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Phenomenon!
Quantitative description!
Equilibrium microstructures!
prediction from phase diagrams!
in typical systems!
!Dr. K. Xia!
!1!
MCEN90014: Materials
!Dr. K. Xia!
!2!
Phase equilibrium!
when a system is at
a system is at equilibrium if the
equilibrium, it attains a
number of phases and their
minimum energy state (with
of
amounts do not change with Concept
minimum free energy) and is
free energy
time!
will be taught said to be stable!
in thermo e.g. ice in water at 0C!
dynamics
when a system at equilibrium
if no heat exchange
contains multiple phases, the
with the environment!
phases are at equilibrium with
dynamic: any ice
each other or phase equilibrium
melting will absorb heat
is reached!
and cause freezing of
Phase equilibrium may be
water at the same time,
destroyed if conditions are
i.e. although the total
changed, most notably by
amount of ice does not
change, the melting
temperature changes!
and freezing processes
liquid water changes into
proceed at the same
vapour if T is raised to 100C!
rate to keep the
!Dr. K. Xia!
!3!
Metastable state!
Microstructure!
an observed state of a system
in addition to the number of
does not necessarily indicate
phases and the amount of each
that the system has attained
phase, microstructure tells the
the lowest energy possible, e.g.
shape and size of each phase
diamond (C) has higher free
and their distribution in space!
energy than graphite (C) at
ambient conditions, but do not
lose your sleep as your
precious diamond is not going
to become cheap pencil lead
A: host
A: host
A: host
overnight (the energy barrier is
B: dissolved
B: fine
B: lamellae
in A
particles
too high for the change to take
place at any detectable rate)!!
microstructure is important as it
MCEN90014: Materials
!Dr. K. Xia!
!4!
Tm of
pure
Ni
liquid field
+ L two
phase field
lower limit of
the liquid field
upper limit of
the solid field
alpha field
: solid solution of
Cu and Ni (FCC)
pure Cu
pure Ni
!Dr. K. Xia!
!5!
Phase present!
A: Cu-60Ni at 1100C!
B: Cu-35Ni at 1250C!
The T and composition define the point in the diagram
a mixture of
and L
100% phase
IMSE:
Phase
Diagrams
MCEN90014: Materials
!Dr. K. Xia!
!6!
mass fraction
of liquid
W + WL = 100%
mass fraction
of
MCEN90014: Materials
!Dr. K. Xia!
!7!
MCEN90014: Materials
!Dr. K. Xia!
!8!
!9!
Eutectic isotherm
: solid
solution
based on
Cu with
dissolved
Ag
: solid
solution
based on
Ag with
dissolved
Cu
Eutectic or
invariant point
solubility limit (how much
solute can be dissolved in
the host). e.g. at 600C, Cu
can dissolve a maximum of
~3 wt% Ag
~3
MCEN90014: Materials
!Dr. K. Xia!
!10!
Eutectic or
invariant point
Eutectic isotherm
L (CE) = (C E) + (C E)
Eutectic
reaction
The eutectic reaction takes place at a constant temperature (TE = 779C).
At the end of the reaction, all liquid has become and and their relative
amounts can be calculated by using the lever law (W=19.3/83.2 = 23.2%
and W = 76.8%).
Alloy: Cu-71.9Ag
MCEN90014: Materials
!Dr. K. Xia!
!11!
Pb-40Sn alloy at
150C!
+ two
phases!
C: Pb-10Sn!
C: Pb-98Sn!
W = 58/88 =
66%!
W: = 30/88 =
34%!
A
D
TE = 183C
18.3
X
61.9
97.8
MCEN90014: Materials
!Dr. K. Xia!
!12!
Microstructures following
equilibrium cooling!
alloy C1!
T > T1: 100% L!
at T1: solidification of
starts!
at T2 solidification of
finishes!
< T2: 100% !
MCEN90014: Materials
T1
T2
!Dr. K. Xia!
!13!
alloy C2!
T > T1: 100% L!
at T1: solidification of
starts!
at T2 solidification of
finishes!
at T3: precipitation of
starts (in the matrix)!
< T3: W as T (using
the lever law)!
< T4: no more change!
Composition of L
T1
T2
T3
Composition
of
Compositions of
are out of range
T4
MCEN90014: Materials
!Dr. K. Xia!
!14!
MCEN90014: Materials
TE
!Dr. K. Xia!
!15!
alloy C4!
At T1,
solidification
starts
+ L
W = 21.9/43.6 = 50.2%
T1
WL = 21.7/43.6 = 49.8%
at TE:
TE
18.3
L (61.9) =
(18.3)+
(97.8)
61.9
97.8
eutectic structure
Just after TE:
+
W = 57.8/79.5 = 72.7%
W = 21.7/79.5 = 27.3%
MCEN90014: Materials
!Dr. K. Xia!
!16!
Homework:
plot the
microstructure
at TR
just above
TE
Primary
(Pb-18.3Sn): 50.2 g
TE
Primary
(Pb-18.3Sn): 50.2 g
18.3
just
below
TE
Liquid
(Pb-61.9Sn): 49.8 g
61.9
Eutectic
(Pb-61.9Sn):
49.8 g
97.8
Eutectic
(Pb-18.3Sn):
22.5 g (45.2%)
Eutectic
(Pb-97.8Sn):
27.3 g (54.8%)
TR
Primary (Pb~3Sn): 42.1 g
(83.9%)
MCEN90014: Materials
at TR
!Dr. K. Xia!
!17!
!18!
Intermetallic
compound
MCEN90014: Materials
!Dr. K. Xia!
Eutectoid reaction
MCEN90014: Materials
!Dr. K. Xia!
= +
!
!19!
Terminology!
system!
component!
phase!
microstructure!
equilibrium!
Equilibrium phase diagram (binary)!
fields: single phase, two phase!
tie lines!
phases present!
composition of each phase!
amount of each phase - the lever
law!
eutectic reaction!
segregation due to nonequilibrium
cooling!
MCEN90014: Materials
!Dr. K. Xia!
Microstructure!
upon cooling from liquid to room
temperature!
process!
change of composition during
cooling!
change of amount of each
phase during cooling!
change of microstructure during
cooling and the final microstructure!
!20!
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