Polymer Science

II
Dr A Ndiripo

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 STRUCTURE AND
PROPERTIES OF CRYSTALLINE
AND AMORPHOUS STATES

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State of Aggregation

State of Aggregation:
There are three states namely solid, liquid and gas.
The differences between them are:

(a) arrangements of molecules/atoms

(b) degree of movements
(c) packing of molecules/atoms

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(a) Arrangement of molecules/atoms

Gases:
There is random distribution and arrangement of molecules.
As the temperature increases so the kinetic energy of the
molecules increases and vice versa.
Liquids:
There is an intermediate distribution and arrangement of the
molecules, and also can be affected by high or low
temperatures.
Solids:
There is a definite distribution and arrangements of
molecules. A very high temperature is required for agitation
of solid molecules.
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(b) Degree of movements

Gases:
Gases experience all three types of movements i.e.,
translational, rotational and vibrational.
Liquids:
Liquids experience rotational and vibrational
movements and very little translational movements due
to the barrier energies and can be increase by
increasing energy.
Solids:
Solids have only vibrational energy.

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(c) Packing of molecules

Liquids and Solids have long-range order and short-range order types of packing.
Gases have no order of packing due to the mobility of molecules.

1. Long range order

2. Short-range order

Long Range Order Packing:

It is an order that is observed through a distance thousands of times the original unit.
There is a repetition of particular arrangement that is constant over a long distance.
Short Range Order Packing:
It is an order that is observed through a very short distance and there is repetition but
no consistence on the arrangement over a long distance.
Both types of arrangement exist in solids as well as liquids.

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Difference between state of
aggregation and the phase state

A phase can be described in two ways.

(i) thermodynamically and
(ii) structurally.

Thermodynamics of phase:
It is a part of a system that is separated from other parts of
the system by an interface and differs from other parts by
way of specific thermodynamic properties like specific
volume, temperature and pressure.

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Difference between (ii) Structure of phase:
state of aggregation A phase can be described by structure e.g., crystalline, amorphous,
liquid or gas.
and the phase state The structure can have a particular packing system, long-range order or
short-range order. If structure has a long-range packing order, it is called
crystalline state, also referred to as a solid state.
On the other hand, if the structure has short-range packing order, it is
called an amorphous state. Short-range packing order is also referred to
as a liquid state.
The temperature of decomposition of a polymer is far above the
melting point of the crystalline polymer.
No polymer exists above its decomposition temperature. It ceases to be
a macromolecule (large molecule) but becomes micromolecule (breaks
down or decomposes).

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STRUCTURE AND PROPERTIES OF CRYSTALLINE AND
AMORPHOUS STATES
Polymers are made up of two main components, units
and chains.

UNITS: Smallest morphological structure of a semi-

crystalline polymer and cannot be subdivided any
further.

CHAINS: Several units (monomers) are joined together

to form a chain (polymer).
It can be linear or branched depending on the unit
structure.

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Structure of
crystals
Structure of an ideal crystal, a crystalline
polymer and an amorphous polymer:
In ideal crystal, units and chains are
aligned.
Generally, this arrangement is found in
micromolecules not in macromolecule.

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 1. Ideal crystal 1

2. In polymer crystal chains

are aligned while units are
randomly arranged.
Structure of 2
crystals
3. Amorphous state of
polymer has short-range
order and units are
aligned but chains are not.
3

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Phase Transition
(PT)
These are the transitions from one
phase to another.
The movement of a phase from
current state to the next state :
Change of phase state from one to
the other state.
Tg: glass transition temperature
Tm: melt temperature
Tc : crystallization temperature

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Phase Transition
(PT)
Change from one phase to another
can sometimes affect the physical
properties of a polymer, e.g., liquid
to solid.
Sometimes no change in physical
properties occurs though there is a
change from one phase to another.
There are two types of phase
transition:
(i) First (1st) order phase
transition and
(ii) second(2nd) order phase
transition.

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Phase Transition (PT)

(i) First (1st) order phase transition: First order phase

transition involve very large changes in energy barriers
e.g., melting, crystallization, evaporation, condensation
and sublimation.

“When crystalline polymer melts, it absorbs a certain

amount of heat (at constant temperature), the latent heat
of melting, and it undergoes a change in its heat capacity.
Any change brought about by heat, whether it is melting
or freezing, boiling or condensation, which has a change
in heat capacity, where a latent heat involved, is called
first order transition.”

Second (2nd) order phase transition: Second order phase

transition is a very smooth transfer or change of phases
with change in enthalpy or entropy that is difficult to
identify. e.g., crystallization, dissolution and melting.

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Phase Transition (PT)

The amorphous polymer does undergo an

increase in heat capacity with increase in
temperature till it reaches to glass transition
state.
At Tg state, on further heating, instead of
temperature stops rising, it rises with slower
rate. Here the phase transition is a very smooth
transfer or change of phases with change in heat
capacity, that is difficult to identify (whether it is
liquid state or solid state).
Because the glass transition involves change in
heat capacity, but it does not involve a latent of
glass transition, Tg, this transition is called
second order transition.

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Phase Transition (PT)
Tg: Glass transition is an average temperature at which the
viscosity of the material reaches about 1013 poises (which is
the viscosity of solid).
It is a movement transition of liquid state of aggregation to a
solid state that does not form crystals. It just solidifies and is
glassy and does not form crystals.
Different macromolecules in the same polymer have different
Tg.

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Phase Transition (PT)
Crystallization: Crystallization is the rearrangement of the
macromolecule from short-range order to a long-range
packing order.
Thermodynamics of crystallization: Crystallization depends
on both inter and intra molecular attractions. There are
certain energy barriers, which have to be overcome to
achieve crystallization. For crystallization to take place ΔG
should be zero or negative.
ΔGo = ΔHo - TΔSo
0 = ΔHo - TΔSo
ΔH 0
T=
ΔS 0

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 Tm: Melt temperature
Normally for the majority of polymers the melt
temperature

0 (1 −
2𝛿
𝑇𝑚 = 𝑇𝑚 )
Δ𝐻𝑚𝑙𝜌
Phase
l = length of the fold of the crystal
Transition Tm0 = equilibrium melting temperature

(PT) ρ = density of the crystals

It is actually the temperature whereby every crystal
has melted completely. It is the precise melting
temperature for all crystalline substances, for
polymer Tm is not a precise temperature but a range
of temperature.

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Phase
Transition (PT)
Tc: Temperature of
crystallization

Beyond Tm0 we do not have any

crystals. Crystallization takes
place or goes through
particular maxima.

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Crystalline polymers
No 100% crystalline polymers exist; only semi-crystalline polymers exist with
a degree of amorphousness.
These polymers have an amorphous "halo”, the component that is not
crystalline.
Degree of Crystallinity:
Quantitative measure of the amount of crystalline material within a given
sample.
Most polymers are polymorphic i.e., having many structures obtained during
different crystallization conditions.
While monomorphic have particular shape when crystallizing of micro
substances.
Different polymers will have different degree of crystallization which depends
on
(i) nature of polymer and
(ii) conditions of crystallization. 20
Crystalline polymers
Assessment of degree of crystallinity:
This can be assessed by a few methods.
(1) Density method and
(2) Volume method
(3) Differential scanning calorimetry
(4) X-ray diffraction spectroscopy
(1) Density method
For any given polymer sample, the volume of the sample is
composed of the volume of the crystalline state (Vc) and the
volume of the amorphous state (Va).

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Crystalline polymers
(b) Volume method
Vtotal = Vc + Va

Also, the weight (mass) of the sample is composed of the weight of

crystalline state (Wc) and the weight of the amorphous state (Wa)
Wtotal = Wc + Wa

𝑊
but density = 𝜌=
𝑉

W= ρV
Wtotal = Wc + Wa
Vtotal = Vc +Va

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 Crystalline polymers
Vtotal =  cVc +  a (Vtotal − Vc ) Vc ( −  a )
=
Vtotal (  c −  a )
Vtotal =  cVc +  aVa
Vc
= c
Vtotal
But Va = Vtotal − Vc
Volume fraction of crystalline
Therefore: component:
Vc
Vtotal =  cVc +  a (Vtotal − Vc ) = c
Vtotal
Vtotal =  cVc +  aVtotal −  aVc Degree of crystallinity (%)
 cVc W
Vtotal −  aVtotal =  cVc −  aVc = c
Vtotal wtotal
Vtotal (  −  a ) = Vc (  c −  a ) Wc V  ( −  a )
= c c = c = c
Wtotal  total  (  c −  a )
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 This method is generally used because it allows
Crystalline for the decrease of volume with a marked
increase in the density especially of the
polymers crystalline component.

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 (c) DSC method

Crystalline polymers Enthalpy of melting ΔHm is determined by integrating the

area of the melting peak.
ΔHm is the divided by the enthalpy of melting of 100%
crystalline material ΔHmΘ
Δ𝐻𝑚
𝑋𝑐 = Θ × 100%
Example: Δ𝐻𝑚

From DSC, it was determined that a PE sample has a

melting temperature of 125°C and am enthalpy of
melting of 125 kJ/mol. Calculate the sample crystallinity
(Xc) given that the melting enthalpy of 100% PE is
298kJ/mol.

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Crystalline polymers

(d) XRD Method

XRD profiles generated can tell us about the

crystallinity of the polymer.
Broad peaks indicate amorphous phases.
Sharp peaks indicate highly crystallinity phases.
We will look at this in detail later.

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Crystalline
polymers
(d) XRD Method

Amorphous Crystalline

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 Orientation
Orientation takes place within a range of temperature, but
emphasis is put on the direction of alignment of the
macromolecule.
Crystalline Uniaxial ↔orientation in one direction or axis
Biaxial ↔ orientation in two directions or axes
polymers It is possible to orient a polymer without necessarily
crystallizing the polymer, but in crystallization there is a
particular orientation. The orientation mainly aimed at
improving mechanical properties of the polymer.

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Crystalline polymers
Characteristics of crystallizable polymers

1.Must have a regular structure, depending on degree of regularity, degree

of crystallinity also differs. Good example is of HDPE and LDPE where HDPE
has a more regular structure and as such has high degree of crystallinity as
compared to LDPE, which has branched due to the high pressure, used in its
production.
2. Flexibility of the polymer chain, ease with which the units move after
application of thermal energy
(i) thermodynamic of flexibility of polymer- difference in energy of a unit
after application of thermal energy, i.e., unit moves from one position with
energy U1 to position with energy U2 → U = U2 — U1.
(ii) Kinetic flexibility: Energy barrier through which the unit undergoes as it
moves from one position to another.

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Crystalline polymers
Characteristics of crystallizable polymers

Movement of atoms within the chain, and also the rotation of the molecule.
The more complex the unit, the more limited rotation becomes and thus
flexibility affected. The intra or inter-molecular interactions also determine
flexibility. The more flexible the polymer, the much easier it is to crystallize
the polymer. More rigid polymer, do vice versa.
3. Very close packing of macromolecules:
Macromolecules should be capable of coming as close together as possible
and this packing depends on the size of the units. e.g. –CH2 –CH2 – CH2- can
attain a better close packing than
CH2 CH CH2 CH CH2
C6H5 C6H5
which is difficult to bring units close together as a result of big –C6H5 and thus
it is an amorphous

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Crystalline polymers
Characteristics of crystallizable polymers

4. Chemical constitution of the polymer

Because of the inter and intra-molecular interactions, polar
and non-polar units, how closely will each unit come to the
next unit, i.e., to what extent can they closely come together.
Steric and intermolecular repulsions lead to a stiff,
irregularity, and twisted backbone chain conformation.

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Crystalline polymers
Characteristics of crystallizable polymers

5. Morphology of crystalline polymer

Morphology describes total structural formations during the process of
crystallization i.e., it describes the dimensions, shapes of the structure
produced, arrangement of structural formations and the relationship
between the units.
Some crystalline polymers undergo process of polymorphism. This is
production of different types of crystals from one and the same nature
of material.
These different types of crystals result from different conditions of
crystallization.
A good example is PP (Polypropylene). It has monoclinic shape in
symmetry, helical shape and triclinic shape.

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Morphological structures (a) Unit cell:
Unit cell is the smallest
morphological structure of a
semi-crystalline polymer and
cannot be subdivided any
further.
Main source of unit cell is very
dilute solution.
If unit cells are arranged in
such a way that there are no
voids between them, then a
SINGLE CRYSTAL is formed.

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Morphological
structures
(b) Lamellae: (Fringed-miscelle
structure theory):
This crystal structure is a result
of crystallization from very
dilute polymer solution (1%).
Crystallization process should
result with very low
evaporation of solvent. There
are three types of lamellae
structure due to the
arrangement of the unit cells.

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Morphological structures

(b) Lamellae: (Fringed-micelle structure theory):

(i) Regular structure:

It has even distribution of unit cells and chains. The height of
the macromolecule folding are even

(ii) Irregular structure:

It has uneven distribution of unit cells and chains. The folds
are not even i.e., some are longer than the other.

(iii) Switch-board structure:

It has completely random distribution of unit cells and chains,
and they are not aligned in any way.

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Morphological
structures
(c) Fibrillar structure:
This structure is produced by
the evaporation of solvent.
The evaporation prohibits the
formation of lamellae
structures.
The polymers that can be super
cooled can produce a good
fibrillar structure.

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Morphological
structures

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Morphological structures
(c) Fibrillar structure:

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Morphological
structures
(d) Globular structure: The
macromolecules are
crystallizing with formation of
coils or globules. e.g., fats and
proteins tend to crystallize in
globular form at specific
conditions such as temperature
and high concentration. This
globular structure sometimes
looks like spherical or small
bulb.

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Morphological
structures
(e) Dendrite structure: The
polymer crystallizes with
formation of scattered
(branched) structures called
dendrites. The conditions
require to obtain this type of
structure include very low
temperature and low
concentration. This type of
structure can also be produced
from melts. As compared to
lamellae, dendrites have bigger
dimensions.

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Morphological structures

(f) Spherulites: Spherulites are the most

common morphological structures produced
mainly from polymer melts. Different polymera
produces different types of spherulites. Most
common spherulites structure is one that has a
shape called Maltese Cross. Maltese cross is
determined by use of polarized light, which gives
bi-fringence, i.e., has two different refractive
indices, (axial direction and radial direction).

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 Morphological structures
Stages in formation of spherulites from a
stack of lamellae:

Depending on the difference between the two refractive indices, spherulite is

classified as Positive spherulite and Negative spherulite.

Positive spherulite: In positive spherulite, refractive index of the radial part is

greater than the refractive index of the axial(tangential) part, i.e., nr > na

Negative spherulite: In negative spherulite, refractive index of the radial part is

less than the refractive index of the axial (tangential) part, i.e., nr < na

There are some polymers, which will produce only positive spherulite while others
only negative spherulite. Hence the formation of spherulite is a characterization
measure and it helps us to identify the polymer.

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The end
Up next: Mechanism and
Kinetics of crystallization

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