POLYMER CRYSTALLINITY

If the atoms or ions of a solid are arranged in a pattern that repeats itself in three dimensions, they form a
solid which is said to have a crystal structure and is referred to as a crystalline solid or crystalline material.
Small molecules and ions form a three-dimensional lattice with an extended regular structure that makes
large crystals possible. A small portion of the NaCl lattice is modeled in the diagram below.

Fig.1

We usually describe such lattices with a unit cell - the smallest repeating unit in the lattice. In the case of
NaCl, the unit cell is said to be face-centered cubic.

Arrangement of Molecular Chains

A picture of an individual molecular chain has been built up as a long randomly twisted thread-like molecule
with a carbon backbone. It must be realised, however, that each chain must co-exist with other chains in the
bulk material and the arrangement and interaction of the chains has a considerable effect on the properties of
the material. Probably the most significant factor is whether the material is crystalline or amorphous.
The crystalline state may exist in polymeric materials also. At first glance it may seem difficult to imagine
how the long randomly twisted chains could exist in any uniform pattern. In fact X-ray diffraction studies
(Fig. 2) of many polymers show sharp features associated with regions of three dimensional order
(crystallinity) and diffuse features characteristic of disordered (amorphous) regions. However, since it
involves molecules instead of just atoms or ions, as with metals and ceramics, the atomic arrangements will
be more complex for polymers. We think of polymer crystallinity as the packing of molecular chains to
produce an ordered atomic array. Crystal structures may be specified in terms of unit cells, which are often
quite complex. By considering the polyethylene molecule again it is possible to see how the long chains can
physically co-exist in an ordered crystalline fashion. This is illustrated in Fig. 3 which shows the unit cell for
polyethylene and its relationship to the molecular chain structure; this unit cell has orthorhombic geometry.

Fig. 2 Wide-angle X-ray scattering

(a) polystyrene, showing a diffuse

halo from an amorphous sample

(b) highly crystalline polyethylene,

showing sharp ‘powder’ rings

Of course, the chain molecules also extend beyond the unit cell shown in the figure. Molecular substances
having small molecules (e.g., water and methane) are normally either totally crystalline (as solids) or totally
amorphous (as liquids). As a consequence of their size and often complexity, polymer molecules are often
only partially crystalline (or semicrystalline), having crystalline regions dispersed within the remaining
amorphous material as shown for instance by the presence of broad halos in WAXS patterns from unoriented
polymers in addition to any sharp rings due to crystalline material..

Fig. 3 Unit cell for polyethylene and its relationship to the molecular chain structure; this
unit cell has orthorhombic geometry. The chain molecules also extend beyond the unit cell.

Any chain disorder or misalignment will result in an amorphous region, a condition that is fairly common,
since twisting, kinking, and coiling of the chains prevent the strict ordering of every segment of every chain.
Other structural effects are also influential in determining the extent of crystallinity which will be discussed
later.
The widths of the rings due to the crystallites indicate that, in some polymers, the crystallite dimensions are
only of the order of tens of nanometres, which is very small compared with the lengths of polymer chains,
which may be of order 3000 nm measured along the chain, i.e. about 100 times the dimensions of
crystallites. The following questions therefore arise.

(i) How can long molecules give rise to small crystallites?

(ii) What are the sizes and shapes of polymer crystallites?
(iii) How are the crystallites disposed with respect to each other and to the non-crystalline material?
(iv) What is the nature of the non-crystalline material?

These questions are the basis of polymer morphology, which may be defined as the study of the structure and
relationships of polymer chains on a scale large compared with that of the individual repeat unit or the unit
cell, i.e. on the scale at which the polymer chains are often represented simply by lines to indicate the path of
the backbone through various structures. In addition to the four questions above, morphology is concerned
with such matters as the directions of the chain axes with respect to the crystallite faces and with the
relationship between the crystallites and the non-crystalline material, a particular aspect of which is the
nature of the crystalline–‘amorphous’ interface. .
The morphology of a polymer plays an important role in determining its properties, but the molecular
motions that take place within the polymer play an equally important role. We will study later the types of
motion that can take place in solid polymers and the evidence for these motions.
Degree of Crystallinity

Before considering the details of how the chains are arranged in the crystalline and non-crystalline regions of
a polymer, it is useful to consider how the amount of material contained within the two types of region can
be determined.

The degree of crystallinity may range from completely amorphous to almost entirely (up to about 95%)
crystalline; in contrast, metal specimens are almost always entirely crystalline, whereas many ceramics are
either totally crystalline or totally noncrystalline. Semicrystalline polymers are, in a sense, analogous to two-
phase metal alloys. In principle, almost any property that is different in the crystalline and non-crystalline
regions could be used as the basis for a method of determining the degree of crystallinity, χ, or, as it is
usually more simply put, the crystallinity, of a polymer sample. In practice the most commonly used methods
involve density measurements, DSC measurements and X-ray diffraction measurements.
.
The crystallization of a polymer from the melt is accompanied by a reduction in specimen volume due to an
increase in density.
The density of a crystalline polymer will be greater than an amorphous (molten or non crystalline) one of the
same material and molecular weight, since the chains are more closely packed together for the crystalline
structure. This effect provides the basis of the density method for the determination of the degree of
crystallinity. The technique relies upon the observation that there is a large and measurable difference (upto
20 %) between the densities of the crystalline and amorphous regions of the polymer. This method can yield
both the volume fraction φc and the mass fraction xc from measurement of sample density ρs.
If Vc is the volume of crystals and Va the volume of amorphous material then the total specimen volume, Vs,
is given by
Vs = Vc + Va
Similarly the mass of the specimen Ws is given by: Ws = Wc + Wa

Where Wc and Wa are the masses of crystalline and amorphous material in the sample respectively. Since
density ρ is mass per volume then it follows that

ρsVs = ρcVc + ρaVa

Substituting for Va and rearranging leads to

Vc / Vs = [ (ρs – ρa) / (ρc – ρa) ] = φc

since φc is equal to the volume of crystals divided by the total specimen volume. The mass fraction χ c of
crystals or degree of crystallinity is similarly defined as

χc = Wc / Ws = ρcVc / ρsVs

Substituting the value of Vc /Vs, χc = [(ρc / ρs) (ρs – ρa) / (ρc – ρa) ]

or
% crystallinity = [ ρc (ρs – ρa) / ρs (ρc – ρa) ] x 100

where ρs is the density of a specimen for which the percent crystallinity is to be determined, ρa is the density
of the totally amorphous polymer, and ρc is the density of the perfectly crystalline polymer. The values of ρa
and ρc must be measured by other experimental means.
The degree of crystallinity of a polymer depends on the rate of cooling during solidification as well as on the
chain configuration. During crystallization upon cooling through the melting temperature, the chains, which
are highly random and entangled in the viscous liquid, must assume an ordered configuration. For this to
occur, sufficient time must be allowed for the chains to move and align themselves.

EXAMPLE PROBLEM

Computations of the Density and Percent Crystallinity of Polyethylene

(a) Compute the density of totally crystalline polyethylene. The orthorhombic unit cell for polyethylene is
shown in Figure 1; also, the equivalent of two ethylene repeat units is contained within each unit cell.
(b) Using the answer to part (a), calculate the percent crystallinity of a branched polyethylene that has a
density of 0.925 g/cm3. The density for the totally amorphous material is 0.870 g/cm3.

Solution
(a) Equation utilized to determine densities for metals, also applies to polymeric materials and is used to
solve this problem. It takes the same form—viz.

ρ = nA / VC NA

where n represents the number of repeat units within the unit cell (for polyethylene ), and A is the repeat unit
molecular weight, which for polyethylene is

A = 2(AC) + 4(AH)

= 2 x (12.01 g/mol) + (4x1.008 g/mol) = 28.05 g/mol

Also, VC is the unit cell volume, which is just the product of the three unit cell edge lengths in Figure 3;

or VC = (0.741 nm) (0.494 nm) (0.255 nm)

= 9.33 x 10 -23 cm3/unit cell

Now, substitution into Equation 3.5, of this value, values for n and A cited above, as well as leads to

ρ = nA / VCNA

_ (2 repeat units/unit cell) (28.05 g/mol)___________

(9.33 x 10-23 cm3/unit cell)(6.023 x1023 repeat units/mol)
= 0.998 g / cm3

(b) We now utilize Equation of % crystallinity to calculate the percent crystallinity of

the branched polyethylene with ρc = 0.998 g/cm3, ρa = 0.870 g/cm3, and ρs = 0.925 g/cm3. Thus,

% crystallinity = [ ρc (ρs – ρa) / ρs (ρc – ρa) ] x 100

= [0.998 (0.925 – 0.870) / (0.998 – 0.870 )] x 100 = 46.4%

POLYMER CRYSTALS
The most obvious question that needs to be answered about polymer crystallites is question (i) How can
long molecules give rise to small crystallites? Two principal types of answer have been given; they lead to
the fringed-micelle model and the chain-folded model for polymer crystallites. A further type of crystallite,
the chain-extended crystal, can also occur when samples are prepared in special ways. These three types of
crystallites are considered in the following sections.

Fringed Micelle Model

During the 1940’s it was proposed that partially crystalline polymers consisted of regions where the
molecular chains were gathered in an ordered fashion whereas adjacent regions had a random distribution of
chains.
It has been proposed that a semicrystalline polymer consists of small crystalline regions (fibrillar
crystallites), each having a precise alignment, which are interspersed with amorphous regions composed of
randomly oriented molecules and which can grow both parallel and perpendicular to the chain axes. The
crystalline regions were considered to be so small that an individual chain could contribute to both
crystalline and amorphous areas as shown in Fig. 4. Thus, a single molecule might pass through several
crystallites as well as the intervening amorphous regions and small crystallites can thus be reconciled with
long chains. This was known as the Fringed Micelle Model and was generally accepted until the late 1950's.

Fig. 4 Fringed Micelle Model

It is now believed to be incorrect as the basic model for polymer crystallites, but it is worth describing for
historical reasons and because it may be a good approximation to the true structure in special cases.

Chain-folded Model

This type of crystallisation was first suggested by Storks in 1938. He made films of gutta percha 27 nm thick
by evaporation from solution. Electron diffraction showed that the films were composed of large crystallites
with the chain axes normal to the plane of the film. The only possibility was that the chains folded back and
forth upon themselves, so that adjacent segments were parallel and in crystal register. This idea lay dormant
until the early 1950s, but then very small single crystals of polymers were produced from dilute solutions.
These crystals are regularly shaped, thin platelets (or lamellae), approximately 10 to 20 nm thick, and on the
order of 10 μm long. Frequently, these platelets will form a multilayered structure, like that shown in the
electron micrograph of a single crystal of polyethylene, Figure 9.
Shortly afterwards (in 1957) Fischer showed by electron microscopy that the crystallites in melt-grown
spherulites of polyethylene and nylon were most likely to be lamellar rather than fibrillar, as would be
expected from the fringed-micelle model.
Studies by Keller and his group using electron diffraction showed that the chain axes were parallel to the
thickness direction of these lamellar crystals (i.e. perpendicular to the flat faces of the platelet). Since the
length of an individual chain could be 1000 times greater than the thickness of the platelet the only
conclusion was that the chains were folded. The molecular chains within each platelet fold back and forth on
themselves, with folds occurring at the faces; and as shown in Figure 5 and Fig . 6 in which the parallel
chains (shown in different colors in the simulated structure) are perpendicular to the face of the crystals.
Appropriately, this was called the Folded Chain Theory. It is now accepted that chain-folded lamellar
crystallites play an important part in the structure of most ordinary crystalline polymers.

Figure 5 The chain-folded structure for a plate-shaped polymer crystallite. ~ 10 nm (~100Å)

Fig. 6

Sometimes part of a chain is included in this crystal, and part of it isn't. When this happens we find the
chains hanging out of lamella everywhere in a disorder randomly coiled state (Fig. 7).

Fig. 7

Of course, the polymer chains will often come back into the lamella after wandering around outside for
awhile and re-enters in some distance away from where it left. When this happens, we get a picture like this:
 Fig. 8

This is the switchboard model of a polymer crystalline lamella. (The name arises from the similarity in the
appearance of the crystal surface in this model to the criss-crossing of the wires on an old-fashioned manual
telephone switchboard.)

When a polymer chain doesn't wander around outside the crystal, but just folds right back in on itself, as
shown in the first pictures, that is called the adjacent re-entry model.

Keller originally suggested that solution-grown crystals exhibited regular sharp folding with adjacent re-
entry. A later model with irregular re-entry, the switchboard model, was proposed by Flory.
For solution-grown crystals adjacent re-entry was found to predominate, whereas for melt-grown crystals
adjacent reentry probably occurs quite frequently, but much less regularly.

There are several proposals to account for the co-existence of crystalline and amorphous regions in the
Folded Chain Theory . In one case, the structure is considered to be a totally crystalline phase with defects.
These defects which include such features as dislocations, loose chain ends, imperfect folds, chain
entanglements etc, are regarded as the diffuse (amorphous) regions viewed in X-ray diffraction studies. (In
other words, in the complex structure of partially crystalline polymers, the crystalline regions consist of
aligned and folded chains and the amorphous regions consist of crystal defects and randomly entangled
chains.) As an alternative it has been suggested that crystalline (folded chains) and amorphous (random
chains) regions can exist in a similar manner to that proposed in the fringed micelle theory.

Frequently, these platelets will form a multilayered structure, like that shown in the electron micrograph of a
single crystal of polyethylene (Fig. 9).

Figure 9. Electron micrograph of a

polyethylene single crystal.

Various pieces of evidence suggest that the fold surfaces are not perfectly regular, particularly for melt-
crystallised materials. Buried folds exist up to 2.5 nm below the surface, but the number of sharp folds
increases as the overall surface is reached and there are many folds near the mean lamellar surface. Outside
this there are loose chain ends and long loops (nonadjacent re-entry). In melt-crystallised material tie
molecules pass from one lamella to adjacent ones in the multi-layer stacks that are generally found in such
material (Fig. 10).
There is thus an amorphous layer between the crystal lamellae. So a crystalline polymer really has two
components: the crystalline portion and the amorphous portion. The crystalline portion is in the lamellae, and
the amorphous potion is outside the lamellae. As the molar mass increases chain folding becomes less
regular and the degree of crystallinity also falls, because the freedom of the chains to rearrange themselves
on crystallisation decreases.

Figure 10

Spherulites

Many bulk polymers that are crystallized from a melt are semicrystalline and form a spherulite structure. As
implied by the name, each spherulite may grow to be roughly spherical in shape; one of them, as found in
natural rubber, is shown in the transmission electron micrograph (Fig. 11). The spherulite consists of an
aggregate of ribbon-like chain-folded crystallites (lamellae) approximately 10 nm thick that radiate outward
from a single nucleation site in the center.

Figure 11

In this electron micrograph, these lamellae appear as thin white lines. The detailed structure of a spherulite is
illustrated schematically in Figure 12.
These lamellae also called “lamellar fibrils” grow out in three dimensions. The whole assembly is called a
spherulite. In a sample of a crystalline polymer weighing only a few grams, there are many billions of
spherulites.

In between the crystalline lamellae, there are regions where there is no order to the arrangement of the
polymer chains. These disordered regions are the amorphous regions. As one can also see in the picture, a
single polymer chain may be partly in a crystalline lamella, and partly in the amorphous state. Some chains
even start in one lamella, cross the amorphous region, and then join another lamella. These chains are called
tie molecules.

Figure 12. Schematic representation of the detailed structure of a spherulite.

As the crystallization of a spherulitic structure nears completion, the extremities of adjacent spherulites begin
to impinge on one another, forming more or less planar boundaries; prior to this time, they maintain their
spherical shape. These boundaries are evident in Figure 13, which is a photomicrograph of polyethylene
using cross-polarized light. A characteristic Maltese cross pattern appears within each spherulite. The bands
or rings in the spherulite image result from twisting of the lamellar crystals as they extend like ribbons from
the center. In a sample of a crystalline polymer there are billions of spherulites.

Spherulites are considered to be the polymer analogue of grains in polycrystalline metals and ceramics.
However, as discussed above, each spherulite is really composed of many different lamellar crystals and, in
addition, some amorphous material. Polyethylene, polypropylene, poly(vinyl chloride),
polytetrafluoroethylene, and nylon form a spherulitic structure when they crystallize from a melt.
 Figure 13

Fig. 14

These spherulites may vary in size from fractions of a micron to several millimetres in diameter, depending
on the cooling rate from the melt. Slow cooling tends to produce larger spherulites than fast cooling. As
stated earlier, it is believed that the spherulites grow in all directions from a central nucleus, by the twisting
of the folded chain platelets ( Fig. 15).
 Fig. 15 Schematic representation of the detailed structure of a spherulite

The size of a spherulite will be limited by the growth of adjacent spherulites. If the polymer melt is cooled
very quickly it may undercool, i.e. remain molten at a temperature below its melting point. This results in a
shower of nucleation sites becoming available and a mass of spherulites will start to grow. The solid polymer
will then consist of a large number of small spherulites.

Crystallization Tendency (Factors Determining Crystallinity of Polymers)

No polymer is completely crystalline. Crystallinity makes a material strong, but it also makes it brittle. A
completely crystalline polymer would be too brittle to be used as plastic. The amorphous regions give a
polymer toughness, that is, the ability to bend without breaking.

But for making fibers, we like our polymers to be as crystalline as possible. This is because a fiber is really a
long crystal. Many polymers are a mix of amorphous and crystalline regions, but some are highly crystalline
and some are highly amorphous. Here are some of the polymers that tend toward the extremes:

Some Highly Crystalline Polymers Some Highly Amorphous Polymers:

Polypropylene Poly(methyl methacrylate)
Syndiotactic polystyrene Atactic polystyrene
Nylon Polycarbonate
Kevlar and Nomex Polyisoprene
Polyketones Polybutadiene

Thermosetting polymers do not crystallize. The ability of a thermoplastic polymer to partially crystallize is
determined by the ease with which the molecules can move and be efficiently packed together to create long-
range order. The ease with which a polymer will form into crystalline regions depends on the chemical
composition and the structural details of particular polymers.

Several factors favor a polymer with a high percent crystallinity, including:

 1. The size of side groups.
2. The extent of chain branching.
3. Tacticity.
4. The complexity of the repeat unit.
5. Strong intermolecular forces (i.e., the degree of secondary bonding between parallel chain segments)
6. A low degree of polymerization.
7. A slow rate of cooling, and oriented molecules.
1. Size of Side Groups or Pendant Groups

Regular polymers with small pendant groups crystallize more readily than do polymers with large, bulky
pendant groups. Thus, one can predict that polypropylene, [C2 H3 (CH3)]n, is less likely to crystallize than
polyethylene, (C2H4)n, but more likely to crystallize than polystyrene, [C2H3(C6H5)]n, since the CH3 group is
larger than a single H atom but smaller than a C6H5 group. Poly(vinyl alcohol) (PVA) is made by the
hydrolysis of poly(vinyl acetate) (PVAc).

PVAc PVA

PVA crystallizes more readily than PVAc because of the bulky acetate groups in PVAc. The -OH groups in
PVA also form strong hydrogen bonds. Hence, the bulkier or larger the side-bonded groups of atoms, the less
tendency there is for crystallization.

2. Chain Branching

For linear polymers, crystallization is easily accomplished because there are few restrictions to prevent chain
alignment. Any side branches interfere with crystallization (although limited crystallization can take place if
a small number of branches are present), such that branched polymers never are highly crystalline; in fact,
excessive branching may prevent any crystallization whatsoever. Crystallization is favored by a regular
arrangement along the polymer chain giving the structure a high degree of symmetry.

Polyethylene is a good example. It can be crystalline or amorphous. Linear polyethylene for example can
form a solid with over 90% crystallinity in some cases. This is made possible by the planar zig-zag structure
easily assumed by the molecule. But the branched stuff just can't pack the way the linear stuff can, so it's
highly amorphous.

The density, strength, and modulus of PE all increase as the degree of crystallization increases. For example
a sample of PE with a moderate concentration of chain branches may be approximately 40 – 60 % crystalline
(LDPE) with a density of ~0.94 g/cm3, a strength of 4 – 16 MPa, and a modulus of 100 – 260 MPa. In
contrast, a sample of PE with a low concentration of chain branches may be ˃95% crystalline (HDPE) with a
density of ~1.0 g/cm3, a strength of 20 – 40 MPa, and a modulus of 400 to 1200 MPa.

For copolymers, as a general rule, the more irregular and random the repeat unit arrangements, the greater is
the tendency for the development of noncrystallinity. For alternating and block copolymers there is some
likelihood of crystallization. On the other hand, random and graft copolymers are normally amorphous.

3. Tacticity

Normal polystyrene is atactic with no regular order in the position of the benzene rings along the chain. The
irregularity prevents the chains from packing closely to each other.

Atactic polystyrene, is amorphous. It is comparatively soft, low melting, and becomes swollen in solvents.

Isotactic and syndiotactic polymers crystallize much more easily because the regularity of the geometry of
the side groups facilitates the process of fitting together adjacent chains.

In syndiotactic polystyrene the benzene rings are on alternate sides of the chain. This allows the chains to
pack into crystals.

Syndiotactic polystyrene is crystalline. It is rigid, high melting, and not penetrated readily by solvents.
As was the case with chain branches, the influence of tacticity on degree of crystallization ultimately
influences the macroscopic properties of the polymer. For example, at room temperature isotactic
polypropylene (~70% crystalline) is hard and rigid while atactic polypropylene (~0% crystallinity) is a
useless gummy substance.

4. Complexity of the Repeat Unit

Crystallization is not favored in polymers that are composed of chemically complex repeat units (e.g.,
polyisoprene). On the other hand, crystallization is not easily prevented in chemically simple polymers such
as polyethylene and polytetrafluoroethylene, even for very rapid cooling rates.

Polymers with long repeat units such as PET and many nylons, require more extensive chain segment motion
to establish LRO. As such they typically crystallize slowly, if at all, and can be easily formed into glasses
using modest quench rates.

5. Intermolecular Forces (Secondary Bonds between Chains)

Intermolecular forces can be a big help for a polymer if it wants to form crystals. A good example is nylon.
You can see from the picture that the polar amide groups in the backbone chain of nylon(6,6) are strongly
attracted to each other. They form strong hydrogen bonds. This strong binding holds crystals together.
Polyesters are another example. Let's look at the polyester we call poly(ethylene terephthalate).

The presence of polar and hydrogen bonding groups favors crystallinity because they make possible dipole-
dipole and hydrogen bonding intermolecular forces. A polyester, such as poly(ethylene terephalate), contains
polar ester groups. Dipole-dipole forces between the polar groups hold the PET molecules in strong crystals.

Crystallinity in poly(ethylene terephalate) is also favored by the structural regularity of the benzene rings in
the chain. The benzene rings stack together in an orderly fashion.

6. Degree of Polymerization

Relatively short polymer chains form crystals more readily than long chains, because the long chains tend to
be more tangled. High crystallinity generally means a stronger material, but low molecular weight polymers
usually are weaker in strength even if they are highly crystalline. Low molecular weight polymers have a low
degree of chain entanglement, so the polymer chains can slide by each other and cause a break in the
material.

7. Processing

A major difference between small molecules and polymers is that the morphology of a polymer is
dependent on its thermal history. The crystallinity of a polymer can be changed by cooling the polymer
melt slowly or quickly, and by "pulling" the bulk material either during its synthesis or during its processing

A. Cooling Rate

When they are processed industrially, polymers often are cooled rapidly from the melt. In this situation,
crystallization is controlled by kinetics rather than thermodynamics. There may not be time for the chains,
which are entangled in the melt, to separate enough to form crystals, so the amorphous nature of the melt is
"frozen into" the solid. A polymer is more likely to have a higher percent crystallinity if it is cooled
slowly from the melt.

B. Orientation

Another important feature of long chain molecules is the ease with which they can be rearranged by the
application of stress. If a plastic is stretched the molecules will tend to align themselves in the direction of
the stress and this is referred to as orientation. Molecular orientation leads to anisotropy of mechanical
properties. This can be used to advantage in the production of fibres and film or may be the undesirable
result of a moulding process. However, it is important that orientation should not be confused with
crystallinity. It is possible to have an orientated polymer which shows no evidence of crystalline regions
when X-ray diffraction studies are carried out. Equally, a polymer may be crystalline but optical
measurements will show no signs of orientation.

Crystallinity can be enhanced by pulling the bulk material either when it is synthesized or during its
processing. This is common for both films and fibers.

When a film is formed the small crystallites tend to be randomly oriented relative to each other. Drawing
(stretching) the film pulls the individual chains into a roughly parallel organization as is shown in the
schematic diagram at the right. Films can either be uniaxially oriented (oriented in only one direction) or
biaxially oriented (oriented in two directions).

Fibers normally are drawn so that they are oriented in one direction. Unstretched nylon fibers are brittle, for
example. When the fibers are stretched the oriented fibers are strong and tough.
Orientation can be introduced into plastics such as polyethylene and polypropylene (both semi-crystalline)
by cold drawing at room temperature. Other brittle plastics such as polymethyl methacrylate and polystyrene
(both amorphous) cannot be cold drawn but can be drawn at elevated temperatures.

Polyethylene can be unentangled by forming a gel with a low molecular weight solvent. When the gel is
drawn, the resulting fibers are highly oriented. Ultra-oriented PE formed in this way is used in bullet-proof
vests.

Most network and crosslinked polymers are almost totally amorphous because the crosslinks prevent the
polymer chains from rearranging and aligning into a crystalline structure. A few crosslinked polymers are
partially crystalline.

In sum, the factors that hinder crystal formation in polymers are an atactic configuration, bulky side groups,
and chain branches. It can be seen, for example, that if the polyethylene molecule has a high degree of
branching then it makes it difficult to form into the ordered fashion. Polar side groups tend to aid in the
formation of crystalline regions in polymers. Polymers with large repeat units are generally slow to
crystallize. Polymer with simple symmetric structures are generally semi crystalline. If the side groups are
large, it is not easy for a polymer with an atactic structure to form ordered regions. On the other hand
isotactic and syndiotactic structures do have sufficient symmetry to be capable of crystallisation. Although
the rules given in this section are incomplete, they lead to correct predictions in most common engineering
situation. We pause to point out that the inability to form extensive crystalline regions is not necessarily a
disadvantages; however, it means that the useful temperature range of the material may be determine by Tg
rather Tm. In fact, the reciprocal property, known as glass-forming ability, is often a highly desired materials
property.

Even polymers for which all factors are favorable (small polar side groups in a stereo regular configuration )
are never fully crystalline. As such, they are referred to as semi crystalline, or partially crystalline, polymers.
Because the macromolecules are highly entangled I the melt and diffusion rates are low, the chains do not
have sufficient time to completely disentangle during solidification.
Amorphous Polymers
* Random structure - The molecular structure
of an amorphous polymer is completely
random i.e., the molecular chains are
randomly oriented and entangled with no
recognized pattern.
* Atactic configuration
* Weak secondary bonding forces
* Broad soflening range – thermal agitation
of the molecules breaks down the weak
secondary bonds. The rate at which this
occurs throughout the formless structure
varies producing broad temperature range
for softening.
* Usually transparent - the looser structure
transmits light so the material appears
transparent.
E.g., PS, Acrylic, PVC, PC.
* Low Strength - Low Strength
than comparable semi-
crystalline polymer
* Tough – Amorphous region gives
toughness to the materials
* Fully amorphous polymers have only Tg
and no Tm.
Amorphous depend upon Tg.
* Low shrinkage – all
thermoplastics are processed in the
amorphous state. On solidification,
the random arrangement of
molecules produces little volume
change and hence low shrinkage.
Semi - Crystalline Polymers
* Ordered structure - In semi-crystalline
polymers, regions of highly ordered
molecular arrays exist in the molecular
structure.
The crystalline region are typically platte
like. (folded chains stacked called lamella)
* Isotactic & Syndiotactic configuration
* Closer molecular spacing hence high
secondary bonding forces
* Sharp melting point – the regular close-
packed structure results in most of the
secondary bonds being broken down at th
same time.
* Usually opaque – the difference in refractive
indices between the two phases (amorphous
and crystalline) causes interference so the
material appears translucent or opaque.
E.g., PE, Polyamides (Nylon).
* Higher strength - Higher
strength, Stiffer and high density
than comparable amorphous
polymer
* Rigid – Crystalline region gives
rigidity to the materials
* Semi-crystalline have both Tm and Tg.
Semi-crystalline depends upon Tm.
* High shrinkage - as the material
solidifies from the amorphous state
the polymers take up a closely
packed, highly aligned structure.
This produces a significant volume
change manifested as high
shrinkage.
Predict which member of each pair of polymers has the better glass-forming ability.

A. Isotactic [C2H3(CH3)], or Syndiotactic [C2H3F],,?

B. Atactic [C2H3CH3],, or isotactic [C2H3CI]

SOLUTION

A. Both configurations are symmetric and can form semi crystalline structures. The relatively
bulky CH3 groups hinders crystal formation in [C2H3(CH3)], the secondary bonds associated
with the polar F side group in [C2H3F] favor crystal formation. Thus, we predict that isotactic
[C2H3(CH3)] is a better former, and syndiotactic [C2H3F] is more likely to form crystalline
regions.

B. Atactic [C2H3Cl] has two factors working against the establishment of extensive crystalline
regions: the atactic configuration and a bulky CH3side group. Isotactic [C2H3Cl] however, has
a regular structure, no bulky side groups, and relatively strong secondary bonds associated
with its Cl atom. Therefore, we predict that atactic [C2H3CH3],, is a better glass former and
isotatctic [C2H3Cl] is more likely to form crystalline region.