0 XB 1
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
Binary solutions with unlimited solubility
Lets construct a binary phase diagram for the simplest case: A
and B components are mutually soluble in any amounts in both
solid (isomorphous system) and liquid phases, and form ideal
solutions.
We have 2 phases liquid and solid. Lets consider Gibbs free
energy curves for the two phases at different T
G solid
B
G solid T1
A
G liquid
B
G liquid
A G solid
G liquid
0 XB 1
and G solid
B Why?
The curvature of the G(XB) curves will decrease. Why?
G solid
B
T2 G liquid
G liquid
A =G solid
A
B
G solid
G liquid
0 XB 1
T3 G solid
B
G liquid
A
G solid
G solid
A G liquid
B
G liquid
solid solid +
liquid liquid
X1 X2
0 XB 1
T4
G liquid
A
G liquid
G liquid
B = G solid
B
G solid
A
G solid
0 XB 1
G liquid G solid
B
A
T3
G solid
G solid
A G liquid
B
G liquid
T1
solid solid +
s liquid liquid
l
T T1
s
T2 T2
l
T3
l T4 T4
T5
s
0 XB 1
Liquid
Solid solution
Liquidus
L
Temperature
liquid solution
+L
Solidus
liquid solution
+
crystallites of
solid solution
A 20 40 60 80 B
polycrystal
solid solution Composition, wt %
Xliquid
B
XB Xsolid
B
W W
C Bwt A A
Weight % to Atomic %: C atB = wt 100
CB AA + CA AB wt
wt
C A AB
C A = wt
at
100
CB AA + CA A B
wt
C atA A A
C wt
A = at 100
CBA B + CAA A at
The tie-line method still works for the liquid phase, where
diffusion is fast. Average Ni content of solid grains is higher.
Application of the lever rule gives us a greater proportion
of liquid phase as compared to the one for equilibrium
cooling at the same T. Solidus line is shifted to the right
(higher Ni contents), solidification is complete at lower T, the
outer part of the grains are richer in the low-melting
component (Cu).
Upon heating grain boundaries will melt first. This can lead
to premature mechanical failure.
G T1 G T2 < T1 G liquid
G solid
G solid
G liquid
0 XB 1 0 XB 1
T
G T3 < T2
G liquid T1
liquid
T2
G solid
T3 1+2
0 XB 1 0 XB 1
At low temperatures, there is a region where the solid solution is
most stable as a mixture of two phases 1 and 2 with
compositions X1 and X2. This region is called a miscibility gap.
T1
T2
1+2
0 XB 1 0 XB 1
0 XB 1
G G T2 < T1
G liquid T1 G liquid
G solid
G solid
0 XB 1 0 XB 1
G T3 < T2 T liquid
liquid
G
T1
1+l 2+l
T2
G solid T3 1 2
1+2
0 XB 1 0 XB 1
G T1 G T2 < T1
liquid
liquid
0 XB 1 0 XB 1
T
G T3 < T2 liquid
T1
+l
+l
T2
liquid T3
+
0 XB 1 0 XB 1
T
G T1 liquid
+l
+l
liquid T1
+
0 XB 1 0 XB 1
dG
=0 - Minimum of G(XB)
dX B
dG
= -G A + G B + 2 X B + RT - ln(1 - X B )
(1 - X B ) + lnX + X B =
dX B (1 - X B ) B
XB
X
= G B - G A + (1 2XB ) + RTln B GB - G A + + RTln(XB ) = 0
1 - XB
G GA +
XB exp B
RT
liquid
+l +l
T1
+
0 XB 1
G GA +
XB exp B
RT
XB XB vs. T T vs. XB
T
T
Te XB
supersaturation with B
phase separation and
precipitation of B-rich intermediate
phase or compound
Liquidus
liquid
Solidus
Temperature, C
Solvus
+
Composition, wt% Ag
Eutectic isotherm
Composition, wt% Sn
Eutectic or invariant point - Liquid and two solid phases co-
exist in equilibrium at the eutectic composition CE and the
eutectic temperature TE.
Eutectic isotherm - the horizontal solidus line at TE.
Eutectic reaction transition between liquid and mixture of two
solid phases, + at eutectic concentration CE.
The melting point of the eutectic alloy is lower than that of the
components (eutectic = easy to melt in Greek).
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
Eutectic systems - alloys with limited solubility (III)
B
Temperature, C
Composition, wt% Sn
Composition, wt% Sn
L +L
Composition, wt% Sn
L
Temperature, C
+L
Composition, wt% Sn
Composition, wt% Sn
L +
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
Development of microstructure in eutectic alloys (IV)
Solidification at the eutectic composition
Composition, wt% Sn
Composition, wt% Sn
Composition, wt% Sn
W = P / (P+Q+R) ( phase)
Temperature, C
Composition, wt% Sn
0 XB 1
Lower
Upper solidus L1 liquidus
Monotectic point L1 + L2
L2
Lower solidus
+ L2
+L2
Monotectic isotherm
+
0 XB 1
F.N. Rhines, Phase Diagrams in Metallurgy, 1956
G T1 G T2 < T1
G
G liquid
G liquid G
0 XB 1 0 XB 1
T3 < T2 T liquid
liquid
G G T1
T2
G
T3
`
`
G 0 XB 1
0 XB 1
At low temperatures, strong attraction between
unlike atoms can lead to the formation of
ordered
MSE phase
3050, Phase `. and Kinetics, Leonid Zhigilei
Diagrams
Binary solutions with Hmix < 0 - intermediate phases
If attraction between unlike atoms is very strong, the ordered
phase may extend up to the liquid.
T
liquid
+
+
0 XB 1
In simple eutectic systems, discussed above, there are only two
solid phases ( and ) that exist near the ends of phase
diagrams.
+
+
0 XB 1
+
+
0 XB 1
T liquid
0 XB 1
Increasing
liquid negative Hmix
T
`
0 XB 1
T
liquid
+
+
0 1
XBand Kinetics, Leonid Zhigilei
MSE 3050, Phase Diagrams
Phase diagrams with intermediate phases: example
intermetallic
compound
T T
liquid liquid
+l +l
l l
l+ + l+AB +
+ + AB
AB
+ + AB
0 XB 1 0 XB 1
non-stoichiometric stoichiometric
Common stoichiometric compounds:
compound AB A6B5 A5B4 A4B3 A3B2 A5B3
composition, at% 50.0 45.5 44.4 42.9 40.0 37.5
Cu-Zn
Eutectoid
Temperature
l
+l Eutectic
l +
temperature
+
+
Eutectoid
temperature
+
Eutectoid Eutectic
composition composition
Composition
+l
l +
+
+
Eutectoid
temperature
+
Composition
These reactions are rather slow as the product phase will form at
the boundary between the two reacting phases thus separating
them, and slowing down any further reaction.
Temperature
+ liquid liquid
+
+ liquid
+
+ liquid
In their simplest form, steels are alloys of Iron (Fe) and Carbon
(C). The Fe-C phase diagram is a fairly complex one, but we
will only consider the steel part of the diagram, up to around 7%
Carbon.
+ + Fe3C
+ Fe3C + Fe3C
Application of the lever rule with tie line that extends from the
eutectoid composition (0.75 wt% C) to ( + Fe3C) boundary
(0.022 wt% C) for hypoeutectoid alloys and to ( + Fe3C) Fe3C
boundary (6.7 wt% C) for hipereutectoid alloys.
Fraction of pearlite:
pearlite
naturally formed composite:
hard & brittle ceramic (Fe3C)
+
soft BCC iron (ferrite)
nondestructive measurements of
composition on ~30 organs
produced from 1624 to 1880
(neutron, X-ray diffraction, SIMS)
Zn is soluble in Cu
Pb is insoluble in Cu and is
distributed non-uniformly in
the alloy
Cu Zn phase diagram
Cu Pb phase diagram
Surprisingly constant Zn
concentration:
Before 1738 Zn was only available as zinc oxide (ZnO) or zinc carbonate
(ZnCO3) and brass was produced by mixing solid Cu and gas-phase Zn in a
process called cementation:
pieces of Cu, coal, and ZnCO3 are heated to above Tb of Zn (907C) but below
Tm of Cu (1083C)
ZnCO3 is reduced and evaporated Zn diffuses into hot solid Cu
Heating much above 907C was not economical temperature was kept slightly
above this temperature experienced craftsman can estimate temperature from
the color of a furnace within ~20C the process was taking place at ~920C
Zn concentration in brass is determined by solidus concentration maximum
solubility of Zn in solid Cu (26 wt.% at 920C)
1738: patent on distilling metallic Zn from ZnCO3, 1781: patent on alloying brass
from metallic Zn concentration of Zn in Cu is no longer limited by the
solubility
MSE 3050,at 920C,
Phase but is 32.5
Diagrams wt.% - maximum
and Kinetics, solubility after crystallization.
Leonid Zhigilei
The Gibbs phase rule (I)
P liquid
solid
In the areas where only one phase
is stable both pressure and
temperature can be independently gas
varied without upsetting the phase
equilibrium there are 2 degrees
of freedom. T
At the triple point, where solid liquid and vapor coexist any
change in P or T would upset the three-phase equilibrium
there are no degrees of freedom.
F = C Ph + 2
F = C Ph + 2
P = const
F = C Ph + 1
C=2
F = 3 Ph
wt. %
wt. %
wt. %