Polymer Science
and Engineering
Zenamarkos B. (PhD)
Process Engineering Program
Faculty of Chemical and Food Engineering
Bahir Dar Institute of Technology (BiT)
Bahir Dar University
Jan, 2022
Polymer Science and Engineering
General Information:
Academic year: 2021/22
Study Points: 3 Cr
Language: English
Duration: 48 hrs
Periodicity: Taught in the 1st semester
Aim: Levelling of students bases in polymer physico-
chemistry and processing.
Course materials:
Text books, PPTs, Articles and Literature
2
Content
I. Polymer Physics and Engineering:
o Fundamentals of polymer science and engineering
o Polymer Synthesis reactions kinetics
• polymerization mechanisms and kinetics
• Polymerization Technologies
o Morphology of Polymers
• Amorphous polymers
• Crystalline polymers
o Properties of Polymers
• Thermal
• Flow
3
Content
II. Polymer Processing:
• Extrusion
• Injection Molding
• Blow Molding
• Thermoforming
• Fiber Spinning
• Compression Molding
4
Text books
5
Course Goal
Polymerization
6
Fundamentals of Polymer
Science and Engineering
7
Fundamentals of Polymer Science and Engineering
֍ Polymer: a macromolecule, composed of many repeated subunits.
Poly- => "many"
+
-mer => "parts" or “segment"
➢ Polymers are created via polymerization of many small molecules, known
as monomers.
Polypropylene
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Fundamentals of Polymer Science and Engineering
❖Polymers range from familiar synthetic plastics such as polystyrene to
natural biopolymers such as DNA and proteins that are fundamental to
biological structure and function.
Double helix DNA
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Fundamentals of Polymer Science and Engineering
Structures of the repeating units of some common polymers
(PET)
(PMMA)
(PIB)
10
Classification of Polymers
֍ There are many possible classifications of polymers.
➢ Polymerization Processes
➢ Structure
➢ Thermal Properties
➢ Physical Aggregation
➢ Chemical Composition
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Classification of Polymers – Polymerization Processes
i) Addition-Condensation Polymers:
➢ based on the compositional differences between the polymer and the
monomer(s) from which the polymers were synthesized.
Addition Polymers:
(diamines) (diacids)
Condensation
Polymers:
(polyamides)
12
Classification of Polymers – Polymerization Processes
ii) Step-growth/Chain-growth Polymers:
➢ based on the mechanisms of the polymerization processes.
➢ most important differences:
➢ Identities of the species that can react with each other
➢ The manner in which polymer molecular size depends on the extent of
conversion
Step-growth
Chain-growth
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Classification of Polymers – Polymerization Processes
Chain-growth
Step-growth
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Classification of Polymers – Structure
Branched
(A)
Linear
Branched
(B)
Branched
(C)
Crosslinked
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Classification of Polymers – Structure
❖ Linear Polymers
➢ Long chains, entangled with each other
➢ Higher molecular weight means higher strength
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Classification of Polymers – Structure
❖ Branched
➢ Leads to higher degree of entanglement
➢ promoted by special catalysts and processing
techniques.
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Classification of Polymers – Structure
❖ Crosslinked Polymers
▪ Crosslinking process:
✓ during polymerization (use of appropriate monomers) or
✓ after polymerization (by various chemical methods)
▪ Degree of crosslinking:
✓ High degree of cross-linking: thermoset resins like epoxy
✓ Lower degree of cross-linking: elastomers
▪ Effects:
✓ Stiffness (modulus) and strength typically increases with the number
of cross-links
✓ Very high cross-link density leads to brittleness
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Classification of Polymers – Thermal Properties
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Classification of Polymers – Thermal Properties
❖ Thermoplastics
➢ Linear or branched macromolecules, but no network.
➢ Macromolecules held together by van-der-Waals bonds, Hydrogen bonds or
polar interactions.
➢ Thermoplastic polymers can MELT !
➢ Typically processed by extrusion or injection moulding.
➢ Can in principle be (‘mechanically’) recycled.
➢ Typically dissolve in suitable solvents (depending on polarity matching)
➢ Polymers like PE, PP, PA, PS, PVC
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Classification of Polymers – Thermal Properties
❖ Elastomers
➢ Lower degree of cross-linking.
➢ Long, flexible chain segments between cross-links, hence elasticity.
➢ Typically, do not dissolve but swell.
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Classification of Polymers – Thermal Properties
❖ Thermoset Polymers
➢ Network polymers with almost infinitely high molecular weight.
➢ Obtained by cross-linking, typically of low molecular weight monomers
(low viscosity fluids); need cure cycle.
➢ Can not melt; decompose at high temperature.
➢ Difficult to recycle; perhaps pyrolysis or energy recovery.
➢ Typically do not dissolve.
➢ Tend to be relatively hard and brittle.
➢ Phenolic resin, PUR, Epoxy, ...
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Classification of Polymers – Physical Aggregation
❖Morphology (Thermoplastics!)
➢ Amorphous
➢ Semi-Crystalline
❖Tacticity
➢ Isotactic
➢ Syndiotactic
➢ Atactic
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Classification of Polymers – Physical Aggregation
❖ Amorphous Polymers
➢ Only physical entanglements.
➢ Transparent.
➢ Typically less resistant to chemicals, relatively easy to dissolve.
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Classification of Polymers – Physical Aggregation
❖ Semi-Crystalline Polymers
➢ Typically non-transparent unless crystallines are very small
➢ Very stiff and strong fibres can be made (increased inter-molecular forces)
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Classification of Polymers – Physical Aggregation
❖ Crystallinity in Polymers
➢ Double bonds in polymer backbones can lead to different configurations:
✓ Cis
✓ Trans
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Classification of Polymers – Physical Aggregation
Trans configuration:
❖ Crystallinity in Polymers
✓ Semi-crystalline, rigid, not
elastomeric
Cis configuration:
✓ Sterically hindered, largely
amorphous, elastic ,e.g., natural
rubber
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Classification of Polymers – Physical Aggregation
❖ Tacticity
➢ Isotactic
➢ Syndiotactic
➢ Atactic
✓ Isotactic polymers are highly crystalline, rigid, and difficult to dissolve.
✓ Atactic polymers are amorphous, soft and more easy to dissolve.
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Classification of Polymers – Chemical Composition
❖ Homo-polymers
▪ One type of monomer
❖ Hetero-polymers (Copolymers): Different types of monomers
✓ Statistical copolymers (random distribution)
✓ (segmented) Block copolymers
✓ Grafted copolymers: side chains
✓ Alternating copolymers
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