Chapter: 08

Crystallinity in
Polymers Prepared By: K.Z.M. Abdul Motaleb & Rois Uddin Mahmud
Department of Textile Engineering, BGMEA University of Fashion and Technology
CONTENTS:
• SOLIDS
• INTRODUCTION
• DEGREE OF CRYSTALLINITY
• CRYSTALLISABLITY
• POLYMER CRYSTALLISATION
• HELICAL STRUCTURES
• SPHERULITES
• LAMELLAR STUCTURES
• FOLDING OF CHAINS DURING CRYSTAL FORMSTION
• CRYSTALLIZATION MECHANISMS
• POLYMER CRYSTALLINITY MEASUREMENTS
• PROPERTIES AFFECTED BY CRYSTALLINITY
 SOLID
S
• CRYSTALLINE SOLIDS : A crystal or
crystalline solid is a solid material whose
constituents (such as atoms, molecules or ions) are
arranged in a highly ordered microscopic structure,
forming a crystal lattice that extends in all
directions.

• AMORPHOUS SOLIDS : An amorphous solid

is any non-crystalline solid in which the atoms
and molecules are not organized in a definite
lattice pattern. Such solids include glass, plastic,
and gel.
 BASIC DIFFERENCES
CRYSTALLINE SOLIDS AMORPHOUS SOLIDS
They have characteristic geometrical Solids that don't have definite
shape geometrical shape
T hey have sharp melting point They melt over a wide range of
temperature
Physical properties of crystalline Physical properties of amorphous
solids are different in different solids are same in different direction.
directions. This phenomenon is amorphous solids are isotropic.
known as Anisotropy.
When crystalline solids are rotated about Amorphous solids are
an axis, their appearance does not unsymmetrical.
change. This shows that they are
symmetrical.
Crystalline solids cleavage along Amorphous solids don't break at
particular direction at fixed cleavage fixed cleavage planes.
planes.
 INTRODUCTIO
Nfibers are determined by their chemical
Properties of textile structure
degree of polymerization, orientation of chain molecules, crystallinity,
package density and cross linking between individual molecules.
Polymer crystallinity is one of the important properties of all
polymers. Polymer exists both in crystalline and amorphous form.
• Figure shows how the arrangement of polymer chain forming
crystalline and amorphous regions. It can be seen that part of
molecules are arranged in regular order, these regions are called
crystalline regions. In between these ordered regions molecules are
arranged in random disorganized state and these are called
amorphous regions.
• Crystallinity is indication of amount of crystalline region in polymer
with respect to amorphous content.
 DEGREE OF
CRYSTALLINITY
• The degree of crystallinity is defined as the fractional amount of polymer
that is crystalline and it is either expressed in terms of the mass fraction
or the volume fraction.
• For semi-crystalline polymers, the degree of crystallinity is one of its most
important physical parameters since it reflects the sample’s morphology
and determines various mechanical properties, such as the Young
modulus, yield stress as well as the impact strength.
• Differential scanning calorimetry is widely used to determine the amount of
crystalline material. It can be used to determine the fractional amount of
crystallinity in a polymer sample. Other commonly used methods are X-ray
diffraction, density measurements, and infrared spectroscopy.
 CRYSTALLISABLIT
Y
• Crystallisabilty is the maximum crystallinity that a polymer can
achieve at a particular temperature, regardless of the other conditions
of crystallization.
• Crystallisablity at a particular temperature depends on the chemical
nature of the macromolecular chain, its geometrical structure,
molecular weight and molecular weight distribution.
 POLYMER
CRYSTALLISATION
• Crystallization of polymers is a process associated with partial
alignment of their molecular chains.
• These chains fold together and form ordered regions
called lamellae, which compose larger spheroidal structures
named spherulites.
• Polymers can crystallize upon cooling from the melt, mechanical
stretching or solvent evaporation. Crystallization affects optical,
mechanical, thermal and chemical properties of the polymer.
CRYSTALLIZATION
MECHANISMS
• Crystallization by stretching
• Crystallization from solution
CRYSTALLIZATION BY STRETCHING

• Crystallization occurs upon extrusion used in making fibers

and films.
• In this process, the polymer is forced through, e.g., a nozzle that
creates tensile stress which partially aligns its molecules. Such
alignment can be considered as crystallization and it affects the
material properties.
• Anisotropy is more enhanced in presence of rod-like fillers such
as carbon nanotubes, compared to spherical fillers.
• Polymer strength is increased not only by extrusion, but also by blow
molding, which is used in the production of plastic tanks and PET
bottles.
• Some polymers which do not crystallize from the melt, can be
partially aligned by stretching.
• Some elastomers which are amorphous in the unstrained state undergo
rapid crystallization upon stretching.
 CRYSTALLIZATION FROM
SOLUTION
• Polymers can also be crystallized from a solution or upon evaporation of
a solvent. This process depends on the degree of dilution.
• In dilute solutions, the molecular chains have no connection with each
other and exist as a separate polymer coils in the solution.
• Increase in concentration which can occur via solvent evaporation,
induces interaction between molecular chains and a possible
crystallization as in the crystallization from the melt.
• Crystallization from solution may result in the highest degree of
polymer crystallinity.
• The crystal shape can be more complex for other polymers,
including hollow pyramids, spirals and multilayer dendritic
structures.
• The rate of crystallization can be monitored by a technique which
selectively probes the dissolved fraction.
 HELICAL STRUCTURES

• To facilitate closer packing of molecules in the crystalline

phase , many polymers tend to assume a helical structure.
• Isotactic vinyl polymers has helical structures.
• Helical structure has a special significance in polymers of
biological origin.

• DNA structure also have helical structures.

• This DNA structures was determined by Watson and Crick.
• Hydrogen bonding plays an important role in the formation of
the double helix of the DNA molecules.
DOUBLE HELIX OF THE DNA MOLECULE BY
WATSON-CRICK
 SPHERULITES

• Spherulites are spherical semicrystalline regions inside non-

branched linear polymers.
• Their formation is associated with crystallization of
polymers from the melt and is controlled by several parameters such
as the number of nucleation sites, structure of the polymer
molecules, cooling rate, etc.
• Spherulites are composed of highly ordered lamellae, which
result in higher density, hardness, but also brittleness of the
spherulites as compared to disordered polymer.
• The lamellae are connected by amorphous regions which provide
certain elasticity and impact resistance.
• Alignment of the polymer molecules within the lamellae results in
birefringence producing a variety of colored patterns.
• Birefringence is the optical property of a material having a refractive
index that depends on the polarization and propagation direction of
light.
• If a molten polymer such as polypropylene is made into thin film between
to hot glass plates and cooled, it is seen that, from different nucleation
centres, spherulites start developing. .
SPHERULITES FORMATION IN SELF-
NUCLEATED TRIGONAL ISOTACTIC
POLY (1-BUTENE)
• Mechanical properties : Formation of spherulites affects many
properties of the polymer material; in particular, crystallinity, density,
tensile strength and Young's modulus of polymers increase during
spherulization. This increase is due to the lamellae fraction within the
spherulites, where the molecules are more densely packed than in the
amorphous phase.
• Optical properties : Spherulites can scatter light rays and hence
the transparency of a given material decreases as the size of the
spherulites increases. Alignment of the polymer molecules within
the lamellae results in birefringence producing a variety of colored
patterns when spherulites are viewed between crossed polarizers in
an optical microscope.
 LAMELLAR
STRUCTURE
• Lamellar structures or microstructures are composed of fine,
alternating layers of different materials in the form of lamellae.
• Such conditions force phases of different composition to form but
allow little time for diffusion to produce those phases equilibrium
compositions.
• Fine lamellae solve this problem by shortening the diffusion distance
between phases, but their high surface energy makes them unstable and
prone to break up when annealing allows diffusion to progress.
 LEFT TO RIGHT: SPHERULITES; BLOCK
COPOLYMER MICRODOMAINS; LAMELLAR
CRYSTALS; CRYSTALLINE BLOCK UNIT CELL.
 FOLDING OF CHAIN DURING
CRYSTAL FORMATION
• For a standard polymer, the lamellar thickness is around 100
Å and the molecular chain length is around 1000 to 10000 Å .
• The accommodation of the long chain into the narrow lamella is by
assuming that chain folding takes place during the process of
crystallization.
• Many experimental techniques such as electron diffraction prove
beyond any reasonable doubt that the chains in a crystal are folded
and oriented perpendicular to the plane of the polymer crystal
lamella.
schematic representation of chain folding taking
place during formation of crystal lamella
 POLYMER CRYSTALLINITY
MEASUREMENTS

• BY DIFFERENTIAL SCANNING CALORIMERTY (DSC)

• BY X-RAY DIFFRACTION (XRD)
 DIFFERENTIAL SCANNING
CALORIMERTY (DSC)
• DSC can be used to determine amount of crystallinity in a
polymer.
• Instrument is designed to measure amount of heat absorbed or evolved
from sample under isothermal conditions.
• DSC contains two pans, one reference pan that is empty and the
other pan has polymer sample.
• In this method polymer sample is heated with reference to a reference
pan. Both polymer and the reference pan are heated at same rate.
• The amount of extra heat absorbed by polymer sample is with
reference to reference material
• DSC curve of a PET bottle sample
 f
%Crystallinity ΔH
obs ×100%
= ΔH f
°
 X-RAY
DIFFRACTION(XRD)
• X-Ray diffraction is also used to measure the nature of polymer and
extent of crystallinity present in the Polymer sample.
• Crystalline regions in the polymer seated in well-defined manner
acts as diffraction grating .
• So the Emerging diffracted pattern shows alternate dark and light
bands on the screen.
• X-ray diffraction pattern of polymer contain both sharp as
well as defused bands.
• Sharp bands correspond to crystalline orderly regions and defused
bands correspond to amorphous regions
• Schematic diagram of X-ray diffraction pattern
• Crystalline structure is regular arrangement of atoms. Polymer
contains both crystalline and amorphous phase within arranged
randomly.
• When beam of X-ray passed through the polymer sample, some of
the regularly arranged atoms reflect the x-ray beam constructively
and produce enhanced intense pattern.
• Amorphous samples gives sharp arcs since the intensity of emerging
rays are more, where as for crystalline samples, the incident rays get
scattered.
• Arc length of diffraction pattern depends on orientation. If the sample
is highly crystalline, smaller will be the arc length.
• X-ray diffraction pattern of (a) amorphous sample and (b) Semi
crystalline polymer sample
 CRYSTALLINITY
CALCULATIONS
• The crystallinity is calculated by separating intensities due to
amorphous and crystalline phase on diffraction phase.
• Computer aided curve resolving technique is used to separate
crystalline and amorphous phases of diffracted graph.
• After separation, total area of diffracted pattern is divided into
crystalline (Ac) and amorphous(Aa).
• Small Angle X-ray Scattering (SAXS), Infrared Spectroscopy, can also be
used to measure crystallinity.
• Percentage of crystallinity Xc % is measured as ratio of crystalline area to
total area.
XC = AC /(AC +AA)
AC = Area of crystalline phase
AA = Area of amorphous phase
 PROPERTIES AFFECTED BY
CRYSTALLINITY
• HARDNESS : The more crystalline a polymer, the more
regularly aligned its chains. Increasing the degree of
crystallinity increases hardness and density.
• YOUNG’S MODULUS : There is steep increase in young's modulus
with increase in amount of crystalline component in the sample.
• TENSILE STRENGTH : This property is directly proportional to the
crystalline structure of a component.
• PERMEABILITY : Crystalline polymers are far less permeable than
the amorphous variety. It means as the polymer crystallinity increases
with decrease in permeability.