Exam Processing and Properties of Polymers

(202000132)

January 24, 2023

8:45-11:45

Description:

• Include your name and student number on all pieces of paper you hand in.
• This is a closed book exam; you may only use a graphical calculator.
• Switch-off your smart phone, tablet and/or smartwatch and store them in your bag.

• Regarding multiple-choice questions: only one answer is correct, you only need to supply the
final answer on the regular exam paper.
• Regarding open questions that involve calculations or explanations: you also get points for
the route towards the answer, do not write down just the final answer.
• Regarding the open questions: make sure that it is clear to which (sub)question your answer
belongs, for example 3a) and 4a)

• Write as clearly as possible.

• The end of the exam is noted. You can take the exam questions home with you.
• Take your time to first go through all questions and information provided.
• Attention: The exam is printed on both sides!

Good luck,

Martin van Drongelen and Leon Govaert

Indication of scoring table.

1a 3 2a 4 3a 4 4a 4 5a 4
1b 3 2b 4 3b 6 4b 6 5b 4
1c 3 2c 4 3c 4 4c 4 5c 4
1d 3 3d 2 4d 6 5d 4
1e 3
1f 3
1g 3
1h 3
Question 1: Multiple choice questions

a) For a standard commercial type of polyethylene, put the following characteristic numbers in
decreasing order. Hint: pay attention to the units.

1. Number averaged molecular weight [g/mol]

2. Bond length between two carbon atoms [nm]
3. Elastic modulus at room temperature [GPa]
4. Glass transition temperature [K]

The correct order is:

A. 4-1-3-2

B. 1-3-2-4

C. 3-1-4-2

D. 1-4-3-2

b) Which statement about the difference between thermoplastics and elastomers is true?

A. Elastomers are strongly crosslinked, where thermoplastics are not crosslinked.

B. The glass transition temperature of elastomers is far below that of most thermoplastics.

C. Thermoplastic elastomers (TPE’s) cannot be processed similar to thermoplastics.

D. Elastomers usually contain fillers, where thermoplastics do not contain fillers.

c) A creep test is performed on a polystyrene (PS) tensile bar. The observed time-to-failure under a
load of 35 MPa and at a temperature of 20 °C is 150 seconds. Assume the following parameters are
valid:

ΔU = 4.0*10-19 J/segment, v*=3.0 nm3, 𝜀𝜀0̇ =1026 s-1

The critical strain of the material is:

A. less than 1%

B. in between 1% and 2%

C. in between 2% and 3%

D. more than 3%.

d) Which of the following methods cannot be used to increase the transparency (or see-through) of a
semi-crystalline polymer bottle?

A. Pre-strain the polymer melt before cooling.

B. Add additives to the polymer melt.

C. Decrease the cooling rate of the polymer melt.

D. Increase the molecular weight of the polymer.

e) What is not an important function of the matrix in continuous fibre reinforced polymers?

A. Provide stiffness in all directions

B. Allow for recyclability of the material

C. Protect the continuous fibres

D. Form the shell of the structure

f) The figure below shows, schematically, two ‘short-shot’ lines for the injection moulding process of
a certain polymer. Herein T is the temperature and p is the injection pressure.

A number of statements is given about this figure. Which of the statements is true?

A. For an equal mould, line B represents a grade with a higher melt-flow index compared to the
grade of line A.

B. The grade of line A has a higher viscosity while processing compared to the grade of line B.

C. For an equal melt-flow index, line A represents a grade with a narrower molecular weight
distribution compared to the grade of line B.

D. For an equal polymer grade, line B represents a mould with higher flow resistance compared to
the mould of line A.
g) How can we best prevent the occurrence of melt-fracture during extrusion of polymers?

A. Decrease the temperature of the melt.

B. Increase the Z-averaged molecular weight of the polymer grade.

C. Increase the channel width within the extruder.

D. Increase the number-averaged molecular weight of the polymer grade.

h) What has the most significant contribution to the level of intermolecular interaction for linear
thermoplastic polymers?

A. The degree of polymerization

B. The chemical composition of the side groups

C. The time scale of the experiment

D. The amount of double bonds in the backbone

Question 2: Processing of Polypropylene

In this question we study the production of semi-crystalline polypropylene (PP) pipes created by the
extrusion process. For this material the glass transition temperature, Tg, and melt temperature, Tm,
are -5 °C and 165 °C, respectively.

In the table below the number averaged, weight-averaged and Z-averaged molar weight, Mn, Mw and
Mz, respectively, are displayed for three PP grades.

Grade Mn [g/mol] Mw [g/mol] Mz [g/mol]

A 100.000 350.000 600.000

B 50.000 200.000 600.000

C 30.000 120.000 600.000

a) A new grade is prepared to be used in the extrusion process. By mixing certain amounts of A and
C, a new grade, D, is created with equal strength compared to grade B. Calculate the weight-
averaged molecular weight of grade D.

b) PP grades can have various tacticity types. Since the final extruded product should be semi-
crystalline, what type of tacticity do you recommend? Briefly explain.

c) Sketch, in one figure, the viscosity as function of shear rate for both grade B and grade C. Clearly
indicate which curve corresponds to which material. Is there a range of shear rates of specific
interest for the extrusion process?
Question 3: Processing of PET

Polyethylene-terephthalate (PET) is a semi-crystalline material. During a certain processing step a

sample is heated well above its melting point, Tm (267 °C) and subsequently treated with the
following consecutive steps:

I. rapid cooling (quenching) to room temperature (25°C), the material remains amorphous
II. heating to 80 °C and maintaining the temperature, the material starts to crystallize
III. cooling down to 20 °C,
IV. heating to above the melting point.

a) From the above observations, what can you conclude about the value of the glass transition
temperature? Briefly explain.

b) Draw the volume changes occurring during steps I, II, III and IV in one volume-temperature
diagram. Clearly indicate the steps in your diagram and include all relevant phase transition
temperatures.

Two co-polymers of PET, A and B, are compared in terms of elastic modulus. The figure below shows
the most important characteristics of both grades.

c) Which of these two co-polymers will have the strongest intermolecular interaction forces? Why?

d) Which of these two co-polymers will have the highest chain flexibility? How can you conclude
that?
Question 4: Polycarbonate Fibres

A weight is put on a polyamide wire hanging from the ceiling in a room at a temperature of 35°C. The
weight is attached at t = 1 hour, and more weight is added in time. At t = 8 hour, all weight is
removed instantaneously.

In the figures below are given: a mechanical model representing the polyamide wire (left) and the
stress in the cable as a function of time (right).

a) Is this a type of creep or relaxation experiment? Briefly explain.

b) Provide the constitutive equation for the mechanical model provided.

c) Use the mechanical model in the figure above. Draw the evolution of strain as a function of time
for 0≤t≤4. Include the most important strain values using model parameters in your graph when
possible.

The strain of the wire can be calculated as function of time with the Kolrausch equation. Parameters
have been determined at a temperature of 20°C: D0 = 8∙10-9 Pa-1, t0 = 1000 hours and m = 0,25.

Further information: the activation energy of the material is 30 kJ/mol. The glass transition
temperature of the polyamide is 60°C.

d) Calculate the strain of the wire at exactly t = 6 hours.

Question 5: Mechanical Properties of Polystyrene

A series of tensile tests is being performed on polystyrene (PS) tensile bars. Just minutes prior to the
first tensile tests, the tensile specimen were produced via injection moulding.

a) Sketch the stress-strain curve for a tensile test performed on the very same day as the samples
were injection moulded.

b) In the same graph as with question a), sketch the stress-strain curve for a tensile test performed
three months after the samples were injection moulded. Clearly indicate this new curve in the
figure.

c) Suggest and describe a sample treatment to the three-months old sample from b) to obtain once
again an equal response to the sample from a). Briefly elaborate on your answer.

d) Why is it often not possible to measure the intrinsic response of a polymer using a tensile test?
Briefly elaborate.

End of this exam

 Formulas
Molar mass
𝑁𝑁
�𝑛𝑛 = Σ𝑛𝑛𝑖𝑖 ∙ 𝑀𝑀𝑖𝑖
𝑀𝑀 with 𝑛𝑛𝑖𝑖 = Σ𝑁𝑁𝑖𝑖
𝑖𝑖

𝑛𝑛𝑖𝑖 ∙𝑀𝑀𝑖𝑖
�𝑤𝑤 = Σ𝑤𝑤𝑖𝑖 ∙ 𝑀𝑀𝑖𝑖
𝑀𝑀 with 𝑤𝑤𝑖𝑖 = �𝑛𝑛
𝑀𝑀

𝑤𝑤𝑖𝑖 ∙𝑀𝑀𝑖𝑖
�𝑧𝑧 = Σ𝑧𝑧𝑖𝑖 ∙ 𝑀𝑀𝑖𝑖
𝑀𝑀 with 𝑧𝑧𝑖𝑖 = �𝑤𝑤
𝑀𝑀

�𝑤𝑤
𝑀𝑀 1
𝐷𝐷 = �𝑤𝑤 = Σ𝑤𝑤𝑘𝑘 ∙ 𝑀𝑀𝑤𝑤,𝑘𝑘 ; 𝑀𝑀
, for polydisperse mixtures : 𝑀𝑀 �𝑛𝑛 = 𝑤𝑤
�𝑛𝑛
𝑀𝑀 Σ(��� 𝑘𝑘 )
𝑀𝑀𝑛𝑛,𝑘𝑘

End-to-end-distance Springs and Dashpots

𝜂𝜂
〈𝑟𝑟02 〉 = 𝑛𝑛 ∙ 𝐶𝐶∞ ∙ 𝑏𝑏02 𝑡𝑡𝑟𝑟 =
𝐸𝐸

Linear mechanics Visco-elastic

𝐹𝐹
𝜎𝜎 = = 𝐸𝐸 ∙ 𝜀𝜀 𝜎𝜎(𝑡𝑡) = 𝐸𝐸(𝑡𝑡) ∙ 𝜀𝜀
𝐴𝐴

𝜎𝜎 = 𝜂𝜂𝜀𝜀̇ 𝜀𝜀(𝑡𝑡) = 𝐷𝐷(𝑡𝑡) ∙ 𝜎𝜎

Dynamic

𝜎𝜎(𝑡𝑡) = 𝜎𝜎0 sin(𝜔𝜔𝜔𝜔 + 𝛿𝛿) = 𝜎𝜎0 sin(𝜔𝜔𝜔𝜔) cos(𝛿𝛿) + 𝜎𝜎0 cos(𝜔𝜔𝜔𝜔)sin (𝛿𝛿)

𝐸𝐸 ′′
tan 𝛿𝛿 =
𝐸𝐸 ′

Superposition Emperical compliance

𝑡𝑡 d𝜖𝜖 𝑡𝑡 𝑚𝑚
𝜎𝜎(𝑡𝑡) = ∫𝑡𝑡 ′ =−∞ 𝐸𝐸(𝑡𝑡 − 𝑡𝑡 ′ ) ∙ ∙ d𝑡𝑡 ′ 𝐷𝐷(𝑡𝑡) = 𝐷𝐷0 ∙ exp �� � �
d𝑡𝑡 ′ 𝑡𝑡 0

𝑡𝑡 d𝜎𝜎
𝜖𝜖(𝑡𝑡) = ∫𝑡𝑡 ′ =−∞ 𝐷𝐷(𝑡𝑡 − 𝑡𝑡 ′ ) ∙ ∙ d𝑡𝑡 ′
d𝑡𝑡 ′

Temperature dependence

Δ𝑈𝑈 1 1
𝑎𝑎 𝑇𝑇 = exp � 𝑅𝑅 �𝑇𝑇 − 𝑇𝑇 �� with R=8,31 J/(mol K)
𝑟𝑟𝑟𝑟𝑟𝑟

−𝐶𝐶1 �𝑇𝑇−𝑇𝑇𝑔𝑔 � 𝑡𝑡 1
log 𝑎𝑎𝑇𝑇 = 𝑡𝑡𝑒𝑒𝑒𝑒𝑒𝑒 = ∫0 𝑎𝑎 ∙ d𝑡𝑡 ′
𝐶𝐶 2 +�𝑇𝑇−𝑇𝑇𝑔𝑔 � 𝑇𝑇 (𝑇𝑇)

Yield Rubber elasticity

−Δ𝑈𝑈 𝜎𝜎𝜎𝜎 1
𝜖𝜖̇ = 𝜖𝜖̇0 exp � � sinh � � with k=1.38*10-23 J/K 𝜎𝜎𝑒𝑒 = 𝑁𝑁 ∗ 𝑘𝑘𝑘𝑘 �𝜆𝜆 − �
𝑘𝑘𝑘𝑘 𝑘𝑘𝑘𝑘 𝜆𝜆2

𝜎𝜎𝜎𝜎 1 −Δ𝑈𝑈 𝜎𝜎𝜎𝜎

In case ≫ 1, 𝜖𝜖̇ = 𝜖𝜖̇0 exp � � exp � �
𝑘𝑘𝑘𝑘 2 𝑘𝑘𝑘𝑘 𝑘𝑘𝑘𝑘
Tables