Answers to Re-Exam Processing and Properties of Polymers

(202000132)

March 1, 2022
13:45-16:45

Question 1: Multiple choice questions

a) D

b) D

c) B

d) A

e) D

f) C

g) A

h) D

Question 2: Production of PET bottles

a) Both monomers are quite similar. The PBT monomer has a longer CH2 section, making the section
to right of the bulky aromatic ring more flexible. This is an intramolecular interaction and causes that
PET has a higher Tg.

b)

c)
1. Above Tg there is sufficient mobility possible for the molecules to start crystallization

2. Because of the stretch of the molecules, the entropy of the molecules is lowered, enabling strain-
induced crystallization

d) see sketch above

Question 3: Testing of Polystyrene

a)

Constant structure. Reciprocity. Linearity

b)

From the asymptotic force at t = 50, E1 can be calculated.

E1 = F(50)/(ε∙A) = 2 GPa
With E1 known, E2 can be calculated from the force at t = 0.

E2 = F(0)/(ε∙A) – E1 = 8 GPa

With E1 and E2 known, pick an easy to read out point (t*,F*) in the mid of the graph and rewrite the
equation:

t0 = -t*/ ln ( ( (F*/ ε∙A) – E1) / E2) = 10.2 sec (may slightly vary depending on (t*,F*).

c) From the graph (or from the equation) it can be obtained that at 20 °C it takes about 15 seconds to
relax to 100 N, while at 40 °C it takes only 10 seconds. This gives aT = 10/15 = 0.6667

Rewrite Arrhenius equation and filling in numbers gives ΔU = 15,5 kJ/mol.

d)

Read out the strain rate from the graph : 0.1/50 = 2e-3 s-1.

The strain continuously increases, the Boltzmann integral has to be used with parameters for TYPE B.
𝑡𝑡 𝑡𝑡
d𝜖𝜖
𝜎𝜎(𝑡𝑡) = � 𝐸𝐸(𝑡𝑡 − 𝑡𝑡 ∙ ′ ∙ d𝑡𝑡 ′ = 𝜖𝜖̇ ∙ � 𝐸𝐸(𝑡𝑡 − 𝑡𝑡 ′ ) ∙ d𝑡𝑡 ′
′)
d𝑡𝑡
𝑡𝑡 ′ =0 𝑡𝑡 ′ =0

𝑡𝑡
𝑡𝑡 − 𝑡𝑡 ′
𝜎𝜎(𝑡𝑡) = 𝜖𝜖̇ ∙ � �𝐸𝐸1 + 𝐸𝐸2 ∙ exp �− � � ∙ d𝑡𝑡 ′
𝑡𝑡0
𝑡𝑡 ′ =0
𝑡𝑡
𝑡𝑡 𝑡𝑡′
= 𝜖𝜖̇ ∙ �𝐸𝐸1 ∙ 𝑡𝑡′ + 𝐸𝐸2 ∙ 𝑡𝑡0 ∙ exp �− � exp � � �
𝑡𝑡0 𝑡𝑡0 0
𝑡𝑡
𝜎𝜎(𝑡𝑡) = 𝜖𝜖̇ ∙ 𝐸𝐸1 ∙ 𝑡𝑡 + 𝜖𝜖̇ ∙ 𝐸𝐸2 ∙ 𝑡𝑡0 ∙ �1 − exp �− �� (3p)
𝑡𝑡0

Filling in the values gives 583.6 MPa (which is very high for polymers)
Question 4: Mechanical properties of polycarbonate

a)

b) As a result of often rapid processing, a polymer glass is not in thermal equilibrium but it will strive
towards it. As a result and with time, the density of the material increases (better packing).

c)

With physical ageing, the yield stress and the amount of strain softening increase. As a result, the
material will exhibit increasingly unstable deformation behaviour. The stress in the neck, required for
stable propagation will increase, at some point, this stress will exceed the tensile strength of the
material. Upon further increase of the yield stress, the failure mode will become gradually more
brittle, the material breaks before stabilizing.

d) Use Eyring to obtain 𝜀𝜀̇𝑝𝑝𝑝𝑝 = 4.98e-4 s-1

tf = 𝜀𝜀𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 /𝜀𝜀̇𝑝𝑝𝑝𝑝 = 30.1 sec.

Question 5: Oil Barrels

a) A low viscosity is required for the low shear stresses occurring during rotational moulding. The
zero shear viscosity should be low, so Mw low. Since Mn will also be low in that case, a narrow
distribution is desired to reach a strength which is as high as possible. Grade B is the best option.

b) Vacuum forming occurs in the rubbery state, therefore a long rubber plateau is required; thus the
Mz should be as high as possible. Grade A is the best option.

c) The product formed with vacuum forming. During vacuum forming orientation of the molecules
with occur in the rubbery state which gets frozen in after quenching. Upon reheating this orientation
will return to its random conformation which goes accompanied with shrinkage of the product.