POLYMER CHARACTERIZATION

MOLECULAR WEIGHT AND ITS DISTRIBUTION

The molecular weight of a polymer is of prime importance in the polymer’s synthesis and
application. It is important because it determines many physical properties. The term molecular
th
weight is a ratio of the average mass per formula unit of substance to 1/12 of an atom of C.
Molecular weight (MW) and its distribution (MWD) has a considerable effect on macroscopic
properties of polymer such as toughness, tensile strength, adherence and environmental
resistance, etc. A simple chemical has fixed molecular weight but when we discuss about the
molecular weight of polymer, we mean something different from that which applies to small
sized compounds.

Since polymers are mixture of molecules of different molecular weight, the molecular
weight is expressed in the term of “average” value. This average molecular weight is basically
based on either average number of repeating units, known as number average molecular weight,
or average weight, known as weight average molecular weight.

NUMBER AVERAGE MOLECULAR WEIGHT

Consider a property which is only sensitive to the number of molecules present — a

property that is not influenced by the size of any particle in the mixture. The best example of
such properties are the colligative properties of solutions such as boiling point elevation, freezing
point depression, and osmotic pressure. For such properties, the most relevant average molecular
weight is the total weight of polymer divided by the number of polymer molecules. This average
molecular weight follows the conventional definition for the mean value of any statistical
quantity. In polymer science, it is called the number average molecular weight — MN.

Where Ni - number of polymers

Mi- molecular weight.

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WEIGHT AVERAGE MOLECULAR WEIGHT

Consider of polymer property which depends not just on the number of polymer molecules
but on the size or weight of each polymer molecule. A classic example is light scattering. For
such a property we need a weight average molecular weight. To derive the weight average
molecular weight, replace the appearance of the number of polymers of molecular weight i or Ni
in the number average molecular weight formula with the weight of polymer having molecular
weight i or NiMi. The result is

POLYDISPERSITY 

To repeat, there is generally a range of molecular weights in a given polymer sample, so we must
also find a way to characterize the distribution of molecular weights. One way is to measure and
record the entire distribution of molecular weights (fraction of polymer molecules with a
particular molecular weight). A simpler method (simpler both in the technique and in the
resulting information) is to express the polydispersity as a ratio of different molecular weight
averages (MW/Mn ).

THERMAL TRANSITIONS: GLASS TRANSITION AND MELTING

GLASS TRANSITION TEMPERATURE

Amorphous polymers are known to exhibit two distinctly different mechanical properties.
Since Some polymers like polystyrene, polyvinyl chloride, polymethyl methacryiate are hard and
rigid glassy materials at room temperature where some other like polybutadiene, polyisoprene
and polyisobutylene are flexible and rubber like. However glassy plastic materials can exhibit
rubber like properties on heating to a certain degree and rubbery material become glassy on

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cooling. Thus all amorphous polymers undergo a change from glassy state to rubbery state and
vice versa at a certain temperature known as glass transition temperature Tg.

Glass transition temperature is, defined as, the temperature below which, an
amorphous polymers is brittle and glassy and above the temperature become soft and
rubbery.
On further heating, the polymer (if it is uncrosslinked) becomes a high viscous liquid and
starts flowing. This state is termed viscofluid state.

FACTORS THAT AFFECT THE VALUE OF Tg

Number of factors affects the value of Glass Transition temperature

1. In crystalline polymers the polymer chains are arranged in a regular parallel fashion. Each
chain is bound to the other by strong bond like hydrogen bonding. Hence crystalline polymers
have higher Tg than amorphous polymers. Segmental and chain motilities are easier in
amorphous polymers than in crystalline polymers.
2. Generally Tg of a polymer increases with molar mass up to a particular value and beyond that
there is no change.
3. The pressure of side chain which hinder free rotation also increase Tg .
4. Linear polymer chains made of C—C, C—Q or C—N single bonds have a high degree of
freedom for rotation. The presence of bulky side group or the presence of aromatic or cyclic
structure in the chain backbone hinders the freedom for rotation. This results in increase of Ta.
5. The presence of plasticizers reduce Tg of a polymer like impurities on
melting point of pure solids.
6. Stereo regularity of polymers increases Tg. Thus Tg of an isotactic polymer is greater than that
of syndiotactic polymer whose Tg is greater than atactic polymer.
7. In case of hydrocarbon polymers only Vander Waals forces act on neighbouring chains. Hence
molecular aggregates are not that strong. Chain segments can slip past each other easily. polymer
chains containing polar groups on the other hand are held together more strongly by
neighbouring dipoles as well as intermolecular hydrogen bonding and are unable to move that
easily. Such polymers have high Tg than hydrocarbon polymers.

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GLASS TRANSITION AND MELTING TEMPERATURE OF SELECTED POLYMERS

Polymer Tg 0C Tm 0C
Cellulose acetate 49-478 306
Cellulose trinitrate 53 700
Natural Rubber -73 36
Nylon-6 50 250
Nylon-6,6 50 270
Polyacrylonitrile 97 341
Polyethyl acrylate -24 —
Polyethylene (High density) -125 146
Polyethylene terephthalate 69 264
Polymethyl acrylate 10 —
Polymethyl methacryiate
Atactic 105 —
Isotactic 38 160
Syndiotactic 105 > 200
Polypropylene
atactic -13 —
Isotactic -18 208
Polystyrene 100 250

Relationship between Glass Transition Temperature and Melting Point

Based on experimental observations Tg and Tm (in kelvin) have. been shown to be related as :
1
Tg = T (for Symmetrical polymers)
2 m
2
Tg = T (for Unsymmetrical polymers)
3 m

A combined form of these two equations, irrespective of molecular symmetry can be shown:
1 Tg 2
2
<¿
Tm
< 3

Since this relation gives a range for Tg I Tm (rather than a sharp value) it may more realistically
reflect the thermal behaveour of polymers.

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CRYSTALLINITY

Unlike simple inorganic compounds (NaCl or KC1), polymers do not have a

perfectly ordered crystal lattice formation and are not completely crystalline.
Infact they contain both crystalline and amorphous regions. For this reason
x-ray diffraction patterns of most polymers contain both sharp as well as broad
and diffuse bands. The sharp bands Crystalline (orderly) regions while the diffuse and broad
corresponds to amorphous (non-orderly) regions. A synthetic polymer may be described as
crystalline if it contains regions of 3-D ordering on atomic length scales usually arising from
inter molecular folding and/or stacking of adjacent chains. Synthetic crystallinity of a polymer
sample is expressed in terms of that traction of the sample which is crystalline, and is known as
degree of crystallinity. The highest crystallinity is-generally associated with polymers which
have a simple unit structure and a relatively high degree, of molecular order.

The highest crystallinity is generally associated with polymers which have a simple unit structure
and a relatively high degree of molecular order. Therefore the overall property ( Q ) of a partially
crystalline polymer is expressed as sum of its two components
Q = Qc + Qa -1-

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Where Qc and Qa are the contribution of the crystalline and amorphous components of the
sample, respectively.
The density of a material increases when it changes its phase from liquid to crystal. This is
also true for polymers. The density of the crystalline component is higher than that of the
amorphous component. The degree of crystallinity of the sample can be calculated by the
knowledge of the densities of the crystalline and amorphous components of a polymer and that
of the aggregate sample.
d−d a
Xv= d −d
c a

Where XV= degree of crystallinity by volume

d = density of sample
da = degree of crystallinityof fully amorphous components
dc = degree of crystallinity of fully crystalline component.
Specific volume (V) of the sample could also be used to measure the degree of crystallinity
V a −V
Xm= V −V
a c

Where Xm = degree of crystallinity by mass

V = Specific volume of the sample
Va= Specific volume of the fully amorphous component
Vc = Specific volume of the fully crystalline component.
The degree of crystallinity of a partially crystalline sample can also be calculated by using
enthalpy (H) as per by equation.
H a−H
Xcal =
H a−H c
Where H = enthalpy of the sample
Ha = enthalpy of amorphous component
Hc = enthalpy of crystalline component
Xcal = degree of crystallinity of partially crystalline sample.
Degree of crystallinity ranging from zero for a completely non-crystalline polymer to one for a
completely a theoretical crystalline polymer. Increasing degree of crystallinity tends to make a

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polymer more rigid. It can also lead to great brittleness. Polymer with a degree of crystallinity
approaching zero or one will tend to be transparent while polymers with intermediate degree of
Crystallinity will tend to be opaque.
The degree of crystallinity by weight may be determined from accurate density measurement
according to:
ρc (ρ s −ρa )
Xm = × 100
ρs ( ρ c −ρa )

Where: s- density of a specimen for which the present crystallinity is to be determined.

a- density of the completely amorphous polymer.

c- density of the completely crystalline polymer.

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. 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.

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.

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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.
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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, [C 2 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 C 6H5 group.
Poly(vinyl alcohol) (PVA) is made by the hydrolysis of poly(vinyl acetate) (PVAc).

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.

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The density, strength, and modulus of PE all increase as the degree of crystallization increases.
For copolymers, as a general rule, the more irregular and random the repeat unit arrangements,
the greater is the tendency for the development of non crystallinity. 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.
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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).

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The presence of polar and hydrogen bonding groups favors crystallinity because they make
possible dipoledipole 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 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.

POINT TO BE REMEMBER
 Rate of cooling during solidification: time is necessary for chains to move and align into
a crystal structure.
 Polymer complexity: crystallization less likely in complex structures, simple polymers,
such as polyethylene, crystallize relatively easily.
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 Chain configuration: linear polymers crystallize relatively easily, branches inhibit

crystallization, network polymers almost completely amorphous, crosslinked polymers
can be both crystalline and amorphous.
 Isomerism: isotactic, syndiotactic polymers crystallize relatively easily - geometrical
regularity allows chains to fit together, atactic difficult to crystallize
 Co-polymerism: easier to crystallize if Polymer arrangements are more regular -
alternating, block can crystallize more easily as compared to random and graft
 More crystallinity: higher density, more strength, higher resistance to dissolution and
softening by heating.

ORIENTATION

Fiber polymers should be capable of being oriented. The polymers are aligned into more or less
parallel order in the direction of the longitudinal axis of the fiber or filament. The orientation of
polymers in the polymer system of any fiber consists of two forms. The two forms of polymer
orientation are:
 amorphous regions (random)
 crystalline regions (highly ordered, highly oriented)
1. Amorphous polymer orientation
a. Amorphous orientation of the polymer system of any fiber is called the amorphous region
b. Polymers are oriented or aligned at random fashion in amorphous region, i.e. shows no
particular order of arrangement.
c. The random orientation, of the polymers are further apart which results in:
 Formation of less effective inter-polymer forces of attraction.
 Permits easier entry of water and dye molecules as well as molecules, ions and/or radicals
of degrading agents.
 Allows the polymers to be more readily displaced when the fiber is subjected to stresses
and strains during wearing.

2. Crystalline polymer orientation

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a. Crystalline orientation of polymers within the polymer system of any fiber is called
the crystalline region
b. In crystalline regions the polymers are oriented or aligned longitudinally into more or less
parallel order.
 c. The more or less parallel orientation of the polymers are often closer together which results in:
 Formation of more effective inter-polymer forces of attraction.
 Restricts the entry of water and dye molecules as well as molecules, ions and/or radicals of

degrading agents.
 Does not allow the polymers to be displaced when the fiber is subject to stresses and
strains during wearing

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