PHASE DIAGRAMS

Phase – a chemically and structurally homogenous region of a material. Region of

uniform physical and chemical characteristics. Phase boundaries separate two distinct
phases. A single phase system is called homogeneous. A system with two or more
phases is called heterogeneous.
Phase Diagram – a graphic representation showing the phase or phases present for a
given composition, temperature and pressure.
Component – the chemical elements which make up the alloy.
Solvent atoms: primary atomic species. Host atoms
Solute atoms: the impurities. Normally the minor component
Solubility Limit - Maximum concentration of solute atoms that may dissolve in
the solvent to form a solid solution. The excess of solute forms another phase of
different composition. Example: water-sugar
Phase Diagrams of Pure Substances
•Predicts the stable phase as a function of Ptotal and T. Example: water can exist in
solid, liquid and vapor phases, depending on the conditions of temperature and
pressure.
•Characteristic shape punctuated by unique points.
– Phase equilibrium lines
– Triple Point (three different phases of water in equilibrium)
– Critical Point
Example: In the pressure-temperature (PT) phase diagram of water there exists a
triple point at low pressure (4.579 torr) and low temperature (0.0098oC) where solid,
liquid and vapor phases of water coexists.
Vaporization Line – Liquid and vapor coexists
Freezing Line – Liquid and solid coexist.
Sublimation Line – Solid and vapor coexist
 Gibbs Phase Rule
From thermodynamic considerations, J.W. Gibbs (1839-1903 American physicist –
University of Yale) derived the following equation:
P+F=C+2
Where: P = number of phases which coexists in a given system; F = degrees of
freedom; C = number of components in the system ; 2 = one can vary temperature and
pressure
F = 0 zero degrees of freedom. Neither P or T can be change (a point–invariant point)
F = 1 one degree of freedom. One variable (P or T) can be changed independently (a
line)
F = 2 two degrees of freedom. Two variables (P or T) can be changed independently
(an area).
Example
- For pure substance where P and T can be changed
P+F=C+2=1+2=3
Pure substance in a triple point, then C = 1 (one component) and P = 3 (number of
phases that coexist)
The value of F is zero (zero degrees of freedom) the three phases coexist in a point.
- For pure substance where P and T can be changed
P+F=1+2=3
Pure substance in a freezing line, then
C = 1 (one component) and P = 2 (number of phases that coexist)
The value of F is one (one degree of freedom) the two phases (solid and liquid)
coexist in a line.
 PHASE
•Homogeneous portion of the system with uniform physical and chemical
characteristics
– Sugar – water syrup (H20 and C12 H22 O11)
– Solid sugar (C12 H22 O11)
•A difference in either physical or chemical properties constitutes a phase
– Water and ice
– FCC and BCC polymorphic forms of an element
Microstructure
The structure observed under a microscope

Iron-chromium alloy – one phase (solid solution)

Al Brake – more than one phase

 Phase Equilibria
• Free energy: a function of the internal energy of a system
• Equilibrium: a system is at equilibrium if its free energy is at a minimum
• Phase equilibrium: for a system which has more than one phase
• Phase Diagram is a diagram with T and Composition as axes. They define the
stability of the phases that can occur in an alloy system at constant pressure (P). The
plots consist of temperature (vertical) axis and compositional (horizontal) axis.
• Constitution: is described by
(a) the phases present
(b) the composition of each phase
(c) the weight fraction of each phase
Binary isomorphous systems
• Binary alloy: A mixture of two metals is called a binary alloy and constitute a two-
component system.
• Each metallic element in an alloy is called a separate component. [Sometimes a
compound is considered a component, (e.g., iron carbide)]
• Isomorphous System: In some metallic systems, the two elements are completely
soluble in each other in both the liquid and solid states. In these systems only a single
type of crystal structure exists for all compositions of the components (alloy) and
therefore it is called isomorphous system.
Example: Binary Isomorphous System (Cu – Ni)

T<1085oC: Cu & Ni are mutually

soluble in solid state – complete
solubility →
• both have the same FCC structures,
• atomic radii and electronegativities
are nearly identical
• similar valences
→ isomorphous

Interpretation of Phase Diagrams

Constitution: is described by
(a) the phases present
(b) the composition of each phase
(c) the weight fraction of each phase
(a) Phases Present
Point A: at T=1100oC
60wt% Ni – 40wt% Cu
Only α phase is present
Point B: at T= 1250oC
35wt%Ni – 65wt% Cu
Both α & liquid phases are present
at equilibrium

(b) Composition of each phase

Single phase:
Point A:
60wt%Ni – 40%Cu alloy at 1100oC
Two-phase region:
Tie line: across the two-phase
region at the temperature of the
alloy
Point B: T=1250oC
Composition of Liquid phase:
CL=31.5wt%Ni – 68.5%Cu
Composition of α phase:
Cα=42.5wt%Ni- 57.5wt%Cu
(c) Weight fraction of each phase
Single phase: 100% Ex: Point A: 100% α phase
Two-phase region:
Ex: Point B
LEVER RULE
(Inverse Lever Rule)
S
WL =
R+S
C − Co
WL = α
Cα − CL

R Co − C L
Wα = =
R + S Cα − CL
 co − c L 35 − 31.5
Example: Point B: Wα = = = 0.32 or 32%
c s − c L 42.5 − 31.5
C0 = 35wt%Ni
c s − co 42.5 − 35
Cα = 42.5%, CL = 31.5% WL = = = 0.68 or 68%
c s − c L 42.5 − 31.5
Volume fraction
For an alloy consisting of α and β phases, the volume fraction of the α phase is
defined as
vα
Vα = , Vα + Vβ = 1 Then, the weight fractions are
vα + v β
v β ρβ Where να and νβ are the
v α ρα
Wα = ; Wβ = volumes of α and β
v α ρα + v β ρ β v α ρα + v β ρ β
Wα W β
ρα ρ
Vα = Vβ =
β
Wα W β W W
+ α
+ β
ρα ρβ ρα ρ β
Derivation of the lever rule
1) All material must be in one phase or the other:
Wα + WL = 1

2) Mass of a component that is present in both phases equal to the mass of the
component in one phase + mass of the component in the second phase:
Wα cα + WL c L = c o
3) Solution of these equations gives us the Lever rule.
cα − c o
co − cL WL =
Wα = cα − c L
cα − c L
Equilibrium Cooling - Development of Microstructure in
Isomorphous Alloys

Example:
35wt%Cu-65wt%Ni
system – Slow cooling
from point a to point e
a: 1300oC: complete
liquid with 35wt%Cu-
65wt%Ni
b: ~1260oC: first solid begin
to form
(α-46wt%Ni)
c: ~1250oC: α-43wt%Ni, L-
32wt%Ni
d:~1220oC: last liquid to
solidify
e: 35wt%Cu – 65wt%Ni
solid phase
Nonequilibrium Cooling - Development of Microstructure
in Isomorphous Alloys

Fast cooling

Compositional
changes require
diffusion
•Diffusion in the solid state is very slow. ⇒ The new layers
that solidify on top of the existing grains have the equilibrium
composition at that temperature ⇒ Formation of layered
(cored) grains. Tie-line method to determine the composition
of the solid phase is invalid.
•The tie-line method works for the liquid phase, where
diffusion is fast.
•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.
Complete solidification
occurs at lower
temperature and higher
Nickel concentration than
equilibrium
Solid can’t freeze fast
enough: solidus line
effectively shifted to
higher Ni concentrations.
Shift increases with faster
cooling rates, slower
diffusion
Mechanical properties of isomorphous alloys

Solid solution strengthening

 Invariant Points in Binary Systems
•Binary alloys – two components at ambient pressure. Gibbs rule
states that
P + F = 2 + 1= 3.
•If three phases coexists (P = 3), they coexist at a point (zero
degrees of freedom – the invariant point, at a specific temperature
and chemical composition
•Types of invariant points:
eutectic, eutectoid, peritectic
peritectoid, monotectic etc.
 Some Important Invariant Points

L+α L
Cooling L →α + β L+β
Eutectic Heating L ←α + β α+β

Cooling γ →α +β α+γ γ β+γ

Eutectoid Heating γ ←α +β
α+β

Cooling δ +L→γ δ +L
Peritectic δ +L←γ
Heating
δ+γ γ +L
γ
eutectic: Liquid/solid reaction
eutectoid: solid/solid reaction