Chapter 4 : Phase Diagrams

Instructor: Prasana Kumar Sahoo

[email protected]
 Binary systems: Cu–Ni Isomorphous Alloys
binary systems: 2 components. independent variables: T and C
If we know T and C, then we know: how many
T(°C)1600 2 phases and 3 phase fields phases and which phases are present.
L (liquid) a (FCC solid solution)

1500 L (liquid)
• Examples:

1400 D
B
1300

1200 a
Melting points:
A
1100 Cu = 1085°C,
(FCC solid solution)
Ni = 1453 °C
1000
0 20 40 60 80 100
Cu
wt% Ni
Effect of Temperature & Composition (Co)
• Changing T can change phases: path A to B.
Solidus - Temperature where alloy is completely solid. Above this line, liquefaction begins.
• Changing C can change phases: path B to D.
Liquidus - Temperature where alloy is completely liquid. Below this line, solidification begins.
 Binary-Eutectic Systems
Upon cooling, a liquid phase is transformed into the two solid α and β phases at TE ; the opposite reaction occurs
upon heating. This is called a
T(°C) Cu-Ag system
Eutectic reaction = 1200
L (liquid)
1000
a L+ a
TE 800 779°C L+b b
8.0 71.9 91.2
• The horizontal solidus line at TE is called the eutectic
600
isotherm
a + b
• The solid product of eutectic solidification is always two 400
solid phases
200
• For a eutectic system, three phases may be in equilibrium, 0 20 40 60 CE 80 100
but only at points along the eutectic isotherm. C , wt% Ag
• Another general rule is that single-phase regions are always
Many pairs of elements e.g.,
separated from each other by a two-phase region that
consists of the two single phases that it separates Bi-Cd, Sn-Zn, Ag-Cu, Al-Si
 Microstructures In Eutectic Systems: Equilibrium Cooling - I
•Composition range: a pure component (e.g. Pb) Pb-Sn system
- its maximum solid solubility at room (20 0C) temperature
L: C0 wt% Sn
e.g. alloys where T(°C)
400
C0 < 2 wt% Sn
L
a
L
T>TL=330 C – liquid alloy with C0 comp 300

L+ a
a
TS< T<TL – very narrow region: a solid phase in 200
TE a: C0 wt% Sn
liquid (L) and compositions of phases are defined
by tie-line method 100
a+ b

T<TS - polycrystal of a grains with

uniform composition of C0 0 10 20 30
C0 C , wt% Sn
2
Result at room temperature is a polycrystalline
with grains of a phase having composition C0 (room T solubility limit)
 Microstructures In Eutectic Systems: Equilibrium Cooling - II
•Composition range: maximum solid solubility at Pb-Sn system
room (20C) temperature (C = 2wt%) and maximum solid
solubility at eutectic temperature, TE=183C (C=18.3%) L: C2 wt% Sn
T(°C)
(e.g. 2 wt% Sn < C2 < 18.3 wt% Sn) 400
L
L
- T>TL – liquid alloy with C2 composition 300 a
L+a
- Tsolidus<T<TL – solid a phase in liquid (L) and a: C2 wt% Sn
compositions of phases are defined by tie-line method a
200
TE
- Tsolvus< T < Tsolidus - polycrystal of a grains with uniform a
b
composition of C2
100
a+ b
- T< Tsolvus - a polycrystal with fine b crystals; the
compositions of phases are defined by tie-line method
and the amount of each phase by Level rule. 0 10 20 30
2 C2 C, wt% Sn
• Results in polycrystalline microstructure with a grains and (sol. limit at T room ) 18.3
small b-phase particles at lower temperatures. (sol. limit at TE)
 Microstructures in Eutectic Systems - III
• T>TE : liquid with C = CE =
61.9 wt% Sn Pb-Sn system

• T<TE: alternating layers of a

and b crystals.

• Ci = CE

• Results in a eutectic
microstructure with
alternating layers of a and
b crystals.

cooling
L(61.9 wt% Sn) a (18.3 wt% Sn) + b (97.8 wt% Sn)
heating
 Lamellar Eutectic Structure
❑ A 2-phase microstructure resulting from the
solidification of a liquid having the eutectic
composition where the phases exist as a
Pb-rich
lamellae that alternate with one another.
Sn-rich

❑Formation of eutectic layered microstructure in the

Pb-Sn system during solidification at the eutectic
composition.
❑Compositions of α and β phases are very different.
Solidification involves redistribution of Pb and Sn
atoms by atomic diffusion.
Microstructure obtained with different compositions
 Microstructures in Eutectic Systems - IV

Microstructure of a lead–tin alloy of composition 50

wt% Sn–50 wt% Pb
To distinguish one α from the other, that which The fraction of the eutectic microconstituent We is just the same as the fraction of
resides in the eutectic structure is called eutectic liquid WL from which it transforms,
α, whereas the other that formed prior to crossing fraction of
the eutectic isotherm is termed primary α. primary α

Microconstituent—an element of the microstructure Fractions of total α, Fraction of β

having an identifiable and characteristic structure
(Example primary α and the eutectic structure)
 Microstructures in Eutectic Systems - IV
• For alloys with18.3 wt% Sn < C0 < 61.9 wt% Sn
• Result: a phase particles and a eutectic microconstituent
Pb-Sn system • Just above TE :
T(°C) L: C0 wt% Sn Ca = 18.3 wt% Sn
a L
L CL = 61.9 wt% Sn
300 L C L - C0
a Wa = = 0.50
L+ a C L - Ca
a WL = (1- W a ) = 0.50
200 L+b b
TE Primary α

• Just below TE :
100 a+b
Ca = 18.3 wt% Sn
eutectic a
eutectic b Cb = 97.8 wt% Sn
Cβ - C0
0 20 40 60 80 100 Wa =
18.3 61.9 97.8 Cβ - Ca = 0.727
C, wt% Sn Wb = 0.273 wt% Sn
 Hypoeutectic & Hypereutectic
T(°C)
(Pb-Sn System) 300 L

L +a
2T00
a L +b
E b
a +b
100
C C
hypoeutectic hypereutectic
0
0 20 40 60 80 100 Co, wt% Sn
eutectic
18.3 61.9 97.8
hypoeutectic: less than eutectoid alloy hypereutectic
Eutectic alloy

a
b
a b
a a a b b
b
a b
160 m
175m
eutectic micro-constituent
 Lamellar Eutectic Structure
lamellar Ti-Fe eutectics Copper phosphorus eutectic Ni-Al

Each eutectic alloy

has its own
characteristic
microstructure :
spheroidal, nodular, or
globular; acicular
(needles) or rod; and
lamellar (platelets)
F. Zhu et al. App. Phys Lett 2011
 Nonequilibrium Solidification Phenomenon : Cooling
Readjustments of phases are accomplished by
diffusional processes—that is, diffusion in both solid
and liquid phases and also across the solid–liquid
interface.
Diffusion rates (i.e., the magnitudes of the diffusion
coefficients) are especially low for the solid phase and, for
both phases, decrease with diminishing temperature.

In most solidification situations, cooling rates are much too

rapid- not allow these compositional readjustments and
maintenance of equilibrium; consequently, microstructures
other than those previously described develops.

• Development of microstructure during the non-equilibrium

solidification of a 35 wt% Ni-65 wt% Cu alloy outcome:
• Segregation-nonuniform distribution of elements within grains.
• Weaker grain boundaries if alloy is reheated.
 Nonequilibrium Solidification Phenomenon : Cooling
At point b′ (~1260°C), α-phase particles begin to form,
Composition 46 wt% Ni–54 wt% Cu [α(46 Ni)].

Point c′ (~1240°C), composition shifted to 40 wt% Ni–60

wt% Cu;
• α phase that solidified is 40 wt% Ni–60 wt% Cu [α(40 Ni)]
• α phase at b′ has not changed composition appreciably,
because diffusion in the solid α phase is relatively slow
• composition of the α grains continuously changes
(46 wt% Ni at centers to 40 wt% Ni outer)
• Volume-weighted average composition
42 wt% Ni–58 wt% Cu [α(42 Ni)]
• Solidus line on the phase diagram has been shifted to
higher Ni contents
The degree of displacement of the nonequilibrium solidus curve from
the equilibrium one depends on the rate of cooling; the slower the
cooling rate, the smaller this displacement; if the diffusion rate in the
solid phase increases, this displacement decreases
 Cored vs Equilibrium Phases
• Ca changes as it solidifies.
• Cu-Ni case: First a to solidify has Ca = 46wt%Ni.
Last a to solidify has Ca = 35wt%Ni.

• Fast rate of cooling: • Slow rate of cooling:

Cored structure Equilibrium structure

• Coring can be eliminated by means of a homogenization heat treatment carried out at temperatures below the alloy’s solidus.
During the process, atomic diffusion produces grains that are compositionally homogeneous.
 Equilibrium Diagrams with Intermediate Phases or Compounds
Terminal solid solutions:
only two solid
Cu-Zn phase diagram
phases/composition extremes
Intermediate solid solutions : other
than the two composition extremes
For example Cu-Zn phase diagram:
there are six different solid solutions
➢ two terminal (α & η)
➢ four intermediate b
▪a and  are terminal solid
solutions: exist near the
P

concentration extremities of the
E
phase diagram
▪b are intermediate solid

solutions (or intermediate phases)
▪new types (not eutectic) of
invariant points (e.g. E, P)
 Eutectoid and Peritectic Reactions
Cu-Zn Phase diagram Peritectic transformation  + L 

Point P (78.6 wt%Zn at 598C): three phases are in

equilibrium (,L,) in this case upon heating a solid phase
transforms to liquid and another solid phases:
peritectic reaction:

⎯→
 (76wt%Zn) + L(88wt%Zn) Cooling  (78.6wt%Zn)
⎯⎯⎯
heating

•Point E (74 wt%Zn at 560C): again (as in eutectic) three

phases are in equilibrium ()
Eutectoid reaction
•but in this case upon cooling a solid phase transforms to two  (74wt%Zn)
cooling
 (69.5wt.%Zn) + (78.6wt%Zn)
⎯⎯⎯
solid phases, so-called a eutectoid reaction: heating
 Eutectic, Eutectoid, & Peritectic
• Eutectic - liquid transforms to two solid phases
cool
L heat a + b (For Pb-Sn, 183C, 61.9 wt% Sn)

• Eutectoid – one solid phase transforms to two other solid phases

Solid1 ↔ Solid2 + Solid3
cool
 heat a + Fe3C (For Fe-C, 727C, 0.76 wt% C)

• Peritectic - liquid and one solid phase transform to a 2nd solid phase
Solid1 + Liquid ↔ Solid2
cool
 +L heat ε (For Cu-Zn, 598°C, 78.6 wt% Zn)
 Mechanical Properties: Cu-Ni System
• Effect of solid solution strengthening on:
--Tensile strength (TS) --Ductility (%EL,%AR)

--Peak as a function of Co
--Min. as a function of Co
 Side-by-Side Eutectics: Phase Diagrams

Equilibrium phase diagram of the Ga-As system Phase diagram of the Al203-Si02 system

(mullite)

One of the important single-crystal growth techniques

employed in the fabrication of compound semiconductor
lasers and diodes is known as liquid phase epitaxy Mullite is a compound with nominal composition 3Al203-2Si02, but it
apparently exists over a broader stoichiometric range than does GaAs
Other Phase Diagrams
MgO-Al2O3 diagram:


Four thermodynamically impossible phase diagrams

23
 Ternary systems
Ternary systems have three components: 3 Composition, T and P
The composition at
E is therefore 50%
A, 30% B and 20% C

Isothermal sections: at a chosen value of

temperature and a pressure of one atmosphere