Crystallinity:

The state where the polymer chains exist in parallel position that a polymer can be achieve at a
particular temperature. It depends on chemical nature, geometrical structure, molecular weight
and molecular weight distribution etc. Maximum crystallinity become possible if the polyer is
annealed just at its Tm (Melting Temperature) for sufficiently long time.
Crystallinity is expressed as degree of crystallinity, given by,

Where,
C= Refractive index/density of whole polymer
Cam = The value of property when the polymer is amorphous.
Ccr = The value of property when the polymer is crystalline.
Crystallinity increases with density.

Amorphous:
The state of polymer where the chains are
palced in haphazard direction is termed as the
amorphousness of polymer. The density of
polymer decreases of this area.

Semi-crystalline:
The state between crystalline and amorphous
of a polymer is called semi crystalline.
Comparison of properties of crystalline and amorphous polymer:

Properties Crystalline Amorphous

1. Strength High Less
2. Melting point high Less
3. Elongation Less high
4. Dye takeup Less high
5. Light deflection Regular Irregular
6. Density high Less
[Link] Crystalline Liquid
8. Structure Linear Branch or random
9. Polarity high Less
10. Flexural Less
high
modulus
11. Hardness high Less
12. Permeability Less high
13. Acid hydrolysis Difficult Attack rapidly
14. Young modulus high Less
15. Chain mobolity easy high

Factor that control crystallinity of polymer:

1. Regularity of the molecular structure of the polymer chain: In general, crystalline substance
is of regular molecular structure.
2. Polarity: Polarity increases the crystallinty of a polymer
3. The mobility of polymer chain: The mobility of polymer chain is another factor that control
crystallinity of polymer. If the polymer chain is mobile, the polymer will be crystalline.

Extended chain crystals:

 Less common, often take a needle form.
 Usually formed with low molecular weight polymer by slow crystallization or under
pressure.

Nucleation – onset of crystallinity.

 Homogeneous nucleation – occur randomly throughout the matrix.
  Heterogeneous nucleation –occur at the interface of a foreign impurity 9e.g. a finely
divided silica).
Crystalline polymers vs amouphous polymers
 Tougher, stiffer (due to stronger interations).
 Higher density, higher solvent resistance ( due to closely packed morphology)
 More opaque (due to light scattering by crystals).

Factors influencing crystallinity:

 Backbone stiffness.
 Backbone symmetry.
 Absence or presence of branches.
 Pendant group size.
 Pendant group polarity.
 Pendant group regularity.

Factors determine the capacity and tendency of a polymer to form crystalline region within
the material:
 Only linear polymers can form crystals.
 Stereo regularity of the molecule is critical.
 Copolymers, due to their molecular irregularity, rarely form crystals.
 Slower and gradual cooling promotes crystal formation and growth.

Effect of Crystallization
 Increases density.
 Increases stiffness.
 Reduces permeability.
 Increases chemical resistance.
 Reduces toughness.
Softening point: The temperature at which a polymer becomes soft is called softening point.
Practically it is the most important temperature. It may be observed and measured in four
different ways which are as follows-
1. Vicat test.
2. Deflection temperature.
3. Polymer melt temperature.
4. Zero strength temperature.
1. Vicat test: It is the temperature at which a flattened needle or pin penetrates
thermoplastic surface to a depth of 1mm under a load of 1 kg. It is a vicat test
temperature.

2. Deflection temperature: According to ASTM, a sample beam (1"×1/2"×5") with the load
of 66 PSI is used the temp at which the beam deflect 0.001 inch is called the distortion
temperature.
Crystalline melting point: The temperature at which the polymer becomes melt i.e. the change
of state occurs (e.g. solid to liquid) is called melting temperature or point.
It is the temperature at which the polymer losses all its crystallinity. It is generally denoted by T m
If the specific volume of a polymer is plotted against temperature, we have a graph like the
following-
Volume change, V

Liquid

C
B
A
Crystalline
solid

O T m
Temperature

Fig: Plot showing trend of change in volume as a function of temperature in the case of low
molecular weight crystalline substances

Polymer Melt Temperature:

It is the temperature at which a polymer sample becomes melted when moved across a hot metal
structure with moderate pressure. It is alternately called ‘sticking temperature.’

Zero Strength Temperature:

It is the temperature at which a polymer sample falls in tension under its own weight. When the
polymer becomes straight from its position (1) , it acquires tension that temperature is termed as
Zero strength temperature.
Glass Transition Temperature: The glass transition temperature, Tg, is temp. below which a
polymer behave like brittle or glass-like, above the temperature the material behave more like
plastic.

The Tg to a first approximation is a measure of the strength of the secondary bonds between
chains in a polymer; the stronger the secondary bonds; the higher the glass transition
temperature.

At glass transition temperature:

 Breakdown of van deer walls forces.
 Onset of large scale molecular motions.
 Polymer goes for glassy/rigid to rubbery behavior.
 Upper service temperature in amorphous polymers.

RUBBERY
GLASS STATE OR VISCO FLUID STATE
VISCO ELASTIC STATE

(Polymer melts)
(Brittle plastic) (Tough plastic
and rubbers)

Temperature

Fig: Change of state with temperature in polymeric materials.

Tg and Tm of some Polymer:

Polymer Tg(0c) Tm(0c)
Poly Ethylene
69 264
Terepthalate(PET)
Poly Vinyl Chloride(PVC) 81 310
Poly amide/Nylon-6,6 50 270
Poly Acrylo Nitrile(PAN) 97 314
Poly styrene 100 250
Natural rubber -73 36
Nylon-6 50 250
Factor influence the Tg:
1. Flexibility of chain bond decrease the value of Tg
2. Composition of ring structure in molecular chain raises the value of Tg
3. Bulky side groups raises the value of Tg
4. Flexibility of side group decrease the value of Tg
5. Tg increases with molecular weight up to 20,000
6. Polarity of side groups increases the value of Tg
7. Random co-polymer has lower value of Tg than homo-polymer.
8. Increase the orientation of fibre chain restrict the chain movement and increase the value
of Tg.

Fig. Effect of glass transition on molecular weight of the polymer.

Relation between Tg and Tm:

For symmetrical polymers-

Tg= Tm
For un symmetricala polymers-

Tg= Tm
A combined version of these equations-

< <
Graphical reprenstation of Tg and Tm:

Melting point depends on:

Composition : Polyester Tm= 264
PVC Tm = 310
Structure : Larger polymer structure = Tm
Rigid structure = Tm
Bonding force : Covalent Bond, Hydrogen bond = Tm

Importance of Glass Transition Temperature

 It is used as a measure for evaluating the flexibility of a polymer molecule and the type of
response the polymeric material would exhibit to mechanical stress.
 The Tg value of a polymer decides whether a polymer at the ‘use temperature’ will
behave like rubber or plastic.
  It would be suffice to know that polymers above their Tg will be soft and flexible and
exhibit a delayed elastic response (viscoelasticity), while those below their Tg will be
hard and brittle and will process dimensional stability.
 The Tg value along with the Tm value gives an indication of the temperature region at
which a polymeric material transforms from a rigid solid to a soft viscous state. This
helps in choosing the right processing temperature, i.e., the temperature region in which
the material can be converted into finished products through various processing
techniques such as moulding, calendaring and extrusion.

Flow temperature(Tf):
The temperature at which the molecular mobility sets in and the polymer passes from the rubbery
state to the liquid state is called its flow temperature or flow point.

Aromaticity promotes crystallinity

• Molecular resonance of adjacent rings keeps all rings in the same plane
• Coplanar rings in series results in a flat, ribbon-like molecule
• Ribbon molecules tend to stack, like boards, which creates repeating order (crystallinity)
• As crystallinity increases, so does strength, modulus, melting point, etc.

Heat Distortion Temperature:

While Tg gives a temperature range over which a hard polymeric material tends to become soft
under static conditions, the heat distortion temperature indicates the temperature range over
which the polymer begins to soften and gets deformed under the influence of a load. In the
polymer industry, the heat distortion temperature is in fact more often used(than Tg) as an
empirical method of comparing the transition behaviour of different polymers form their hard
solid state to the soft viscous state.
 Cross-linking, Plasticizers and Fillers

In general, the simple homopolymers are made as pure. Only a few of these are finally sold as
“Pure” polymers, such as polyethylene drinking cups and polyethylene films. Usually, polymers
are sold with various additives.

Cross-linking:
On heating, linear polymers flow and are termed thermoplastics. To prevent flow, polymers are
sometimes cross-linked. A cross-link is a bond that links one polymer chain to another. They can
be covalent bonds or ionic bonds. "Polymer chains" can refer to synthetic polymers or
natural polymers (such as proteins).

Figure. Cross-link polymerization

The cross-linking of rubber with sulfur is called vulcanization. Cross-linking bonds the chains
together to form a network. The resulting product is called a thermoset, because it does not flow
on heating.

Plasticizers:
Plasticizers are small molecules added to soften a polymer by lowering its glass transition
temperature or reducing its crystallinity or melting temperature. The most widely plasticized
polymer is Poly Vinyl Chlorite. The distinctive odor of new “Vinyl” shower curtains is caused
by the plasticizer.

Fillers:
Fillers are defined as materials that are added to a polymer formulation to lower the compound
cost or to improve properties. Fillers may be of two types, reinforcing and non-reinforcing.
Common fillers are the silicas and carbon blacks.
The carbon blacks are most widely used in automotive tires to improve wear characteristics such
as abrasion resistance.

Non-reinforcing fillers, such as calcium carbonate, may provide color or opacity or my merely
lower the price of the final product.

Importance of inter-molecular bonds

Polymer materials fail along inter-molecular bonds. Longer polymers chains mean that more
bonds must be broken.
Liquid Crystalline Polymer

Liquid crystals form from organic compounds and is thought of as the phase matter between the
solid and liquid state of a crystal. This phenomena was discovered in 1988 by Austrian chemist
Frederich Reinitzer.

The liquid crystalline polymer is a thermoplastic polymer material with unique structural and
physical properties. It contains rigid and flexible monomers that link to each other.

When flowing in the liquid crystal state, rigid segments of the molecules align next to one
another in the direction of shear flow. On this orientation is formed, their direction and structure
persist, even when LCP is cooled below the melting temperature. This is different from most
thermoplastic polymers (e.g., Kapton) whose molecules are randomly oriented in the solid state.

Uses of Liquid Crystals

 Flat Screen Televison.
 Wrist Watches.
 Laptop Screens.
 Digital Clocks.
 Thermometers.
 Polymeric fibres.

 The polymers of para-aramids are stiff and rod-like and can orientate themselves with
respect to each other in the liquid crystal phase. In contrast the meta-aramids form chains
that are more irregular.

Liquid Crystalline Polymers

• Lyotropic
Poly(p-phenylene terephthalamide)
 PPTA ® aramids - “Kevlar” etc
Poly benzimidazoles:
 PBI
Polybenzoxazoles:
 PBO
• Thermotropic
2.6 naphthalene terephthalate copolymers
 “Vectran”
Spinning of a conventional & liquid crystal polyester: 2 views
Basic requirements for Liquid Crystal Formation
 There must be a first-order transition between the true crystalline state at the lower
temperature bound leading to the liquid crystalline state, and another first-order transition
leading to the isotropic liquid state at the upper temperature bound of the liquid
crystalline state.
 A liquid crystal must exhibit one or two-dimensional order only; true crystals have three-
dimensional order and the isotropic liquid is completely disordered.
 A liquid crystalline must display some degree of fluidity.

Manufacture of Liquid Crystal Polymer (LCP) Fibers

 Lyotropic LCPs (e.g. aramids)
(“liquid” is an acid solution)
 Thermotropic LCPs (e.g. Vectran)
(“liquid” is a melt phase)

Structure of Liquid Crystalline Polymers

Liquid crystalline structures can be organized into several classes. The major liquid
crystalline structures are:
 Nematic:
 The nematic liquid crystals are organized in one dimension only.
 Their chains lying parallel to each other at equilibrium.
 Molecules in this phase are long and rod-like in shape.
 They are free to move in space.

 Smectic:
 The smectic liquid crystals are ordered in two dimensions only.
 This phase can be reached at lower temperatures than the nematic
phase.
 Molecules align themselves in layers.(They are restricted to their
plane).
 More order and higher viscosity.
 Figure. Liquid Crystalline Structures

A Liquid Crystalline Polymer may exhibit multiple structures at different temperatures or

pressures. As the temperature is raised, the polymer then goes through multiple first-order
transitions from a more ordered to a less ordered state.

“Clearing Temperature”, is the temperature at which the last(or only) Liquid Crystalline phase
gives way to the isotropic melt or solution.

Types of Polymeric Liquid Crystals

Lyotropic Liquid Crystals
 A liquid crystalline (LC) material is called lyotropic if the ordering effects in it are
induced by changing its concentration within a solvent.
 Frequently rod-shaped polymer chains are dissolved to concentrations of about 30% for
processing purposes, particularly for fibre formation.
 The main reason for using solutions rather than melts is that the polymers decompose
below their high melting temperatures.
 Most of the lyotropic LC polymers form nematic structurs.
 Most of the polymers in this class are aromatic polyamides with aromatic ring structures.

Thermotropic Liquid Crystals

 A liquid crystal (LC) is called thermotropic if the order of its components is determined
or changed by temperature.
 They are usually processed in the melt state.
Phase change in Liquid Crystalline Polymer:
 If the temperature is too high, the rise in energy and therefore in motion of the
components will induce a phase change: the LC will become an isotropic liquid.
 If on the contrary, temperature is too low to support a thermoptropic phase, the LC will
become a crystal.
 There is therefore a range of concentrations and/or temperatures at which we observe
LCs; and most of these have several “subphases” (nematic, smetic ...) which we may
observe by changing the parameters.

liquid → liquid crystal → crystal (solid)

3. stage of matter

Typical Thermal Properties of Aramids (Lyotropic LCP)

 Theoretical melt temp >600oC
 Begins to char/decompose at 400oC
 Cannot be melted to form liquid
 Cannot be spun using a melt-spinning process
 Answer: form the polymer in a very strong acid, then spin the solution
 In the solution the polymer forms a liquid crystal, a lyotropic LCP.

Dry-Wet Spinning of Aramids

Chemistry of LCP Fibers

 Molecular design of LCPs is based on aromatic enhancement of common polymers; PA

(nylon) for aramids, PET (polyester) for Vectran
 Many chemical properties in LCPs can be linked to similar properties in nylon and PET
 Aramid fibers typically produced using acid-spinning techniques; Vectran produced
using melt-spinning process
 Some notable differences from PET/nylon…
 LCPs more difficult to bond to resins
 LCPs have better resistance to chemical attack
 LCPs have higher max-use temperatures