal ions.

66
Polymerization Processes
Two broad classifications in polymerization processes:
1. Homogeneous Processes
All the reactants including monomers, initiators
and solvents are mutually soluble and compatible
with the resulting polymer.
2. Heterogeneous Processes
In these processes, the catalyst, monomer, and
the polymer product are mutually insoluble.
Various techniques of polymerizations reside in
these two broad classifications.
2
Polymerization Techniques
Following are the polymerization techniques which
can be carried out in either homogeneous or
heterogeneous systems.
1. Bulk (mass) polymerization
2. Solution Polymerization
3. Suspension (bead or pearl) Polymerization
4. Emulsion Polymerization
We will discuss a few more techniques as well.

3
1. Bulk (Mass) Polymerization
General Description
Carried out to high conversion Monomer
Free radical kinetics apply +
Used for ethylene, styrene, methyl methacrylate Initiator
Homogeneous
Polymer remains dissolved in monomer. Ex:
PMMA in MMA
(When a solution of methyl methacrylate and thermal initiator contacts
a polymer seed (a small piece of poly(methyl methacrylate), a viscous
region is formed in which the polymerization rate is faster than in the
bulk solution)

Heterogeneous
Precipitation pzn. Ex: Polyacrylonitrile, PVC
Requirement for Continuous
Operation Advantage
Keep low conversion: separate and Minimum contamination
recycle the unreacted monomers. of the products
4
1. Bulk (Mass) Polymerization
Trommsdorff Effect
 fkd  I  
1/2
Sometimes called auto-acceleration
effect or gel effect. Rp  k p  M   
 kt 
As the polymer chains are formed in
1/2
the reactor, the viscosity increases to  fkd 
several orders of magnitude. R p k p  
Increase in viscosity further produces
 kt 
patches of polymer chains, resulting in
decreased termination rate. MMA in benzene

When very slow termination is

happening, that means propagation is
very fast, leading to large molecular
weight. MMA with BPO in
Benzene at 50°C
Temperature increases rapidly even in
isothermal pzn reaction. (Isothermal frontal
polymerization is a directional polymerization that utilizes the
Norish-Trommsdorff (gel) effect to produce optical gradient
materials) 7
1. Bulk (Mass) Polymerization
Advantages Disadvantages
 Obtain purest possible  Difficult to control
polymers
 Reaction has to be run
 Conveniently cast to slowly
shape
 Cannot get high rate
 Obtain high polymer and high molecular
yield per reactor weight at the same
volume time
 Difficult to remove last
traces of unreacted
monomer
11
2. Solution Polymerization
The conducting of polymerization reactions in a solvent is an
effective way to disperse heat; in addition, solutions are much
easier to stir than bulk polymerizations.
Solvents must be carefully chosen, however, so that they do not
undergo chain-transfer reactions with the polymer.
Because it can be difficult to remove solvent from the finished
viscous polymer, solution polymerization lends itself best to
polymers that are used commercially in solution form, such as
certain types of adhesives and surface coatings.
Polymerization of gaseous monomers is also conducted with
the use of solvents, as in the production of polyethylene.

12
2. Solution Polymerization
Monomer is dissolved into an
inert solvent/inhibitor. Check the
solvent now
Components
Monomer
Initiator
CTA
Inert solvent (for
controlling heat MMA with BPO in Benzene
at 50°C
transfer)

Homogeneous
If everything is dissolved in the solvent
Heterogeneous
If the polymer precipitate immediately- insoluble
13
2. Solution Polymerization
Effect of solvent solubility on the molecular weight of
polyurethane produced by solution method
Viscosity
Precipitation of polymer
Solvent of polymer
out of the solution
solution

Xylene 0.06 Precipitates immediately

Chlorobenzene 0.17 Precipitates immediately

Nitrobenzene 0.36 Precipitates within 0.5 hr

Polymer remains dissolved in

Dimethyl sulfoxide 0.69
solution

Viscosity of polymer  MWpolymer

 High viscosity = high molecular weight !
16
2. Solution Polymerization
Advantages Disadvantages
 Solvent acts as a diluent  Solvent may not be 100%
and increases heat transfer inert (can act as Chain
transfer agent, CTA)
 Reduces viscosity, making
 Chain transfer to solvent
easier processing
leading to low molecular
 Thermal control is easier weight
compared to that in bulk  Solvent waste –
polymerization Environmental effects
 Additional solvent
separation and recovery
required
 Final polymer contains
traces of solvent and 17
3. Suspension Polymerization
Suspension polymerization is a heterogeneous radical
polymerization process that uses mechanical agitation to mix a
monomer or mixture of monomers in a liquid phase, such as
water, while the monomers polymerize, forming spheres of the
polymer.
From: Nanocomposite Structures and Dispersions (Second
Edition), 2019
Suspension polymerization involves polymerization in an
aqueous system with monomer as a dispersed phase, resulting
in polymer as a dispersed solid phase. The process differs from
the emulsion polymerization in terms of the location of’the
initiator and the kinetics. In typical suspension
polymerization the initiator is dissolved in the monomer phase,
and the kinetics is the same as that of bulk polymerization.
18
3. Suspension Polymerization
A typical recipe for suspension polymerization is given in Table
1.5. The method is used commercially to prepare hard,
glassy vinyl polymers such as PS, poly(methy1 methacrylate),
poly(viny1 chloride), poly(vinylidine chloride),
and polyacrylonitrile.
Table 1.5. Recipe for suspension polymerization.
Empty Cell Parts per 100 parts of monomer
Methyl
Components methacrylate Vinyl chloride
Peroxide initiator ~0.5 0.1–0.5
Water ~350 150–350
Stabilizersa 0.01–1 0.01–1

aTypical stabilizers include methyl cellulose, gelatin, poly(viny1 alcohol),

and sodium polyacrylate.
19
3. Suspension Polymerization
Advantages Disadvantages
 Cannot be used for polymers
whose Tg < Tpzn, or otherwise,
aggregation will occur.
 It is easy to control the heat of
 Continuous agitation is required.
polymerization.
 Contamination by stabilizer is
 Suspension or the resulting possible.
granular polymer could be  Washing, drying, and
directly reusable. compacting may be required.
 Easy heat removal due to the  Must separate and purify
high heat capacity of water polymer, or accept the
contaminated product.
 Polymer yield is finely divided,
stable latexes and dispersions to
be used directly in coatings,
paints, and adhesives.
24
4. Emulsion Polymerization
Emulsion polymerization is a process where a monomer is emulsified into an
aqueous solution with a surfactant, forming droplets that polymerize to create
polymer particles of controlled size, typically ranging from 50 to 500 nm.
(AI generated definition based on: Journal of Molecular Liquids, 2022)

During emulsion polymerization processes by the conventional method, the

instability of the colloidal particles induces a decrease in the rate of
polymerization, which consequently affects the yield and causes an increase of
particle size (Nagatomo et al., 2016). Furthermore, the final polymer may
exhibit impurities due to the difficulty of separating the initiator from the
polymer chain (Bhanvase and Sonawane, 2014).

The use of chemical activation methods in the reaction medium have been
proposed to minimize these problems by acting as an initiator to improve rate
of polymerization. Among these, it should be highlighted processes from
energy sources such as visible light, ultraviolet, ultrasonic energy and radiating
microwave.

25
4. Emulsion Polymerization: Stages
There are 3 stages which are encountered during
emulsion polymerization:

Stage 1: low conversion is achieved

Stage 2: Medium level conversion
Stage 3: High Conversion

28
4. Emulsion Polymerization
Advantages Disadvantages
 Ease of control:  Difficult to obtain pure polymer.
ηreaction mass << ηtrue solution of The tremendous surface area of
comparable polymer the tiny particles provides plenty
of room for adsorbed impurities
concentration.
including water attached by
 High pzn rate and high avg. residual soap, traces of which
chain length by using high soap cause issues during processing.
and low initiator.  Considerable technology required
 The latex produced can be to recover solid polymer.
valuable or can be compounded  The water in the reaction mass
through master batching. lowers the yield per reactive
 Small size of latex particles volume.
allows the attainment of low  Can’t be used for condensation
residual monomer levels. polymers, or for ionic or Z-N pzns.

34
5. Interfacial Polymerization
Interfacial polymerization is a type of condensation polymerization in which
polymerization occurs at an interface between an aqueous solution containing one
monomer and an organic solution containing a second monomer.
From: Stimuli Responsive Polymeric Nanocarriers for Drug Delivery
Applications, Volume 1, 2018

Different from the traditional polymerization in aqueous solution, the interfacial

polymerization is carried out in an organic and aqueous immiscible two-phase
system, which initiates the polymerization reaction with fewer nucleation sites.
Interfacial polymerization is a template less method, in which dopant anions and
monomer are used at the liquid/liquid interface to facilitate the aggregation of
monomer-anions.

It can synthesize conducting polymers films with high specific surface area
or electrochemical properties.
https://www.sciencedirect.com/science/article/abs/pii/S2352152X
2201012X
35
Polymer Characterization
1. Polymer architecture
 Atomic force microscopy, e.g., crystal structures.
 Electron microscopy.
 X-ray diffraction, e.g., crystal structures.
 Optical microscopy.
2. Determination of MW by dilute solution viscosity
 Dilute solution viscosity. Dilute solution polymers typically have a dilute solution viscosity greater
than 0.1 dL/g. Dilute solution viscosity measurements are used for initial characterization.
 Viscometry.
 Gel permeation chromatography.
3. Chain structure
 NMR spectroscopy.
 IR spectroscopy is a practical method to obtain data from thin film specimens.

2
Polymer Characterization
4. Thermal transition
 Thermal microscopy.
 Differential scanning calorimetry. DSC is used to obtain the
glass transition temperature, but not the melt points, for
amorphous polymers. Melt points are created in the crystalline
segment of semicrystalline polymers.
5. Polymer degradation
Differential thermal analysis.
Thermogravimetric analysis (TGA).
Chemical hydrolysis and viscometry.
3
Mechanical Behavior
• A number of mechanical properties evaluation tests can be performed in user-defined
methods or following standards such as American Standards for Testing Materials
(ASTM) or similar.
• In broad spectrum, the mechanical properties evaluation is carried out in the following
fashion:
A. Stress-strain Experiments
B. Creep Experiments
C. Stress Relaxation Experiments
D. Dynamic Mechanical Experiments
E. Impact Experiments

4
A. Stress-Strain Experiments
• Most widely used but least understood
behavior of polymers in terms of
interpretation.
1. Sample is pulled (deformed) at a
constant rate.
2. Stress required for this deformation is 
E
measured simultaneously. 
• Different Results:
1. Hard materials
2. Soft materials The utility of stress-strain tests for design
3. Ductile with polymeric materials can be greatly
4. Brittle enhanced if the tests are performed over a
5. Yielding wide range of temperatures and strain rates.
6. Cold drawing

5
D. Dynamic Mechanical Experiments
• A dynamic (periodic, sinusoidal) stress
is applied, and response is measured
in the same way.
• A number of tests can be performed
for dynamic mechanical properties.
• Evaluated properties: Elastic and viscous
response

E /  Elastic Modulus
E / /  Viscous Modulus
E //
tan   /  Dissipation Factor
E

8
Stress-Strain Behavior of Polymers
• Testing Standard: ASTM D638
• Sample: Rectangle or dog-bone
• Failure: Encouraged in thin section
• Measurement: Through a gauge

12
Elastic Stress-Strain Relations
• Under small stress, materials respond elastically:
1. Strain produced is reversible with stress
2. Magnitude of strain is directly or linearly proportional to the magnitude of stress
that exhibits Hookean behavior.
• Hook’s law: linear relation between stress and strain

• Stress can act differently and the constant is a function of how the stress is applied.
• Two most common types of stresses are shear (in-plane), and tensile (normal to the plane). Normal
stress can be tensile or compressive.

14
Elastic Stress-Strain Relations
• Let’s consider a shear stress, τ is applied producing shear strain, γ:
x

h

For small strains;  G  Shear Modulus


• Deformation due to pure shear does not result in change in volume, but produces a
change in shape.
• For normal stress, let’s assume the shape remains unchanged but the volume changes. It is
called pure dilation. Consider the case of compression, e.g.

V
Dilation Strain=D=
V

 K  Bulk Modulus
D

16
Elastic Stress-Strain Relations

17
Deformation in Solid Polymers

20
 Morphological Properties
• Morphology of the biocomposites investigated by using
scanning electron microscope(SEM).
• The samples were mounted onto SEM holder using double
sided electrically conducting carbon adhesive tapes to
prevent surface charge on the specimens when exposed to
the electron beam.
• The fracture surfaces of samples obtained from tensile and
impact testing were sputter with gold prior to their
morphological observation.
• The SEM micrographs were obtained under conventional
secondary electron imaging conditions with an acceleration
voltage of 5 kV.

2
 Energy Dispersive X-Ray Analysis (EDX)
• Energy Dispersive X-Ray Analysis (EDX), referred to as EDS or EDAX, is an
x-ray technique used to identify the elemental composition of materials.
Applications include materials and product research, troubleshooting,
deformulation, and more.
• EDX systems are attachments to Electron Microscopy instruments
(Scanning Electron Microscopy (SEM) or Transmission Electron
Microscopy (TEM)) instruments where the imaging capability of the
microscope identifies the specimen of interest.
• The data generated by EDX analysis consist of spectra showing peaks
corresponding to the elements making up the true composition of the
sample being analyzed.
• Elemental mapping of a sample and image analysis are also possible.

sa
 Structural properties
• The structure of materials affects their properties and
service behaviour.
• Based on their structure, materials can be classified as
either crystalline or non-crystalline (or amorphous)'.
• Crystalline structures are organized structures in which
atoms and molecules of solids arrange themselves in a
regular and repeating manner that is called lattice.
• On the other hand, amorphous structures have some level
of local order relative to their neighbours, but globally, they
do not have an ordered structure like crystalline materials.

3)
 X-ray Diffraction(XRD)
• X-Ray Diffraction (XRD) provides important solid-state
structural information for polymers and composites.
• Useful XRD analysis data is obtained from crystalline,
semi-crystalline, amorphous polymeric and composite
materials.

% crystallinity in XRD
is calculated using
the formula:
% Crystallinity = (total
area of crystalline
peaks) x 100 / (total
area of all peaks)

32
X-ray Diffraction Analysis of Polymers
By Simon Welzmiller 03.11.2021 33
The Amorphous State
• Definition
• “a” means without; “morph” shape or form.
• That means, amorphous solid is a solid without a particular form inside.
• An amorphous solid or non-crystalline solid is a solid that lacks long-range order
that is characteristic of a crystal (sometimes called glassy polymers).
• Completely amorphous polymers such as atactic polystyrene, exist as long,
randomly coiled, interpenetrating chains that are capable of forming stable, flow-
restricting entanglements at sufficiently high molecular weight.

34
Amorphous State: Chain Movement
• The state of polymer chains inside an
amorphous polymer resemble a bowl of
spaghetti.
• The random chain arrangements in
amorphous or molten polymer create extra
spaces, called free volume. The free volume
essentially consists of holes in the matrix.

The complete movement of a chain cannot remain

unaffected by the surrounding chains since considerable
entanglements exist in the melt, and any motion will be
retarded by other chains.
35
Amorphous State: Chain Movement
• Bueche Theory
• The polymer molecule may drag along several others during flow, causing energy
dissipation due to friction. The length of polymer chain in the sample would thus be
expected to play a significant role in determining the friction and resistance to flow.
• The effect of chain length on melt viscosity is measured at low shear rates (The
Newtonian Flow).
• Fox & Flory in 1951 showed the dependence of melt viscosity on chain length “v” defined
as the weight average number of chain atoms in the polymer molecule.

36
Crystalline State of Polymers
• Three methods of crystallization of polymers:
1. Solidification from melt
2. By stretching
3. From solution

Model of a spherulite
45
Crystallinity in Polymers: Density
• Polymers crystallized from melt are seldom fully crystalline.
• Due to extensive entanglements, impossible to prepare 100% crystallinity during
solidification.
• The degree of crystallinity is of considerable importance as it influences properties and hence
applications of polymers.
• Usually, crystalline region has higher density compared to amorphous regions
(ρdiff ~ 20%). This provides a basis for determining degree of crystallinity of a
polymer using density method.

49
Bulk Polymer Structure
• Most polymers are partially crystalline.
• Direct and quick evidence of crystallinity from XRD.
• Sharp peaks correspond to crystallites (ordered regions) whereas diffuse features correspond to
liquid like regions (amorphous or not ordered).
• XRD in conjunction with electron microscopy have shown that crystallites are made up
of lamellae, which are built-up of folded chains.

52
Bulk Polymer Structure: Spherulites
• The most prominent entity in a polymer crystallized from melt is the spherulite.
• Spherulites are aggregates of lamellar crystallites, and the lamellar structure
persists throughout the body of spherulites.

54
 Fourier Transform Infrared Spectroscopy (FT-IR)
• The aim of using FT-IR is to measure the change of surface
composition(Functional gr.) of the fibres after treatment.

g6

Article in Journal of Applied Polymer Science · January 2018

DOI: 10.1002/app.46194
 Thermal properties (TGA-DSC,DMA,TMA)
Thermo gravimetric analysis (TGA)
• Thermal gravimetric analysis(TGA)-It measure the weight
and hence mass of a sample as function of temperature. The
acronym TG was previously used. Nowadays TGA is preferred
in order to avoid confusion with Tg, the glass transition
temperature.
TGA allow you to-
• Detect changes in sample mass (gain or loss)
• Determine stepwise changes in mass, usually as a
percentage of the initial sample mass,
• Determine temperatures that characterize a step in the mass
loss or gain curve.

G8
Thermal Transitions in Polymers
• Transition means change of state induced by changing the temperature or pressure.
• There are two major transitions:
• Glass transition temperature, Tg
• Melting Temperature, Tm
• Broadly, thermal transitions are classified into two classes based on the first law of thermodynamics:
• First order Transitions
• Second order transitions
~

59
Differential Scanning Calorimetry
• One of the most common type of machines used for crystallization from melt.
• In this method, difference in the amount of heat required to increase the temperature of a sample and
a reference is measured as a function of temperature.
• The reference must have a well-defined heat capacity over the temperature range to be scanned.

Experimental

Q
Xc 
H f

Theoretical for
100% crystalline
material

66
 Differential Scanning Calorimetry (DSC)
• In DSC, the heat flow in and out of a sample and a reference
material is measured as a function of temperature as the
sample is heated, cooled or held isothermally at constant
temperature.
• The measured signal is the energy absorbed by or released by
the sample in milli watts.

DSC allows you to-

↑

• Detect endothermic and exothermic effects

• Determine peak areas (transition and reaction enthalpies)
• Determine temperatures that characterize a peak or other
effects
• Measure specific heat capacity
• Tg
67
 DMA
• Dynamic Mechanical Analysis,
otherwise known as DMA, is a
technique where a small
deformation is applied to a sample
in a cyclic manner.
• This allows the materials response
to stress, temperature, frequency
and other values to be studied.
• The term is also used to refer to the
analyzer that performs the test.
DMA is also called DMTA for
Dynamic Mechanical Thermal
78
Analysis.
 Dynamic Mechanical Analysis(DMA)
• In DMA, the sample is subjected to sinusoidal mechanical stress
and the force amplitude, displacement(deformation) amplitude
and phase shift are determined.
• DMA allows you to detect thermal effect based on changes in
the modulus or damping behaviour.
• The most important results are:
• Temperature that characterize a thermal effect (Tg)
• The loss angle (phase shift)
• The mechanical loss factor (Tangent of the phase shift)
• The elastic modulus or its components the storage and loss
moduli.
• The shear modulus or its components the storage and loss
moduli. The sine wave or sinusoid is a mathematical curve that
describes a smooth repetitive oscillation. It is named after
the function sine, of which it is the graph.

A
Modulus values change with temperature and transitions in
materials can be seen as changes in the E’ or tan delta curves.

Fi
Courtesy: Perkin Elmer
 DMA
• These transitions are labelled by counting back from
melting temp, so the glass transition (Tg) here is also
the alpha transition.
• As the Tg or Tα can be assigned to gradual chain
movement, so can the Tβ be assigned to other
changes in molecular motions. Tβ is often associate
with side chain or pendant group movements and can
often be related to the toughness of a polymer.
• An idealized scan of various DMA transitions is shown
in figure., along with molecular motions associated
with the transitions.

F3
·

.
Regions of Viscoelastic Behavior
• Viscoelasticity
• The property of materials that
exhibit both viscous and elastic
beavior when undergoing
deformation.
• Viscous materials resist shear
flow and strain linearly with
time when a stress is applied.
• On the other hand, elastic
materials strain when stretched
and quickly return to their
original state once the stress is
removed.

77
 Biodegradation
• Major constituent of cell wall responsible for
various types of degradation
Biological Ultraviolet Thermal Strength Moisture
degradation degradation degradation absorption

Hemicellulose Lignin Hemicellulose Crystalline cellulose Hemicellulose

Non-crystalline Hemicellulose Cellulose Non-crystalline cellulose Non-crystalline

cellulose cellulose

Crystalline Non-crystalline Lignin Hemicellulose + lignin Lignin

cellulose cellulose

Lignin Crystalline Lignin Crystalline

cellulose cellulose

Source: Jawaid et al., 2016

8
Biodegradation mechanisms of natural and synthetic polymers. 83
10.3390/polym13071105
Factors affecting Tg
• There are a number of factors which affect glass transitions of polymers. We
will discuss briefly some factors here:
a. Chain flexibility
b. Molecular structure (steric effects)
c. Molecular weight
d. Branching and crosslinking
e. Composition of mixture
f. Pressure and heating rates

84
Factors: Chain Flexibility
• Both Tg and Tm increase with
decreasing chain flexibility.
• Flexibility decreases by:
• Increasing aromatics in the
chain
• Incorporating bulky side
groups
• Incorporating non-
rotational groups in main
chain

85
Polymer Processing
Polymer synthesis techniques produce pellets or powders which
need further shaping into final products.
Some famous techniques are as follows:

a. Compression Molding f. Calendaring

b. Transfer Molding g. Thermoforming
c. Injection Molding h. Thin Films
d. Extrusion i. Fibers
e. Blow Molding

2
Before Processing, Remember!
Thermoplastics Thermosets
• Can be reversibly • When heated, form a
cooled and reheated, network
i.e., recycled.
• Degrade (not melting)
• Heat till soft, shape as when heated
desired, then cool.
• Mold the pre-polymer
Ex: PE, PP, PS, PMMA, PET and then allow further
etc. reaction
Ex: PU, Epoxy etc.

3
a. Compression Molding
Thermosets: heated by hot molds and cured (crosslinked) it
into a solidified desired shaped molded plastic product.
Thermoplastics: Granules/pellets are heated and molded into
desired shapes.

4
a. Compression Molding Products

5
Hand lay-up
Hand lay-up is the simplest and oldest open molding
method for fabricating composites. At first, dry fibers in the
form of woven, knitted, stitched, or bond fabrics
are manually placed in the mold, and a brush is used to
apply the resin matrix on the reinforcing material.

https://www.eppcomposites.com/hand-layup-
process.html

6
Filament Winding
Filament winding is a technique primarily used to
manufacture hollow, circular, or prismatic parts such as
pipes and tanks. It is performed by winding
continuous fiber tows onto a rotating mandrel using a
specialized winding machine
https://www.addcomposites.com/post/filament-
winding

7
Resin transfer moulding
Resin transfer molding (RTM) is a method for the
productionof components made from fiber plastic
composites.

https://www.youtube.com/watch?v=1u-2GvhghQA

8
Injection Moulding
Injection molding is a method to obtain molded
products by injecting plastic materials molten by heat
into a mold, and then cooling and solidifying them.
The method is suitable for the mass production of
products with complicated shapes, and takes a large
part in the area of plastic processing.
https://www.polyplastics.com/en/support/mold/outlin
e/
https://www.youtube.com/watch?v=sBEzE4PCmqM