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
August, 2019
 Polymer Science and Engineering
General Information:
Academic year: 2018/2019
Study Points: 3 Cr
Language: English
Duration: 48 hrs
Periodicity: Taught in the 2nd semester

Aim: Levelling of students bases in polymer physico-chemistry and

processing.

Course materials:
Text books, PPTs
Articles and literature
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 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

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 Polymer Science and Engineering
Content

II. Polymer Processing:

• Extrusion
• Mixing (Compounding)
• Injection Molding
• Blow Molding

• Thermoforming
• Fiber Spinning
• Compression Molding
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 Polymer Science and Engineering
Text books

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Course Goal

Polymerization

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Fundamentals of Polymer
Science and Engineering

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 Fundamentals of Polymer Science and Engineering
֍ Polymer: a macromolecule, composed of many repeated subunits.
Poly- => "many" + -mer => "parts" or “segment"

➢ Polymers, both natural and synthetic, are created via polymerization of many
small molecules, known as monomers.

Polypropylene 8
 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

➢ Their consequently large molecular mass relative to small

molecule compounds produces unique physical properties, including:
✓ toughness
✓ viscoelasticity
✓ tendency to form glasses and semicrystalline structures rather
than crystals.

➢ Because of their broad range of properties, both synthetic and natural

polymers play an essential and ubiquitous role in everyday life.

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 Fundamentals of Polymer Science and Engineering
Structures of the repeating units of some common polymers
(PET)

(PMMA)

(PIB)

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 Fundamentals of Polymer Science and Engineering
Classification of Polymers

֍ There are many possible classifications of polymers.

➢ Polymerization Processes

➢ Structure

➢ Thermal Properties

➢ Physical Aggregation

➢ Chemical Composition

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 Fundamentals of Polymer Science and Engineering
Classification of Polymers

❑ Polymerization Processes:

❖ Step-growth

❖ Chain-growth

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 Fundamentals of Polymer Science and Engineering
Classification of Polymers
❑ Structure:

❖ Linear Polymers
▪ Long chains, entangled with each other
▪ Higher molecular weight means higher strength

❖ Branched
▪ Leads to higher degree of entanglement
▪ promoted by special catalysts and processing
techniques.

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 Fundamentals of Polymer Science and Engineering
Classification of Polymers
❑ Structure:

❖ Network
▪ High degree of cross-linking: thermoset resins like epoxy
▪ Lower degree of cross-linking: elastomers
▪ Stiffness (modulus) and strength typically increases with the
number of cross-links
▪ Very high cross-link density leads to brittleness

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 Fundamentals of Polymer Science and Engineering
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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 Fundamentals of Polymer Science and Engineering
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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 Fundamentals of Polymer Science and Engineering
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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 Fundamentals of Polymer Science and Engineering
Classification of Polymers
❑ Physical Aggregation

❖ Morphology (Thermoplastics)
• Amorphous
• Semi-Crystalline

❖ Tacticity
• Isotactic
• Syndiotactic
• Atactic

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 Fundamentals of Polymer Science and Engineering
Classification of Polymers
❑ Physical Aggregation

▪ Amorphous Polymers
✓ Only physical entanglements
✓ Transparent
✓ Typically less resistant to chemicals, relatively easy to dissolve

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 Fundamentals of Polymer Science and Engineering
Classification of Polymers
❑ Physical Aggregation

▪ Semi-Crystalline Polymers
o Non-ordered semi-crystalline polymers:
✓ Crystalline segments are oriented randomly
✓ Typically non-transparent unless crystallines are very small

o Ordered semi-crystalline polymers:

✓ Aligning of crystals typically by processing (stretching in
solid, melt or solution)
✓ Very stiff and strong fibres can thus be made (increased inter-
molecular forces)
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 Fundamentals of Polymer Science and Engineering
Classification of Polymers
❑ Physical Aggregation

▪ Semi-Crystalline Polymers
✓ Many physical characteristics depend on degree of crystallinity:
- melting behaviour
- Solubility
- mechanical properties
✓ Crystallization can be increased by:
- Regular structures, e.g., rigid double bonds, certain
‘tacticity’
- Limiting side groups and branches
- Increase in inter-molecular forces, e.g., by permanent
dipoles

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 Fundamentals of Polymer Science and Engineering
Classification of Polymers
❑ Physical Aggregation

❖ Crystallinity in Polymers

▪ Double bonds in polymer backbones can lead to different configurations:

✓ Cis
✓ Trans

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 Fundamentals of Polymer Science and Engineering
Classification of Polymers
❑ Physical Aggregation

❖ Crystallinity in Polymers

o Cis configuration:
✓ Sterically hindered, largely
amorphous, elastic ,e.g.,
natural rubber

o Trans configuration:
✓ Semi-crystalline, rigid, not
elastomeric

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 Fundamentals of Polymer Science and Engineering
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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 Fundamentals of Polymer Science and Engineering
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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