Phase Diagrams (also called equilibrium or

constitution diagrams)
Uses
1. phases present – regions of stability
2. chemical composition of each phase
3. amount of each phase (using lever rule)
Coordinates
- temperature
- composition in wt% (practical metallurgy);
in some cases, could be atomic %
Constructed under the condition of constant
pressure (atmospheric)
Apply only under equilibrium conditions –
equilibrium heating or cooling means a very
slow rate of temperature change
In contrast, drastic or rapid cooling from a high
to a low temperature would produce non-
equilibrium phases and would tend to reflect
the high temperature phases
Isomorphous System – complete solubility in both the liquid and solid state
with a single crystal structure (forms an ideal solution in both phases)
• Consider point x in the previous slide
• Also, consider point y which is in a two phase
region; this represents the average
composition of the alloy
• Note the pertinent parts of the phase diagram
 In a two phase region (mixture of two phases), alloy composition is the
average composition of the alloy as a whole with compositions of the phases
fixed at a constant temperature and pressure (atmospheric)
• By shifting alloy composition from point y to
point z, the compositions of the phases
present remain the same;
• However, only the relative amounts of the
phases change
• (Solve problem 11.2 in the textbook for
assignment)
• Note the reverse process of melting follows
the same principles
From points c to b, both liquid and solid phases become richer in component
B but their relative amounts change while average alloy composition is
constant; Steady diffusion of B atoms from the liquid towards the center of
the solid and a corresponding diffusion of A atoms in the reverse direction
Free energy curves – points of contact of the common tangent determine the
compositions of the phases in a two-phase mixture; note shifting of the point
of intersection of the free energy curves from pure nickel to pure copper
 Maxima and Minima
• Alloy systems whose free energy-composition
curves intersect at two compositions unlike
the isomorphous system which intersects at
only one composition
• As a result, liquidus and solidus of these phase
diagrams are shaped to form either a
minimum or a maximum
 Solid curve has less curvature; With decreasing temperature,
intersections of the free energy curves occur first at the pure
components and afterwards move inwards toward the center; Note
the two common tangents at Tb
Solid curve has more curvature; As temperature is lowered, it first
meets at a single point and afterwards splits into two intersections
• When boundaries of a two phase region
intersect, they meet at a maximum or a minimum
and both solidus and liquidus curves are tangent
to each other and to an isothermal line (at Tc and
Tb, respectively) at the point of intersection
• Congruent points – freezing is completed with no
change in composition or temperature (in this
case, however, it is a solid solution);similar to
freezing of a pure metal;
Singular points – congruent points or at the
compositions of the pure components (define
the limits of a two phase region)
Important rule in an equilibrium diagram –
single phase regions or fields are always
separated by two phase regions except at
singular points
Maxima appears at 601◦C and 13% Li
 Superlattice or superstructure
Component elements at proper compositions
arrange themselves in a stable configuration
over a long range order called an ordered
structure particularly at low temperatures
Notice in the next slide that while gold and
copper form a continuous series of solid
solutions at high temperatures
At low temperatures, gold and copper atoms alternate to form
the maximum number of Au-Cu bonds and the minimum Au-Au
and Cu-Cu bonds; Note the presence of five superlattices in the
gold – copper phase diagram (each superlattice is a phase)
 Negative deviations of the activities- components have a definite
attraction for each other or a preference for an opposite atom as a
neighbor
 Two opposing factors at high temperatures
which merely lead to short range order and not
long range order

1. Attraction of unlike atoms for each other

2. Disrupting influence of thermal motion
(atomic movements are too rapid which
destroys the extensive periodic arrangement
of alternating gold and copper atoms)
Domain – ordered region of a crystal; a grain will
contain a number of domains
• Upper left grain contains 3 domains
• Lower right grain has two domains
• Dashed line are the domain boundaries where an
A atom faces another A atom; also, a B atom
faces another B atom (inside the domain, each
atom is surrounded by atoms of the opposite
kind)
• At the juncture between two domains, the
sequence of A and B atoms reversed; they are
referred to as antiphase domains and antiphase
boundaries
Referring to left figure, copper atoms at face
centers and gold atoms at the corners
 Miscibility Gaps
• Referrring to next slide, gold and nickel forms
an alloy system that freezes into solid
solutions in all proportions
• However, Au and Ni tends to segregate as
temperature is lowered
• Below 810.3◦C, presence of two phases which
are both FCC – α1 (based on gold with nickel as
solute) and α2 (based on nickel with gold as
solute)
This two-phase field in the previous slide –
miscibility gap
Conditions for its formation
1. both components of same crystal
structure
2. two solvus lines meet at a high
temperature to separate two phase
region from the single phase regions
 Two possible types of atomic bonds
1. Bonds between atoms of the same kind (A-A or B-B)
2. Bonds between unlike atoms (A-B)

Chemical bonding energy – associated with each bond

between a pair of atoms (εAA or εBB , and εAB)

Total energy – sum of the energies of all the bonds

between neighboring atoms
- the lower the total energy, the more
stable the metal
 If εAB = ½ (εAA + εBB ) random solid
solution
If εAB < ½ (εAA + εBB ) short range order
at higher temperatures and long range
order at lower temperatures (negative
deviation)
If εAB > ½ (εAA + εBB ) segregation and
precipitation (positive deviation)
Eutectic Systems
• Unlike the miscibility gap, components in eutectic
systems do not need to have the same crystal
structure or necessarily have to be chemically
similar
• Locate eutectic point
• Eutectic composition – freezes at a lower
temperature than all other compositions (note
that it freezes at a constant temperature called
the eutectic temperature);
-It freezes to form a mixture of two
different solid phases (relative amount is
100% eutectic mixture)
• Describe freezing of an alloy with 24% copper
• Describe freezing of an alloy with less than 8.8%
copper; Note the solvus line indicating decreasing
solubility with decreasing temperature
• Distinguish components from constituents
(distinct appearance under the microscope)
- Also distinguish pro-eutectic or primary
phase from eutectic mixture (composed of two
phases)
• Continuous matrix is alpha phase (pro-eutectic or
primary alpha is continuous with eutectic alpha)
• Small dark platelets is beta phase (called eutectic
beta) in the eutectic mixture
• In the next slide, describe freezing of an alloy with 50%
copper
- Primary or pro-eutectic beta is the oval-shaped dark
areas
- note the eutectic mixture comprising of eutectic
alpha and eutectic beta
- Eutectic alpha is the continuous phase (primary or
pro-eutectic beta is not continuous with the eutectic
beta)

• Describe also freezing of an alloy with a composition of

more than 92% copper
• Peritectic transformation – a reaction between
a liquid and a solid that forms a new and
different solid phase
• In the next slide, a peritectic point appears at
the upper left hand corner
 Considering the iron and nickel
components
• Identical apparent atomic diameters
• Belong to group VIII and are chemically similar
• Ni is FCC; In contrast, Fe is FCC only at
intermediate temperatures while BCC at
temperatures above 1394◦C and below 912◦C
(consequently, iron-nickel alloys are BCC at the
upper and lower left hand corners of the phase
diagram); Addition of nickel to iron increases the
stability of the FCC phase
• Presence of a superlattice FeNi3
• Alloys with less than 3.4% Ni freeze directly to
δ BCC while alloys with more than 6.2% Ni
freeze directly to ϒ FCC
• Peritectic point (describe freezing of peritectic
composition)
• Describe freezing of alloys immediately to the
left and to the right of the peritectic
composition
• Monotectics – a liquid phase transforms into a
solid phase and a liquid phase of different
composition; miscibility gaps in the liquid
state (liquid miscibility gap or a condition
where two liquids are immiscible lies just to
the right of the monotectic point as shown in
the next slide)
• Note the eutectic point at the lower right
portion of the phase diagram
• Representative of an alloy system where
components that do not mix in the solid state
(terminal solid solutions are nearly pure
elements)
• Intermediate phases or intermetallic phases
- solid solutions
- intermetallic compounds – single phase
fields that are vertical lines
• Terminal phases
Non-equilibrium Solidification of Alloys
(i.e., as cast cored structure)
• Homogenization – as cast ingots or castings
are heated to elevated temperatures below T7
to accelerate solid state diffusion in order to
eliminate the cored structure