MSE405

INTRODUCTION TO POLYMERS
Serife AKKOYUN, PhD

Metallurgical and Materials Engineering Department, Ankara, TURKEY

Fall 2020-2021
 Textbooks & References

• Paul C. Painter; Michael M. Coleman, Fundamentals of polymer science:

An introductory text, CRC PRESS

• Christopher W. Macosko, Rheology: Principles, Measurements and

Applications, Wiley/VCH; Poughkeepsie, NY, 1994.

• R.J. Young; P.A. Lowell, Introduction to Polymers, Second Edition, Chapman

&Hall, 1994.

• M. T. Shaw, Introduction to Polymer Rheology, John Wiley & Sons, Inc.

Hoboken, New Jersey, 2012.

• Other resources:
-Groupe Français de Rhéologie,
-Groupe Français d’études et d’Application des Polymères

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 CHAPTER I
-
GENERALITIES ON POLYMERS

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 Polymers and Polymer Materials
Everywhere: DNA, packaging…
Countless applications:
- packaging (PE)
- bottles (PET)
- pipes (PVC)
- paper (cellulose)
- rubber
- textile fibers (polyester, polyamides…)
- polyurethane foams, polystyrene foams
- adhesives (AralditeTM…)
- coatings, painting, varnish, nail polish
- transport
- prostheses
...

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 Polymer Science
Polymer Science involves different aspects of Science:

Chemistry: Synthesis of monomers, polymers

Development of novel monomers and polymers
Chemical modification of polymers

Physical chemistry: Polymer solutions

Physics, Rheology
Engineering: Processing

Growth in industrial applications of polymers due to:

- Processing ease
- Various structures can be obtained
Wide range of properties accessible
- Possibility to modify the polymer according to the desired properties

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1 - Terminology
Polymer: (Greek ‘poly’ meaning ‘many’ and ‘meros’ meaning ‘parts’)
Very long-chain molecule, also denominated as macromolecule, of very high
molecular weight, often measured in hundreds of thousands and composed of
smaller building blocks linked with covalent bonds

Polyethylene (PE), synthetic polymer

DNA, natural macromolecule

Macromolecules usually have a random coil conformation and sometimes rod

conformation

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 1 - Terminology
Monomer: Building block of a polymer also called subunit or repeating unit

Polymerization

MONOMERS
POLYMER CHAIN

Plastic: Polymer + Additives (plasticizers, stabilizers, surfactants…)

Homopolymer: All the monomers are the same

Copolymer: Polymer composed of different monomers

Blend: Mixture of polymers

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1 - Terminology
• Polymer materials are often composed of entangled random coils.
• Entanglements and macromolecular character bring specific properties to
Polymer Materials and Polymer Solutions:

Polymer Materials:
- Elastomers,
- Thermoplastics,
- Thermosets …

Polymer Solutions:
- High viscosity even at low
concentrations,
- Thickeners, gelling agents…

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 2 - Classification
2.1 - Natural Polymers - Synthetic Polymers

NATURAL POLYMERS
• Extracted from nature and purified
- natural rubber latex,
- polysaccharides: cellulose, starch, carrageenans,…
- polypeptides: collagen, gelatin…

• Obtained from chemical modification of natural polymers

- cellulose acetate,
- viscose (artificial silk),…
- nitrocellulose (highly flammable, expolsive)
- celluloid…

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 2 - Classification
2.1 - Natural Polymers - Synthetic Polymers
SYNTHETIC POLYMERS
• Obtained from the polymerization of synthetic monomers
Chain-growth polymerization Step-growth polymerization
(polyaddition): (polycondensation):
polystyrene (PS),
polyesters (PET),
polyethylene (PE),
polyamides (NylonTM),
polypropylene (PP),
polyurethane (LycraTM),
polyvinyl chloride (PVC),
epoxy resins (AralditeTM)
polyacrylic acid (PAA),
…
polyvinyl alcohol (PVA)
polyethylene oxide (PEO)
silicones
…
• Obtained from chemical modification of synthetic polymers

polyacrylonitrile (PAN) : carbon fibers precursor

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 2 - Classification
2.2 - Thermoplastics - Thermosets

THERMOPLASTICS (TP):

• No covalent bonding between polmer chains but only

entanglements.
• Flow more easily when squeezed, pushed or stretched by a load,
usually at elevated temperatures.
• Reprocessable

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 2 - Classification
2.2 - Thermoplastics - Thermosets

THERMOSETS (TS):

• Covalent bonding between polmer chains.

• Cross-links are formed between the chains when heated/cured.
• Liquid or solid form at ambiant temperature.
• Not reprocessable

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 2 - Classification
2.2 - Thermoplastics - Thermosets
THERMOPLASTICS (TP): soften when heated
Injection
TP pellets Heating Softer and molding
TP will harden in the shape
or powder more fluid of the mold
Cool mold
can be reprocessed many
times

THERMOSETS (TS): cure or harden into a given shape when heated

Irreversible chemical reaction, polymer chains are crosslinked

Sulfur
PBD Network a TS doesn’t remelt
Three-dimensional or regain
Curing / vulcanization structure the processability it had before
Irreversible chemical
being cured
reaction (cross-links)

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 2 - Classification
2.3 – Polymer Performances Pyramid

/Engineering

C&EN, 2016, 94 (9), pp 23–24

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 3 – From Monomer to Macromolecule
Synthetic Polymers : Examples

Propylene Polypropylene
CH3 CH3 n
(propene)

n
Styrene Polystyrene

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 3 – From Monomer to Macromolecule
Synthetic Polymers : Examples

HO O C (CH 2) 4 COOH + H 2N (CH 2) 6 N H2

HOOC (CH 2) 4 CON H (CH 2) 6 N H2 + H 2O

OC (CH 2) 4 CON H (CH 2) 6 NH

n
Polyamide 6,6

! 2 Monomers here

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 3 – From Monomer to Macromolecule
Natural Polymers :
Examples of Starch and Cellulose OH
OH
O
HO O
HO O
OH HO OH
OH OH

O Cellulose: b (1-4) bond

HO
HO OH OH
OH
b-D-glucose O
HO OH
HO
OH O
O
HO OH
Starch : a (1-4) bond OH

The only difference is the type of the glycosidic bond:

cellulose : b (14) Different properties
starch : a(14)
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 3 – From Monomer to Macromolecule

Example of DNA: double helix

Monomers: Nucleotides

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 3 – From Monomer to Macromolecule
Polymers are high molecular weight compounds
Molecular weight has an influence on the properties of the material

polymer
oligomer

Properties

log M

Schematic representation of the evolution of the properties

 Generally, the higher the molecular weight, the tougher/stiffer the polymer.
But, too high molecular weight polymer processing difficulties.

 Optimum molecular weight depends on: - the chemical structure

- the application of the polymer.
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 4 – Molecular Weight & Molecular Weight Distribution
A polymer sample = mixture of chains of different lengths

 Distribution of chain lengths / molecular weights

 Average molecular weights

Number of Molecules

114,1

Molecular Weight
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 4 – Molecular Weight & Molecular Weight Distribution

M : Molecular weight of the macromolecule

X : Degree of polymerization = Number of repeating unit into the macromolecule
M0 : Molecular weight of the subunit

M = M0.X

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 4 – Molecular Weight & Molecular Weight Distribution
• A mixture of chains of different lengths is considered: X1 = 10; X2 = 20
• Molecular Weight of the repeating unit assumed to be M0 = 100 g/mol

Chain 1 X1 = 10, M1 = 1000 g/mol

Chain 2 X2 = 20, M2 = 2000 g/mol

If a mixture of 1 mole of each polymer is considered:

1 chain of length 10
1 chain of length 20

What is the Number Average Molecular Weight of the sample?

What is the Weight Average Molecular Weight of the sample?

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 4 – Molecular Weight & Molecular Weight Distribution
Number Average Molecular Weight of the mixture
X1 = 10, M1 = 1000 g/mol

X2 = 20, M2 = 2000 g/mol

Number of chains: Nb of Chain 1 (N1) + Nb of Chain 2 (N2) = 2 moles

Molecular weight of the sample (mixture) : 1000 + 2000 = 3000 g/mol

Number Average Molecular Weight :

Generally,

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 I.4 – Molecular Weight & Molecular Weight Distribution
Number Average Degree of Polymerization (or average length of chains)

X1 = 10, M1 = 1000 g/mol

X2 = 20, M2 = 2000 g/mol

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 I.4 – Molecular Weight & Molecular Weight Distribution
Generalization of the equations

N1 = 1 mol, X1 = 10, M1 = 1000 g/mol

N2 = 1 mol, X2 = 20, M2 = 2000 g/mol

N3 = 1 mol, X3 = 25, M3 = 2500 g/mol

Xn  10  20  25  18,33....
3

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 I.4 – Molecular Weight & Molecular Weight Distribution
Weight Average Molecular Weight & Weight Average Degree of Polymerization

N1 = 1 mol, X1 = 10, M1 = 1000 g/mol

N2 = 1 mol, X2 = 20, M2 = 2000 g/mol

N3 = 1 mol, X3 = 25, M3 = 2500 g/mol

The first macromolecule corresponds to 1/3 of the number of chains in the

sample but only to 18,18% of the total molecular weight
Weight Average

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 I.4 – Molecular Weight & Molecular Weight Distribution

Effect of Averages

An African Elephant of 5 tonnes with

99 mosquitos of 1 mg each on it.

 Calculate the Number Average and Weight Average Molecular Weights.

 If your car crashes on this ensemble (elephant + mosquitos), which average
should be taken into account to estimate the damages?

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 I.4 – Molecular Weight & Molecular Weight Distribution

Polydispersity index

Ip = 1 All the chains have the same length

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 I.4 – Molecular Weight & Molecular Weight Distribution
Experimental determination of MW
Different methods exist but they don’t give access the same average:
 Generally, diluted polymer solutions

Absolute methods:
-Number Average Molecular Weight: Osmotic Pressure, NMR, Maldi Tof
-Weight Average Molecular Weight: Light Scattering
Relative methods:
-Viscosimetric Average Molecular Weight Mv : Viscometer measurements
Mv Mw Mark – Houwink
- Size Exclusion Chromatography (SEC) (Calibrations: PS, POE, PMMA…)
Global methods:
- Pecipitation and dissolution

 Polymer melts: Comparison of melt viscosities

Viscosity Index (Melt Index) 27
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