Rudin & Choi: The Elements of Polymer Science & Engineering, 3rd Edition

Chapter 4

Solutions Manual

4-1
Nylon 6,6 is a crystallizable polymer. It can be oriented at temperatures between Tg and
Tm to enhance its tensile strength. Release of the orienting stress does not result in loss of
orientation because the fibre structure is anchored by crystallites formed during the
drawing process. Polyisobutene is elastomeric and normally not crystalline. Orientation at
any temperature above the low Tg of this polymer has no permanent effect. The structure
retracts when the drawing load is removed.

4-2
Cross-link or copolymerize with comonomers whose homopolymers have higher Tg’s
than polystyrene. Alpha-methylstyrene, metha-crylonitrile, maleic anhydride or
acrylonitrile could be used as comonomers.

4-3
Densities of crystalline and amorphous polyethylene:

When sample ,

When sample ,

When sample ,

Assumed that the mass and volume of the crystalline and amorphous parts are additive.

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Solutions Manual 4-2

4-4
Tm (°C) Tm (°C)
n
observed calculated
8 -56.8 -52.2
10 -29.7 -29.2
12 -9.7 -11.1
14 2.5 3.5
16 14.7 15.7
24 47.6 48.6
32 67.0 68.0
∞ - 143.5

160.0
140.0
120.0
100.0
80.0

T 60.0
(°C) 40.0
20.0
0.0
0 50 100 150 200 250
-20.0
-40.0
-60.0 n

When ,
( )

( )

( )

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Solutions Manual 4-3

4-5

∫ ∫

However, (vol. change of melting)

( )
where M = 28 g/mol.

ρ before melting = 955 kg/m3 = 0.955 g/cm3

ρ after melting = 855 kg/m3 = 0.855 g/cm3

( )

4-6
(b) has a higher Tm and higher Tg because the phenyl group stiffens the macromolecular
chain.

4-7

( ( ))
( ( ))

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Solutions Manual 4-4

4-8
(a) ( )

( )

( )
( )
WLF: ( )
( )
( ) ( )
( )
( ) ( )
( )
( )( )

( )
T = Tg,

(b) C1 = 17.4, C2 = 51.6, Tg = 200 K, R = 8.314,

(c)
( ) ( )
( ) ( )
( )
( )

( )

4-9

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Solutions Manual 4-5

For small amount of solvent .

Also, .

Let M be the mass of polymer + solvent per mole of mixture and Me be the mass of the
polymer.

Let

4-10
( )

( )( ) .
- ( )( )

( )

Original length of specimen = 10 cm.

Therefore, the specimen will elongate 0.76(10) cm = 7.6 cm.

4-11
This is because work done on stretching the rubber must result in a release of heat under
isothermal condition. This leads to a positive ( ) ; therefore ( ) is negative at small
extensions.

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Solutions Manual 4-6

4-12

( )
( )
( )
( )

[ ( )( ) ( )( )]
(no volume change)

At 27 °C, 1% elongation, i.e. .

( )( )
( )

4-13
There are 150 C atoms between cross-links on the average. This corresponds to 150/4 =
37 monomer units between cross-links (see structure 1-19).
Formula weight of an isoprene monomer = 68 g/mol.
molecular weight between cross-links,

( )( )( )

4-14
(a) Ideal rubber
〈 〉
〈 〉
( )

.
( )

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Solutions Manual 4-7

(b)

(c) Upon stretching, the entropy of the rubber sample decreases.

4-15
Refer to Section 4.8.
Units of force = ml/t2
Units of elongation = l
Units of area under force-elongation curve () units of work.

4-16
From Table 4.2 for polyisobutene,

We have to calculate a temperature (T) change corresponding to a shift factor of 10, i.e.,
( )
( )
( )

4-17
(a) ( )
( )
( )

( )

(b) :
( )

:
( ) ( )

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Solutions Manual 4-8

(c) ( )

( )
( )
Percentage of original stress ( )

(d) It is because the Maxwell model would yield zero stress when while there is a
residual stress in this model.

4-18
( )

( )

( )

Energy dissipated
( )

4-19
(a) ( ) ( )

( )
(b) ( )

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Solutions Manual 4-9

( )

(c) ( ) ( )

( )
(d)

(e)

0 γ0
π/2 0 ( )
π -γ0

3π/2 0 ( )
2π γ0

( )
Note:

(f) At low ω, the material has sufficient time to relax, and (i.e., storage
compliance > loss compliance). On the other hand, at high ω the opposite is true:
.

4-20
( )

Boundary conditions:

( )
( )
∫ ∫
( )
( )| |

( ) ( ( ))
but, ( ) in this case and so:
( )
( ) ( ( ))

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Solutions Manual 4-10

4-21
Cut tensile specimens at right angles to each other from the film. The more highly
oriented samples will have higher moduli and lower elongations to break. These will be
machine direction specimens in films with unbalanced properties. (As a check, the
shrinkage of the samples can be measured, e.g., after immersion in boiling water for a
given time. The more highly oriented direction will exhibit greater shrinkage.)

4-22

( )

For brittle fracture,

√ √
Since is significantly above the yield stress ( ), the pipe will fail by
yielding.

When it fails,

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