Zenamarkos B.

(PhD)

Chemical Engineering Program

Faculty of Chemical and Food Engineering
Bahir Dar Institute of Technology (BiT)
Bahir Dar University
April, 2022
Semi-crystalline Amorphous
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 Morphology of Polymers
Morphology (Thermoplastics!)
 Amorphous
 Semi-Crystalline

Tacticity
 Isotactic
 Syndiotactic
 Atactic
 Morphology of Polymers
 Amorphous Polymers
 Only physical entanglements.
 Transparent.
 Typically less resistant to chemicals, relatively easy to dissolve.
 Morphology of Polymers
 Semi-Crystalline Polymers
 Typically non-transparent unless crystallines are very small

 Very stiff and strong fibres can be made (increased inter-molecular forces)
 Morphology of Polymers
 Tacticity
 Isotactic
 Syndiotactic
 Atactic

 Isotactic polymers are highly crystalline, rigid, and difficult to dissolve.

 Atactic polymers are amorphous, soft and more easy to dissolve.
 Thermal Properties of 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

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 Thermal Properties of Amorphous Polymers

Glass transition temperature (Tg):

 the temperature at which the polymer softens because of the onset of long-range coordinated molecular
motion.
 is the most important single parameter that determines the application of many non-crystalline polymers.
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 Thermal Properties of Amorphous Polymers
Glass transition temperature (Tg):

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 Thermal Properties of Amorphous Polymers
Thermal transitions of amorphous polymers

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 Thermal Properties of Semi-Crystalline Polymers
Melting Behaviour

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 Thermal Properties of Semi-Crystalline Polymers
Modulus-Temperature Behaviour

Effect of degree of crystallinity

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 Thermal Properties of Semi-Crystalline Polymers
Degree of Crystallinity

• Melting enthalpy = integral of peak

area

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 Thermal Properties of Semi-Crystalline Polymers
 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
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 Thermal Properties of Semi-Crystalline Polymers
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

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 Introduction

 Rheology => the science of deformation and flow.

Hooke’s law Newton’s law

(solid mechanics) (fluid mechanics)

What is real material behaviour?

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 Introduction
Ideal Solid
Elongation
Stress α Deformation

Material Properties:

o Elongation modulus: E (Pa)

o Shear modulus: G (Pa)

o E = 3G

Classical solid state mechanics Shear

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 Introduction
Ideal Liquid
Shear

Stress α Rate of Deformation

Newton’s law

Material Properties: Elongation

o Shear viscosity: ƞ (Pa.s)

o Extensional viscosity: ƞext (Pa.s)

o 3ƞ = ƞext

Classical fluid mechanics

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 Introduction
What is real material behaviour?

Newtonian behaviour
o Constant viscosity
o (ƞext)/(ƞshear) = 3

It is a single value, f(temp, pressure).

Is this typical?

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 Introduction
Do real materials behave according to Newton’s law?

Deviations:

Mayonnaise: resistance (viscosity) decreases with increasing shear rate (-dvx/dy): shear
thinning

Starch solution: resistance (viscosity) increases with increasing shear rate (-dvx/dy) :
shear thickening

This is a non-linearity: 21
 Flow of Polymers
Continuous Processes
e.g., Extrusion

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Flow of Polymers

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 Flow of Polymers
Relevant shear rates for polymer processing operations

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 Flow of Polymers
 Shear flow: shear rate dependent viscosity
 shear thinning behaviour
 different constitutive relationship needed to describe the flow behaviour

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 Flow of Polymers
 Shear viscosity is dependent on temperature

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 Flow of Polymers
 Shear viscosity is dependent on pressure (e.g., Injection moulding)

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