States of order in polymers

States of Order in Polymers

Configuration and conformation
Polymer chain shape

Macromolecules in:
Solution
Molten state
Solid state
 Solid State Properties of Polymers

PPE-206 Polymer Structure and Synthesis

 Polymer Phases

Viscous Liquid

Polydimethylsiloxane Tg = -123°C; Tm = -40 °C

Elastomeric
Polyisoprene Tg = -73 °C
Polybutadiene, Tg = -85 °C
Polychloroprene, Tg = -50 °C
Polyisobutylene, Tg = -70 °C
Semi-Crystalline
Nylon 6,6, Tg = 50 °C; Tm = 265 °C
Poly ethylene terephthalate, Tg = 65 °C; Tm =270 °C

Glassy
Polystyrene Tg = 100 °C
Polymethyl methacrylate, Tg = 105 °C
 Glass-rubber-liquid
Amorphous plastics have a complex
thermal profile with 3 typical states:
Glass phase (hard plastic) Polystyrene
9

8
Leathery phase Tygon (plasticized PVC)
Log(stiffness) 7
Pa 6 Rubber phase (elastomer)
5 polyisobutylene
Tg
4
Liquid PDMS
3

Temperature
 Physical States of Polymers

 Liquids
 Silicon oils
 Specialty rubbers

Solids
 Elastomers
 Amorphous
 Semicrystalline
 Macromolecules in Solution

Importance of polymer solutions

 Polymer syntheses

Molecular characterization

Polymers processing to fibers
 Preparation of polymer blends, coatings and adhesives
 Polymer solutions (thickeners)
 Polymer mixtures/blends

Polymer solutions are important because many polymer
syntheses as well as most procedures for their molecular
characterization are carried out in solution. Polymer solutions
are furthermore essential in the processing of some polymers to
fibers, preparation of polymer blends, coatings, and adhesives.
Moreover, polymer solutions are applied because of their high
viscosity (thickeners).
Factors affecting properties of
macromolecules
Chemical composition
Chain length
Conformation
Configuration

Shape of isolated macromolecules:

х compact sphere
х extended rigid chain
 Loose coil shape
Factors affecting coil shape

 Fixed bond angles

 Restricted rotation about the bonds
 Branching
 Incorporation of rigid chain components

Aromatic rings

Heterocyclic rings
 Intermolecular/intramolecular interactions

H-bridges

Electrostatic forces

 Fixed bond angles and restricted rotation about the bonds affect
the shape of the coil. Branching and incorporation of rigid chain
components (aromatic rings, heterocyclic rings) also influence the
coil form. Finally, the shape of the coil is determined by
intermolecular or intramolecular interactions, such as H-bridges or
electrostatic forces
 Macromolecules in Solution
Dilute polymer solution vs. low
molecular weight compounds solution

Swollen state (viscous effect)
 Polydispersity
 Coil shape
 Methods of the property measurement
Solvents and Solubility

Poor solvents (unperturbed coils)
 Good solvents (perturbed coils, swelling)
Concentrated solution

Critical concentration c*
 Macromolecules in Solution

Molecular colloids

Coil volume of macromolecules in solution
 20-1000 times larger than chain volume itself
 Swollen gel particle may consist of more than
99% solvent

Dependence of solutions properties

 Solvent
 Temperature
 Molecular weight of the chain molecules
 Macromolecules in Solution

Swelling

Limited swelling (marked by volume increase)
 Unlimited swelling (complete dissolution)
 Crosslinked polymers: measure of degree of
crosslinking
 Macromolecules in Solution

Incompatibility of mixtures of polymer

solutions
 10% solutions of polystyrene and poly(vinyl
acetate), each in benzene
Factors

Structure of the macromolecule

Molecular weight

Mixing ratio

overall polymer concentration
 Temperature
 Macromolecules in Solution

Polyelectrolytes

Polymers that fall apart into charged
polyions and many oppositely charged
counterions

Solution expands, becomes thick and
syrupy
 Macromolecules in Molten State

 Coiled chain conformation

Types of motion
 Micro-Brownian (near Tg)
 Macro-Brownian (reptation) (in Tg range)

 Deformation under external forces

 Entropy-elasticity
 Macromolecules in Elastomeric State

 Non-crosslinked rubbers: do not return completely

to their original length after stretching
 Elastomeric networks: return completely to their
original length after stretching

 Correlation between degree of crosslinking, elasticity

and elastic modulus
Macromolecules in Amorphous (Glassy) State

Noncrystalline amorphous phases are

obtained below Tg
Glasses are formed best when
macromolecular chains are:

Irregular in structure (atactic, branched,
crosslinked)
 Regular (isotactic, syndiotactic unbranched) if
cooled down suddenly
Macromolecules in Amorphous (Glassy) State
Ordered orientation of the macromolecular
coils can also occur by:

stretching
 casting films from solution during the drying
stage of the film as a result of shrinkage

pulling thin film away from the support

Orientation causes anisotropy of various

physical properties (light scattering)
 Macromolecules in Amorphous (Glassy) State
Characteristics of amorphous polymers:

transparent
 very often soluble in common organic
solvents at room temperature

Important amorphous polymers:

 Poly(vinyl chloride) 
Cycloolefine

Polystyrene copolymers

Poly(methyl methacrylate)

Polysulfone
 ABS-polymers

Poly(ether sulfone)

Polycarbonate

Poly(ether imide)
 Macromolecules in the Crystalline State

Formation

Slow cooling of solutions/melts of
macromolecules having:
 no branching
 no copolymers
 regular substitution pattern
 highly iso- or syndiotactic
 Macromolecules in the Crystalline State

Degree of crystallinity

fraction of semi crystalline material is termed
as degree of crystallinity.

Reason of reduced crystallinity

 Difficulty in changing their shape from the
coiled state in the melt into the ordered one
necessary for their incorporation in a crystal
 Macromolecules in the Crystalline State
Models of crystallization process
 Fringed micelle model (Natural polymers)
 Cellulose and proteins (collagen, silk)
 Folded lamella model (Synthetic polymers)
 Polyethylene and polypropylene
 Macromolecules in the Crystalline State
Folded lamella model
 Growth of single crystals

Lamellae thickness (10-1000 micro meter)
 Role of tie molecules
 Macromolecules in the Crystalline State
Conformation of folded lamella
 Planar zigzag
 Crystalline polyethylene
 Helix (3-, 4-, or 5-fold)
 Polypropylene
 Polyoxymethylene
 3-fold helix of isotactic PP

A = carbon chain

B = cross-section

C = position of H atoms

Polymorphism
 Macromolecules in the Crystalline State

 Effect of elongational flow on crystallization

from solution

Fibrils: fibrillar crystals

 Crystallization from melt


Spherulites: containing both amorphous and crystalline
regions
 Recognizable under microscope (diameter: micro meters)

 Chain folding is not as regular as in single crystals

 Macromolecules in the Crystalline State

Factors affecting structure (morphology) of

spherulites
 Radial disposition
 Longitudinal extension
 Temperature
 External conditions

Pressure

Orientation
 Number of nuclei
 Macromolecules in the Crystalline State

Factors affecting degree of crystallization

1. Structure(banda kesa he)
2. Branching (khaandan kesa he)
3. Polar groups(dost keese hain)
4. Annealing: long heating at a certain temperature(terbiat)
5. Slow cooling of the molten polymer(mizaj kesa he)
6. Contact with a suitable swelling agent(bahair kese jaye ga)
7. Symmetry along the main chain(zindgi me tawwazan)
8. Number and length of side chains(talaqat)
9. Nucleating
 Macromolecules in the Crystalline State

Basic properties of crystalline polymers

 Opaque
 Soluble in few organic solvents at elevated
temperature

Technical important crystalline polymers

• Polyethylene • Aliphatic/aromatic polyesters
• Polypropylene • Aliphatic/aromatic polyamides
• Aliphatic polyamides • Polytetrafluoroethylene
• Polyoxymethylene • Poly(phenylene sulfide)
• Poly(arylene ether ketone)s