1

Summary of previous lecture

Crystalline polymer  Crystalline state

Amorphous polymer  Glassy state

Minimum energy configurations at various levels:

Intramolecular  zigzag for PE, helix for PTFE
Intermolecular  chains folded on themselves
 formation of lamellae and spherulites

Crystallization of polymers depends on:

Intramolecular configuration
 isotactic, syndiotactic, atactic
 chemistry (side groups size, etc.)
Cooling rate
 Polymers: molecules → solids – Summary
Amorphous parts

Chain folded Crystalline parts

Chain on itself
Amorphous Crystal Linking
regions Center molecules

A stack of chains folded on Lamellae

themselves is called a lamellae
Spherulite
http://pslc.ws/french/crystal.htm
 Polymers: molecules → solids

Structure of PE

Any mis-placed chains (bent, entanglements) result in amorphous

areas. The degree of crystallinity can go from completely amorphous to
almost completely crystalline (up to about 95%).
 4
Polymers: molecules → solids

Crystalline planes in PE: lamellae & spherulites.

Superimposed
lamellae…
(thickness ~
10 nm)

…separated by
matter in glassy
state.

Spherulite
 Polymers: molecules → solids

Percentage of crystallinity in weigth:

ρ c (ρ s − ρ a )
%crystallinity =
ρ s (ρ c − ρ a )
Where ρ c is the density of a perfectly crystalline polymer, ρ s is the
density of the whole sample and ρ a is the density of the completely
amorphous polymer.

The degree of crystallinity depends on the cooling rate and the chains
configuration.
 Polymers: molecules → solids

Density and crystallinity calculations for PE:

a) Calculate the density of a perfectly crystalline PE sample.
b) Using the previous answer, calculate the percentage of crystallinity
of a branched PE that has a density of 0.925 g/mol.
The density of the amorphous phase is 0.870 g/mol.

Solutions: Number of base units in the primitive cell = 2

a) Molar mass of base unit = 12*2+1*4=28 g/mol
nA
ρ=
Vc N A Avogadro Number = 6.022.1023 base units/mol

Volume of the primitive cell = 0.741*0.494*0.255=9.33.10-23 cm3

ρ = 0.998 g / cm3
b) We use the crystallinity equation to find the percentage of crystallinity in
the branched PE:
ρ c = 0.998 g / cm3 ρ a = 0.870 g / cm3 ρ s = 0.925 g / cm3
ρ (ρ − ρ a )
%crystallinity = c s = 46.4%
ρ s (ρ c − ρ a )
 7

MCG 2361
Engineering Materials II

Lecture 7: Molecular structure and materials structure

of polymers (3/3)
 8
Polymers: states & transitions

Glassy state: - no long distance order ( → liquid / amorphous )

- no molecule mobility ( → solid)

Glassy state: thermodynamically instable state, would transform into

crystal given sufficient time, in appropriate thermal conditions.
Metal:
Volume
A: liquid state
Slow cooling: volume ↓ , density Cooling
↑ (typically +3%) at Tf :
crystallisation: → D
(Very) Fast cooling: overcooled
liquid → B (liquid, T < Tf )
Glass transition at Tg : liquid →
Temperature
- amorphous solid in glassy state
-C. (…note density values!)
 9
Polymers: states & transitions

Glassy state: - no long distance order ( → liquid / amorphous )

- no molecule mobility ( → solid)

Glassy state: thermodynamically instable state, would transform into

crystal given sufficient time, in appropriate thermal conditions.
Metal:
Volume
Tf > Tg What is Tg ??
Cooling
Why 2 different T°s ?
Because you need more energy
to break cohesion of atoms /
molecules that are well aligned
into a crystalline structure vs.
energy required to break cohesion Temperature
of atoms / molecules assembled
into an amorphous solid.
 10
Polymers: states & transitions

Glassy state: - no long distance order ( → liquid / amorphous )

- no molecule mobility ( → solid)

Glassy state: stable in practice: cannot transform into crystals

because of entanglement, on top of temperatures T that are too low.
Polymer: Volume

T ↓ Tf : a fraction of the polymer

solidifies into a crystalline phase; Cooling
T ↓ Tf : a fraction does not crystallise:
becomes amorphous… PE

Amorphous phase with T > Tg :

rubbery state
Amorphous state with T < Tg : Tf
Temperature
glassy state
← Tg
 11
Polymers: states & transitions

Polymers: states

Crystalline state ( T < Tf ) :

Molecules aligned and stable. Solid.

Glassy state ( T < Tg ) :

Molecules not aligned but stable. Solid. Stability results from
entanglement of molecules and from low temperatures T.

Rubbery state ( Tf > T > Tg ) :

Molecules not aligned and more or less stable. Viscoelastic solid.

Stability results only from entanglement of molecules and from the fact
that they are part of a number of crystals.
 12
Polymers: states & transitions

Polymers: states, phases and aggregation

Phase: microscopic state (structure)

Aggregation: macroscopic state (what it feels like in practice)

State Phase Aggregation Mobility

Amorphous, liquid liquid entire

liquid molecules

Amorphous, liquid solid segments of

rubbery molecule

Amorphous, liquid solid none

glassy

Crystalline solid solid none

 13
Polymers: states & transitions

Polymers: states, phases and aggregation.

The science and engineering

of materials, Askeland & Phulé,
Thomson Ed.
 14
Polymers: states & transitions

Polymers: transition temperatures

Tf : Fusion temperature

T↑ : crystalline fraction goes from solid state to liquid state

amorphous fraction goes from rubbery state to liquid state
…transformation happens over a range of temperatures.

Above Tf : only one phase, liquid.

Below Tf : two phases: crystalline et rubbery.

Tg : Glass transition temperature

T↑: crystalline fraction stays crystalline: solid → solid, no change.

amorphous fraction goes from glassy state to rubbery state:
solid & brittle → solid + resilient.
 15
Polymers: states & transitions

Polymers: transition temperatures

Tg : Glass transition temperature

Above Tg: two phases, crystalline and amorphous. The

amorphous phase is in rubbery state.
Below Tg: two phases, crystalline and amorphous. The
amorphous phase is in glassy state.

Glassy transition happens over a range of temperatures!

When going below Tf , the proportion of liquid that becomes crystalline

solid vs. rubbery amorphous solid depends on the cooling rate…

…and this proportion stays essentially constant below Tf.

(see va , v , vc in above graph).
 16
Polymers: states & transitions

Polymers: range of fusion temperatures

Amorphous Liquid
polymer

Tf
 17
Polymers: states & transitions

Polymers: glass transition

Tg : Glass transition temperature?

- Temperature at which viscosity reaches 1012 Pa⋅s

- Temperature below which motions in amorphous segments of

macromolecules are ‘frozen’…

- Temperature above which motions in amorphous segments of

macromolecules begin to ‘thaw’…
 18
Polymers: states & transitions

Amorphous polymers:

Three possible states:

PS
Glassy state
- liquid

Module de relaxation
viscosity depends on n Glass transition

- rubbery
Rubbery state
exists only in polymers
Transition
rubbery-liquid

- glassy Liquid state

relatively rigid and brittle

Tg Temperature Tf
 19
Polymers: states & transitions

Amorphous polymers: Note: courbe pour PS (generally amorphous)

Rubbery state:

Range of temperatures
Covered by rubbery state

Module de relaxation
increases towards higher T
when n↑

n→∞

n<∞

Tg Temperature
 20
Polymers: states & transitions

Semi-crystalline polymers: Note: the curve is not for PE

Crystalline state:

Most representative is PE:

the ‘most crystallisable’

Relaxation modulus
polymer.

Crystalline phase provides

better rigidity between n→∞
Tg et Tf .

n<∞

Tg Temperature
Tf
 21
Polymers: states & transitions

Polymers: states and variable crystallinity

A:
Amorphous polymer

B:
Semi-crystalline
polymer

C:
Crystalline polymer
(‘hypothetical’)
 22
Polymers: states & transitions

Semi-crystalline polymers:
Spherulites
Crystallisation

Liquid

Impurities:
onset of
crystallisation
 23
Polymers: states & transitions

Semi-crystalline polymers:

Aptitude to crystallize: chain length (LLDPE)

Number of C
atoms on chain

A*: slow crystallisation at 131 °C for 2 weeks

B*: fast cooling to -78°C
 24
Polymers: states & transitions

Semi-crystalline polymers:

Aptitude to crystallisation: branching (PE)

X
1.0

0.8

0.6

0.4

0.2

0.0
20 40 60
Number of branches par 1000 carbons
 25
Polymers: states & transitions

Semi-crystalline polymers:

Aptitude to crystallisation: time & temperature (PP)

Nucleation
of X starts
earlier when
X T is lower

Avrami Equation
(
y = 1 − exp − kt n )

Time (minutes – log scale)

 26
Polymers: states & transitions

Semi-crystalline polymers:

Transition temperatures Tg (°C) Tf (°C)

Polyethylene PE -120 140

Polypropylene PP -18 170

Polyoxymethylene POM (acetal) -50 181

Polyamide PA (Nylon) 50 267

Polyvinyl chloride PVC 90 Amorphous

Polymethyl metacrylate PMMA 105 Amorphous

Polystyrene PS 100 Amorphous

 27
Polymers: states & transitions

Semi-crystalline polymers:

The more C black content,

the faster is the X because
there are more X sites
 28
Polymers: states & transitions

Semi-crystalline polymers:

The higher the temperature

(but < Tf), the more energy
the chains have and the faster
the they can organize
themselves into crystals.
 29

Questions

1. Draw the states of matter from liquid to solid for PE and PMMA.
2. Describe the evolution of the relaxation modulus vs. temperature for
PE, PMMA, UHMWPE
3. What is the difference between glassy and rubbery states?
4. Describe the evolution of the specific volume vs. temperature from
solid to liquid for amorphous, semi-crystalline and 100% crystalline
(ideal) polymers
5. What is the effect on crystallisation of:
crystallisation temperature?
Impurities?
Branching on polymer chains?
Degree of polymerization?
Cooling rate?
6. Explain the sigmoidal shape of the curve representing the crystallised
fraction vs. time.