Polymer Science and Engineering - Part III

Characterization and
Analysis of Polymers
Zenamarkos B. (PhD)
Process Engineering Program
Faculty of Chemical and Food Engineering
Bahir Dar Institute of Technology (BiT)
Bahir Dar University
August, 2019
1
Polymer Science and Engineering
Content
I. Polymer Physics and Engineering:
o Fundamentals of polymer science and engineering
o Polymer Synthesis reactions kinetics
• polymerization mechanisms and kinetics
o Morphology of Polymers
• Amorphous polymers
• Crystalline polymers
o Properties of Polymers
• Flow
• Mechanical
• Thermal
2
Introduction
Why do polymers need more and different characterization techniques?
o If the polymer contains pendant groups (‘side chains’), are they stereoregular
or randomly oriented and how along the chain distributed?
o Is the polymer linear or branched (only a very small, localized number of
monomeric units in a chain is “branching”, but the effects are global)
o How are different monomeric units distributed along the chain (block
copolymers, grafted copolymers)?
o Is the polymer cross-linked, and if yes, how dense?
o What is the conformation of the polymer chain in solution, melt or solid state?
o What is the nature of the end groups of a polymer chain?
o How long is the chain, how does the molecular weight distribution look like?
3
Introduction
Structures and Conformations of Polymer Chains
❖ Different from low molecular weight molecules, the many possible

conformation of the long polymer chains in melt, solution or the solid
state have an impact on the properties of the polymer
4
Introduction
Structures and Conformations of Polymer Chains
5
Introduction
Why do we need to know those structural characteristics?
❖ Structure-Property relationships: Knowing the structure helps to explain

and predict the properties of a polymer
- Mechanical properties (strength, toughness, hardness…)
- Thermal Properties
- Flow Properties
❖ Very often empirical (but tabulated) structure-property relations exist, that

allow the determination of a certain property from an easy accessible
structural characterization (and vice versa!)
6
Molecular Weight (Distribution)
7
❖ A polymeric material consist of polymer chains of various lengths or

repeat units.
➢ Hence, the molecular weight is determined by the average or
mean molecular weight.
Relative
fraction
Molecular weight
Representative differential weight distribution curves
8
❖Number average: simply counts the molecules.
Average Molecular Mass

o We add up the mass of all molecules and
divide by the number of molecules:
o This is equivalent to adding up the molar

fractions of each molecular weight.
9
❖Weight Average: adding up the weight

fractions of each molecular.
10
❖ Z-average: determined with ultra-

centrifugation.
✓ not as intuitive to understand as the
number or weight average.
11
Polydispersity Index (PDI)
➢A measure of the breadth of the molecular-weight distribution
12
❖The properties of polymeric

material are strongly linked to
the molecular weight of the
polymer.
Relationship of polymer properties to molecular weight

13
Relation between molecular weight, temperature and properties of a typical thermoplastic

for a given time scale.
14
❖ Hence, it is necessary to find the molecular weight that renders ideal

material properties for the finished polymer product, while having flow
properties that make it easy to shape the material during the
manufacturing process.
➢ The flow properties (temperature) are highly influenced by the

time scale required for a polymer molecule to flow or deform.
➢ At a specific temperature, a polymer melt may behave as

a solid if the time scale is reduced sufficiently.
=> Time-temperature superposition principle

15
➢Low polydispersity index-grade

materials render higher-strength
properties and flowability, or
processing ease, than high
polydispersity index grades.
Fig. Effect of molecular weight on the strength-

melt flow index interretationship of polystyrene for
three polydispersity indices.
16
Morphology of Polymers and
their Thermal Properties
17
Morphology of Polymers
❖Molecular shape and the way molecules are arranged in a solid are
important factors in determining the properties of polymers.
❖The molecular structure, conformation and orientation of the polymers

can have a major effect on the macroscopic properties of the material.
✓ From polymers that crumble to the touch to those used in bullet

proof vests
Semi-crystalline Amorphous
18
Morphology of Polymers - Amorphous Polymers
❖High molecular weight linear amorphous polymers which can be

considered as entangled coil-like chains can display different types of
behaviour depending on the temperature.
✓ as the temperature increases, they can show glassy, viscoelastic,

rubbery, and viscous liquid behaviour.
Polymer chains with entanglements

19
Glassy state:
- polymer: hard and elastic
- chain segments are ‘frozen’
- no rotational and translational motions
- only local vibrations
At glass transition temperature (Tg):
- segment rotation
- start of short range diffusional motions of chain segments
- width of Tg region: 5-20 °C
Above Tg region: Rubbery State:
- fast short range motions
- restricted long range motion due to entanglements!
Flow region:
- long range motion: viscous liquid
20
21
Modulus-Temperature Behaviour
1. glassy state: high modulus
2. glass transition region: diffusional motion

of chain segments ~ 10s
3. rubber plateau, elastic,

entanglement limited motion
4. flow region: viscous liquid,

translational motion:
not for crosslinked materials!
Schematic modulus-temperature curve showing various regions of viscoelastic behaviour

22
identical behaviour determined by

short range movement
Molar mass dependence:

determined by long
Low Mn: Mn = 104 range movement;
- Tg shifts i.e. entanglement density
- (more free volume ~ mobility due to chain ends)
- no rubber plateau (critical molar mass for
entanglements!)
10 sec modulus versus temperature curves for polystyrene of different molecular weights
23
o Highly cross-linked
amorphous polymers do not
flow.
o Decomposition at high T.
o For high cross-linking also
increase in Tg.
24
Glass Transition
25
❖ The following structural factors have an influence on the value of Tg of

amorphous polymers:
➢ Chemical structure of the main chain
➢ Side groups and branching
➢ Molar mass and degree of cross-linking
➢ crystallinity
26
27
28
known as the Fox-Flory equation where

Tg∞ is the value of Tg for a polymer
of infinite molecular weight, K is a
constant.
29
Morphology of Polymers - Semi-Crystalline Polymers
Tm<Tf
❖ Example of semi-crystalline polymer
with Tm<Tf
o Crystalline segments melt at Tm
o At low Tf, entanglements
disappear
o Tg effect is more modest (limited
to amorphous segments)
o Better dimensional stability
above Tg
Tm>Tf
❖ Example of semi-crystalline polymer
with Tm>Tf
o After melting, no rubbery state
o Lower melt viscosity
30
Morphology of Polymers - Semi-Crystalline Polymers
❖Example of Tm>Tf
o Crystallinity reduces Tg effect
o Crystal regions increase E
o Crystals act as entanglements
31
Morphology of Polymers - Crystalline Polymers
Melting Behaviour
32
Melting Behaviour
33
Degree of Crystallinity
34
❖ For semi-crystalline polymers, the degree of crystallinity can be controlled.
❖ Many polymer properties improve/increase with improved crystallization:

o Density o Dimensional stability
o Hardness o Abrasion resistance
o Yield stress o Resistance to ageing
o Creep resistance o Chemical resistance
❖ Some properties decrease with crystallinity improvement:

o Permeability
o Water absorption
o Thermal expansion coefficient
35
Experimental Study of Melting Behaviour - DSC
❖ Measures difference in heat flow between sample (S2) and reference (S1) =
measures differences in heat capacity of the sample.
5-20 mg sample
Al as reference
• Melting enthalpy = integral of peak area

36
Mechanical Properties
of Polymers
37
Mechanical Properties of Polymers
38
39
40
41
42
43
1) Tensile testing on dumbbell/dogbone shaped samples

• To concentrate high stress and deformation in central region.
• Best to measure elongation with extensometer (or by strain mapping)
• Standard conditions: 23oC and 50% RH
44
❖ Flexural Strength
• Easy to measure
• Combination of tension (zone 3), compression (zone 1) and shear (zone 2)
• Shear can be neglected for span/thickness > 16: pure bending
• If no failure, e.g., stress at 5% strain is used for strength
45
❖ Compression Strength
• Care should be taken to prevent buckling
• Use relatively short test span
46
❖ Heat Deflection Temperature

• Critical creep temperature
• Temperature at which sample slags more than certain value under constant
load, at certain heating rate.
47
❖ Heat Deflection Temperature
• HDT as function of Tg
48
❖ Vicat Softening Point

• Temperature at which vicat needle penetrates sample for more than 1 mm
• (cross-section of needle 1mm2, 1 kg weight)
49
❖ Strength of polymers is
strain rate dependent
➢ On slow loading, lower strength due to creep 50
3) Plastic drawing above the Tg

(~ 50oC above Tg)
• Referred to as cold drawing
• Orientation of the polymer
chains
• E.g., used to make fibers
(with up to 8 times higher
strength and modulus)
51
52

Polymer Science and Engineering - Part III

Uploaded by

Document Information

Original Description:

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Polymer Science and Engineering - Part III

Uploaded by

Copyright:

Available Formats

Characterization and

❖ Different from low molecular weight molecules, the many possible

❖ Structure-Property relationships: Knowing the structure helps to explain

❖ Very often empirical (but tabulated) structure-property relations exist, that

❖ A polymeric material consist of polymer chains of various lengths or

❖Number average: simply counts the molecules.

Average Molecular Mass

o This is equivalent to adding up the molar

❖Weight Average: adding up the weight

Average Molecular Mass

❖ Z-average: determined with ultra-

Average Molecular Mass

➢A measure of the breadth of the molecular-weight distribution

Average Molecular Mass

❖The properties of polymeric

Relationship of polymer properties to molecular weight

Relation between molecular weight, temperature and properties of a typical thermoplastic

❖ Hence, it is necessary to find the molecular weight that renders ideal

➢ The flow properties (temperature) are highly influenced by the

➢ At a specific temperature, a polymer melt may behave as

=> Time-temperature superposition principle

➢Low polydispersity index-grade

Fig. Effect of molecular weight on the strength-

❖The molecular structure, conformation and orientation of the polymers

✓ From polymers that crumble to the touch to those used in bullet

❖High molecular weight linear amorphous polymers which can be

✓ as the temperature increases, they can show glassy, viscoelastic,

Polymer chains with entanglements

1. glassy state: high modulus

2. glass transition region: diffusional motion

3. rubber plateau, elastic,

4. flow region: viscous liquid,

Schematic modulus-temperature curve showing various regions of viscoelastic behaviour

identical behaviour determined by

Molar mass dependence:

❖ The following structural factors have an influence on the value of Tg of

known as the Fox-Flory equation where

o Crystallinity reduces Tg effect

o Crystal regions increase E

o Crystals act as entanglements

❖ Many polymer properties improve/increase with improved crystallization:

❖ Some properties decrease with crystallinity improvement:

• Melting enthalpy = integral of peak area

1) Tensile testing on dumbbell/dogbone shaped samples

❖ Heat Deflection Temperature

❖ Heat Deflection Temperature

❖ Vicat Softening Point

3) Plastic drawing above the Tg

You might also like