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Phase Diagrams - MMM2008 Final Exam 04.06.2015

Name: Learning Outcomes LO 2, 5 LO 5, 6 LO 7 LO 1 LO 3
Surname: Question 1 2 3 4 5
No: Points 15 30 20 15 20 100
How many hours have you studied for the exam

1. Sketch phase diagram for the following system characterized as follows

even though in some cases data is not complete. Chose reasonable points and reasonable
constructions which comply with Phase Rule requirement. Do not include features which are
not required by the data. Label the fields to demonstrate which phases are at equilibrium. (25).
System description and data: Cobalt melts at 1480 oC, CoSb melts at 1190 oC, CoSb2
decomposes at 900 oC into CoSb and liquid containing 91 percent Sb and pure Sb melts at
630 oC. There are eutectics at 1090 oC and 40 percent Sb, and 620 oC and 99 percent Sb, and
solid solution exists up to 12 percent Sb.
Answer 1

2. A ternary phase diagram with a binary incongruently melting compound

AxBy and the primary crystallization spaces are given as shown below. Answer the following
a. Find the weight percentage of the three components A, B and C in compositions X and Y (5).
b. Describe the binary and non-binary joints and indicate which one of these exist in the given
phase diagram (5)?
c. Clarify the composition triangle where composition X and Y go through final solidification
d. Indicate the path of solidification and the invariant point where the reaction of final
solidification (the invariant reaction) for both compositions take place (5).

e. Calculate the weight percentage of the

phases that exist at TE

( Above eutectic temp .) and TE
(Below eutectic temp .) and indicate the
amount of liquid phase taking part in
ternary eutectic reaction for composition
Y (10).
f. Calculate partial amount of A (x) and B (y)
in compound AxBy (4).

Answer 2
a. Percentage amount of component for X and
Y are indicated in figure on the right in
proportion to the side of the triangle. AX, BX
and CX for X and AY, BY and CY for Y,
b. Binary joint: It is also called Alkemades line connecting two composition points whose
primary fields are adjacent and have intersection with the border line separating their primary
Non-binary joint: It is the line connecting two composition points and having the intersection
with the border line separating the adjacent fields at its extension.
c. Comp. X solidifies in comp. Triangle AXBY-B-C
Comp. Y solidifies in comp. Triangle A-AXBY-C
d. For X: XXP. The final solidification point is P(peritectic).
For Y: YYPE. The final solidification point is E(ternary eutectic). The ternary eutectic
reaction: Liq. AXBY+A+B
e. For Y at T :

Liq%: 13.6 ; (AXBY+C)%:86.4 To calculate the partial amount

of AXBY and C the second lever arm is used:
AXBY%: 44.9 ; C%:41.5

For Y at T E : Amount of liquid (Liq%) taking part in ternary eutectic reaction is: 13.6
The ternary eutectic reaction: Liq.%(13.6) A(5%)+AXBY(2.15%)+C(6.45%). To calculate the
products of the reaction the perpendiculars drawn from E to each of the side of triangle are used.
E E3
A% =36.8 , 13.6*0.368 = 5%
E E 1+ E E 2 + E E 3
E E1
AXBY% = =15.8 13.6*0.158 = 2.15%
E E 1+ E E 2+ E E 3
E E1
C% = =47.4 13.6*0.474 = 6.45%
E E 1 + E E 2+ E E 3

C% (Total) = 41.5+6,45=47,95

AXBY % (Total) = 44.9+2.15=47.05


f. A% = 31.25
B% = 68.75 x=1 ; y=2.2 AXBY = A1B2.2

3. A schematic free energy curves at different temperatures (T1, T2, T3, T4 and T5) leading to a
binary phase diagram are given in Figure below. By making use of the free energy curves
given, draw the phase diagram having eutectic and eutectoid reactions in Fig. at bottom right.
It is known that element A goes an allotropic transformation at temperature between T 3 and

Answer 3

4. Mixing X A mol A and X B mol B atoms ( X A + X B =1 mol ), into a large amount of

a system will increase the free energy of the system by the molar free energy, G. Assume that
the molar free energy G is given as a function of X A X B as such that G= A X A + B X B
where A B is partial molar free energy of A and B in the system respectively.
a. Show that A B can be obtained by extrapolating the tangent to the G curve drawn
from the original phase composition (Y) extending to
the sides of the molar free energy diagram as
indicated on the diagram below.
b. Using equations

Eqn. (1) G= X A G B + X B G B + RT ( X A ln X A + X B ln X B ) and

Eqn. (2) G= A X A + B X B ,
Show that A B can be numerically calculated as
A GA + RTln X A and B = GB + RTln X B respectively.

Answer 4

a. G= A X A + B X B ( B A) X B

G= A ( 1X B ) + X B= A +
tg = =B A = Since AB=1 and RZ=PX (See the diagram)
tg = =B A = =VZRX Therefore; B =VZ and A =PX
dX B 1

G= X A G A+ X B G B + RT ( X A ln X A + X B ln X B )
(b) Eqn. (1)
Eqn. (2) G= A X A + B X B
G= X A ( G A + RT ln X A ) + X B ( G B + RT ln X B )
By rearranging Eqn. (1) and comparing this
with Eqn. (2)
A =G A + RT ln X A and B =GB + RT ln X B are obtained.
5. Answer the questions below as regards to the following phase diagram
which forms under equilibrium cooling condition.
a. How can you explain the decrease in melting temperature of the terminus metals as they are
mixed in each other?
b. Calculate the partial amount of and for an alloy
X at temperature T 2

c. Clarify the formation of the two-solid solution region

(or the miscibility gap) defined by the solvus line (or
the boundary of the two-solid region).
d. What kind of changes would you expect to see in this
phase diagram, if cooling proceeds under non-
equilibrium cooling condition? Clarify your reasoning
by providing the information on two types of barriers
that the embryonic nucleus has to surmount.
Answer 5
a. Excess free energy of solid upon mixing is more
positive than that of liquid, therefore liquid is more
stable in a mixed state. The reason is that the unlike atoms repels each other and melting
temperature decreases upon mixing.
b. %=X 2 X 0 / X 2 X 2 The intersection of isothermal temperature T 2 with alloy X 0
is being the point where the fulcrum is positioned.
c. When two different atoms are mixed together they form a single solid solution at low
temperature as long as the excess amount of enthalpy created upon mixing is negative (
H <0 ). This means that the attraction of unlike atoms are stronger than that of like
atoms causing a decrease in enthalpy and yield no tendency for A and B-rich phases to form.
Otherwise if like atoms attract more strongly than unlike atoms H xs becomes positive,

which corresponds to a situation where a tendency for separation of A-rich and B-rich phases
exists as a results of mixing.
d. A spinodal transformation takes place when the cooling proceeds under non-equilibrium
condition, due to the slow rate of diffusion with high rate of decrease in temperature.
Formation of a new phase starts with an embryonic transformation which needs an
overcooling to be able to create an embryo big enough in size which helps overcome the size
barrier providing a decreasing a surface-to-volume ratio which results in a decrease in bulk
free energy overriding the increasing free energy due to the interface formation. Formation of
B-rich embryo formation is enhanced by undercooling below the spinodal only when the free
energy change on forming an embryo becomes negative.