MS31007: Chapter 6

Phase Diagrams
(I-II)

Instructor: Prasana Kumar Sahoo

[email protected]
 Phase diagram
• Solubility Limits
• Phases
• Phase Equilibrium
• Interpretation of Phase Diagrams
• Binary Isomorphous Systems (Cu-Ni)
• Development of Microstructure
• Mechanical Properties
• Binary Eutectic Systems
• Development of Eutectic Alloy Microstructure
• The Kinetics Of Phase Transformations

•
 ISSUES TO ADDRESS...
•When we combine two elements... What equilibrium state do we get?
• In particular, if we specify...
--a composition (e.g., wt%Cu - wt%Ni), and a temperature (T)
then...
How many phases do we get?
What is the composition of each phase?
How much of each phase do we get?
 Alloy, Components and Phases
An alloy is a combination, either in solution or compound, of two or more components
(elements), at least one of which is a metal.
An alloy with two components is called a binary alloy; one with three is a ternary
alloy; one with four is a quaternary alloy.
• Components:
The elements or compounds that are Aluminum- Copper Alloy
mixed initially (Al and Cu).

• Phases:
A phase is a homogenous, physically
distinct and mechanically separable
portion of the material with a given
chemical composition and structure
(a and b).
 Phase Equilibria: Solubility Limit
• Solubility Limit: Maximum concentration for which only a single phase solution exists.

Question: What is the solubility limit for sugar in EFFECT of T and COMPOSITION
water at 20°C?
• Changing T can change number of phases: path A to B
Sugar/Water Phase Diagram • Changing Co can change number of phases: path B to D
100
Solubility
L
Temperature (°C)

80 Limit
(liquid) B(100,70) D(100,90)
60 L + 1 phase 2 phases

(liquid solution S
40
i.e., syrup) (solid
20 sugar)

Water 0 20 40 60 80 100 Sugar A(70, 20)

65
C = Composition (wt% sugar) 2 phases
Answer: 65 wt% sugar.
At 20°C, if C < 65 wt% sugar: syrup
At 20°C, if C > 65 wt% sugar: syrup + sugar
 Phase Diagrams
A phase diagrams is a type of graph used to show the equilibrium conditions between the
thermodynamically-distinct phases; or to show what phases are present in the material system at
various temperature, pressure, and compositions.

• Equilibrium phase diagrams represents relations between 3 phases: solid, liquid, vapour
Triple point: 4.579Torr, (~603Pa; 0.006 atm),
T, P, compositions and quantities of phases at equilibrium. 0.01oC
• Phase diagrams are determined by using slow cooling
conditions, but no information about kinetics
• Phase diagrams allows to predict phase transformations
which occur during T change

One component Phase diagram

The following type of binary systems (contains only two
component) will be discussed:
- complete solubility: isomorphous • Field – 1 phase
• Line – phase coexistence, 2 phases
- eutectic • Triple point – 3 phases 0.01°C, 0.006 atm.
- with intermediate phases or compounds
- involving eutectoid and peritectic reactions Chapt
 A cooling curve showing supercooling

(a) A small part of the water phase diagram. (b) The cooling curve generated as a 7
uniform sample of water cools from temperature TA, liquid, to temperature TC, solid.
 Gibbs Phase Rule
Gibbs' phase rule describes the possible number of degrees of freedom (F) in a closed
system at equilibrium, in terms of the number of separate phases (P) and the number of
chemical components (C) in the system (derived from thermodynamic principles by Josiah W. Gibbs in the 1870s)
Gibbs
F+P=C+2
P: number of phases present at equilibrium
C: number of components needed to describe the F=2
system • salt water. C = 2 (NaCl and water)
• solid magnesium silicates. C = 2 (MgO and SiO2)
• solid MgAl silicates. C = 3 (MgO, Al2O3, SiO2)
F: number of degrees of freedom, e.g. T, P, composition

H2O, C=1 • P = 1 … F = 2 (bivariant phase field) F=0 F=1

• P = 2 … F = 1 (univariant phase curve)
• P = 3 … F = 0 (invariant phase point)

Phase rule: Boiling Water

P = 2 (vapor + liquid) F = 1 (either T or P, but not both)
→ coexistence curve
*once we specify either T or P of boiling water, the other variable is specified automatically
Ice – 18 different crystalline phases!

Pressure inside Earth's inner

hex ice core
(3.64 million bar/ 360 Gpa)

Supercritical
carbon
dioxide
 Phase diagram of hydrogen in the pressure-temperature plane.

The notations are:

C1 , critical point of the liquid-gas transition;
C 2 , critical point of the plasma phase
transition;
Tr 1 , triple-point dielectric solid/dielectric
liquid/dielectric gas;
Tr 2 , triple-point dielectric solid/dielectric
fluid/metallic fluid (dense fully ionized plasma);
Tr 3 , triple-point dielectric solid/metallic
fluid/metallic solid.

The dotted curve corresponds to shock-wave

data in hydrogen (H) and deuterium (D). W is
the metallization area according to Weir et al
(1996).
10
One Component Phase Diagrams : Carbon
 Phase Diagram: Binary Isomorphous Alloy System (C = 2)
Isomorphous: Two elements are completely soluble in each other in solid and liquid state: substitutional
solid state solution; single type of crystal structure exist
Reminder: Hume-Rothery rules: (1) atoms have similar radii; (2) same crystal structure; (3) similar
electronegativity (otherwise may form a compound instead); (4) solute should have higher valence

Degrees of freedom (F): p, T, composition

F+P=C+2=4 F=4-P
T At p = const (or T=const)

F=3-P

0 weight % of B 100%
100% 100%
A B

1. Two components are completely mixable in liquid and solid phase (form a solid state solution), and don’t react
chemically
2. Two components (A and B) can form stable compounds or alloys (for example: A, A2B, A3B, B)
 Phase Diagram: Binary systems
• Indicate phases as a function of T, C and Pressure.
• Focus on: T(°C) Cu-Ni system
- binary systems: 2 components. 1600

- independent variables: T and C 1500 L (liquid)

(P = 1 atm is almost always used).
1400 D
B

Phase Diagram for Cu-Ni system 1300

• 2 phases: 1200 a
• 3 different phase fields
L (liquid) A
L L +a a
a (FCC solid solution) 1100
(FCC solid solution)
1000
Solidus - Temperature where alloy is completely solid. 0 20 40 60 80 100
Cu
Above this line, liquefaction begins. wt% Ni

Liquidus - Temperature where alloy is completely liquid.

Effect of Temperature & Composition (Co)
Below this line, solidification begins. • Changing T can change phases: path A to B.
• Changing C can change phases: path B to D.
 Determination of phase(s) present
A cooling curve for a sample passing • Rule 1: If we know T and C, then we know: how
through a two-phase liquid þ solid region many phases and which phases are present.

• Examples:

Melting points: Cu-Ni phase

Cu = 1085°C, Ni = 1453 °C diagram
 The Lever Rule
If the composition and temperature position is located within a two-phase region, things are more complex. The tie line must be
used in conjunction with lever rule
• Tie line – connects the phases boundary lines on either side in equilibrium– also sometimes called an isotherm. The following
procedure is used:
1. A tie line is constructed across the two-phase region at the temperature of the alloy.
2. The intersections of the tie line and the phase boundaries on either side are noted.
3. Perpendiculars are dropped from these intersections to the horizontal composition axis, from which the composition of each of
the respective phases is read.
lever rule
T(ºC) 1. The tie line is constructed and the overall alloy composition is located
tie line on the tie line.
1300 L (liquid) 2. The fraction of one phase is computed by taking the length of tie line
from the overall alloy composition to the phase boundary for the other
B phase and dividing by the total tie-line length.
TB 3. The fraction of the other phase is determined in the same manner.
a
4. If phase percentages are desired, each phase fraction is multiplied by 100.
1200 (solid) When the composition axis is scaled in weight percent, the phase fractions
R S computed using the lever rule are mass fractions—the mass (or weight) of
a specific phase divided by the total alloy mass (or weight). The mass of
20 3 0C 40 50 each phase is computed from the product of each phase fraction and the
L C0 Ca
wt% Ni total alloy mass.
 Derivation of Lever Rule
Consider the phase diagram for Cu-Ni alloy of composition at C0

Lever rule derivation is accomplished through two conservation-

of-mass expressions.

1. The sum of their mass fractions must be equal to unity

Wα + WL = 1

2. The mass of one of the components (either Cu or Ni) that is

present in both of the phases must be equal to the mass of that
component in the total alloy, or
What fraction of each phase?
Think of the tie line as a lever
ML Ma

ML S C − C0 R C − CL
R S WL = = = a Wa = = 0
ML + Ma R + S Ca − CL R + S Ca − CL
Ma x S = ML x R
 Development Of Microstructure In Isomorphous Alloys
Condition: The cooling occurs very slowly, in that phase equilibrium is continuously maintained
Phase diagram: Cu-Ni system
T(°C) L (liquid) L: 35wt%Ni
Cu-Ni
1300 A system
L: 35 wt% Ni
a: 46 wt% Ni B
35 46
32
C 43

24 D 36 L: 32 wt% Ni
a: 43 wt% Ni
120 0 E
L: 24 wt% Ni
a: 36 wt% Ni
a
(solid)

• Consider Microstructural changes that 110 0

20 30 35 40 50
wt% Ni
accompany the cooling of a C0 = 35 wt% Ni alloy C0
 Eutectic
The term comes from the Greek 'eutektos', meaning 'easily melted’
• A eutectic or eutectic mixture is a mixture of two or more phases at a composition that
has the lowest melting point.
• The phases simultaneously crystallize from molten solution
• The eutectic point is the point where the liquid phase borders directly on the solid α + β phase;
it represents the minimum melting temperature of any possible A B alloy.
The phase diagram displays a simple binary
• The temperature that corresponds to this system composed of two components, A and
point is known as the eutectic temperature. B, which has a eutectic point.
• The proper ratios of phases to obtain a
eutectic is identified by the eutectic point on a
binary phase diagram.
• Not all binary system alloys have a eutectic
point: those that form a solid solution at all
concentrations, such as the gold-silver system,
have no eutectic. An alloy system that has a
eutectic is often referred to as a eutectic system,
or eutectic alloy.
 Binary-Eutectic Systems: Cu – Ag System
Single phase Double phase Three phases
• Solvus – (solid solubility line) BC, GH
• Solidus – AB, FG, BEG (eutectic isotherm)
• Liquidus – AEF

Below line BEG only a limited concentration of Ag

dissolves in Cu (a phase) and vice versa (β phase)

3 single phase (L, a, b)

a: FCC Ag is the solute
β: FCC Cu is the solute

a: mostly Cu
Limited solubility:
b: mostly Ag

• CE : Composition at temperature TE
TE : No liquid below TE
 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
 Solidification of Eutectic Mixtures
• A mixture of lead & tin that is eutectic is only partially soluble when in the solid state. Pb & Sn have
different crystal structures (FCC versus BCC) and Pb atoms are much larger.

• No more than 18.3 weight % solid Sn

can dissolve in solid Pb
• No more than 2.2% of solid Pb can Solidus
dissolve in solid Sn Solidus Liquidus

• The solid lead-tin alloy consists of a

mixture of two solid phases, one
consisting of a maximum of
18.3 wt% Sn (the alpha phase) and Solidus
one consisting of a maximum of
2.2 wt% Pb (the beta phase). Solvus
Solvus

The eutectic invariant point is located at

61.9 wt% Sn and 183°C
 Eutectic lead–tin solder
• For lead & tin the eutectic composition is 61.9 wt% tin and the eutectic temperature is
183ºC -- which makes this mixture useful as solder.
• At 183ºC, compositions of greater than 61.9 wt% tin result in precipitation of a tin-rich solid in
the liquid mixture, whereas compositions of less than 61.9 wt% tin result in precipitation
of lead-rich solid.
The tin-rich side of the silver–tin phase diagram.
 Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 150°C, determine:

-- the phases present at B

Answer: a + b T(°C) Pb-Sn system
-- the phase compositions
Answer: Ca = 11 wt% Sn 300 L (liquid)
Cb = 99 wt% Sn
a L+ a
-- the relative amount of each phase 200 183°C L+b b
18.3 B 61.9 97.8
C - C0
Answer: W = b 150
a Cb - C a
100
a + b
99 - 40 59
= = = 0.67
99 - 11 88
W b = C 0 - Ca 0 11 20 40 60 80 99100
C b - Ca Ca C0 C, wt% Sn Cb
40 - 11 29
= = = 0.33
99 - 11 88
 Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 220°C, determine:
-- the phases present:
Answer: a + L
T(°C)
-- the phase compositions
Answer: Ca = 17 wt% Sn 300
CL = 46 wt% Sn L (liquid)
L+a
-- the relative amount of each phase 220 a
200 L+b b
Answer: 183°C
CL - C0 46 - 40 100
Wa = = a + b
CL - Ca 46 - 17
6
= = 0.21 0 17 20 40 46 60 80 100
29
Ca C0 CL C, wt% Sn
C0 - Ca 23
WL = = = 0.79
CL - Ca 29
 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

T>TL=330 C – liquid alloy with C0 comp 300 L

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
a+ b
100

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)
300
(Pb-Sn System) 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
 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
 Equilibrium Diagrams with Intermediate Compounds
Example: Magnesium-Lead System

M
a+L
L+Mg2Pb ▪Mg2Pb is a intermetallic compound with
a distinct chemical formula (not a
a b+
19 wt% Mg-81 wt% Pb
L+ L solution)
Mg2Pb
▪for this specific example, the intermediate
a+Mg2Pb
b compound exists by itself only at this
Mg2Pb b+ precise composition (region of its existence
Mg2Pb has small width-just a line!!)
▪the phase diagram in Mg- Pb system can
be thought of a two simple eutectic
diagrams joined back to back, one for Mg-
• Mg2Pb melts at approximately 550°C Mg2Pb system and other Mg2Pb-Pb system
• The solubility of Pb in Mg is rather extensive
• Solubility of Mg in Pb is extremely limited
 Eutectic, Eutectoid, & Peritectic
• Eutectic - liquid transforms to two solid phases
L heat a + b
cool
(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)
 Congruent Phase Transformations
Phase transformations may be classified according to whether there is any change in composition for the phases involved.

There are no compositional alterations are said to Incongruent transformations, at least one of the phases experiences a
be congruent transformations change in composition.

Cu-Zn Phase diagram

Ni–Ti phase
diagram, showing a
congruent melting
point for the γ-
phase solid
solution at 1310°C
and 44.9 wt% Ti

• solid solution at 1310C and C = 44.9 wt% Ti

melts without changing of the composition
•P melting at 598C:   +L (peritectic reaction) occurs with
•Congruent transformation: melting of pure metals, changing of phase composition
allotropic transformations are congruent • Incongruent phase transformation
The intermetallic compound Mg2Pb melts congruently •Eutectic, eutectoid and peritectic reactions are examples of
at the point designated M on the Mg-Pb phase diagram incongruent transformations