Polymer Science and Analysis MATS545

by Dr. Igor Krupa, QAPCO Polymer Chair,

Center for Advanced Materials, QU

T +974 4403 5671

M +974 7778 9361
E-mail: [email protected]

1
 Electrostatic forces and their influence on polymer properties
in solutions and solid phase
1. Solubility of polymers in solvents
2. Mutual miscibility/immiscibility polymers
Behavior of polymers which strongly depends on EF.
3. Crystallization behavior
4. Mechanical properties

Types of Attractive Intermolecular Forces

1.Dipole-dipole forces: electrostatic interactions of permanent dipoles in molecules;
includes hydrogen bonding.
2.Ion-dipole forces: electrostatic interaction involving a partially charged dipole of one
molecule and a fully charged ion.
3.Instantaneous dipole-induced dipole forces or London dispersion forces: forces caused
by correlated movements of the electrons in interacting molecules, which are the
weakest of intermolecular forces and are categorized as van der Waals forces.
 Amorphous and crystalline state

Amorphous state (from the Greek a, without, morphé, shape, form) is a

solid without any long-range order characteristic.

A crystal or crystalline solid is a solid material whose constituent

atoms, molecules, or ions are arranged in an ordered pattern extending
in all three spatial dimensions.

Crystalline state Amorphous state

Na

Cl

NO Geometrical structural unit

Geometrical structural unit No pattern repeats
NaCl (it repeats infinity times)
 Glass transition temperature (Tg) and melting temperature (Tm)

• The glass transition temperature, Tg, is the temperature at which the

amorphous domains of a polymer take on characteristic glassy-state
properties; brittleness, stiffness and rigidity (upon cooling)

• Tg is also defined as the temperature at which there is sufficient energy for

rotation about bonds (upon heating)

• The melting temperature, Tm, is the melting temperature of the crystalline

domains of a polymer sample

• The operating temperature of polymers is defined by transition

temperatures
 Amorphous state

• Completely amorphous polymers exist as long,

randomly coiled, interpenetrating chains

• Chains are capable of forming stable, flow-restricting

entanglements at high molecular weight:
• In the melt, long segments of each polymer chain moves in
random Brownian motions
• As the melt is cooled, a temperature is reached at which all
long range segmental motions cease (glass transition
temperature, Tg)

• In the glassy state, at temperatures below Tg, the only

molecular motions that can occur are short range
motions i.e. secondary relaxations
 Amorphous state

The glass-liquid transition is the reversible transition in amorphous materials (or in

amorphous regions within semicrystalline materials) from a hard and relatively brittle
state into a molten or rubber-like state. An amorphous solid that exhibits a glass transition
is called a glass.
Random coil (chain)

NO Geometrical structural unit

Nothing repeats
 Effect of the main chain structure on glass transition (Tg)

• Ring structures or unsaturated chemical bonds in the polymer

backbone stiffen the chain structure and increase the Tg

• Strong polar interactions increase the glass transition temperature

• Side groups in polyacrylnitrile are not large but due to polarity Tg is (104 °C)
 Effects of the structure on glass transition (Tg)

• Glass transition temperature is affected by:

• Polar, intermolecular forces increase Tg

• Bulky side groups increase Tg
• Syndiotacticity increases Tg
• Trans-isomers have higher Tg than cis-isomers
• Main chain flexibility lowers Tg
 Effect of molecular weight on Tg

• For many polymers, Tg increases as average molecular weight increases until a

limiting value. After this any further increase in molecular weight does not
increase the Tg
• Fox-Flory equation can be used to estimate the dependence of Tg on molecular weight:
K
Tg  Tg 
Mn
Tg = the limiting value of Tg at high molecular weight

K = constant for a given polymer

M n = number average molecular weight

• K is not constant for molecular weights below 10 000 g/mol

 Effect of branching on glass transition (Tg)

• Branches lower the glass transition temperature which is mainly due

to the increased number of end groups

• Poly(vinyl acetate)
• Highly branched Tg = 25.4 °C
• Only few branches Tg = 32.7 °C
 Effect of crosslinking on glass transition (Tg)

• Long range segmental motion is restricted by crosslinking, thus

crosslinking elevates the glass transition temperature
• Tg increases with an increase in the degree of crosslinking

• Note! Extensive crosslinking causes high chain rigidity which

completely prevents crystallization
 Effect of plasticizer on glass transition (Tg)

• Tg of a good plasticizer needs to be lower than the Tg of the polymer

• Inverse rule of mixtures (Fox equation when applied to Tg):

1 w1 w2
 
Tg TgP Tg1

Tg = glass transtion temperature of the composition

Tgp = glass transition temperature of the polymer
Tg1 = glass transition temperature of the plasticizer
w1 = weight fraction of the polymer (%)
w2 = weight fraction of the plasticizer (%)
 Parameters affecting glass transition temperature: summary

Polymer based: Processing based:

• Chain stiffness: • Plasticizers and solvents
• Structure of the backbone • Blends
• Side groups and • Fillers
branching
• Stereoregularity • Orientation
• Crosslinking • Rate of cooling
• Copolymers
• Intra- and intermolecular
secondary interactions
• Average molecular weight
• Degree of crystallinity
 Behavior of selected physical properties near Tg

v α Cp λ E

Tg T Tg T Tg T Tg T Tg T

v [m3 / kg] α [K-1] Cp [J/kg.K] λ [W/m.K] E [Pa]

Specific volume Thermal expansion Specific heat Thermal Young’s modulus
coefficient capacity conductivity
 Crystallinity in polymers

• Crystallinity depends on the molecular structure of polymers

• No bulk polymer is completely crystalline

• In semi-crystalline polymers, regular crystalline units are linked by un-

orientated, random conformation chains that constitute amorphous
regions

• Presence of crystalline structures has a significant influence on physical,

thermal and mechanical properties
• Highly crystalline: polyolefins
• Totally amorphous: atactic PS and PMMA

The (Tm) is not a solid-liquid phase transition, but a transition from a

crystalline phase to a solid amorphous phase.
 Semicrystalline polymers

• Areas in polymer where chains

packed in regular way.
• Both amorphous and
crystalline areas in same
polymer.
• Crystalline - regular chain
structure - no bulky side
groups.
• More crystalline polymer -
stronger and less flexible.
 Structure at Different Length Scales

• Chains weave back and forth to create crystalline sheets, called

lamella.
• A chain is not usually entirely contained within a lamella:
portions of it can be in the amorphous phase or bridging two
(or more) lamella.
• The lamella thickness, L, is typically about 10 nm.

Lamella stacks
L

From R.A.L. Jones, Soft Condensed Matter, O.U.P. (2004) p. 130

 Semicrystalline polymers
Random coil in the molten state (PE, PP)

Cooling of the melt

Lamellae formed during crystallization from Schematic model of a spherulite. Black arrows
the melt. indicate direction of molecular alignment

Typical size is of the order 1 micrometer

Factors that Inhibit Polymer Crystallisation

1. Slow chain motion (associated with high

viscosity) creates a kinetic barrier

2. “Built-in” chain disorder, e.g. tacticity

3. Chain branching
 Tacticity Builds in Disorder

Isotactic: identical repeat units

Easiest to crystallise

Syndiotactic: alternating repeat

units

Atactic: No pattern in repeat units

Usually do not crystallise

R.A.L. Jones, Soft Condensed Matter (2004) O.U.P., p. 75

 Polymer Architecture

Linear

Branched

Side-branched

Star-branched
Conformation and configuration of polymer chains in the lamellae

• For many polymers, the lowest energy conformation is

the extended chain or planar zig-zag conformation (for
example PE, polymers capable of hydrogen bonding)

• For polymers with larger substituent groups, the lowest

energy conformation is a helix (for example in PP, three
monomer units form a single turn in the helix)
 Crystallinity and the effect of hydrogen bonding

• Specific interactions (hydrogen bonding between

chains) enhance crystallinity

• Within nylons, hydrogen bonding between;

• Amide carbonyl group on one chain
• Hydrogen atom of an amide group of another chain
 Melting temperature of polymers

• Loss of crystalline structure causes many changes in properties when a

material changes into viscous fluid

• Polymer melting takes place over a wide temperature range due to the
presence of different sized crystalline regions and the complicated process
for melting large molecules

• Changes in various properties can be used to measure Tm:

• Density
• Refractive index
• Heat capacity
• Enthalpy
• Light transmission
 Effect of crystallinity on physical properties of polymers

• In most common semi-crystalline thermoplastic polymers, the crystalline

structure contributes to the strength properties of the plastics
• Crystalline structures are tough and hard and require high stresses to break them

• Mechanical properties of semi-crystalline polymers are mostly dependent

on the average molecular weight and degree of crystallinity

• Crystallinity affects the optical properties

• The size and structure of crystallites