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UNIVERSITY OF PRETORIA
DEPARTMENT OF CHEMICAL ENGINEERING
CHEMICAL ENGINEERING MATERIALS CIM 210
SEMESTER TEST 2

TIME: 90 mins 27 May 2022

BEng (Chem) II Total = 80

ANSWER ALL THE QUESTIONS

QUESTION 1:

Use the provided Fe-Fe3C phase diagram to answer the following questions for a 1020 (0.35
wt% Carbon) steel. Assume the steel has been austenitized for 1 hour at 850°C then, slow
cooled to 725°C.

(a) Briefly explain why the solubility of carbon in austenite is higher than in α and δ
ferrite. (5)
Carbon forms an interstitial impurity with iron. Both α and δ ferrite have a BCC unit
cell structure. The spacial arrangement of atoms in this unit cell allows for limited
solubility of carbon. Austenite on the other hand has an FCC structure, this has more
space for the uptake of carbon as an interstitial impurity and hence the higher solubility
(b) Define eutectic and eutectoid systems. What are eutectic and eutectoid reactions in the
Fe-Fe3C phase diagram? (6)
A eutectic system is a mixture of chemical compounds or elements that has a single
chemical composition that solidifies at a lower temperature than any other composition
made up of the same ingredients. This composition is known as the eutectic
composition and the temperature is known as the eutectic temperature. On a phase
diagram the intersection of the eutectic temperature and the eutectic composition gives
the eutectic point.
When the solution above the transformation point is solid, rather than liquid, an
analogous eutectoid transformation can occur.

The eutectic reaction:

L → γ (austenite) + Fe3C (cementite)

The eutectoid reaction:

γ (austenite)→ α (ferrite) + Fe3C (cementite)

(c) (i) What is the proeutectoid phase, and what is its composition in terms of wt.%
carbon? (3)
The proeutectoid phase is α-Ferrite.
Its composition is 0.0022 wt% C since 725°C is close to the eutectoid temperature of
727°C.
(ii) What is the total wt. fraction of ferrite (Wα) and the total weight fraction of
cementite (WFe3C) at 725°C? (4)
Wα = (6.7 – 0.35) / (6.7 – 0.022) = 0.951
WFe3C = 1- Wα = 0.049
(iii) What is the wt. fraction of Pearlite (Wpearlite)? (3)
Wpearlite = (0.35 – 0.022) / (0.76 – 0.022) = 0.444
(iv) What are the wt. fractions of ferrite (Wα-pearlite) and cementite (WFe3C-pearlite) in the
pearlite? (6)
Wα = Wα-pearlite + Wα-proeutectoid
Wα-proeutectoid = (0.76 – 0.35) / (0.76 – 0.022) = 0.556
Wα-pearlite = Wα - Wα-proeutectoid
= 0.951 – 0.556
= 0.395
WFe3C-pearlite = 0.05 same as total (Fe3C)

Sketch the and clearly label the microstructures you would expect to form when a Fe-
C alloy with 1.5 wt.% carbon is slowly cooled at points A, B and C . Are these
microstructures classified as hypoeutectoid or hypereutectoid alloys? (8)
Hypereutectoid alloy
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Question 2
The expression for the total free energy change for homogeneous nucleation assuming s
spherical nucleus is given by the expression:

ΔG = 4/3 πr3 ΔGv + 4π r2γ

(a) Using a well annotated diagram, express the different components of the total free energy
change given above indicating the position of the important parameters that influence the
formation of a stable nucleus (5)

(b) (i) Rewrite the expression for the total free energy change for nucleation in the case of a
body centred cubic nucleus of edge length a. (2)
Volume of a cube = a3
Surface area of a cube = 6a2
Therefore ΔG = a3ΔGv + 6a2γ
 (ii) Using the expression from (b) derive the expressions for the critical cube edge length
a* and ΔG* (6)
∆ ∆

= 3a2ΔGv + 12aγ = 0
a* = -4γ / ΔGv
Substituting the expression for a* into the initial equation
ΔG = (a*)3ΔGv + 6(a*)2γ
= (-4γ/ Gv) 3ΔGv + 6(-4γ/ΔGv) 2γ
= 32 γ3/( ΔGv) 2

(iii) Is ΔG* greater for a cube or a sphere? Why? (3)

 3   16     3 
ΔGv for a cube—i.e., (32)   —is greater that for a sphere—i.e.,    =
 (Gv ) 2   3   (Gv ) 
2

 3 
(16.8)   . The reason for this is that surface-to-volume ratio of a cube is greater than for
 (Gv )2 

a sphere.

(c) Compute the rate of some reaction that obeys Avrami kinetics, assuming that the
constants n and k have values of 3.2 and 7 × 10−3, respectively, for time expressed in seconds
(5)
Avrami equation: y = 1 – exp (-ktn)

(d) Name the phases you expect to get after each of the heat treatments shown in the figure
below. (5)
A. Pearlite
B. Bainite
C. Martesite
D. Spherodite
E. Tempered martensite

QUESTION 3:
(a) (i) Polypropylene is a semi-crystalline polymer which is widely used as packaging
material. Draw the structure of a, polypropylene chain consisting of four repeat units with
syndiotactic stereoisomerism. (4)

(ii) Safripol supplies a grade of polypropylene with a weight average molecular weight
of 78500 g/mol, what is the weight average degree of polymerization? (4)

Degree of polymerization = Average molecular weight/molecular weight of repeat unit

The repeat unit is the structure drawn in (ii) it has a molecular weight of 42 g/mol
Therefore DP = 78500 gmol-1/42 gmol-1 = 1869.04 ≈ 1869

(iii) Is it possible for a polymer to be 100% crystalline? Motivate your answer (4)
 No it is not possible. In order for polymers to form crystalline zones, the polymer chains
need to align themselves in a well packed order. This is however difficult to achieve since
the polymer chains tend to take a “spaghetti” like structure due to the ability of the polymer
chains to rotate around the C-C bond. Small segments of the polymer structure tend to
form the crystalline phase hence the term semi-crystalline.

(a) State and briefly explain 4 factors that affect the degree of crystallinity in a polymer. (8)

Degree of crystallinity is determined by:

 Rate of cooling during solidification: time is necessary for chains to move and align
into a crystal structure
 Mer complexity: crystallization less likely in complex structures, simple polymers, such
as polyethylene, crystallize relatively easily
 Chain configuration: linear polymers crystallize relatively easily, branches inhibit
crystallization, network polymers almost completely amorphous, cross-linked polymers
can be both crystalline and amorphous
 Isomerism: isotactic, syndiotactic polymers crystallize relatively easily - geometrical
regularity allows chains to fit together, atactic polymers is difficult to crystallize
 Copolymerism: easier to crystallize if mer arrangements are more regular - alternating,
block can crystallize more easily as compared to random and graft

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