INSTITUTE OF SPACE TECHNOLOGY

MSE 241 Polymers

BS-5 (MS&E)
OHT-3
Spring 2014 06 June, 14
Time Allowed: 1 Hr Max Marks: 50
Name:

Attempt all questions.

Q. 1 Make a schematic plot of the logarithm of relaxation modulus versus temperature for an
amorphous polymer. On the other plot, indicate the change in behavior with increasing
crosslinking. [5+5=10]

We are now asked to make a plot of log Er(10) versus temperature demonstrating how the
behavior changes with increased crosslinking. Such a plot is given below. Increasing the
degree of crosslinking will increase the modulus in both glassy and rubbery regions.

Q. 2 For each of the following pairs of polymers, plot and label schematic specific volume
versus temperature curves on the same graph [i.e., make separate plots for parts (a), (b),
and (c)]. [5x3=15]
a. Polypropylene, of 25% crystallinity, and having a weight-average molecular
weight of 75,000 g/mol; Polystyrene, of 25% crystallinity, and having a weight-
average molecular weight of 100,000 g/mol.
b. Graft poly(styrene-butadiene) copolymer with 10% of available sites crosslinked;
random poly(styrene-butadiene) copolymer with 15% of available sites crosslinked
c. Polyethylene having a density of 0.985 g/cm3 and a degree of polymerization of
2500; polyethylene having a density of 0.915 g/cm3 and a degree of polymerization
of 2000
(a) Shown below are the specific volume-versus-temperature curves for the polypropylene and
polystyrene materials. Since both polymers are 25% crystalline. However, polystyrene will
have higher melting and glass transition temperatures due to the bulkier side group in its repeat
unit structure, and since it has a higher weight-average molecular weight.

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(b) Shown below are the specific volume-versus-temperature curves for the graft and random
poly(styrene-butadiene) copolymers. Since these materials are graft and random copolymers,
both will be highly noncrystalline. However, since the random has the greater degree of
crosslinking, it will also have the higher glass transition temperature.

(c) Shown below are the specific volume-versus-temperature curves for the two polyethylene
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materials. The polyethylene having a density of 0.985 g/cm will be highly crystalline. On the
other hand, the other material, of lower density will have some branching and also be
semicrystalline. In addition, the melting temperature of the higher density material will be
greater since it has less branching and a higher degree of polymerization.

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Q. 3 In polymerization of equimolar mixture of a diacid and diamine to form a nylon

(molecular weight of repeat unit = 103 g/mol), 99.5 % of acid groups are known to have
reacted. [10]
a. Calculate the number average and weight average molecular weights of the reaction
mixture at this conversion? (5)
b. Calculate the number fraction and weight fraction of species containing 20 monomer
units? (5)

Solution
a. Xn = 1/1 – p
Mn = Xn Mo
Mn = Mo (1/1 – p) = 103/1 - 0.995 = 20,600 g/mol
Mw = X w M o
Xw = 1 + p/1 – p
Mw = Mo (1 + p/1 – p) = 103 (1 + 0.995/1 - 0.995) = 41,100 g/mol
b. nx = px-1 (1 - p)
x = 20
n20 = 0.995p20-1 (1 – 0.995)
n20 = 0.0045
wx = x px-1 (1 - p)2
w20 = 20 (0.995)20-1 (1 – 0.995)2
wx = 0.0005

Q. 4 a. Explain why dilute solutions are used for polymer molecular weight determination
using viscometry technique? (2)
b. What is the reason to avoid too dilute solutions in viscometry? (2)
c. What is the initial concentration for solution viscometry of most polymers? (1)

a. The contributions of the individual macromolecules to the viscosity increase will be

independent and additive only when the polymer molecules are infinitely far from each other.
In other words, the effects of polymer concentration can only be eliminated experimentally
when the solution is very dilute.
b. Of course, if the system is too dilute,  — o will be indistinguishable from zero. Therefore,
solution viscosities are measured at low but manageable concentrations
c. Initial concentration for solution viscometry of most synthetic polymers is about 1g/dL =
1g/100 cm3

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Q. 5 Complete the following with appropriate answers: [10]
i. Above Tm, polymer is in________________ state
ii. Below Tm, polymer forms ________________ state
iii. Above Tg, polymers are in________________ state
iv. Below Tg, polymers are in________________ state
v. DSC plot of completely amorphous polymer shows ____________________________ only
vi. DSC plot of completely crystalline polymer shows _____________________________ only
vii. DSC curve of semi-crystalline shows _____________________________________________
viii. Polymers have a higher heat capacity ______________ the glass transition temperature
than they do ____________________ it.
ix. Tg is called a ___________________________________ order transition
x. Measuring the area of the dip for Tc will tell us the value of
____________________________________________________ for the polymer

i. Above Tm, polymer is in liquid state

ii. Below Tm, polymer forms flexible crystalline solid state
iii. Above Tg, polymers are in rubbery state
iv. Below Tg, polymers are in glassy state
v. DSC plot of completely amorphous polymer shows glass transition temperature (Tg) only
vi. DSC plot of completely crystalline polymer shows crystalline melting point (Tm) only
vii. DSC curve of semi-crystalline shows both Tg & Tm
viii. Polymers have a higher heat capacity above the glass transition temperature than they do
below it.
ix. Tg is called a second order transition
x. Measuring the area of the dip for Tc will tell us the latent energy of crystallization for the
polymer

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