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4. Properties of Polymeric Materials

Physical Properties

- Molecular Weight

- Molar Volume

- Density

- Degree of Polymerization

- Crystallinity of Material

- Others

Thermal Properties

- Melting Point and Glass Transition Property

Mechanical Properties

- Strength

- Percent Elongation to Break

- Young’s Modulus (Modulus of Elasticity or Tensile Modulus)

- Toughness

- Viscoelasticity

4.1. Degree of Polymerization and Molecular Weight

- Degree of Polymerization — the number of repeating units in the polymer chain

- Molecular Weight of a Polymer Molecule — product of the degree of polymerization

and the molecular weight of the repeating unit

- Polymer molecules are not identical but are a mixture of many species with different
degrees of polymerization, i.e., with different molecular weights

- Polydispersity Index or Heterogeneity Index — the ratio of the weight-average

molecular weights to the number-average molecular weights

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4.2. Polymer Crystallinity: Crystalline and Amorphous Polymers

- Polymer chains, being large, are found in two forms as follows:

- Lamellar crystalline form in which the chains fold and make lamellar structure
arranged in a regular manner

- Amorphous form in which the chains are in irregular manner

4.2.1. Amorphous State

- Amorphous polymers exist as long, randomly coiled, interpenetrating chains that are
capable of forming stable, flow-restricting entanglements at sufficiently high
molecular weights.

- A good analogy is a bowl of noodles or spaghetti. If the strands of the spaghetti/

noodles are long, it is very difficult to separate one from the others. However, when
the strands are short, they can be removed easily.

- Entanglements have significant importance in relation to viscoelastic properties, melt

viscosity, and mechanical properties.

- Critical Molecular Weight — the minimum polymer chain length, Mc, for the
formation of stable entanglements; depends upon the flexibility of a polymer chain.
Molecular Weight Between Entanglements — Me. As a rule of thumb, Mc ~ 2Me.

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TABLE 4.2.1. ENTANGLEMENT MOLECULAR WEIGHTS FOR LINEAR POLYMERS

Polymer Mc Me
Polycarbonate 4,800 2,490
cis-Polyisoprene 10,000 5,800
Polyisobutylene 15,200 8,900
Polydimethylsiloxane 24,400 8,100
Poly(vinyl acetate) 24,500 12,000
Poly(methyl methacrylate) 27,500 5,900
Poly(a-methystyrene) 28,000 13,500
Polystyrene 31,200 18,100

- Reptation — a theory developed by Pierre-Gilles de Gennes for fixed networks such

as a polymer gel and later extended to include melts and concentrated polymer
solutions. In the melt state, individual polymer chains can move by Brownian motion
restricted by the topological constraint of neighboring chains. Movement can be
visualized as snakelike motion (i.e. reptation) of the chain within the virtual tube,
which is defined by the locus of its entanglements with neighboring chains.

REPTATION MODEL

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4.2.2. The Glass Transition

- The temperature that marks the transition from amorphous solid state to the melt
state.

- Isoviscous state — as a polymer is cooled from its melt state, viscosity increases
rapidly to a common (maximum) value, ca. 10^12 Pa-s (10^13 poise) at Tg for all
glassy materials, both low-molecular-weight and polymeric.

- Isofree Volume, Vf — difference between the actual volume, V, of the polymer at a

given temperature and its corresponding equilibrium volume at absolute zero, Vo.

Vf = V - Vo

- Isentropic State — there is a temperature at which the conformational entropy, Sc (a

measure of the total number of ways of arranging a polymer molecule or collection
of chains), goes to zero.

- Factors Affecting the Glass Transition Temperature — The glass transition

temperature depends on the mobility and flexibility (ease of the chain segment to
rotate along the chain backbone) of the polymeric chains. If the polymeric chains can
move easily, then the glassy state can be converted to the rubbery state at lower
temperature, that is, the glass transition temperature is lower. If somehow the
mobility of the chains is restricted, then the glassy state is more stable, and it is
difficult to break the restriction causing the immobility of the polymer chains at the
lower temperature, because more energy is required to make the chains free. Thus,
in this case, the glass transition temperature is raised.

1. Intermolecular Forces — Strong intermolecular forces cause higher Tg. For

example, PVC (Tg = 80∘C) has stronger intermolecular forces than
polypropylene (Tg = −18∘C) because of the dipole–dipole forces from the C—Cl
bond.

2. Chain Stiffness — The presence of the stiffening groups (such as amide,

sulfone, carbonyl, p-phenylene etc.) in the polymer chain reduces the flexibility
of the chain, leading to higher glass transition temperature. For example,
poly(ethylene terephthalate) is stiffer than polyethylene adipate due to the
presence of benzene ring (see Fig. 4.2.2.1). Therefore, Tg value is higher for
polyethyleneterephthalate.

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3. Cross-Linking — The cross-links between chains restrict rotational motion and

raise the glass transition temperature. Hence, higher cross-linked molecule will
show higher Tg than that with lower cross-linked molecule.

4. Pendant groups — The presence of pendent group can change the glass
transition temperature.

a. Bulky pendant groups — the presence of bulky pendant groups such as a

benzene ring, can restrict rotational freedom, leading to higher glass
transition temperature. As in polystyrene, the presence of benzene ring
increases the Tg (see Fig. 4.2.2.1.). In polypropylene, there is no benzene
ring that leads to lower Tg value.

FIG. 4.2.2.1. ROLE OF BULKY PENDANT GROUPS IN AFFECTING GLASS TRANSITION

TEMPERATURE.

b. Flexible pendant groups: the presence of flexible pendant groups, for

example, aliphatic chains, limits the packing of the chains and hence
increases. Presence of benzene in polyethyleneterephthalete (top molecular
chain) makes it stiffer (hence higher Tg) than polyethylene adipate (bottom
molecular chain).

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FIG. 4.2.2.2. PRESENCE OF BENZENE IN POLYETHYLENETEREPHTHALATE (TOP MOLECULAR

CHAIN) MAKES IT STIFFER (HENCE HIGHER TG) THAN POLYETHYLENE ADIPATE (BOTTOM
MOLECULAR CHAIN).

FIG. 4.2.2.2. ROLE OF FLEXIBLE PENDANT GROUPS IN AFFECTING GLASS TRANSITION

TEMPERATURE.

5. Plasticizers. Plasticizers are low molecular weight and non-volatile materials

added to polymers to increase their chain flexibility. They reduce the
intermolecular cohesive forces between the polymer chains, which in turn
decrease Tg.

6. Molecular Weight. The glass transition temperature is also affected by the

molecular weight of the polymer. Tg is increased with the molecular weight. The
molecular weight is related to the glass transition temperature by the Fox–Flory
Equation:

Tg = Tg,∞ − K/Mn

where Tg,∞ is the glass transition temperature at the molecular weight of

infinity, and K is the empirical parameter called Fox–Flory parameter related to
the free volume inside the polymer. It is observed that Tg is increased up to the
molecular weight of approximately 20,000, and after this limit, the Tg is not
affected appreciably.

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FIG. 4.2.2.4. VARIATION OF GLASS TRANSITION TEMPERATURE

WITH MOLECULAR WEIGHT OF POLYMER

TABLE. 4.2.2. GLASS TRANSITION TEMPERATURE OF POLYMERS

Polymer Tg (C) Polymer Tg (C)

Polydimethylsiloxane -123 Poly(methylmethacrylate) (atactic) 105

Poly(vinyl acetate) 28 Nylon 6,6 57

Polystyrene 100 LDPE -120

Poly(methyl methacrylate) 105 HDPE -90

Polycarbonate 150 PP (atactic) -18

Polysulfone 190 Poly(vinyl acetate) 28

Poly(2,6-dimethyl-1,4-phenyl oxide) 220 Polyester (PET) 69

PTFE -97 Poly(vinyl alcohol) 85

PP (isotactic) 100 Poly(vinyl chloride) 87

4.2.3. The Crystalline State

- Typical range of crystallinity can be defined as amorphous (0%) to highly crystalline

(>90%).

- Highly crystalline polymers:

• The polymers having simple structural chains as linear chains and slow cooling
rate will result in good crystallinity as expected.

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• In slow cooling, sufficient time is available for crystallization to take place.

• Rigid and have high melting point, but their impact resistance is low.

• Examples of crystalline polymers: polyethylene, and PET polyester.

- Amorphous polymers:

• Soft and have lower melting points.

• Examples of amorphous polymers: polystyrene and poly(methyl methacrylate).

- For a solvent, it is important to state that it can penetrate the amorphous part more
easily than the crystalline part.

- Lamellae — consists of arrays of folded chains. The basic units of crystalline polymer
morphology.

- Spherulite — Contains arrays of lamellar crystallites that are typically oriented with
the chain axis perpendicular to the radial direction.

SEMI-CRYSTALLINE POLYMER

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A TYPICAL STRUCTURE OF SPHERULITE.

- Conformation of polymer molecules:

• High thermal energy favors a large number of conformations in the melt.

• As the melt is cooled, the low-energy conformations are favored and chains are
free to organize into lamellar structure. The lowest energy conformation may be:

1. Extended chain or zigzag — includes polyethylene, syndiotactic vinyl

polymers and polymers capable of hydrogen bonding between chains such
as poly(vinyl alcohol) and nylons.

2. Helical — polymers with large substituent groups, including isotactic PP, and
other isotactic polymers, polymers of 1,1-disubstituted ethylenes like
polyisobutylene.

4.3. Mechanical Properties

- It is of great importance to be familiar with some basic mechanical properties of the
material before its application in any field, such as how much it can be stretched,
how much it can be bent, how hard or soft it is, how it behaves on the application of
repeated load and so on.

4.3.1. Strength

- Strength is the stress required to break the sample.

- Types of strength:

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• Tensile (stretching of the polymer),

• Compressional (compressing the polymer)

• Flexural (bending of the polymer)

• Torsional (twisting of the polymer)

• Impact (hammering) and so on.

- The polymers follow the following order of increasing strength: linear < branched <
cross-linked < network.

Factors Affecting the Strength of Polymers

1. Molecular Weight: The tensile strength of the polymer rises with increase in
molecular weight and reaches the saturation level at some value of the molecular
weight. The tensile strength is related to molecular weight by the following
equation.

𝜎= 𝜎∞−A M

𝜎∞ is the tensile strength of the polymer with molecular weight of infinity. A is some
constant, and M is the molecular weight. At lower molecular weight, the polymer
chains are loosely bonded by weak van der Waals forces and the chains can move
easily, responsible for low strength, although crystallinity is present. In case of large
molecular weight polymer, the chains become large and hence are entangled, giving
strength to the polymer.

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VARIATION OF TENSILE STRENGTH WITH MOLECULAR WEIGHT OF THE

POLYMER.

2. Cross-linking: The cross-linking restricts the motion of the chains and increases
the strength of the polymer.

3. The crystallinity of the polymer increases strength, because in the crystalline phase,
the intermolecular bonding is more significant. Hence, the polymer deformation can
result in the higher strength leading to oriented chains.

4.3.2 Percent Elongation to Break (Ultimate Elongation)

- It is the strain in the material on its breakage.

- It measures the percentage change in the length of the material before fracture. It is a
measure of ductility. Ceramics have very low (<1%), metals have moderate (1–50%)
and thermoplastic (>100%), thermosets (<5%) value of elongation to break.

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FIG. 4.3.2. ELONGATION TO BREAK OF THE POLYMER

4.3.3. Young’s Modulus (Modulus of Elasticity or Tensile Modulus)

- Young’s Modulus is the ratio of stress to the strain in the linearly elastic region.
Elastic modulus is a measure of the stiffness of the material.

Tensile Stress (σ )
E=

Tensile Strain (ε )

FIG. 4.3.3. YOUNG’S MODULUS OF THE POLYMER

4.3.4. Toughness

- The toughness of a material is given by the area under a stress–strain curve.

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Toughness = ∫ 𝜎 d𝜀

- The toughness measures the energy absorbed by the material before it breaks.

FIG. 4.3.4.1. THE TOUGHNESS OF POLYMER MATERIAL

FIG. 4.3.4.2. STRESS–STRAIN BEHAVIOR OF

DIFFERENT TYPES OF MATERIALS

- Stress–strain behavior of different types of materials (refer to Fig. 4.3.4.2):

1. Rigid materials (brittle polymers): possess high Young’s modulus

2. Ductile polymers: possess elastic modulus similar to brittle polymers, but with
higher fracture toughness.

3. Elastomers: Low values of Young’s modulus and are rubbery in nature.

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- Yield strength of the plastic polymer is the corresponding stress where the elastic
region (linear portion of the curve) ends (Fig. 4.3.4.3).

- Tensile strength is the stress corresponding to the fracture of the polymer. The
tensile strength may be higher or lower than the yield strength (Fig. 4.3.4.3).

FIG. 4.3.4.3. YIELD STRENGTH AND

TENSILE STRENGTH OF POLYMER

- The mechanical properties of the polymer are strongly affected by the temperature. A
typical plot of stress versus strain is shown in Fig. 4.3.4.4. From the plot, it is clear
that with increase in the temperature, the elastic modulus and tensile strength are
decreased, but the ductility is enhanced.

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FIG. 4.3.4.4. EFFECT OF TEMPERATURE ON THE

MECHANICAL PROPERTIES OF POLYMER

4.3.5. Viscoelasticity

- There are two types of deformations:

• elastic

• viscous

- Elastic deformation (Fig. 4.3.5.1), the strain is generated at the moment the
constant load (or stress) is applied, and this strain is maintained until the stress is not
released. On removal of the stress, the material recovers its original dimensions
completely, that is the deformation is reversible (Fig. A1.17), that is:

𝜎 = E𝜀

where E is the elastic modulus, 𝜎 is applied stress, and 𝜖 is the strain

developed.

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4.3.5.1. CONSTANT STRESS APPLIED TO A POLYMER.

4.5.3.2. ELASTIC DEFORMATION.

- However, in viscous deformation (Fig. 4.5.3.3), the strain generated is not
instantaneous and it is time dependent. The strain keeps on increasing with time on
application of the constant load, that is, the recovery process is delayed. When the
load is removed, the material does not return to its original dimensions completely,
that is, this deformation is irreversible (Fig. 4.5.3.3).

𝜎 = 𝛾 d𝜀/dt

where 𝛾 = viscosity, and d𝜖/dt = strain rate.

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4.5.3.3. VISCOUS DEFORMATION.

4.5.3.4 VISCOELASTIC DEFORMATION: THE COMBINED BEHAVIOR OF

VISCOSITY AND ELASTICITY
- Usually, polymers show a combined behavior of elastic and plastic deformation (Fig.
4.5.3.4) depending on the temperature and strain rate.

• At low temperature and high strain rate, elastic behavior is observed

• At high temperature but low strain rate, the viscous behavior is observed.

• At intermediate temperature and strain rate values, the combined behavior of

viscosity and elasticity is observed . This behavior is termed as viscoelasticity,
and the polymer is termed as viscoelastic.

4.3.6. Viscoelastic Relaxation Modulus

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- Stress Relaxation — It is when, at a given temperature, when the polymer is

strained to a given value, then the stress required to maintain this strain is found to
decrease with time (Fig. 4.3.6.1).

- The stress required to maintain the constant strain value is decreased with time,
because the molecules of polymer get relaxed with time, and to maintain the level of
strain, somewhat lower value of stress is sufficient.

Erel(t) = 𝜎(t)/ 𝜀0

FIG. 4.3.6.1. STRESS RELAXATION IN POLYMER

FIG. 4.3.6.2. VARIATION OF RELAXATION MODULUS

WITH TEMPERATURE AND TIME

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FIG. 4.3.6.3. VARIATION OF RELAXATION MODULUS

WITH TEMPERATURE AFTER A GIVEN TIME T.

- The decrease in stress follows the exponential decay:

𝝈 = 𝝈oe−t∕𝝉

where

𝜎 =stress at time t,

𝜎o =peak stress level, and

𝜏 =relaxation time constant.

The relaxation modulus is found to decrease with increase in temperature and time as
shown in Fig. 4.3.6.1.

Now, consider the time t1. Measure the values of relaxation modulus at time t1 at
different temperatures, say T1, T2, T3 ... for the viscoelastic polymer and plot the
relaxation modulus versus temperature. A typical plot is shown in Fig. 4.3.6.2. The
glass transition temperature lies near the upper temperature extremity.

4.3.7. Viscoelastic Creep

- Creep can be considered as the opposite of stress relaxation (lowering of the stress
with time maintaining the constant strain level) where the polymer suffers time-
dependent deformation (increasing strain with time) at constant stress level.

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- Viscoelastic Creep — At a given temperature, when a constant load is applied to

the material, there is a time-dependent increase of strain in the material (Fig. 4.3.7).
The increase in molecular weight and stiffness of the chains results in better creep
resistance of the material.

FIG. 4.3.7. VISCOELASTIC CREEP

- We can define the time-dependent creep modulus as follows:

ECreep(t) = 𝜎0/𝛆(t)

Or we can define the creep compliance as follows:

JCreep(t) = 𝛆(t)/𝜎0

where 𝜎o = constant applied stress, 𝜖(t) = strain at time t.

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