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MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Binary phase diagram and Gibbs free energy
A binary phase diagram is a temperature - composition map
which indicates the equilibrium phases present at a given
temperature and composition.
The equilibrium state can be found from the Gibbs free energy
dependence on temperature and composition.
0 XB 1
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Binary solutions with unlimited solubility
Let’s 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. Let’s 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
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Binary solutions with unlimited solubility (III)
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
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Binary solutions with unlimited solubility (IV)
T4
G liquid
A
G liquid
G liquid
B = G solid
B
G solid
A
G solid
0 XB 1
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Binary solutions with unlimited solubility (V)
Based on the Gibbs free energy curves we can now construct a
phase diagram for a binary isomorphous systems
G liquid G solid
B
A
T3
G solid
G solid
A G liquid
B
G liquid
T1
solid solid +
liquid liquid
T T1
T2 T2
T3
T4 T4
T5
0 XB 1
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Binary solutions with unlimited solubility (VI)
Example of isomorphous system: Cu-Ni (the complete solubility
occurs because both Cu and Ni have the same crystal structure,
FCC, similar radii, electronegativity and valence).
Liquid
Solid solution
Liquidus
L
Temperature
liquid solution
α+L
Solidus
liquid solution
α +
crystallites of
solid solution
A 20 40 60 80 B
polycrystal
solid solution Composition, wt %
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Interpretation of Phase Diagrams
Xliquid
B
XB Xsolid
B
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Interpretation of Phase Diagrams: the Lever Rule
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Composition Conversions
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
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Phase compositions and amounts. An example.
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Development of microstructure in isomorphous alloys
Equilibrium (very slow) cooling
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Development of microstructure in isomorphous alloys
Equilibrium (very slow) cooling
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Development of microstructure in isomorphous alloys
Non-equilibrium cooling
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Development of microstructure in isomorphous alloys
Non-equilibrium cooling
• 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.
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Binary solutions with a miscibility gap
Let’s consider a system in which the liquid phase is
approximately ideal, but for the solid phase we have ∆Hmix > 0
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 α
T3 α1+α2
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 α1 and α2 with
compositions X1 and X2. This region is called a miscibility gap.
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Eutectic phase diagram
For an even larger ∆Hmix the miscibility gap can extend into the
liquid phase region. In this case we have eutectic phase
diagram.
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
α1+l α2+l
T2
G solid T3 α1 α2
α1+α2
0 XB 1 0 XB 1
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Eutectic phase diagram with different crystal
structures of pure phases
A similar eutectic phase diagram can result if pure A and B have
different crystal structures.
G T1 G T2 < T1
α β α
β
liquid
liquid
0 XB 1 0 XB 1
T
G T3 < T2 liquid
T1
β α
α+l
β+l
T2
α β
liquid T3
α+β
0 XB 1 0 XB 1
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Eutectic systems - alloys with limited solubility (I)
Liquidus
liquid
Solidus
Temperature, °C
Solvus
α+β
Composition, wt% Ag
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Eutectic systems - alloys with limited solubility (II)
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, α + β 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 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Eutectic systems - alloys with limited solubility (III)
•A
•B
Temperature, °C
•C
Composition, wt% Sn
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Development of microstructure in eutectic alloys (I)
L → α +L→ α
Composition, wt% Sn
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Development of microstructure in eutectic alloys (II)
At compositions between the room temperature solubility limit
and the maximum solid solubility at the eutectic temperature, β
phase nucleates as the α solid solubility is exceeded upon
crossing the solvus line.
L
Temperature, °C
α +L
α +β
Composition, wt% Sn
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Development of microstructure in eutectic alloys (III)
Solidification at the eutectic composition
Composition, wt% Sn
L → α +β
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Development of microstructure in eutectic alloys (IV)
Solidification at the eutectic composition
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Development of microstructure in eutectic alloys (V)
Compositions other than eutectic but within the range of
the eutectic isotherm
Primary α phase is formed in the α + L region, and the eutectic
structure that includes layers of α and β phases (called eutectic α
and eutectic β phases) is formed upon crossing the eutectic
isotherm.
L → α + L → α +β
Temperature, °C
Composition, wt% Sn
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Development of microstructure in eutectic alloys (VI)
Microconstituent – element of the microstructure having a
distinctive structure. In the case described in the previous page,
microstructure consists of two microconstituents, primary α
phase and the eutectic structure.
Composition, wt% Sn
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
How to calculate the total amount of α phase (both eutectic
and primary)?
Fraction of α phase determined by application of the lever rule
across the entire α + β phase field:
Wβ = P / (P+Q+R) (β phase)
Temperature, °C
Composition, wt% Sn
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Binary solutions with ∆Hmix < 0 - ordering
If ∆Hmix < 0 bonding becomes stronger upon mixing → melting
point of the mixture will be higher than the ones of the pure
components. For the solid phase strong interaction between
unlike atoms can lead to (partial) ordering → |∆Hmix| can
become larger than |ΩXAXB| and the Gibbs free energy curve for
the solid phase can become steeper than the one for liquid.
G T1 G T2 < T1
Gα
G liquid
G liquid Gα
0 XB 1 0 XB 1
T3 < T2 T liquid
liquid
G G T1
T2
Gα α
T3
α`
α`
G 0 XB 1
0 XB 1
At low temperatures, strong attraction between
unlike atoms can lead to the formation of
ordered
MSE phase
305, Phase α`. and Kinetics, Leonid Zhigilei, Fall 2004
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
β γ
α+β
β+γ
0 XB 1
In simple eutectic systems, discussed above, there are only two
solid phases (α and β) that exist near the ends of phase
diagrams.
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
∆Hmix<0 - tendency to form high-melting point intermediate phase
T liquid
0 XB 1
Increasing
liquid negative ∆Hmix
T
α`
0 XB 1
T
liquid
α β
γ
α+β
β+γ
0 Xand
MSE 305, Phase Diagrams B 1
Kinetics, Leonid Zhigilei, Fall 2004
Phase diagrams with intermediate phases: example
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Phase diagrams for systems containing compounds
For some sytems, instead of an intermediate phase, an
intermetallic compound of specific composition forms.
Compound is represented on the phase diagram as a vertical line,
since the composition is a specific value.
When using the lever rule, compound is treated like any other
phase, except they appear not as a wide region but as a vertical
line
intermetallic
compound
Cu-Zn
Eutectoid
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Eutectic and Eutectoid Reactions
Temperature
l
γ +l Eutectic
γ l +β
temperature
γ +β
α+γ
Eutectoid α β
temperature
α +β
Eutectoid Eutectic
composition composition
Composition
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Peritectic Reactions
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
α + liquid liquid
α +β
β β + liquid
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Example: The Iron–Iron Carbide (Fe–Fe3C) Phase Diagram
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.
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Phases in Fe–Fe3C Phase Diagram
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
A few comments on Fe–Fe3C system
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Eutectic and eutectoid reactions in Fe–Fe3C
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Microstructure of eutectoid steel (II)
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Microstructure of hypoeutectoid steel (I)
γ → α + γ → α + Fe3C
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Microstructure of hypoeutectoid steel (II)
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Microstructure of hypereutectoid steel (I)
γ → γ + Fe3C → α + Fe3C
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Microstructure of hypereutectoid steel
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Microstructure of hypereutectoid steel (II)
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
How to calculate the relative amounts of proeutectoid phase
(α or Fe3C) and pearlite?
Application of the lever rule with tie line that extends from the
eutectoid composition (0.75 wt% C) to α – (α + Fe3C) boundary
(0.022 wt% C) for hypoeutectoid alloys and to (α + Fe3C) – Fe3C
boundary (6.7 wt% C) for hipereutectoid alloys.
Fraction of pearlite:
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
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
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
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
The Gibbs phase rule (II)
F = C − Ph + 2
P = const
F = C − Ph + 1
C=2
F = 3 − Ph
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Temperature dependence of solubility
T
G T1 liquid
β α
α+l
β+l
α β
liquid T1
α+β
0 XB 1 0 XB 1
dG
=0 - Minimum of G(XB)
dX B
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Temperature dependence of solubility (II)
dG ⎡
= -G A + G B + Ω − 2Ω 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 + Ω(1 − 2XB ) + RTln⎜⎜ B ⎟⎟ ≈ GB - G A + Ω + RTln(XB ) = 0
⎝ 1 - XB ⎠
⎛ G − GA + Ω ⎞
XB ≈ exp⎜ − B ⎟
⎝ RT ⎠
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Multicomponent systems (I)
wt. %
wt. %
wt. %
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Multicomponent systems (II)
The Gibbs free energy surfaces (instead of curves for a binary
system) can be plotted for all the possible phases and for
different temperatures.
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Multicomponent systems (III)
A three-phase equilibrium in the ternary system for a given
temperature can be derived by means of the tangential plane
construction.
α β
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Another example of ternary phase diagram:
oil – water – surfactant system
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004
Summary
Make sure you understand Elements of phase diagrams:
language and concepts:
Eutectic (L → α + β)
L
¾ Common tangent construction α β
¾ Separation into 2 phases α+β
¾ Eutectic structure
Eutectoid (γ → α + β)
¾ Composition of phases
¾ Weight and atom percent γ
¾ Miscibility gap α β
α+β
¾ Solubility dependence on T
¾ Intermediate solid solution Peritectic (α + L → β)
¾ Compound
α+L
¾ Isomorphous α L
¾ Tie line, Lever rule β
¾ Liquidus & Solidus lines
¾ Microconstituent Peritectoid (α + β → γ)
¾ Primary phase α+β
α β
¾ Solvus line, Solubility limit
γ
¾ Austenite, Cementite, Ferrite
¾ Pearlite Compound, AnBm
¾ Hypereutectoid alloy
¾ Hypoeutectoid alloy
¾ Ternery alloys A useful link:
¾ Gibbs phase rule http://www.soton.ac.uk/~pasr1/index.htm
MSE 305, Phase Diagrams and Kinetics, Leonid Zhigilei, Fall 2004