Polymeric Materials – Part I

Vitor Sencadas
victors@uow.edu.au
B1.121
 After this unit you should be able to:

• Know what polymers are and understand their classification based on structure,
properties and chemical composition;
• Estimate the number and weight-average molecular masses of polymers given
the degree of polymerization and mass fraction of chains present;
• Identify the glass transition temperature
• Classify polymers according to their steric structure
• Understand the concept of elastomeric materials

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 Polymer Structure
Let’s recall the ubiquitous triangle which defines materials science as the study and application
of the relationships between the material properties, the structure required to obtain these
properties, and the processing methods which can be used to obtain these properties.

Processing

Characterization

Structure Properties

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 What is a Polymer?

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 Definition
Poly mer

Many Unit

Nature also poduce polymers

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 There is another word to identify these materials

Any suggestion?

Plastic – from Greek, πλαστικός (Plastickos)

Meaning, capable of being shaped or “molded”

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 Introduction

Polymers can be classified according to their source

Natural Polymers – cellulose, lignin and proteins, providing the mechanical basis
of most plants and animals

Synthetic Polymers – Industrially produced from Brent

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 Natural Polymers

 Cellulose and lignin – paper

 Collagen and elastin – muscle and bone

 Chitosan – from shell fish, applied as biomaterials

 Gelatine – sweets but also as a promising biomaterial

 Silk – clothes, biomaterials, air and water filters

 Lactoferrin – milk protein used as potent antibacterial

 Etc….

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 Introduction

• Polymers  Poly (many) + mer (unit)

– Material composed by long molecular chains, that is built from smaller units
(monomer)

PE – Poly(ethylene)

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 Synthetic Polymers
Polymer Chain
PE – Poly(ethylene)
H Hydrogen

C Carbon
Monomer

Repeat Unit

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 Synthetic Polymers

• The chemical reaction forming polymers from monomers is called polymerization

• In the end of polymerization long chains are obtained

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 Synthetic Polymers Repeat unit (monomer)
Gas at 25ºC Initiator = Radical

• The initiator will break the double bond

• This continue until there is no more ethylene monomer available or we shut down the
reactor
• The number of units (n) can reach higher numbers: 100 < n < 10000
• The polymer can be a short-chain polymer or a long-chain polymer, depending of number n
• n is also known has Degree of Polymerization (DP)

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 Synthetic Polymers

Degree of polymerization (DP)

where
• is the number average molecular weight of the polymer chain
• a is the atomic weight of the monomer

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 Example – single polymer chain

If we think about PE atomic mass (Ma): = 12 ∗ 2 +1∗4 = 28 /

• If n = 10000 How much does a mole of PE weight?

Mn = 280,000 g/mol or Da (Dalton)

H 1 g/mol

12 g/mol This for a single PE chain

C

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 Example – two polymer chains

Imagine that the PE has a equimolar mixture of two chains with:

• DP1 = 3,000
How the final number average molecular
• DP2 = 10,000 weight of the polymer will be affected?

Previously,

• DP1 = 3,000;  Mn1 = 28*3,000 = 84,000 g/mol

Two number average
• DP2 = 10,000;  Mn2 = 28*10,000 = 280,000 g/mol molecular weight?????

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Molecular weight distribution

The repeat unit for this polymer consists of a blue and green unit, together = Monomer

This molecule has N=3 This molecule has N=10.5

• The degree of polymerization (n or DP) is the number of repeating units for a single molecule.
• Due to the statistical nature of the polymerization process (we can chains with different
lengths), a broad distribution of molecular weights is often obtained.
• Various averages are typically used to characterize the molecular weight distribution.

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 Example
- molecular weight of a chain
number-average molecular weight ( ): - is the number of molecules
with weight

∑ Mn1 = 28*3,000 = 84,000 g/mol

=
Mn2 = 28*10,000 = 280,000 g/mol

Equimolar = 0.5Mn1 + 0.5Mn2

0.5 ∗ 84,000 + 0.5 ∗ 280,000

= = 182,000 /
0.5 + 0.5

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 Example - molecular weight of a chain
weight-average molecular weight ( ): - is the number of chains
- weight fraction of a polymer
with molecular weight

∑ ∑
= or =

Equimolar = 0.5Mn1 + 0.5Mn2

(0.5 ∗ 84,000 ) + (0.5 ∗ 280,000 )

= = 234,769.2 /
0.5 ∗ 84,000 + 0.5 ∗ 280,000
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 Example – two polymer chains

Same polymer with two different solutions?????????

0.5 ∗ 84,000 + 0.5 ∗ 280,000

= = 182,000 /
0.5 + 0.5

(0.5 ∗ 84,000 ) + (0.5 ∗ 280,000 )

= = 234,769.2 /
0.5 ∗ 84,000 + 0.5 ∗ 280,000

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Molecular weight distribution
The complete distribution of molecular sizes can be described by a histogram:

: number of molecules with degree of polymerization = N

: weight of all molecules with degree of polymerization = N

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 Why two different solutions?????

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 Example

~ ,
= = = 1.29
,

Polydispersivity (PDI)

The ratio between and is called polydispersivity or dispersion.

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 Distribution of the molecular weights for a typical polymer

Can the PDI be less than 1?????

= <1

If this happen, revise your calculations

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 ~ ,
= = 1.29
,
3

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 Let´s get back to a single PE polymer chain

PE monomer atomic weight (Ma): = 12 ∗ 2 +1∗4 = 28 /

• If n = 10000 How much does a mole of PE weight?

Mn = 280,000 g/mol or Da (Dalton)

H 1 g/mol

C 12 g/mol

This for a single PE chain

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 In liquid state how is this single molecule going to be?

Solid? or Viscous?

If they are viscous, what will happen to

their structure after crystallization?

• Are they form ordered solid? With one

molecule at each lattice side?

or

• Will they form disordered solids?

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How Polymer Chains held together when forms a solid?
• Is a Ionic bonding
• Is a Metallic bonding
• Is a Hydrogen bonding?
or

• Is it a Van der Walls bonding?

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 During Crystallization…….

Liquid = Amorphous chains

When cooling

• Some regions can achieve some order lowering the energy of the system

What will happen to Polymer Mechanical Properties?

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 Example – Polymer chain length (L)

Calculate the average of total chain length, L, for a linear polyethylene polymer with
an average molecular weight of 300,000 g/mol?

Previously……

= ma(PE) = 12*2(C)+1*4(H) = 28 g/mol

300,000
= = = 10,714  The number of repeating units along the chain
28

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 Example – Polymer chain length (L)

Two C – C in each monomer, there will be a total of

(2*10,714 = 21,428) chain bonds in the molecule n.

C – C = 0.154 nm,

Q = 109º for PE Polymer chain length (L)

109 = . sin( )
= 10,714 ∗ 2 ∗ 0.154. sin( ) 2
2

= 2686 which is higher than the wavelength of visible light

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 But, what does this number means?

= 2686 or ≈ 3

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 How about the end – to end – distance?

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Freely Joined Chain Model: polymer chain end-to-end distance
 The real chain is replaced by a set of points joined by n equal one-dimensional links of
length l. The fully extended length is then nl.
 It is assumed that there is no restriction on the angles between the links: the angles are not
restricted to lie on cones.
 It is assumed that no energy is required to change the angles.
 In this picture 12 individual backbone bonds are represented by the black vectors. The end-
to-end distance (shown in red) is obtained by adding up all Nb bond vectors.

end-to-end distance

= = ⃗ + ⃗ + ⃗ + ⃗ + …… + ⃗

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 Return to the Example How about the distance between the end and
the beginning of the Polymer Chain?

- chain end – o – end distance

– distance between the C – C
– number or C – C bonds in the molecule

= 0.154 21,428 = 22.5

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 Key Ideas

• Solid at room temperature  Van der Walls bonding is present everywhere

• Viscous as liquids

• Can be amorphous solids

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 If  = and >
V

<

Vf

Vs

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 For PE Same material, with different processing: HDPE and LDPE

V <
Faster cooling or quenching leads to
more free volume

LDPE
>
Vf
- is a measure of disorder
Vs
HDPE
T

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 What is the difference between:

high disorder low disorder The amount of organized

regions increase

• E increases
• Stiffness increases
• Improved mechanical properties

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 Applications:

Food wrap, where you can stretch and align the polymer
chains in the draw direction

Plastic bags or shampoo bottles, etc…..where mechanical

properties are important

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  Photon energy
Optical properties:
nc If the material is amorphous  is
transparent

But

Due to the light interaction with the

na
crystalline and amorphous regions, there
will be diffraction and the material will
≠ appear to be white

REMEMBER that material density is

Interface between the amorphous different
and crystalline regions <

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How can I distinguish this regions?

Crystalline region

PE = orthorhombic cell unit

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Amorphous region
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Tailoring molecular properties of polymers

PE PVC
• Synthesis
• Processing
• Composition
• Catalysis

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 Tailoring molecular properties of polymers

• “Pure”  homopolymer, same mer used, e.g. PE

• “Alloy”  Copolymer, more than one mer type, e.g. PE-c-PVC

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Tailoring molecular properties of polymers

PE-a-PVC

PE-r-PVC

PE-b-PVC

PE-g-PVC

Long side chain of other polymer

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Tailoring molecular properties of polymers
Acrylonitrile – Butadiene - Styrene

Backbone
Side chains S S

B–B–B–B–B–B–B–B–B–B–B–B–B–B–B–B–B–B

A A

A Graft copolymer
A

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Steric Structure
Isotactic Polymer

Position of functional
groups

Syndiotactic Polymer

Atactic Polymer

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Backbone configuration
Homopolymer cartoons

Linear Polymer Chain

• Which of the chains occupy higher volume? Branch Polymer Chain, in this
case, the branches are made
• How about crystallization?
from the same homopolymer

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Backbone configuration
- Tg value depends on the molecular characteristics that affect chain stiffness;
- Chain flexibility is decreased and Tg is increased by the presence of the following:

1. Bulky side groups PP

Tg = -18 ºC PS (polystyrene)
Tg = 100 ºC

2. Polar groups
Tg = 185 ºC
PE PVC
Tg = -78 ºC Tg = 80 ºC
3. Aromatic groups in the backbone, which tend to stiffen the polymer chain

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Backbone configuration
1

3
What will happen if I place these
covalent bridges between the
1 chains?

2 How about the mechanical

properties of this polymer?
3

Cross-linked polymers are Rubbery or Elastomers

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Elastomers How to link this two Polymer chains by covalent bonding?

–C–C–C–C C–C–C–C–C–

–C–C–C–C C–C–C–C–C–

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Elastomers How to link this two Polymer chains by covalent bonding?

–C–C–C–C C–C–C–C–C–

If I make this connection between chains, it

will break the chain.

–C–C–C–C C–C–C–C–C–

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Elastomers How to link this two Polymer chains by covalent bonding?

–C–C–C–C C–C–C–C–C–

What feature should chain displays after

polymerization?

–C–C–C–C C–C–C–C–C–

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Elastomers
How to link this two Polymer chains by covalent bonding?

We will need to have double bonds after

–C–C–C–C C–C–C– polymerization

–C–C–C–C C–C–C– How do I do that?

We will need to have double bonds, one for the chain polymerization and the other for
cross-link

Looking to Natural Rubber chain, they have butadiene:

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Elastomers
How about put a spacer in between?

–C–C–C–C C–C–C– What atom can do two covalent bond?

It could be O2, but it is to small and has to

? much strength.

How about sulphur?

–C–C–C–C C–C–C–

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Elastomers
How about put a spacer in between?

–C–C–C–C C–C–C–

–C–C–C–C C–C–C–

Sulphur can perform the

same double bonds as O2

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Elastomers

–C–C–C–C C–C–C–

S
Disulphide linkage – makes a good rubber
S

–C–C–C–C C–C–C–

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The Tyre Industry

Charles Goodyear

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 Polymer
(long chain molecules)

Plastics Rubbers
(rigid materials, E > 1 GPa) (flexible materials, E < 1 MPa)

TPEs
(thermoplastic elastomers)

Thermoplastics Thermosets Vulcanized rubbers

(uncrosslinked, heat reversible) (cross-linked, rigid) (flexible to rigid)

Fibres Composites
(any thermoplastic polymer)
(thermoplastics and thermosets)

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 After this unit you should be able to:
• Identify the melting transition temperature
• Briefly describe the crystalline state of polymers
• Describe/diagram the spherulitic structure for a semicrystalline polymer
• Make schematic plots of the characteristic stress-strain behaviour for polymers
• Describe/sketch the various stages in the elastic and plastic deformations of
semicrystalline polymers
• Name and briefly describe the five processing fabrication techniques used for
polymers processing

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During Crystallization…….

Liquid = Amorphous chains

When cooling

• Some regions can achieve some order lowering the energy of the system

What will happen to the Mechanical properties of the Polymer?

Crystallinity vs Liquid phase

V Glass transition temperature

Melting temperature

Vf
Does a pure amorphous Polymer melt?

Vs

T
The Practical importance of: &

• Both values are of practical importance

• In the solid, glassy state molecules possess little freedom of motion

• represents the onset of segmental motion

• Sets the upper temperature for the use of amorphous polymers: PMMA, PS

• Sets the lower limit of rubbery behaviour for elastomers, PB, SBS, SBR

• begins the fluid flow, chains actually entangle and begin free movement
Crystallites and Lamella

• Ordered regions of highly crystalline polymers are called crystallites

• Folded chain crystallites are termed lamellae
Semicrystalline Macrostructure

• During crystallization, the polymer microstructure present

several polycrystalline regions, called spherulites
• Formed from build-up of lamellar units
• Size varies with thermal history.
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Thank You!!!!!!!!!!!