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TXL212

Manufactured Fibre Technology

Model fibre- Silk, Introduction (type of polymerization etc),

Molecular architecture, configuration, conformation, Molecular
modeling
Basic idea of Polymer: amorphous and crystalline phases, glass
transition, plasticization, crystallization, melting, factors affecting Tg and
Tm. (TXL211)
Polymerization of nylon-6, nylon-66, PET, polyacrylonitrile

Important reactions and kinetic rate equations, modification of

PET and nylon, polymer rheology, shear flow through a
capillary, elongational flow in a spinning line, melt instabilities,
basic principles of melt spinning, stress induced crystallization,
spin finish

Dry and wet spinning, effect of parameters on fibre breakage

and fibre structure, dry jet wet spinning of PAN, Drawing and
heat setting

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1. Manufactured Fibre Technology- Ed. VB Gupta, VK

Kothari
2. Handbook of Fiber Chemistry- Ed. Lewin, Pearce
3. NPTEL

1.Minor 1: 25%
2.Minor 2 : 25%
3.Quiz: 10%
4.Major : 40%

Attendance policy: downgrading below 75%

Class coordinator

Textile fibres

Natural Manufactured

Vegetable Bast Leaf Nut Animal Mineral

Fibre fibre fibre
Asbestos
Cotton Flax Abaca Coir
Ceramic
Jute Pineaple
Hemp Animal Secreted
Ramie Hair Protein
Wool
Silk
Mohair
Casein
cashmere

Natural Fully Inorganic

synthetic materials
• Cellulose, Viscose • Polyamide
Glass
• Modified Cellulosic • Polyester
Ceramic
Acetate, triacetate • Polyacrylonitrile
Metallic
• Alginate, chitosan • Polyolefin
• PVA

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Polymers are long chains of organic molecules= ‘Macromolecules’

- Built up from smaller units called monomers

‘Poly’ = ‘many’ ‘mer’ = ‘unit or part’

- The nature/structure of polymers was a big question in early 1900’s

Huge Debate:
‘Colloidal aggregates’ ‘Macromolecules’;
vs small molecules held together
‘Mysterious forces’
by covalent bonds

Hermann Staudinger, 1920’s (Nobel Prize 1953)

for his discoveries in the field of macromolecular chemistry
Paul Flory (Nobel Prize 1974): “tangled behavior” of polymers.

Professor of Organic Chemistry at Eigenössische Technische Hochschule

(ETH) Zurich, Switzerland

(1881 to 1965)

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Proteins 22 amino acids monomers self-assembly

DNA and RNA A, T, G, C (4 bases) (Sugar phosphate backbone)

understanding of these structures at intermediate length scales, organization

of the polymers, properties
Backbone
or
Main Chain

Side Group
n (if long… ‘side
Poly(propylene) chain’)

Repeat
Unit Degree of
Polymerization
(DP)

chain length, different side groups, chain branching,

stereoregularity, chain flexibility, cross linking.

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Silk

Pupa
Sericin
(protein) Fibroin
(protein)

20~30 m Made at room temperature via self- assembly

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Greek physician Aelius Galenus 131 AD

Prof Linus Pauling

In 1955 he detailed the molecular structure of silk fibroin

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Other producers of Silk

(least known)
Honeybee Wasp

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Bumble bee nests have silk in the walls.

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Glycine Alanine Serine

What is a polypeptide
Polymer of a amino acids

R O R’ O

H2N – CH – C – OH H2N – CH – C – OH

R O O

H2N – CH – C –HN – CH – C – OH

R’

http://silkwormmori.blogspot.in/p/movies.html

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Conc

(12-15%) C, D
23-30% B

Dehydration

60%- 15%

Shear stress

pH

ion conc

Handbook of Fibre Chemistry

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Sericin
Fibroin

20~30 m
Silk

Bombyx mori silkworm

Silk fibroin is a high-molecular-weight block copolymer consisting of a

heavy (≈370 kDa) and light (≈26 kDa) chain, linked together by a
disulfide bond.
The heavy chain consists of alternating hydrophobic, repetitive
oligopeptides, separated by smaller charged and amorphous sequences.
The hydrophobic domain is rich in alanine & glycine, while the
hydrophilic spacers give the heavy chain a polyelectrolyte nature.
The sequence of light chain is less repetitive, contains high conc of
glutamic and aspartic acid residues.

Nephila clavipes (spider silk)

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primary sequences and secondary structures

alanine,
glycine-alanine,

glycine-alanine-serine

Random coil, unordered structure

Silk I: S-shaped zigzag/crankshaft or repeated β-turn type II
structure
Silk II: crystalline β-sheets: contribute to the high tensile strength
of silk fibers
β-turn, helical structures: provide elasticity

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Secondary structures, α-helix and β-sheet,

have regular hydrogen-bonding patterns.

α-helix β-sheet

Assemblying folding packing

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Primary structure
(Amino acid sequence)
↓
Secondary structure
（α-helix, β-sheet）
↓
Tertiary structure
（Three-dimensional structure formed by assembly of
secondary structures）
↓
Quaternary structure
（Structure formed by more than one polypeptide
chains）

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Silk fibers Silk gel Silk film Silk scaffold

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Spider silk
orb weaving spiders 6 types of spidroin proteins

7 different glands

Adhesive coating : lipids,

phosphorylated glycoproteins and
organic low molecular weight
components such as γ-
aminobutyramide, choline, betaine
and isethionic acid

Spider silk is highly elastic (up to 300%) and perfectly dissipates

the impact energy of prey.

Typical body weight of a bee/fly = 120 mg

maximum flight velocity = 3.1 m/s
kinetic energy = 0.55 mJ.

Dragline silk secreted by major ampullate silk gland has toughness of 180 MJ/m3

Auxiliary spiral thread secreted by minor ampullate silk gland has toughness of 150
MJ/m3

The aciniform silk secreted by aciniform silk gland responsible for soft inner egg
case wrapping has a toughness of 250 MJ/m3

Toughness is the ability of a material to absorb energy and plastically deform

without fracturing
Spider silk shows a torsional shape memory that prevents the spider
from twisting and turning
after being twisted, to oscillate only slightly

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Supercontraction of spider silk

Contraction leads to changes in orientation

of molecular chains due to rupture of H
bonds and conformations

deformational energy is stored in the form

of conformational entropy

recoverable disorientation of the molecular chains in fibre’s oriented

amorphous region.

During supercontraction, well-defined crystalline region retains

considerable order because solvent molecules cannot penetrate
it, ….. at the same time the degree of orientation in the oriented
amorphous, and poorly defined crystalline regions decreases
appreciably

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During supercontraction, water plasticizes silk fibers by

breaking hydrogen bonds between polymer chains,
allowing re-orientation of silk molecules to lower energy
levels. This allows the random- coil macromolecular
regions to move rapidly to more disordered, higher
entropy configurations. This movement causes length-
wise contraction of spider silk.

During drying, silk may also contract. Reformation of

hydrogen bonds results in organization of the silk
proteins.

Restores shape and tension after prey capture

Recovers from slackness of the webs

poly(dimethylsiloxane) Silk 0.22 mm/s

soft lithography PEO 0.62 mm/s

PEO is used for the

outer streams at a 8% w/v , pH 6.6
concentration chosen
to match the viscosity
of the silk solution to
avoid pearling
instabilities that arise
with use of water or
other lower viscosity
solutions.

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Controlled elongational flow- fluid hydrodynamics

Controlled fibre diameter

Post-spinning drawing

RSF fibers (black boxes) and drawn RSF fibers (white boxes)
Young’s modulus

Single fiber
uniaxial tensile
testing of native
Breaking stress
B. mori silk

Young’s
Modulus- 13 GPa,
failure stress- 590
MPa, Breaking strain

failure strain 11%

average as-spun
diameter 12 μm

Failure stress and failure strain are defined as the maximum stress value reached prior
to failure and the strain value at failure, respectively.
Young’s modulus is calculated by fitting a straight line to the linear elastic region of the
stress-strain plot and determining its slope.

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amide-I band
(1720-1580 cm−1)

Melt Spinning

1. Drying of chips
2. Melting
3. Extruder: mixing,
homogenization
4. Filtration
5. Spinneret
6. Dieswell effect: release of
stored elastic energy
7. Quenching
8. Collection/ drawing

Thermo-oxidative degradation
Hydrolysis

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Dry Spinning
1. Dope: volatile solvent,
should not degrade, toxicity,
flammability, can be reused
2. Adjust conc for flowability,
rheology
3. Filtration, deaerated
4. Spinneret
5. Gas flow rate (1-2 m/s),
temp (80-90 degree C)
6. Spin finish: Lubrication, anti-
static, anti-corrosive,
biocidal, antioxidant

Spinnability: too low viscosity

Or too high viscosity
Cellulose diacetate, triacetate, PU Irregular cross-section

Wet Spinning
1. Dissolve in suitable solvent (lower % of polymer)
2. Air bubble, filter
3. Extruded in a liquid bath: coagulation, precipitation

Viscose, acrylic

Solvent
Polymer
Temp
Non-solvent
Flow rate/hydraulic
drag
Drawing force
Gelation kinetics

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Types of Polymerizations

Step growth Chain growth

polymerization polymerization (or addition
(or condensation polymerization) polymerization)

Free radical Ionic Co-ordination

polymerization polymerization polymerization

Cationic Anionic

Techniques of Polymerizations

Bulk Solution Suspension Emulsion

polymerization polymerization polymerization polymerization
a monomer is heterogeneous radical polymerization water,
add soluble initiator dissolved in a non- process that uses mechanical agitation monomer,
to pure monomer reactive solvent that to mix a monomer or mixture of surfactant
(no solvent) contains a catalyst monomers in a liquid phase monomer must be
insoluble in water

Polymer of two amino acids

R O R’ O

H2N – CH – C – OH H2N – CH – C – OH

R O O

H2N – CH – C –HN – CH – C – OH

R’
Monomer should be at least bifunctional. Molecular weight
increases “slowly” as dimers become trimers, which in turn
become tetramers.
Mass of polymer is less than mass of reactants

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Polyamide Nylon 6,6

hexamethylene diamine

adipic acid

Polyester PET
Ethylene Glycol

Terephalic Acid 2

Diglycol terephthalate

PET

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Chain growth the reactive double bond of the monomer is

polymerization activated and opened up to form new bonds

The monomer is activated and

polymerization propagates by activating
neighboring monomers.
The process is very fast and high MW
polymers are achieved quickly.

* represents the activated monomer. This

can be a free radical, positive charge or
negative charge.

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Poly-Isoprene 1,3 diene polymerization

Configuration : fixed relative arrangements of atoms

of a molecule in space

TWO distinct configurations

- These are different configurations

- Can not be interchanged by bond rotations
- These may seem like a small difference…

- Three important classes of configurations:

-Isotactic (same side)
polymer
-Syndiotactic (alternating)
‘tacticity’
-Atactic (random)

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- Isotactic PP: - Regular stereochemistry

-Chains can pack closely
-Highly crystalline
-Good mechanical properties
-Tough, impact resistant
-Opaque (scattering from crystalline
regions)

- Atactic PP:
- Irregular stereochemistry
-Chains cannot pack closely
-poor packing, Non-crystalline
-Completely amorphous
-Soft

- Syndiotactic PP: - Regular stereochemistry

Regular alternation of the side
groups promotes close packing and
crystallization
-Has ‘in between properties’
-Tough and transparent

Polyester

Polyethylene terephthalate

Poly-butylene terephthalate

Poly(1,4- bismethylene cyclohexane

terephthalate

Polyglycolide

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DMT process
step growth

dimethyl terephthalate ethylene glycol

ester interchange / transesterification Catalysts, 150°- 210° C

diglycol terephthalate
distillation
catalyst must be deactivated by a
sequestering agent (phosphoric
acid )
polycondensation
EG is removed from melt using
high vacuum

Catalysts in DMT process

Metal oxide or salts of a weak or volatile acid, such as Pb2+, Zn2+, Mn
2+, Ca2+ or Cd

Catalytic activity of acetates: Zn > Pb > Mn > Co > Mg > Ca > Sn >
Na

Most powerful catalysts lead to undesirable side effects (ether

formation)
Many of these cationic species are also known to catalyze ester
interchange, thermal degradation reaction at polycondensation step.
…. Low molecular weight, yellow color, crystallization of PET

Catalyst deactivator in polycondensation step (Antimony trioxide,

Antimony triacetate, phosphoric acid)……... Prevent precipitation of
aggregates
Titanium esters cause degradation, discoloration

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Advantage of DGT formation compared to direct polycondensation

1) Polycondensation process is applied to a uniform, chemically pure,

monomeric starting materials

2) Wider choice of catalysts

3) Less side reactions

4) High speed reaction

5) Good color of the polyester

6) Better thermal stability of the melt

7) Better drawability

PTA process

low solubility of terephthalic acid in boiling glycol,

reaction temperature 240-260 °C
pressure 4 x 105 Pa……. to obtain adequate reaction rate

Purified Terephalic Acid

direct esterification

diglycol terephthalate

Phosphite or phosphate ester to stabilize the polymer

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TPA route is advantageous compared to DMT route

1) The yield of polymer (by weight) obtained from the monomer is

higher in PTA route, because, DMT is a diester with 2 methanol
molecules which needs to be removed during ester interchange
reaction.

2) EG/TPA ratio is much lower in TPA route than EG/DMT ratio

used in DMT route, therefore lower amount of EG needs to be
removed during the polycondensation step to achieve same
molecular weight.

3) The cost of TPA is lower than that of DMT

4) Methanol obtained from ester interchange reaction, needs to

be collected, purified by distillation and sold as a byproduct,
which makes DMT route more expensive.

Side reactions

Dye affinity
Poor mechanical property
density, thermal,
oxidative and hydrolytic degradation,
light-stability,
thermal transitions

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3. Cyclic oligomer

1. Oligomer migrates to surface and cause serious problems in spinning,

dyeing, and subsequent processing steps.
2. It exudes to hot polymeric surface and coats spinneret surface, ……..
frequent filament breakages.
3. During dyeing process it causes the coating of dyeing equipment and
interferes with the process.

Moisture 0.005% Hydrolytic, thermo-oxidative degradation

Nitrogen gas
Catalysts used in transesterification and polycondensation
stages can catalyze degradation reactions

Thermal degradation
Chain end

Yellow coloration due to aldehyde formation

Mol wt reduction

Acetaldehyde in PET-bottles
below 1 ppm

Thermal stabilizers

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Hydrolysis

acidic

alkaline

Stress induced crystallization

LOY: low speed spinning, 500-

1500 m / min (as-spun)
Nominal crystallinity

POY: 1500- 4000 m/ min

HOY: high speed, 4000-6000 m/

min
Large no of small nuclei come closer
to form crystallite
Air drag, threadline tension,
crystallization
Higher spinning speeds gives rise to
the higher necking tendency, which
FOY: above 6000 m/min leads to more orientation and higher
Neck formation crystallinity.

Moves towards spinneret.

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Difference of refractive index measured in parallel and

perpendicular to fibre axis
Birefringence

Distance from spinneret

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The ethylene glycol monomer is not a

strong enough base to give rise to a salt
with the other monomer, terephthalic
acid, therefore the route to exact
stoichiometry is not taken for PET
synthesis.

High DP: Longer chains make stronger polymers

Higher orientation

• greater resistance
to deformation,
• greater breaking
load,
• lower extension to
break.

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Molecular orientation /crystallinity

All polymers are not suitable as fibres

• Optimum mol wt. to get mech. propts

• Adequate intermolecular forces & capacity
to orient through molecular alignment.

• Spinnability
Orientation , semi crystalline

Morphology
- crystallite size
- arrangement of crystalline & amorphous regions
- fibrillar structure etc

fibril : an assembly of molecules

Structure
fine structure
inter molecular distances
inter planes distances
molecular orientation etc

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Classification according to back bone Structure:

- There are many ways to classify polymers by their structure:

- Linear Two end groups

Contour length

- Branched

More than 2 end groups

Branch Points

branching has a substantial impact on properties: Crystallization, density,

strength, Chemical activity etc.

Hyperbranched Polymers

Many, many end groups

- Many branches, but branching in uncontrolled or ‘random’

-Very low density materials (e.g., ULDPE: ultra-low density polyethylene)

-Fillers in resin matrix, coating, additives

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Hyperbranched Polymers -Many branches, but

branching is
uncontrolled or
‘random’

Ring-opening
polymerization of
aziridine

Poly(ethylene imine)

Dendrimers or ‘Dendritic Polymers’

-Compared to hyperbranched polymer, Dendrimers have
PERFECT branching emanating from a core

“Tree-like Branching”
- Every branch point has exactly three branches - Globular, 3-D structure
~ 1 to 100 nm in diameter
-Specific number of endgroups

-Chemical detection (dye, radionucleotide, phamaceutical), drug delivery

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Ladder Polymers:

- Double-stranded
- High thermal and oxidative stability
- Must cut at least two bonds to break a chain…

Crosslinked Polymers
- Branched polymers…

- If the branches link to the backbones of other polymer molecules…

Crosslinked or
Network Polymer

- Crosslinks can be short or long

- The material can be: - lightly crosslinked

- highly crosslinked

- Crosslinked polymers typically do not dissolve, melt, or flow

(But they may swell in certain solvents)

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Structure vs. Conformation

- Polymers are rarely stretched out in solution or in the melt

- Assume a ‘random coil’ conformation

- The angle between the singly bonded carbon atoms is ~109 degree
carbon atoms form a zigzag pattern in a polymer molecule.

- while maintaining the 109o angle between bonds

polymer chains can rotate around single C-C
bonds

- (double and triple bonds are very rigid).

- Random kinks and coils lead to entanglement

Isotactic PP 160 - 170 °C

Syndiotactic PP 125 - 130 °C
Atactic PP < 0 °C

melting point = ratio of latent heat of melting to entropy

of melting

molar cohesion energy (of the whole molecule for

monomers, or per chain unit for polymers),
molecular flexibility (due to rotation around bonds),
molecular shape effects

- The summation of subtle effects and weak forces play imp

roles in properties

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Molecular architecture
configuration, conformation

Polymer architecture
- Microstructure: how individual monomers or atoms are arranged

- Alternating v. random copolymers

- Stereochemical configurations

- Macrostructure: how the whole polymer molecule looks like

- Significant influence on properties ---> viscosity, etc.

Gross Fibrillar structure Stereogenic

Center

Conventional View

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Hermann Emil Fischer

Nobel prize 1902

Sir Norman Haworth

Nobel prize 1937

Cellobiose

Microfibrils: 36
parallel, interacting
cellulose chains.

impart strength and rigidity to plant cell walls,

can withstand high hydrostatic pressure gradients

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Chitosan

Alginate

brown algae
bacteria

high-G alginates a rigid gel

low-G alginates more flexibility.

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Molecular interactions
in wool fibre

Nylon 66 [-(CH2)6 -NH-CO-(CH)4 -CO-NH-]n

PAN

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Lycra Spandex

CH3

-CH2-C=CH-CH2-

Elastomer of at least 85% of a segmented polyurethane

Cotton Viscose PET PP

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Adsorption
Bound water- inter-crystalline region, surface of crystallites

Viscose
Skin swells less than core
Lateral swelling, longitudinal shrinkage

Skin contains numerous small crystallites, core has fewer but

larger crystallites
Skin: more number of hydroxyl groups available for bound
water, due to large total surface area of numerous smallaer
crystallites

Polyester
Do not swell much in water

Amorphous & crystalline phases,

Crystallization,

Effect of Crystallinity on properties

of polymers

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Why do polymers crystallize ?

Random coil : conformational entropy
of a random coiled chain is very
large, due to significant number of
accessible conformations.

crystallization

melting

Higher entropy state

3D ordered lattice
Fully extended conformation
Favourable process Lowest energy conformation

Only polymers of a regular configuration can crystallize (

isotactic, syndiotactic )

1. Polymer crystals are formed by lateral alignment of extended

chains
2. Alignment is a 3D order

A. Chains will maintain their lowest energy conformation in

crystal lattice

B. Chains will pack as close as possible. Distance of closest

packing is given by van der waal’s radii

C. Equivalent atoms of different monomer units along the chain

axis tend to assume equivalent positions w.r.t. the atoms of
neighboring chains

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Can 100% polymer crystallize in bulk?

Theoretical density of a crystalline polymer
Experimental density of a crystalline polymer

In bulk, polymer chains entangle with each other. To

crystalline it is necessary to release of entanglement
constraints imposed by other chains. As crystallization
proceed, it will squeeze amorphous portion.
Movement of chain will be more and more difficult.
Then crystallization will stop.
Semicrystalline material
It is impossible to reach 100% crystallinity with the
lowest free energy because polymers do not have a
uniform molecular weight.

Kinetics of Polymer Crystals formation

A. Nucleation and Spherulitic growth

Spherulite Growth

Nucleation-1

Nucleation-2

B. Spherulite

Branching Spherulite

primary nucleation, crystalline conditions,

molecular formula

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Why polymer chains want to fold upon crystallization?

Polymer crystallizes because its energy can be

lowered by transforming into a lower energy
conformation.

Since some bonds in the folds have to assume

gauche conformation in order for to re-enter the
crystal the energy of the folded chain is higher
than that of fully extended chain where only
trans bond conformation exists. So folded chain
is a more unfavourable state than fully extended
chain.

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D. Orientation of chains
in an enlarged portion
C. Spherulite structure having of lamellae having
radial growth & branching chain folding

Nucleation at a reasonable rate of growth must

Linear PE involve chain folding.

The fully extended chain crystal (most

stable) requires unreasonably long
time to form. Chain folding is a
compromise between thermodynamics
and kinetics of crystallization.

So, polymer chains choose an alternative way

to crystallize, i.e. through chain folding.

Lamellae form because it is the fastest way for long molecules to

crystallize

E. Chain folding in the formation of

single crystal lamella

100 Ao

F. Ideal Stacking of G. Interwoven Structure of polymers

lamellar crystal through folded chain lamellae

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H. Interlamellar amorphous str of semicrystalline polymer

I. Fringed micelle concept of partly

crystalline polymer

Shick-Kabab form

J. Folded chain lamellar structure c

b
a
Thinness of polymer lamellae is very imp to
crystallize polymers because of the many
surfaces it creates that directly affect the
imp properties such as melting pt, chemical
reactivity, mechanical prop.

Thickness is related to crystallization, rather

than depending on chemistry of polymer
chain. It is affected by H- bonding, it
increases with crystallization temp.

Drawn

Drawn spherulite Fibrils

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TEM: Silk fibrils

200 nm

Extended
The growth of these structures
Noncrystalline Crystallites impeded by the presence of
molecules entanglements and strained
regions, which constitute the
Microfibrils
amorphous phase

Fringed fibrillar model

Fringed micelle model
Folded chain lamellar model

(A) Crystallization during polymerization

(B) Crystallization induced by orientation

stretching of long chains to form fibrous crystals
decrease in the conformational entropy

(C) Crystallization under quiescent condition

(1) Crystallization from dilute solutions
(2) Crystallization from the melt

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melting temp to pre-determined crystallization temp

small-angle x-ray scattering

Density fluctuations (nucleation and growth processes)

Plain polarizing microscopy,
Rheological and light
scattering studies
Development of network structure
(very early stages of crystallinity development)
TEM, Birefringence
Onset of autocatalytic, observable crystallization
(1) fringed micelle, (2) lamellar type of morphology

pseudo-equilibrium level of crystallinity

Degree of crystallinity is determined by:

Molecular conformation & chain flexibility

Structural regularity & Chain configuration: linear polymers

crystallize relatively easily, branches inhibit crystallization,
network polymers almost completely amorphous,
crosslinked polymers can be both crystalline and amorphous

Complexity: crystallization less likely in complex structures.

Simple polymers, such as PE, crystallize relatively easily

Rate of cooling during solidification: time is necessary for

chains to move and align into a crystal structure

Isomerism: isotactic, syndiotactic polymers crystallize relatively

easily - geometrical regularity allows chains to fit together, atactic
difficult to crystallize

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Copolymerism: easier to crystallize if monomer arrangements

are more regular - alternating, block can crystallize more easily
as compared to random and graft

Presence of Intermolecular forces: polarity, H-bonding etc

Branching / bulkyness of side groups:

Short irregular branches tend to decrease crystallinity %
Regular short branch, small side groups able to produce
coiling, favours crystallization

Molecular weight: low mol wt favours mobility, higher

crystallization

Impurities present

More crystallinity: higher density, more strength, higher resistance to dissolution and
softening by heating

GLASS TRANSITION, Tg

Rubber band vs PET bottle

PMMA 100 oC 120 oC

at RT
Starts to soften Rubbery state
Glassy state

Tg = -70 oC, can we use it for making window pane ?

Tg = 100 oC, can we use it for making car tire ?

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What happens on polymer molecules at Tg?

Hardness is related to polymer mobility

Below Tg, molecules are “frozen in”.
When polymer is heated above Tg, thermal
energy imparted on the molecules is sufficient
to overcome the energy barrier for translational
& rotational motions.
Onset of large scale motion
Entanglement restrictions
Degradation

Definitions

Tg is the temp at which the polymer

molecules start to perform large scale
(translational & rotational motions) motion
when we heat the polymer from glass state

Tg is the temp at which the polymer

molecules are ‘frozen’ into a state where
large scale motion is prohibited when we
cool the polymer from the rubbery state

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Does every material have a Tg?

Only amorphous materials

Crystals do not exhibit Tg, but shows melting phenomenon

Only vibrational motion is allowed

How do we measure Tg?

Rubbery state
Specific
vol Glassy state

Tg Temp

Rubbery state
Enthalpy
H Glassy state

Tg Temp

Change of heat capacity (Cp)

Differential Scanning Calorimeter

Rubbery state

Cp Glassy
state

Tg Temp

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Modulus
(=Stress/strai
n)

Tg Tem
p

Viscosity
Dielectric relaxation (change of the electric polarization
following application of an electric field to a sample.)
Refractive index

Theories about Glass transition

1. Free volume theory- does not involve microscopic

description

2. Thermodynamic theory-
Tg is a thermodynamic 2nd order transition, which occurs as
the conformational entropy of polymer chains reaches
zero.

3. Kinetics theory- Tg is the point where the relaxation

of molecules is unable to catch up with the experimental
cooling rate, so the molecules are ‘frozen’ into a non-
equilibrium state.

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Free volume Vf = V – V0
Vf = Free volume
V = total volume
V0 = occupied volume

Empty space = free volume

If the system has a larger free volume, the molecules

have more space to undergo motion …. The molecules
have a larger mobility.

Doolittle equation

Free volume reaches a constant value at and below Tg.

At Tg the fractional free volume is too small to allow large-
scale molecular motion to occur.

When the temp is further decreased, molecules can not

move anymore , thus the fractional free volume is ‘frozen
in’ at the value of fractional free volume (fg).

Free volume theory is useful in interpreting effects of

external factors (pressure, mol wt, etc) on Tg.

Concept underlying free vol may not be strictly true.

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1. Effect of increasing pressure on Tg

P1 < P2

Tg1 Tg2

A Polymer has less free volume at higher pressure.

So, a polymer has a higher Tg at higher pressure.

2. Effect of Mol weight on Tg

Tg

Mol wt

Chain ends are connected only at

one side, they have more freedom
to move, compared to internal
segments

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Polymer with lower MW has more free volume.

Lower mol wt polymer has a lower Tg

M1 < M2

Free volume

Tg1 Tg2 Temp

Thermodynamic theory

Glassy state is thermodynamically equilibrium state.

But properties like volume, enthalpy, mecha properties of
glassy polymer change with time.

Consider phase transition from phase 1 to phase 2.

At phase transition temp T, Gibbs free energy G1 = G2

But if their volumes & entropies are not equal, then the
phase transition is called 1st order transition.
Melting
Crystallization
Vaporization
Condensation

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1st order transition is the phase transition where properties

related to 1st partial derivatives of G exhibit discontinuities at
the transition temp.

2nd order transition is the phase transition where

properties related to 2nd partial derivatives of G exhibit
discontinuities at
the transition temp.

Cp = Specific heat capacity

at constant pressure

volumetric coefficient of
thermal expansion

Tg is 2nd order transition

Tg is the temp where the conformational entropy of a
polymer approaches zero

No conformational arrangement will be possible.

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Polymer molecules are randomly placed.

Equal probability

Can have any conformation

Trans: Low energy

Gauche: high energy conformation

Repulsive interaction between segments will make

some bond conformation less accessible… effect of
interaction energy.

Conformational entropy is function of temp

At high temp a very great no of conformational states

are accessible to each chain… at high T thermal
energy can easily overcome the hindrance to rotation
and hence high energy conformation are accessible to
the chain…….. No of ways of arranging the polymer
molecules and holes are large.

As T is lowered, no of accessible conformation is

drastically reduced (high energy conformations are no
longer accessible).
When temp is reduced to Tg only ONE conformation
is accessible to the chain. So during glass transition
from rubbery to glassy state occurs, Glassy state
should be an eqlbm state whose properties will not
change with time.

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Criticism: 1. Glass state is a nonequilibrium state,

rather than equilibrium state. Properties change with
time.
Cooling a polymer to Ta (below Tg)

Volume relaxation or physical ageing

Vol

Temp

2. Value of measured Tg is dependent on rate at

which the experiment is done.
Higher Tg with faster cooling rate.

Kinetic theory

If Tg is measured in infinitely slow rate, it would be

true 2nd order transition. But such extremely slow
experiment is impossible to conduct.

Change of molecular mobility with temp

A system has an eqlbm state at every temp. If we

cool a polymer from 100 degree C to 99 degree C
polymer molecules will rearrange themselves to
reach eqlbm state at 99 degree C.

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Structural parameters affecting Tg

1. Chain flexibility: stiffer chain has higher difficulty to perform
motion (less free volume), hence has higher Tg.
O
O O C PEEK

-(CH2-CH2)n- PE Tg = 145 oC
Tg = - 100 oC

2. Side groups : Polymer containing bulky side groups will

have more difficulty to move chains (less free vol), hence
higher Tg
-(CH2-CH2)n- -(CH2-CH)n-

Tg = - 100 oC Tg = 100 oC

3. Chain branching:

Branched chains polymers will have more chain ends,

hence free volume of the molecule will be more, so Tg
will be less.

Chain branching will make the branch points in the

molecule less mobile, as internal segments are
connected to each other. So free vol will be less, and
higher Tg.

Chain branching decreases Tg

4. Cross linking: decreases free vol, increases Tg

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Methods of Fibre preparation

wide range of properties depending on the processing conditions

1. Dry spinning: Solution of cellulose nitrate in a

alcohol/ether solvent…. Solidification by solvent
evaporation

2. Viscose: Wet spinning: solidification by chemical

coagulation

3. PET, PP, Nylon: Melt spinning: solidification by

cooling

Birefriengence Maximum draw ratio

Stress
Natural draw ratio

Diameter

Crystallization Elongation %
point Distance from spinneret

Drawing : as-spun fibres have poor elasticity, they undergo plastic

deformation on application of low stress. Polymer chains are in partially
folded conformation, can extend easily.

Heat setting: Progressive enhancement of crystalline perfection:

Polymer chains are unfolded, improved, more elastic network of
polymer is formed. Polymer chains assume extended conformation, do
not recover back to their original state when stress is released.

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Structure formation during spinning

Liquid crystal Conventional melt spg (PET)

Solution
Nematic structure
Low entropy Random coil
High entropy
Extrusion

Solid
state

Extended chain structure Folded chain structure

High chain continuity Low chain continuity
High mechanical properties Low mechanical properties

Gel spinning
Dilute solution of (super) high molecular weight PE
extruded into water by wet spinning, so that gel like
fibers are formed.

Air gap : polymer chains orient in the direction of fiber

axis and then produce highly oriented crystallization of
rigid polymers

Then hot drawing is applied (30 times in length)

Classical PE drawn only up to 10 times in length.

Dyneema, Spectra, Tekmilon.

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Melt spun PET: Tensile modulus 10 GPa

Melt spun HDPE: 5 GPa

Gel spun PET: Tensile modulus 110 GPa

Gel spun HDPE: 324 GPa

Melt spun: Over all orientation is less due to

1)significant amount of chain folding may occur, which
allow only limited chain continuity in axial direction
2)Entanglement

Gel spun: most of the molecules are highly extended,

so offer much higher resistance

Polyethylene fibers
Normal PE Dyneema or Spectra
Orientation low Orientation > 95%
Crystallinity < 60% Crystallinity up to 85%

Stretching

Entanglement network Fibrillar crystal

The theoretical elastic modulus of the covalent C-C bond in the fully
extended PE molecule is 220 Gpa.
Experimental value in PE fibres - 170 Gpa.

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Extended chain polyethylene

minimum chain folding

UHMPE fibre structure: (a) macrofibril consists of array of microfibrils;

(b) microfibril; (c) orthorhombic unit cell; (d) view along chain axis

Mechanical behaviour of polymers

Load intensity or Stress = Force P / cross sec area A

Intensity of deformation
Elongation
or = l/L =
Strain
Unstretched length
1. Stress-Strain curve
Rigid plastic Glassy

Flexible plastic
leather like
Stress

Elastomers
Φ Rubber like
Strain %

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For small values of strain, stiffness or Young’s modulus (E) is

equal to the tangent of the stress strain curve

E = tan Φ

Adv:
1.Stiffness, stress at which fracture occurs.
2. relation between force and deformation at every point.

Limitation:
1.Applicable to the particular mode of loading.

Diff in mechanical behaviour due to the mode of loading (tension

vs compression) are not so serious at small deformations but is
significant at large deformation.

1. Load: application of a load to a specimen in its

axial direction causes a tension to be developed in the
specimen. The load may be expressed in Newtons (N)
or in gm force.
2. Breaking load: This is the load at which the
specimen breaks, usually expressed in gms, lbs or
Newton.
3. Stress: Load
Area of cross section dyn
/ cm2, N/m or Pascal
2

4. Specific stress: Cross section of many fibres are

irregular in shape, and difficult to measure the area.
Specific stress = Load / linear density
Gm per tex or gm per denier

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5. Breaking length: length of the fibre which will just

break under its own weight when hung vertically.

6. Strain: when a load is applied to a specimen a

certain amount of stretching or elongation takes place.

Strain = Elongation / Initial length

7. Initial modulus: slope of the stress-strain curve at

the origin

Flax, Jute: high initial modulus, low extension at break

Wool, Acetate rayon: low initial modulus, high extension at break
Silk, Nylon: strength and extension at break both high

2. Modulus – temperature curves

Polymeric fibres are Viscoelastic, i.e. their mechanical

properties depend on rate of loading or on time under load. So
it is necessary to specify the time interval under load at which
the E-T data were obtained. 10 sec

1
Tg
Semicrystalline

E Tm
2 2 Region 1: Glassy
2. Transition or leather
N/m2 like
3
Amorphous Crosslinked 3. Elastomeric or
rubber like
Uncrosslinked 4 4 4. Liquid flow

To C
E-T curves of amorphous (atactic),
semicrystalline (isotactic) polystyrene

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3. Regions of mechanical equivalence

Polymer at a given temp can be said to be in one of four

regions of mechanical equivalence.

(i)Glassy region: Modulus E takes values in the range 109 –

1010 N/m2 in this region which is found below Tg. A polymer
below Tg is stiff, hard, brittle.

For many applications involving small deformations, polymers

in region 1 can be designed by use of the theory of Linear
elasticity.

This theory assumes that the stress-strain relation is linear and

that recovery of original shape, following unloading, is
instantaneous and complete, occuring along the identical
stress-strain path which was traversed during loading.

(ii) Transition region: The modulus of amorphous polymer

drops from about 109 – 106 N/m2 as the material is heated
above Tg in the transition region between glassy (region 1)
and rubber-like (region 3) behaviour.

The modulus of semicrystalline polymer drops only from

about 109 – 107.5 N/m2 as the material. is heated from Tg to
Tm. Mechanical properties of semicrystalline polymer in
this region resemble those of rather stiff leather.

Polymers in region 2 are typically ductile. Their mech

behaviour is strongly time-dependent. So the branch of
mechanics which may be used to describe small-
deformation behaviour in region 2 is the theory of linear
viscoelasticity, ……a modification of theory of linear
elasticity which accounts for time effects.

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(iii) Elastomeric (rubber like) region: Rubber like behavior is

monopolized by amorphous polymers. Crystallites stiffen the
structure and tie down macromolecules, thereby preventing
their large-scale unfolding.

Characteristics of region 3: Extension 500-1000 %, moduli 105

– 106 N/m2
Crosslinked rubbers are capable of recovering their original
shape fully after being released from very large extensions of
indefinite duration. Uncrosslinked rubbers may recover fully
only if stretched to a small extent over a short period of time.

Modulus of uncrosslinked suffers a dramatic drop with temp, &

the polymer flows like a viscous liquid (Region 4). But
crosslinking preserves the modulus almost intact until the temp
level above which 3D network undergoes chemical
decomposition.

(iv) Liquid flow region: Crosslinked polymer decomposes if

heated to a high temp but it does not undergo flow.

But uncrosslinked amorphous polymer gradually loses its

ability to recover from deformation while undergoing
permanent deformation (flow) as the temp is increased. At high
temp, amorphous polymer in region 4 behaves as a liquid with
very high viscosity, very limited elasticity.

When heated above Tm, semicrystalline polymers melt and

behave similarly to amorphous polymer in region 4.

In general, polymer fluids are non-Newtonian i.e., their flow

properties can be characterized by a nonlinear relation
between shear stress and flow rate.

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