POLYMER MORPHOLOGY AND DETERMINATION OF CRYSTAL GROWTH

The modern study of polymer morphology began with the discovery that single crystals of
polyethylene could be grown from dilute solution. These single crystals provided the basis for an
academic study of the nature and process of polymer crystallization. A typical electron micrograph
and electron diffraction pattern of a monolayered single crystal of LDPE having a lozengelike
lateral shape. The lamellar thickness was determined by electron microscopy and small-angle x-ray
scattering takes values in the range of 10 to some tens of nanometers.

The necessity to reconcile the far excess of the mean length of the polyethylene
macromolecule over the small thickness of the monolayered crystal with the fact that the c-
crystallographic axis is tilted by at most 45 degree to the normal to the surface of the lamella led
Keller in 1957 to propose that the macromolecules in a polyethylene lamella are folded back and
forth between the upper and lower surfaces. The loops resulting from these folds form the two
surfaces of the lamellar crystals, also termed fold surfaces. The lamellar character is the
fundamental feature of the habits of polyethylene crystals (and polymer crystals in general) and is
the consequence of the fact that the macromolecules adopt a folded conformation during the process
of crystallization.

A crystal or a crystalline region is a portion of a material in which the molecules or atoms

are arranged in an ordered pattern as opposed to a random arrangement. Crystals can also exhibits
in many types of polymers. The fringed micelle model was the earliest concept of large molecules
formed crystals that being introduced. In this, portions of the polymer chains were visuallized as
aligning with one another in small regions (crystallites). These aligned regions were separated by
regions of nonaligned or amorphous polymer molecules.

According to the fringe micelle model, the crystallites are about 100 A long. The disordered
regions separating the crystallites are amorphous. The chain wander from the amorphous region
through a crystallite, and back out into the amorphous region. The chains are long enough to pass
through several crystallites, binding them together.
 When stresses exist during crystallization, a more fibrous type of structure can formed and
the structures resembled the shape of shish kebab making contrast to spherullites. The platelets in
these structures are interconnected with bundles of parallel molecular segments which is fibrous in
nature and are aligned in the direction of the applied stress. This would expect the relatively high
tensile strength and modulus in the alignment direction when these structures exist.

The refractive indices of crystalline and amorphous regions are usually different making can
be easily to estimate whether a polymer is crystalline or non-crystalline. The light that passes
through a crystalline polymer is scattered by the crystallites, and the object appears translucent.
While in an amorphous polymers, there are no abrupt internal boundaries as far as refractive index
is concerned, so the materials tend to appear transparent.

Two fundamental requirements must be met in order for crystallization to be a possibilty.

These involved intermolecular bond strength and the regularity of the molecular structure and are
discussed in the sections that follow. The molecule must have a rather regular, ordered structure to
have an ordered arrangement of molecules. For example, the presence of random short-chain
branching in some polymers correlates with lower crystallinity. In the polyethylene there is a
temdency for short branches (typically ethyl or butyl groups) to form along the chain. In low
density polyethylene (LDPE) these short branches are fairly numerous (15 to 30 branches per 1000
carbons) while in high density polyethylene (HDPE) there are less frequent (1 to 5 branches per
1000 carbons).
 The crystalline morphologies of polymers that forming spherulites and more fibrous type of
structure are rather complex. The most important note is that polymers are not 100% crystalline.
The spherulitic structure of polymer has significant amorphous components associated with the
chain fold surfaces of the platelets, chain ends and spherullite boundaries. Bulk polymerrs are never
highly crystalline as metals, the defects typically represent a very small percentage of the structure.
Low and high-density crosslinked polyethylenes are now commonly used in industrial
fields. Indeed the irradiation processing of manufactured devices for dimensional stability
importance. The effect of a crosslinked network on the crystallization process is of particular
interest. Generally irradiation, often carried out in the solid state, has been used to produce
crosslinks. High-energy radiation produces crosslinks essentially in the amorphous phase and in the
fold surfaces, so that unhomogenously crosslinked networks are produced. Charlesby et al. and
Mandelkern et al. have investigated PE crosslinked by irradiation. Although details of the
crosslinking process remain controversial, the overall effects on the morphology are well known.

HDPE molecules align to a higher degree than LDPE molecules showing the most obvious
result of higher crystallinity in polyethylene is higher density. HDPE has a density of between 0.941
and 0.965 g/cm^3 whereas LDPE has a density between 0.910 and 0.925 g/cm^3 because of the
closer packing (higher crystallinity) of the less branched material. The presence of chlorine, fluorine
and methyl groups on the backbone of the chain can also influence the geometrical regularity of the
molecular structure, since these atoms and molecular groups are larger than hydrogen, under some
circumstances they can interfere with the alignment processes.
 THEORY OF CRYSTALLINITY AND CHAIN FOLDED THEORY

The formation of polymer crystals with folded chains was set fourth decades ago found by
John Hoffman and John Lauritzen owes its origin to the discovery in 1957 that characteristically
thin single crystals of polyethylene can be grown from dilute solutions, known as The Hoffman-
Lauritzen theory of the formation of polymer crystals. As first proposed by Keller of the University
of Bristol stated the long polymer chains are more or less regularly folded between the upper and
lower lamella surfaces with the chain stems between successive folds oriented preferentially normal
to the plane of lamellae. Chain folding was an essential feature of the crystallization of polymers
from the molten state.

Polymers were found to undergo spherulitic crystallization but the spherullites were
composed of radiating structural units that were found to be lamellar and bore a kinship to solution
grown crystals. In short, following the events of 1957, it was evident that a theory was needed to
explain the starttling effects on polymer crystallization.

A molecular theory is proposed to account for the regular folding of polymer chains during
crystallization. It predicts that an isolated polymer chain greater than some critical length can lower
its energy by crystallizing into a regular folded-chain conformation. Similarly, a single molecular
chain crystallizing upon an infinitely large substance will also lower its free energy by regular
folding.

In a crystal composed of polymer molecules all having the same length the lowest free
energy occurs when all chains are completely extended. However, there are also exists a whole
series of metastable states corresponding to one, two, three, folds per molecule. When the crystal is
composed of a distribution of molecular lengths, the lowest free energy corresponds to a folded
chain crystal whose thickness is a sensitive function of the distribution. If the low end of the
molecular-length distribution is assumed to be truncated at the observed length of extended chain
crystals, the theory satisfactorily predicts the observed thickness of folded-chain crystals obtained
by melt crystallization of both fraction and whole polymer.
 The fringe micelle model was used with great success to explain a wide range of behavior in
semi-crystalline plastics, and also in fibers. If they were above T g then they were rubbery and were
held together by the hard crystallites, this explains the leathery behavior of ordinary polyethylene
plastics, for example. The greater tensile strength of polyethylene over that of low molecular weight
hydrocarbon waxes was attributed to amorphous chains wandering from crystallite to crystallite,
holding them together by primary bonds. The flexible nature of fibers was explained similarly, but
the chains were oriented along the fiber axis. The exact stiffness of the plastic or fiber was related to
the degree of crystallinity, or fraction of the polymer that was crystallized.

Polymer crystals showed that there are more complex than the fringed micelle model
suggests after few studies which is introduced lamellar structures (platelets) consisting of aligned,
looped molecules have been identified in many polymers. The structures of this molecules fold back
on themselves and are aligned so that their lengths are perpendicular to the large faces of the
platelets.

Although lamellar crystals were originally discovered as single crystals grown from dilute
polymer solutions, they also been found as components of larger ordered structures in melt-
crystallized bulk polymers and depends on the crystallization conditions. For example, polyethylene
(PE) was crystallized from the melt under no external stress, results of spherullites was formed and
in aggregation are somewhat analogous to the grain structure in metals. Spherulites form by
crystallization that begins at a site of local order and then proceeds in all direction until other
growing spherullites are encountered.

Ideally the molecules fold back and forth with hairpin turns. While adjacent reentry has been
generally confirmed by small-angle neutron scattering and infrared studies for single crystals, the
present understanding of bulk crystallized polymers indicates a much more complex situation.

EFFECT OF CRYSTALLIZATION ON POLYMER PROPERTIES MECHANICAL AND

OPTICAL

MECHANICAL PROPERTIES

Of the various measurements of mechanical properties made on materials stress-strain

behavior in tension is one of the most common. For many polymers this is specified by
ASTMD638, Standard Method of Test for Tensile Properties of Plastics. In this test a dumbell-
shaped sample is clamped in the jaws of a testing machine, and the load that us required to elongate
it at given rate is recorded. Ideally, the elongation is measured over a portion of the narrowed
section of the sample (termed the gage length) by means of an extensometer. When polymers are
tested in tension according to ASTMD638, four general types of behavior are frequently observed.
These are:
1. low modulus, weak and with low toughness
2. high modulus, strong and with low toughness
3. high modulus, strong and tough
4. low modulus, strong and tough
any molecular feature that increases the strength and stiffness of the secondary bonds and reduces
the flexibility of the chains will tend to increase modulus. Crystals increase modulus through both
of these mechanisms, since the crystalline lattice involves molecules that are relatively close to one
another. The bonds are stronger and stiffer, since the intermolecular distances are shorter, and the
flexibility of the chains is hindered by adjacent molecules. The orientation of the crystals also
influences modulus. In an oriented polymer the modulus tends to be highest in the orientation
direction because a greater proportion of the load is carried by stiff, strong covalent bonds in the
backbone of the molecules. In compliant secondary bonds, and the moduli in these directions are
therefore lower. Generally, the strength, toughness and stiffness increases with degree of
crystallization.

OPTICAL PROPERTIES

Crystalline polymers are usually opaque because of light scattering on the numerous
boundaries between the crystalline and amorphous region. The crystallization in polymers results in
essentially a mass of crystallites dispersed in an amorphous matrix. The density of the crystallites is
usually greater than the amorphous regions, and consequently the crystallites have a higher average
refractive index. The mismatch in refractive indices of the two phases results in relatively large light
scattering and the familiar 'milky' appearance of crystalline polymers. It has been found that the
crystallites tend to form in a spherical manner around the crystallization initiation points and give
rise to longer-range ordered structures-spherulites. Chain alignment is controlled not only by the
orientation stresses but also by the crystallization forces. Very slight chain orientation controls the
direction of growth of crystallites, and oriented crystalline polymers will often show a very high
birefringence. The density of such boundaries is lower and thus the transparency is higher either for
low (amorphous polymer) or high (crystalline) degree of crystallinity. Generally decrease with
increasing degree of crystallinity.

REFERENCES
1. Moore, G. R., Kline, D. E., Properties and Processing of Polymers for Engineers, Prentice-
Hall International, Inc., London (1984).
2. Manas Chanda, Introduction to Polymer Science and Chemistry, Taylor & Francis Group,
London (2006)
3. Sperling, L.H., Introduction to Physical Polymer Science Fourth Edition, A John Wiley &
Sons, Inc., Pennsylvania ( )
4. Nedhal K. Al-Nidawy, Handbook of Polymer Science and Technology, Marcel Dekker, Inc.,
Iraq ( )