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= S
T
2G
c
S
2 = = P
T
T P
T P
GA
GB
0
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
XB
G solid
B
G
T1
solid
A
G liquid
A
G liquid
B
G solid
G liquid
XB
GA
solid
and G liquid
G
will
increase
more
rapidly
than
B
A
and G solid
B
Why?
solid
component A, where G liquid
=
G
A
A
liquid
A
=G
G solid
B
T2
solid
A
G liquid
B
G solid
G liquid
Why?
XB
T3
G liquid
A
G solid
B
G solid
G solid
A
G liquid
B
G liquid
solid
X1
solid +
liquid
XB
liquid
X2
T4
G liquid
A
G liquid
solid
G liquid
=
G
B
B
G solid
A
G solid
XB
liquid
A
T3
G solid
A
G solid
B
G solid
G liquid
B
G liquid
T1
solid
solid +
liquid
liquid
l
s
T2
T1
T2
l
s
T3
T4
T4
T5
XB
Liquid
Liquidus line
Solidus line
Solid solution
Liquidus
Temperature
liquid solution
+L
Solidus
liquid solution
+
crystallites of
solid solution
polycrystal
solid solution
20 40 60 80
Composition, wt %
2.
3.
XB
Xliquid
B
Xsolid
B
2.
3.
Composition/Concentration:
weight fraction vs. molar fraction
Composition can be expressed in
Molar fraction, XB, or atom percent (at %) that is useful when
trying to understand the material at the atomic level. Atom
percent (at %) is a number of moles (atoms) of a particular
element relative to the total number of moles (atoms) in alloy.
For two-component system, concentration of element B in at. %
is
nB
C at =
n Bm + n Am
100
C at = X B 100
C wt =
mB
100
mB + mA
n Am =
mA
AA
n Bm =
mB
AB
Composition Conversions
Weight % to Atomic %:
C atB
C Bwt A A
= wt
100
wt
CB AA + CA AB
wt
C
at
A AB
C A = wt
100
wt
CB AA + CA A B
Atomic % to Weight %:
C Bwt
C atB A B
= at
100
at
CBA B + CAA A
wt
A
C atA A A
= at
100
at
CBA B + CAA A
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.
T1
T2 < T1
G liquid
G solid
G solid
G liquid
XB
liquid
XB
T
T1
T3 < T2
liquid
T2
G solid
T3
0
XB
1+2
XB
T
G
liquid
T1
T2
XB
XB
1+2
XB
T1
liquid
G liquid
G solid
T3 < T2
G
G
G solid
XB
liquid
XB
0
T
T1
T2
T3
G solid
T2 < T1
XB
liquid
1+l
2+l
1+2
XB
T1
T2 < T1
liquid
liquid
XB
T2
liquid
T3
XB
liquid
T1
XB
T3 < T2
+l
+l
XB
T1
T
liquid
+l
liquid
T1
XB
+l
XB
- Minimum of G(XB)
(1 - X B ) + lnX + X B =
dG
= -G A + G B + 2 X B + RT - ln(1 - X B )
B
(1 - X B )
dX B
XB
G GA +
XB exp B
RT
Minimum of G(XB)
+l
liquid
+l
T1
XB
G GA +
XB exp B
RT
XB
XB vs. T
T vs. XB
T
Te
XB
supersaturation with B
phase separation and
precipitation of B-rich intermediate
phase or compound
Liquidus
liquid
Temperature, C
Solidus
Solvus
+
Copper Silver phase diagram
Composition, wt% Ag
Temperature, C
Composition, wt% Sn
Eutectic or invariant point - Liquid and two solid phases coexist 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).
Temperature, C
A
B
Composition, wt% Sn
Temperature, C
Composition, wt% Sn
Temperature, C
L +L
Composition, wt% Sn
Temperature, C
+L
Composition, wt% Sn
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
Temperature, C
Composition, wt% Sn
L +
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
Temperature, C
L + L +
Composition, wt% Sn
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
W = Q / (P+Q) (primary)
Temperature, C
We = P / (P+Q) (eutectic)
Composition, wt% Sn
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
Temperature, C
Composition, wt% Sn
Temperature, C
W = P / (P+Q+R) ( phase)
Composition, wt% Sn
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
liquid
XB
Monotectic system
+ L1
Upper solidus
L1
Monotectic point
Lower solidus
Limit of liquid
immiscibility
Lower
liquidus
L1 + L2
L2
+ L2
+L2
Monotectic isotherm
0
F.N. Rhines, Phase Diagrams in Metallurgy, 1956
XB
T1
T2 < T1
G
G liquid
G liquid
0
G G
XB
liquid
0
T
T1
T3 < T2
XB
liquid
T2
T3
G
XB
XB
liquid
XB
liquid
XB
liquid
XB
liquid
XB
Increasing
negative Hmix
liquid
XB
liquid
intermetallic
compound
T
liquid
liquid
+l
l+
l+AB
+ AB
AB
+l
XB
non-stoichiometric
+ AB
XB
stoichiometric
AB
composition, at%
50.0
45.5
44.4
42.9
40.0
37.5
compound
A2B A5B2
A3B
A4B
A5B
A6B
composition, at%
33.3
25.0
20.0
16.7
14.3
28.6
Eutectoid Reactions
The eutectoid (eutectic-like in Greek) reaction is similar to the
eutectic reaction but occurs from one solid phase to two new solid
phases.
Eutectoid structures are similar to eutectic structures but are much
finer in scale (diffusion is much slower in the solid state).
Upon cooling, a solid phase transforms into two other solid
phases ( + in the example below)
Looks as V on top of a horizontal tie line (eutectoid isotherm) in
the phase diagram.
Cu-Zn
Eutectoid
Eutectoid
temperature
+l
Eutectic
temperature
l +
Eutectoid
composition
Eutectic
composition
Composition
The above phase diagram contains both an eutectic reaction and
its solid-state analog, an eutectoid reaction
Temperature
Eutectoid
temperature
+l
l +
+
Composition
Peritectic Reactions
A peritectic reaction - solid phase and liquid phase will together
form a second solid phase at a particular temperature and
composition upon cooling - e.g. L +
Temperature
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.
+ liquid
+
liquid
+ liquid
Temperature
+ liquid
+
liquid
+ liquid
L + Fe3C
+ + Fe3C
+ Fe3C + Fe3C
pearlite
naturally formed composite:
hard & brittle ceramic (Fe3C)
+
soft BCC iron (ferrite)
MRS Bulletin
Vol 32, March
2007, 249-255
Cu Zn phase diagram
Cu Pb phase diagram
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
MSE 3050,at
Phase
Diagrams
and Kinetics,
Leonid Zhigilei
solubility
920C,
but is 32.5
wt.% - maximum
solubility after crystallization.
solid
liquid
gas
T
F = C Ph + 2
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
- Ph-1 equations
P = P = P =
- Ph-1 equations
A = A = A = ...
- Ph-1 equations
= = = ...
- Ph-1 equations
C sets of equations
F = C Ph + 2
P = const
F = C Ph + 1
C=2
F = 3 Ph
wt. %
wt. %
wt. %
Representation of the composition in a ternary system (the Gibbs
triangle). The total length of the red lines is 100% :
XA +XB + XC =1
Summary
Make sure you understand
language and concepts:
Miscibility gap
+
Solubility dependence on T
Intermediate solid solution
Peritectic ( + L )
Compound
+L
Isomorphous
L