POLYMER PROCESSING Dr Wan Zaireen Nisa Yahya

CEB4423 Email: zaireen.yahya@utp.edu.my

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Office: 05-3687584 ( 04-03-24)
 CDB 4423
Polymer
Process
Engineering
Chapter 5:
Structure and
Thermal
properties
 1. Selection of plastics

2. Thermal transition of polymers

 Glass transition temperature and melting

Contents point

 Factors affecting Tg and Tm

 Thermal analysis

3. Mechanical properties

4. Permeability

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Lesson Outcome

At the end of this lecture, students should be able to;

• Understand and describe different thermal
transition of polymer
• Describe the factors effecting glass transition and
melting temperature

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 SELECTION OF PLASTICS
How do we decide which plastic, if any, is best for a particular application?

1. First steps in the design process are to define clearly the purpose and
function of the proposed product and to identify the service
environment.

2. Then to assess the suitability of a range candidate materials.

3. The most important characteristic for engineering components:

 Mechanical properties-strength stiffness, fatigue and toughness
 Corrosion susceptibility
 Special properties; permeability, thermal, electrical, optical,
damping capacity etc
 Method of fabrication
 Cost and manufacturing route

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Open
 What factors are important for proper
plastic selection?
• Operating temperature • Fracture toughness, Kic
– Tm • Impact
– Tg • Environmental exposure
• Mechanical Stress • Dimensional stability
– Ultimate strength and • Fatigue
stress rupture – Repeated loading
• Creep • Flammability
• Stress Relaxation
• Stiffness (modulus)

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Open
What factors are important for proper
plastic selection?
• Wear • Secondary:
• Chemical exposure – Thermal conductivity
• Cosmetics (color) – Electrical conductivity
– Transparency
• Aging
– Surface finish
– Manufacturing process

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 Thermal
Transition
of Polymers

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Amorphous
Amorphous polymers appear random and jumbled when
allowed to cool in a relaxed state. They appear very
similarly to their molten state, only the molecules are
closer together.
They can be described as being similar to a large pot of
spaghetti noodles.

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Semi-crystalline
A portion of the molecular chains in semi-crystalline polymers
tend to ‘fold-up’ into densely packed regions called crystals as
the polymer cools.
If more than 35% of the polymer chain will form these crystals –
the polymer is classified as semi-crystalline.

Semi-crystalline Amorphous
regions regions

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CRYSTALLINITY EFFECTS ON PROPERTIES

Increase crystallinity Reduce crystallinity

increases: increases:

 Opacity  Permeability
 Tensile strength  Solubility
 Rigidity  Elongation
 Melting point  Impact strength
 Dielectric strength  Stress crack resistance

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Thermal transitions of polymers
• Completely amorphous polymer: Tg only
• Completely Crystalline: Tm only
• Semi-crystalline: Both Tg & Tm
For any new polymer, Tg is among
the most important mechanical
property and the first properties
measured
For low molecular compound, the
states of matter:
Crystalline, liquid and gas
(melting point and boiling point)
For polymer: no boiling point but
decomposition. And no complete
crystallisation
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Amorphous polymers

 Can exist in many states depending upon

temperature and molecular weight (MW).
Refer plot T vs MW.  At low T, amorphous
polymers are glassy,
 At low MW, exist as glassy solid below
hard and brittle
certain temperature and as viscous fluid
above it.  As the T raised, they
go through the glass-
 At high MW, a rubbery intermediate zone is rubber transition
observed with two transition temperatures.
 Glass transition: rigid solid – rubber
 Flow temperature : rubber – liquid
(indefinite)

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 Five Regions of Viscoelastic Behavior

Young modulus vs Temperature plot

Glassy Five regions :

1. Glassy
• Poly(methyl metacrylate),
Glass transition plastic
crystallinity
2. Glass Transition
• (Poly(vinyl acetate), paint
cross-linked 3. Rubbery Plateau :
Rubbery
• (Cross-poly(butadiene-stat-
transitio Rubber styrene), rubber bands
n y flow 4. Rubbery Flow:
• chewing gum
Liquid flow 5. Liquid Flow,
• Poly(dimethyl siloxane)
Temperature PDMS Lubricant
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Molecular Structure Effect

SemiCrystalline (isotactic PS)

Highly crosslinked

Amorphous

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 Semicrystalline polymers

Two major types of thermal transitions:

• Crystalline melting point, Tm, at which the crystalline domains

melt.
• Above this temperature, polymer is liquid.
• Below this temperature, polymer forms flexible crystalline solid.

• Tg, glass transition temperature.

• Below this, polymer exists as hard, rigid glassy solid.
 Glass Transition Temperature (Tg)

The sample to the left experienced a brittle

failure
• The material did not yield before
failure
• The material broke like glass

The sample to the right broke in a ductile

manner
• The material yielded (stretched)
before failure
• The material behaved more like
a rubber 17
Is Glass transition and melting point the
same?

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Properties: Amorphous vs. semi – Cristalline
Chemical Resistance
• Plastic materials are used in virtually every aspect of today’s
activities and they come into contact with a wide variety of
chemical substances that they need to resist.
• As a general rule S/C materials are more resistant to chemical
attack than amorphous materials.
• It is more difficult for the chemical media to penetrate the dense
crystalline structure to damage the polymer chains.
• Polyethylene is used to store everything from detergent to mineral
spirits to gasoline. Polypropylene is only slightly less chemically
resistant than Polyethylene.

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Properties
Optical Properties
Amorphous materials have a much higher clarity than S/C materials.
The crystals that form in the material diffract the light as it passes
through giving the material a translucent to opaque appearance.
If the crystallinity is disrupted by adding a copolymer or other additive or
by quenching the material so quickly the crystals don’t have enough time
to form, the material may appear somewhat clear.
Amorphous Acrylic more commonly known as Plexiglas and
Polycarbonate used in safety glasses and optical lenses are far superior in
terms of optical properties.

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Properties
Impact Resistance
The material structure determines the impact resistance,
but as a general rule, S/C materials are more brittle than
Amorphous.
The chain portions that are folded up in the crystal restrict the
polymer chains as they try to move past one another when a
force is applied making the S/C materials more brittle.
Polycarbonate is used in safety glasses, but General Purpose
Polystyrene (GPPS) is very brittle – both are amorphous, but have
different polymer structures.
On the S/C side, Polyethylene is very ductile at room temperature
because it is above its Tg, but Nylon and Polyester are brittle at
room temperature. 21
Properties
Viscosity
S/C materials by their very nature flow more easily than Amorphous
materials.
The same mechanism that allows the material to fold up into dense
crystals allows the polymer chains to slide past one another easily in
the melted state.

For this reason materials like Nylon require

very tight tolerances on their tooling to
prevent melted plastic from leaking out of
the cavities causing flash.

Flash
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Properties
Weather Resistance
When it comes to weather resistance, the most damaging
aspect of weathering is generally considered to be
Ultraviolet light.
The UV light breaks down the chains of the polymers
making them more brittle, causing colors to fade or
yellow, and causing additives in the polymers to migrate to
the surface (chalking).

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Properties
Weather Resistance
Amorphous polymers have better chemical resistance to
weathering effects than S/C polymers.
The crystals in the S/C polymers diffract the light so the UV
rays spend more time within the polymer structure and do
more damage. The clear amorphous polymers allow the
damaging radiation to pass through doing less damage.

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Properties
Shrinkage
Because they fold up into crystal structures, S/C materials
have higher shrinkage rates when compared to Amorphous
materials.
In injection molding most amorphous materials will shrink
between 0.003-0.007 in/in (0.3-0.7%)
S/C materials shrink differently depending
upon the level of crystallinity that they achieve.
Some will shrink over 0.025 in/in depending
on processing variables, part thickness, and
additives.

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Material Types
Semi-crystalline
Polyethylene (PE, HDPE, LDPE, etc.)
Polypropylene (PP)
Polyamides (PA – Nylon)
Polyesters
• Polyethylene Terephthalate (PET)
• Polybutylene Terephthalate (PBT)
Polyoxymethylene (POM - Acetal)
Polytetrafluoroethylene (PTFE – Teflon)

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Factors affecting Tg

What makes a high Tg and low Tg?

How easily the chains move. A polymer chain that can move around
fairly easily will have a very low Tg, while one that doesn't move so
well will have a high one.

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 Think Pair share

• Discuss on the trend of the Tg

Tg = -127 C No Tg decompose at T> 500 C Tg = 160 C

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WHICH ONE HAS A LOWER TG?

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Factors affecting Tg

• Chain flexibility, interactions and structure

• Nature of polymer backbone.
• C-C and C-O bonds are flexible.
• Nature of groups directly attached to the backbone (due to
repulsion and tendency to form hydrogen bonding).
• Flexibility enhanced by methylene groups.
• Flexibility reduced by ring structures (phenylene and
amide) & by substitution of H atoms by hydrocarbon
groups (eg. polytetrafluoroethylene, PTFE, has much
higher Tg compared to polyethylene).

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…cont’…Factors affecting Tg

• Inclusion of double bond stiffens it but increases flexibility of

adjacent bonds.
• Segmental rotation is affected by other chains in the same
region (mainly dipole interaction and hydrogen bonding).
• Tg for PVC is higher than polyethylene (more polar).
• Tg for polyvinylidene is lower than PVC (less polar due to
symmetrical substitution.
• Hydrogen bonding also significantly increases Tg.

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 Values of Tg & Tm

Polymer Repeating Unit Tg (˚C) Tm (˚C)

Polyethylene -CH2CH2- -125 137

Natural rubber -CH2C(CH3)=CHCH2- -73 28

Polypropylene -CH2CH(CH3)-- -13 176

Polyvinylchloride -CH2CHCl- 81

Polystyrene -CH2CHØ- 100

Polymethylmethacrylate -CH2C(CH3)(CO2CH3)- 105 200

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 Factors affecting Tm

• Same factors affect both Tg & Tm. Usually high Tg & high Tm are found
together and vice versa.

• Asymmetrically structured polymers have higher Tm (eg PVC (--

(CH2CHCl)-- vs polyvinylidene chloride --(CH2CCl2)— PVDC=Tm =220C ;
PVC, Essentially atactic, but contains syndiotactic to give 10%
crystallinity, Tm=250C

• High polarity and hydrogen bonding increases Tm.

• Molecular symmetry leads to high Tm.

Eg: Polyethylene has high Tm due to tightly packed crystals although Tg
is low due to flexibility of the chain.

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 Class activity: Group investigation
• 1. Which of the polymer(s) in the table that would be suitable for the
fabrication of cups to contain hot coffee? Why
• 2. Which polymer(s) would be best suited for use as ice cube trays? Why?

Polymer Repeating Unit Tg (˚C) Tm (˚C)

Polyethylene -CH2CH2- -125 137

Natural rubber -CH2C(CH3)=CHCH2- -73 28

Polypropylene -CH2CH(CH3)-- -13 176

Polyvinylchloride -CH2CHCl- 81

Polystyrene -CH2CHØ- 100

Polymethylmethacrylate -CH2C(CH3)(CO2CH3)- 105 200

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 Thermal analysis of polymers

Technique Quantity measured Applications

Differential Scanning Heat flow Reaction kinetics,
Calorimetry (DSC) purity analysis,
polymer cures

Differential thermal Temperature Thermal stability,

analysis (DTA) difference phase diagram

Thermogravimetric mass Thermal stability,

analysis (TGA) compositional
analysis

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TGA =Thermogravimetric analysis DTA = Differential thermal analysis

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Differential Scanning Calorimetry (DSC)
• Polymer and reference samples are heated in such a way
that they are kept at the same (increasing) temperature.
• When a thermal transition occurs thermal energy is supplied
to the polymer or reference.
• The energy transferred is equivalent to the energy absorbed
or evolved in the transition.

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 Heat required to raise the
Temperature of one gram of the
matter one degree Celsius is called

DSC Plot the heat capacity,Cp.

• The resulting plot of differential rate of heating Vs

temperature can be studied to measure heat capacity,
melt enthalpy and transition temperature.

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Characteristics of a DSC curve
• Each substance has a characteristic DSC curve that can be
used for qualitative identification.

• Endotherms generally represent physical changes while

exotherms indicate crystallization, polymerization, curing,
decomposition etc.

• The area under the peak is proportional to the heat

evolved or absorbed during the reaction.

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 Melting point from DSC curve
• Can determine the exact melting point as the temperature at which
melting is complete.

• The actual melting of the polymer takes place at a range of

temperature.
• On-set
• Mid-point/peak Temperature

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 Thermogravimetric analysis TGA

 Measurement of the mass vs temperature.

 Plotted as mass vs time or mass vs temperature.

 Characteristics
 Unique shape for each substance.
 Temperature at which changes occur.
 Each plateau indicates stable state and any deviation or changes
shows the presence of a reaction.

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TGA CURVES of Polymers

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 • Factors affecting polymer
properties ( Tg and Tm) :
 Chain entanglement
 Sum of intermolecular
forces
 Free volume ( easiness to
motion)
Summary • Crystallinity affects Tm and Tg:
Completely amorphous
polymer: Tg only
Completely Crystalline: Tm
only
Semi-crystalline: Both Tg &
Tm

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