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5. Structure-Property Relations

Control of Tm and Tg
CHAIN STIFFNESS

For the general structure [ (CH)2 − X ]n where m and n vary:

• The following will increase chain flexibility:

- ( O ), ( COO ), ( OCOO )

- increasing the ( CH 2 ) section

• The following groups will increase Tm (because of intermolecular bonding):
- ( SO2 ) , ( CONH ) — because of intermolecular bonding
- aromatic ring — restricts the rotation on the backbone and reduces the number of
conformations a polymer can adopt.

INFLUENCE OF VARIOUS LINKS ON Tm WHEN INCORPORATED IN AN ALL-CARBON CHAIN

SOURCE: POLYMERS: CHEMISTRY AND PHYSICS OF MODERN MATERIALS, 3RD EDITION, BY J.M.G.
COW AND VALERIA ARRIGHI, CRC PRESS, 2008
Tm (K)

Polymer Repeat Unit m 2 3 4 5 6

Group

Polyethylene [ (CH 2 ) m ] 400 — — — —

Polyester [ (CH 2 ) m COO ] 395 335 329 335 325

Polycarbonate [ (CH 2 ) m OCOO ] 312 320 330 318 320

Polyether [ (CH 2 ) m CH 2 − O ] 308 333 — — —

Polyamide [ (CH 2 ) m CO NH ] 598 538 532 496 506

Polysulfone [ (CH 2 ) m CH 2SO 2 ] 573 544 544 493 —

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EFFECT OF AROMATIC RINGS ON CHAIN STIFFNESS, AS SHOWN BY THE VALUES OF Tm AND Tg

INTERMOLECULAR BONDING

In polyamides and polyurethanes, the additional cohesive energy of the hydrogen bond
(about 24 kJ/mol-1) strengthens the crystalline regions and increases Tm. The effect is
strongest when regular, evenly spaced groups exist in the chain, as with nylon-6,6.

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CHANGE IN THE PROPERTIES AND MELTING TEMPERATURE OF NYLON-6,6 AS THE HYDROGEN-

BONDING CAPACITY IS REDUCED BY CHANGING THE PERCENTAGE P OF AMIDE SUBSTITUTION

In the graph above, the hydrogen bonding is impaired by the replacement of the hydrogen
in the amide group by the methyl group. With little substitution, the polymer is suitable as
fibers, but as the hydrogen is replaced, they change and become more elastomeric, then
like balsams and finally, liquid.

An alternative method is to increase the ( CH 2 ) section. The effect is seen in the table
below.

MELTING TEMPERATURES OF LINEAR ALIPHATIC POLYAMIDES

Monadic Nylon Tm (K) Dyadic Nylon Tm (K)

4 533 4,6 581

6 496 5,6 496

7 506 6,6 538

8 473 4,10 509

9 482 5,10 459

10 461 6,10 495

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11 463 6,12 482

12 452

RANDOM COPOLYMERS

One method of altering the crystalline content is to incorporate some structural irregularity in
the chain.

A controlled inclusion of linear symmetrical homopolymers chain ( A ) n in a crystal lattice

This can be achieved by copolymerizing A with varying quantities of monomer B, whose
purpose is to destroy the regularity of the structure.

SCHEMATIC REPRESENTATION OF TM AND TG PLOTTED AS FUNCTIONS OF COPOLYMER

COMPOSITION, SHOWN AS MOLE FRACTION X(B) OF B. THE BROKEN LINES REPRESENT THE
POSSIBILITY THAT STRUCTURAL IRREGULARITIES ARE SO GREAT THAT NO CRYSTALLIZATION OF
THE POLYMER CAN OCCUR.

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An example is in polyamides:
- An improvement in elastic qualities of polyamide fiber is obtained if the modulus is
reduced, as the factors that affect the melting temperature also affect the modulus.
- This can be achieved by starting from nylon-6,6, or nylon-6,10 and forming (66/610)
copolymers.

- This random inclusion of the two types of unit in the chain disturbs both symmetry and the
regular spacing of the hydrogen-bonding sites, resulting in a drop in Tm.

*Tg is not affected in the same way as Tm because Tg is more a function of the difference
in chain flexibility than the packing efficiency. This means that the response of Tg to a
change in copolymer composition is quite different, and this affords a means of controlling
the magnitudes of Tm and Tg independently. This is not available for any other method.

BLOCK COPOLYMERS

*Random copolymers — if a narrower gap between Tm and Tg is required

*Block copolymers — if a wider interval between Tm and Tg is required

• This is done by synthesizing sequences that are long enough to crystallize

independently, the combination of a high-melting block A with a low-melting block B will
provide a material with a high Tm from A and low Tg from B.

• A slight depression in Tm arising from the presence of block B, is sometimes

encountered, but this is rarely large.

• The change in Tg is rather variable and certain pairs of monomers will form block
copolymers possessing two glass transitions.

Example: SBR
- Behaves as though cross-linked at ambient temperatures.
- This is due to the presence of two glass transitions: butadiene block at 210 K and
styrene block at 373 K.
- At 373 K, plastic flow is observed but between 210 K and 373 K, the glassy
polystyrene block acts as cross-links for the elastomeric polybutadiene, and the
copolymer exhibits high resilience and low creep characteristics.

• The arrangement of the blocks are important — high tensile strength materials, with
elastomeric properties similar to a filler-reinforced vulcanizate, are obtained only when
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the copolymers contains two or more more polystyrene (S) blocks per molecule. Thus,
copolymers with structure {S.B.} or {B.S.B} are as brittle as polystyrene, but {S.B.S}
and {S.B.S.B} copolymers are much tougher. At ambient temperature, they behave like
conventional cross-linked rubbers, but they have the additional advantage that their
thermal behavior is reproducible.

• The property enhancement of these block copolymers is usually explained in terms of

domain concept. The glassy polystyrene blocks tend to congregate in domains that act
as cross-linking points and filler particles. The glassy regions serve to anchor the
central elastomeric polydiene blocks securely at both ends and act as effective cross-
linked rubbers, thereby precluding the necessity of vulcanizing the material.

PLOT OF MELTING TEMPERATURE Tm AGAINST GLASS TRANSITION TEMPERATURE Tg FOR LINEAR

HOMOPOLYMERS WITH (Tg/Tm) LYING IN THE RANGE 0.5 TO 0.8.

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MODULUS-TEMPERATURE BEHAVIOR OF POLYESTER-POLYSTYRENE BLOCK COPOLYMERS: (1)

POLYESTER; (2) POLYESTER CONTAINING 20% PS; (3) CONTAINING 45% PS; (4) CONTAINING 60%
PS; (5) PURE POLYSTYRENE

PLASTICIZERS

Plasticizers are high-boiling point, low-molar-mass compounds that are incorporated into
polymers which lowers the Tg and makes the polymer more pliable.

- Plasticizers must be compatible with the polymer.

- The plasticizers action is that of a lubricant, where the small molecules ease the
movement of the polymer chains by pushing them apart.
- Since they lower the Tg and the modulus, their main use is to increase the flexibility of a
polymer for use in tubing and in films.
- The low volatility of the plasticizer ensures that it is not lost by evaporation.
- In the oil industry, plasticizers are called oil extenders.
Examples of Use:

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- In Poly(vinyl chloride), the Tg is 354 K, and contains 30 to 40 mass percent of plasticizers,
such as dioctyl or dinonyl phthalate, to increase its toughness and flexibility at ambient
temperatures. This depresses the Tg to 270 K and makes the polymer suitable for plastic
raincoats, curtains and “leather-cloth.”
- In fiber technology, water tends to act as plasticizer, thus, as the moisture content
increases, the modulus drops, but there is corresponding improvement in the impact
strength. In fibers such as nylon-6,6, water acts as a plasticizers to depress the Tg below
room temperature. Thus when nylon shirts are washed and hung up to drip-dry, the
polymer is above the Tg, and this helps creases to straighten out thereby giving the
clothing an “ironed’ appearance.

CRYSTALLINITY AND MECHANICAL RESPONSE

The mechanical response of a polymer is profoundly influenced by the degree of

crystallinity in the sample.

INFLUENCE OF CRYSTALLINITY AND CHAIN LENGTH ON THE PHYSICAL PROPERTIES OF

POLYETHYLENE.

The major effect of the crystallite in a sample is to act as a cross-link in the polymer matrix.
This makes the polymer behave as though it was cross-linked network, but, as the
crystallite anchoring points thermally labile, they disintegrate as the temperature
approaches the melting point, and the material undergoes a progressive change in structure
until, beyond Tm, it is molten. Thus, crystallinity is described as a form of “thermoreversible
cross-linking.”

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Effects of the restraining influence of crystallites:

- Raises the relaxation time 𝝉, and changes the distribution of relaxation and retardation
times in the sample. Consequently, there is an effective loss of short 𝝉, causing both the
modulus and yield point to increase.
- The creep behavior is also curtailed and stress relaxation takes place over much longer
periods.
- Semicrystalline polymers are also observed to maintain relatively higher modulus over a
wider temperature range than an amorphous sample.

ILLUSTRATION OF THE VARIATION IN THE MODULUS-TEMPERATURE CURVES FOR THREE TYPES

OF POLYSTYRENE.

From the illustration above of the elastic relaxation modulus for crystalline (isotactic),
amorphous and chemically cross-linked (atactic) polystyrene:
- For amorphous polymer, crystallinity has little effect below Tg, but as the molecular motion
increases above Tg, the modulus drops more sharply

- For crystalline polymer, the elastic relaxation modulus remains high until a rapid decrease
at the melting point.

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- The cross-linked polymer follows that of the amorphous polymer but maintains its
modulus level as the cross-links are not thermally labile and do not melt.

Rapid quenching of the isotactic polymer destroys crystallinity and reduces behavior
identical to the atactic material.

The spherulite size also affects the response, slow cooling from the melt promotes the
formation of large spherulites and produces a polymer with a lower impact strength than
one cooled rapidly from the melt

Summary:

1. Crystallinity only affects the mechanical response in the temperature range Tg to Tm, and
below Tg the effect on the modulus is small.

2. The modulus of a semi-crystalline polymer is directly proportional to the degree of

crystallinity and remains independent of temperature if the amount of crystalline order
remains unchanged.

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