Polymer Structure-Properties Relationship

At the end of this lecture, you should be able to:

- Understand Crystallization, Melting, and Glass-Transition

Phenomena in Polymers.
- Understand the Mechanical Behavior of Polymers.
- Understand the Effect of Temperature on Mechanical Behavior of
Polymers
- Understand the polymer Viscoelastic Behavior.
Crystallization, Melting, and Glass-Transition Phenomena in Polymers

Three phenomena that are important with respect to the design and processing of polymeric materials are
crystallization, melting, and the glass transition. Crystallization is the process in which an ordered solid phase
(i.e., crystalline) is produced by cooling a liquid melt having a highly random molecular structure. The melting
transformation is the reverse process that occurs when a polymer is heated. The glass-transition phenomenon
occurs when a liquid melt of amorphous (noncrystallizable) polymers become solids by cooling, keeping the
disordered molecular structure that is characteristic of the liquid state.

Of course, alterations of physical and mechanical properties of polymers are related to crystallization, melting
and the glass transition. Furthermore, for semicrystalline polymers, crystalline regions will experience melting
(and crystallization), whereas noncrystalline areas pass through the glass transition.

MELTING AND GLASS TRANSITION TEMPERATURES

Melting and glass transition temperatures (Tm and Tg) are important parameters relative to in-service
applications of polymers. They are considered , respectively, the upper and lower temperature limits for
numerous applications, especially for semicrystalline polymers. The glass transition temperature may also define
the upper use temperature for glassy amorphous materials. Furthermore, Tm and Tg also influence the fabrication
and processing procedures for polymers and polymer-matrix composites.
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Some polymers are used below their Tg (in glassy state)

like polystyrene and poly(methyl methacrylate).

Some polymers are used above their Tg (in rubbery state),

for example, rubber elastomers like polyisoprene and
polyisobutylene.
 Polymer Crystallinity

Crystalline is a state at which the molecular structure is capable of forming regular order (crystallizing) with
molecules or portions of molecules regularly stacked in crystal-like fashion. The opposite of this state is known
as ‘Amorphous’. Crystalline state may exist in polymeric materials. polymer molecules are often only partially
crystalline (or semicrystalline), having crystalline regions dispersed within the remaining amorphous material (as
shown in the figure). Any chain disorder or misalignment will result in an amorphous region, a condition that is
fairly common, because twisting, kinking, and coiling of the chains prevent the strict ordering of every segment
of every chain.

1. The degree of crystallinity may range from completely

amorphous to almost entirely (up to about 95%) crystalline; in crystalline
contrast, metal specimens are almost always entirely region
crystalline, whereas many ceramics are either totally
crystalline or totally noncrystalline. Semicrystalline polymers
amorphous
are, in a sense, analogous to two-phase metal alloys. region

ASE: REVIEW THE CLASSIFICATION Based on Polymer Microstructure (Amorphous or Crystalline)

2 The molecular chemistry as well as chain configuration also influence the ability of a polymer to crystallize.
Crystallization is not favoured 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.

3. For linear polymers, crystallization is easily accomplished because there are few restrictions to prevent chain
alignment. Any side branches interfere with crystallization, such that branched polymers never are highly
crystalline; in fact, excessive branching may prevent any crystallization whatsoever. 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. With
regard to the stereoisomers, atactic polymers are difficult to crystallize; however, 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. Also, the bulkier or larger the side-bonded groups of atoms, the less
tendency for crystallization.

4. For copolymers, as a general rule, the more irregular and random the repeat unit arrangements, the greater 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.

5. To some extent, the physical properties of polymeric materials are influenced by the degree of crystallinity.
Crystalline polymers are usually stronger and more resistant to dissolution and softening by heat.
 Degree of Crystallinity Calculation

Q3.1: Compute the following:

(a) The density of totally crystalline polyethylene, taking the the unit cell volume equals to 9.33X10 -23 cm3/unit
cell and the equivalent of two ethylene repeat units is contained within each unit cell.
(b) The crystallinity percent of a branched polyethylene that has a density of 0.925 g/cm 3. The density of totally
amorphous material is 0.870 g/cm3.

Solution: The repeating unit of polyethylene is C2H4

(a) The density of totally crystalline polyethylene can be calculated using the following relation:
𝑛𝐴
𝜌= … … … …(1)
𝑉𝑐 𝑁 𝐴
Where n represents the number of repeat unit within the unit cell (for polyethylene n = 2), and A is the repeat
unit molecular weight, which for polyethylene is:

A= 2 (12.01)+4(1.008)= 28.05 g/gmol

Vc is unit cell volume and equals to 9.33X10-23 cm3/unit cell, NA is Avogadro number (6.022 X 1023 repeat
unit/mol).

Now, substituting the above parameters in Eq.1, one can find the density of totally crystalline polyethylene:

(b) Now, we can use the given information and the calculated density value of totally crystalline polyethylene to
find the degree of crystallinity as follows:
Percent of Crystallinity Vs. Molecular Weight
 Glass Transition Temperature
• Glass transition temperature is a temperature at which the
polymer experiences the transition from the glassy state to the
rubbery state.
• Glassy state is hard & brittle state of material which is consist of
short-range vibrational & rotational motion of atoms in polymer
chain, while Rubbery state is soft & flexible state of material
which is a long-range rotational motion of polymer chain
segments.

Glassy State Rubbery State

Hard & Brittle Soft & Flexible
Tg

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• Some polymers are used above their glass transition
temperature, and some are used below.
• Hard plastics like polystyrene and poly methyl
methacrylate are used below their glass transition
temperature; that is in their glassy state. Their Tg’s are
well above room temperature.
• Elastomers like polyisoprene and polyisobutylene are
used above their Tg’s, that is in the rubbery state, where
they are soft & flexible.

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 Heating Through Tg Leads To Following
• Break down of Van Der Waals Forces.
• Onset of large scale molecular motion.
• Polymer goes from glassy/rigid to rubbery behaviour.
• Upper service temperature in amorphous polymers.

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 Free Volume Theory
• One of the most useful approaches to analysing the glass
transition temperature of polymer is to use the concept of Free
Volume.
• The free volume is the space in a solid or liquid sample that is not
occupied by molecules, that is the ‘empty space’ between
molecules.
• Free volume is high in liquid state than solid, so molecular motion
is able to take place relatively easy because the unoccupied
volume allows the molecules to move.
• The theory was originally developed for amorphous polymers and
the glass-transition in those polymers.

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• But semi-crystalline polymers also consist of
amorphous regions, so this theory can
also be applied to semi-crystalline polymers.
• An amorphous polymer can be considered to be made
up of occupied volume and free volume. As the
temperature is changed, the free volume and the
occupied volume both will change.
• As the temperature of the melt is lowered, the free
volume will be reduced until eventually there will not be
enough free volume to allow molecular motion or
transition to take place.
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 Greater local Free
motion volume

Restricted
local motion
V

Tg
T

Brittle and glassy Soft and Flexible

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Schematic illustration of the total, free, and occupied
volume

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• The total sample volume V therefore consists of volume occupied by
molecules V0 and free volume Vf such that
V= Vf +Vo
• At any given temperature, the fraction of the free volume is
Where, the
approximation is based on
Vf << V0.
• Around Tg and above Tg, the fraction of free volume can be expressed as,

• Where fg is the fraction of free volume at Tg and αf is an expansion

coefficient for the fraction free volume. αf is approximately αm – αg, or the
difference between the thermal expansion coefficients of the polymer above
and below Tg.
• αm stands for melt
• αg stands for glass
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 Factors Influencing Glass Transition Temperature

• From the previous discussion we know that at the glass

transition temperature there is a large scale cooperative
movement of chain segments. Therefore it is expected
that any structural features or externally imposed
conditions that influence chain mobility will also affect
the value of Tg.

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• Some of these factors are shown below.

1. Chain Flexibility & Rigidity

2. Steric Effects

3. Effect of Intermolecular Forces

4. Copolymerization

5. Cross linking & Crystallinity

6. Plasticizer
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 1. Chain Flexibility &
• As Tg depends on theRigidity
ability of a chain to undergo internal rotations, we
expect chain flexibility to be associated with low glass transitions.
• For Example, Poly(dimethyl siloxane) is an extremely flexible polymer due
to the large separation between the methyl substituted silicon atoms. As
compared to other polymeric materials, poly(dimethyl siloxane) has the
lowest glass transition temperature (Tg = -123.15°C)

-93.15°C
-67.15°C

89.85°C

n
79.85°C

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• As shown in previous slide, polymers that contain
−CH2−CH2− sequences and ether linkages in the main-
chain have relatively easy internal rotations and
therefore low Tg values.
• While substitution of ethylene groups with p-phenylene
units leads to increased chain rigidity and high glass
transition temperature.

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 2. Steric
Effects
• The presence of bulky side groups hinders rotation of the
backbone atoms due to steric hindrance, and therefore results in
an increase in Tg. The magnitude of this effect depends on the
size of the side groups.
• This is illustrated in the following Table for vinyl polymers
having the general structure,
—[CH2 — CHX ]—
-93.15°C

-20.15°C 99.85°C

134.85°C

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 3. Effect of Intermolecular Forces

• The presence of polar side groups leads to strong intermolecular

attractive interactions between chains which hinders molecular
motion thus causing an increase in Glass transition
temperature.
• This effect is illustrated in the following table for the polymers of
type −[CH2−CHX ]−

-20.15°C 80.85°C

84.85°C

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 4.
Copolymerization
• It is possible to alter the glass transition of a homo polymer by
copolymerisation with a second monomer. If the two homo polymers
prepared from the monomers have different Tgs, then it is reasonable to
expect that their random copolymer should have a glass transition which
is intermediate between the Tgs of the homo polymers. This is observed
experimentally.
• The glass transition of a random copolymer is related to the Tgs of the
homo polymers, Tg1 and Tg2, as follows

1/Tg = w1/Tg1 + w2/Tg2*

• Where w1 is the weight fraction of homo polymer 1 and w2 is the weight
fraction of homo polymer 2.

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 5. Cross-linking & Crystallinity

• Both cross-linking and crystallinity cause an increase of the

glass transition temperature.
• It is very easy to explain why cross-linking increases Tg since
the presence of covalent bonding between chains reduces
molecular freedom and thus the free volume.
• Similarly, the presence of crystalline regions in an semi-
crystalline material restricts the mobility of the disordered
amorphous regions; thus the glass transition temperature
increases which is totally depends on the percentage of
crystallinity.

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 6. Plasticizer
• Sometimes, a polymer has a high Tg than our requirement. To
tackle this proble we just mix something in it called a plasticizer.
• Plasticizers are small molecules which will get in between the
polymer chains, and space them out from each other. Thus
the free volume will increase. When this happens they can slide
past each other more easily. When they slide past each other
more easily, they can move around at lower temperatures than
they would without the plasticizer.
• By this way, the Tg of a polymer can be lowered, to make a
polymer more applicable, and easier to work with.

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 Mechanical Behavior of Polymers
stress–strain behavior

• Polymers fall within three general

classifications (shown in Figure 1): brittle
(curve A), plastic (curve B), and highly
elastic (curve C).

• Polymers are neither as strong nor as

stiff as metals. However, their high
flexibilities, low densities, and resistance
to corrosion make them the materials of
choice for many applications.

• The mechanical properties of polymers

are sensitive to changes in temperature
and strain rate. With either rising
temperature or decreasing strain rate,
modulus of elasticity diminishes, tensile
Figure 2: stress–strain behavior for brittle (curve A),
strength decreases, and ductility
plastic (curve B), and highly elastic (elastomeric)
increases. (curve C) polymers 27
 Effect of Temperature on Mechanical Behavior of Polymers
stress–strain behavior at different temperatures
In addition, the mechanical characteristics
of polymers are much more sensitive to
temperature changes near room
temperature. Consider the stress—strain
behavior for poly(methyl-methacrylate)
(Plexiglas) at several temperatures
between 4 and 60 oC. Increasing the
temperature produces (1) a decrease in
elastic modulus, (2) a reduction in tensile
strength, and (3) an enhancement of
ductility. At 4oC Increasing the temperature
produces (1) a the material is totally brittle,
whereas there is considerable plastic
deformation at both 50 and 60 oC.

Figure 3: The influence of temperature on the stress–strain characteristics of poly(methyl methacrylate).

(From T. S. Carswell and H. K. Nason, “Effect of Environmental Conditions on the Mechanical Properties of
Organic Plastics,” Symposium on Plastics, American Society for Testing and Materials, Philadelphia, 1944.
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Copyright, ASTM, 1916 Race Street, Philadelphia, PA 19103. Reprinted with permission.)
Comparison among Metals, Ceramics, polymer and Composites

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Comparison among Metals, Ceramics, polymer and Composites
Comparison among Metals, Ceramics, polymer and Composites

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Comparison among Metals, Ceramics, polymer and Composites

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Viscoelastic Behavior
An amorphous polymer may behave like a glass at low temperatures, a rubbery solid at intermediate
temperatures [above the glass transition temperature)], and a viscous liquid as the temperature is
further raised. For relatively small deformations, the mechanical behavior at low temperatures may be
elastic; that is, in conformity to Hooke’s law. At the highest temperatures, viscous or liquid- like
behavior prevails. For intermediate temperatures the polymer is a rubbery solid that exhibits the
combined mechanical characteristics of these two extremes; the condition is termed viscoelasticity.

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Predeformation by Drawing

On a commercial basis, one of the most important techniques used to improve mechanical strength and tensile
modulus is to permanently deform the polymer in tension. This procedure is sometimes termed drawing and
corresponds to the neck extension process. In terms of property alterations, drawing is the polymer analogue of
strain hardening in metals. It is an important stiffening and strengthening technique that is employed in the
production of fibers and films. During drawing the molecular chains slip past one another and become highly
oriented; for semicrystalline materials the chains assume conformations similar to that represented schematically
in Figure below.

Figure: Orientation of block segments and tie chains with the tensile
axis in the final plastic deformation stage
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NOTES:
1. Degrees of strengthening and stiffening will depend on the extent of deformation (or extension) of
the material. Furthermore, the properties of drawn polymers are highly anisotropic. For materials
drawn in uniaxial tension, tensile modulus and strength values are significantly greater in the direction
of deformation than in other directions. Tensile modulus in the direction of drawing may be enhanced
by up to approximately a factor of three relative to the undrawn material.

2. For an amorphous polymer that is drawn at an elevated temperature, the oriented molecular
structure is retained only when the material is quickly cooled to the ambient; this procedure gives rise
to the strengthening and stiffening effects described in the previous paragraph. On the other hand, if,
after stretching, the polymer is held at the temperature of drawing, molecular chains relax and assume
random conformations characteristic of the predeformed state; as a consequence, drawing will have
no effect on the mechanical characteristics of the material.

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