PHASE DIAGRAMS AND MICROSTRUCTURES

Lecture 9

ChEg_3161
Year III

SCBE-AAiT-AAU
Taye Zewdu

Focal points in this lecture:

(1) Terminology associated with phase diagrams and phase
transformations;
(2)Pressuretemperature phase diagrams for pure materials;
(3)The interpretation of phase diagrams;
(4)Some of the common and relatively simple binary phase
diagrams, including that for the ironcarbon system; and
(5)The development of equilibrium microstructures, upon
cooling,

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Key Words
(1)Component: pure metal and/or compound of which an alloy
is composed
(2)System: a specific body of material under consideration or
series of possible alloys consisting of the same components
(3)Solubility limit: a maximum concentration of solute atoms
that may dissolve in the solvent to form a solid solution
(4)Phase: a homogeneous portion of a system that has uniform
physical and chemical characteristics
(5)Microstructure: Visible under optical or electron microscopes
(6)Equilibrium: When the free energy of a system is at a
minimum under some specified combination of temperature,
pressure, and composition.

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phases: path A to B.
Changing Co can change # of
phases: path B to D.

80

L
(liquid)

60

40

(liquid solution
i.e., syrup)

20

Pure
Water

Aluminum-Copper alloy

B
Solubility
Limit

+
S
(solid
sugar)

20
40
6065 80
100
Co=Composition (wt% sugar)

Pure
Sugar

Changing T can change # of

Temperature (C)

100

Water-Sugar System

b (lighter
phase)
a (darker
phase)

Adapted from Callister

6e.

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Phase Diagrams
Tell us about phases as function of T, Co, P.
Tools to determine:
the number and types of phases,
the wt% of each phase, and
the composition of each phase
Independent variables: T and Co (P = 1atm is always used).
Unary, binary and ternary phase diagrams
The phases can be liquidus, solidus or the combination
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One-component (Or Unary) Phase Diagrams

Also called P-T diagrams
The phase diagram is for a pure substance; this means that
pressure and temperature are the variables
A good example is Pressuretemperature phase diagram for H2O

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Binary Phase Diagrams

Maps that represent the relationships between temperature and
the compositions and quantities of phases at equilibrium, which
influence the microstructure of an alloy
Isomorphous systems refer to complete liquid and solid
solubility of two components.
Cu-Ni system PD

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Understanding Phase Diagrams

Rule 1 Phases Present: If we know T and Co,
then we know the # and types of phases present.

Cu-Ni
phase
diagram

Example

B(T, Co) has two phases: + L

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If we know T and
Co, then we know the composition of each phase.
Rule 2 Determination of Phase Compositions:

Example

T(C)
TA

Co = 35wt%Ni
1300 L (liquid)
At TA:
B
Only Liquid (L)
TB
CL = Co ( = 35wt% Ni)
a
+
At TD:
L
1200
D
T
Only Solida)(
D
Ca = Co ( = 35wt% Ni
)
20
3032 35
CLCo
At TB:
Botha and L
CL = Cliquidus( = 32wt% Ni here)
Ca = Csolidus( = 43wt% Ni here)

tie line dus

i
liqu

a
L + dus
sol

a
(solid)
4043

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Ca wt% Ni

If we know T and
Co, then we know the amount of each phase (weight fractions of
phases, wt%).
Rule 3 Determination of Phase Amounts:

Example

T(C)

Co = 35wt%Ni
At TA: Only Liquid (L)
WL = 100wt%, Wa = 0
At TD: Only Solid (a)
WL = 0, Wa = 100wt%
At TB: Both a and L

S
43 35
73wt %
WL
R S 43 32
Wa

R
RS

TA
1300

L (liquid)

B
R S

TB
1200

TD
20

tie line dus

i
liqu

L+

a
+
L
s
idu
sol

a
(solid)

3032 35 4043

CLCo

50

Ca
wt% Ni

= 27wt%
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Derivation of the Lever Rule

- Sum of weight fractions:

WL Wa 1

- Conservation of mass (Ni):

Co WL CL Wa Ca

- Combine above equations:

Ca Co S

WL
Ca CL R S

Co CL R
Wa
Ca CL R S

- A geometric interpretation:

Co

CL
R

WL

Ca
S

Wa

moment equilibrium:

WLR WaS
1 Wa
solving gives Lever Rule
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Here you have a class exercise!

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Calculate the amount of each phase present in 1 kg of a 50 wt.% Ni50 wt.% Cu alloy at
a) 1400C,
b) 1300C and
c) 1200C.

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Adapted from Fig. 9.3, Callister 8e.

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For multiphase alloys, it is convenient to specify relative phase

amount in terms of volume fraction rather than mass fraction.
For an alloy consisting of and phases, the volume fraction of the
phase,V, is defined as:

However, the densities are computed from

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Lecture 10

Equilibrium Cooling

Microstructure in Isomorphous Alloys

Case I- Solidification at
very slow cooling
Phase equilibrium is
continously maintained
Compositions of the L
and phases follow the
Liquidus and solidus lines.

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Adapted from Fig. 9.4, Callister 8e.

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Non-equilibrium Cooling

Case II- Solidification at

slow diffusion rates
Assume equilibrium in
liquid phase
Average composition
Segregation
Cored structures

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Adapted from Fig. 9.5, Callister 8e.

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Equilibrium Vs Non-equilibrium Cooling

Ca changes as we solidify.
Cu-Ni case:

First a to solidify has Ca = 46wt%Ni.

Last a to solidify has Ca = 35wt%Ni.

Fast rate of cooling:

Cored structure
First a to solidfy:
46wt%Ni
Last a to solidfy:
< 35wt%Ni

Slow rate of cooling:

Equilibrium structure
Uniform Ca:
35wt%Ni

MECHANICAL PROPERTIES: Cu-Ni System

Effect of solid solution strengthening on:

Tensile strength (TS)

Peak as a function of Co

Adapted from Fig. 9.6, Callister 8e.

Ductility (%EL,%AR)
Min. as a function of Co

Binary-eutectic Systems
Eutectic- has a special composition with a min. melting T.
Ex.: Cu-Ag system
3 single phase regions
(L, a b)
Limited solubility:
a: mostly Cu
b: mostly Ni
TE: No liquid below TE
CE: Min. melting T
composition

Eutectic reaction

Pb-Sn EUTECTIC SYSTEM

For a 40wt%Sn-60wt%Pb
alloy at 150C, find...
the phases present: a + b
the compositions of
the phases:
Ca = 11wt%Sn
Cb = 99wt%Sn
the relative amounts
of each phase:

59
67wt %
88
29
33wt %
Wb
88

Wa

Tinbismuth (Sn-Bi) phase diagram.

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Microstructures in Eutectic Systems-I

Co < 2wt%Sn
Result:

polycrystal of a grains.

Pb-Sn
system
Adapted from Fig. 9.9, Callister 8e.

Microstructures in Eutectic Systems-II

2wt%Sn < Co < 18.3wt%Sn

Result:

a polycrystal with fine b crystals

Pb-Sn
system
Adapted from Fig. 9.10, Callister 68.

Microstructures in Eutectic Systems-III

Co = CE
Result: Eutectic

microstructure
--alternating layers of a and b crystals.

Pb-Sn
system

Micrograph of Pb-Sn
eutectic
microstructure

160m
Adapted from Fig. 9.12, Callister 6e.
(Fig. 9.12 from Metals Handbook, Vol.
9, 9th ed., Metallography and
Microstructures, American Society
for Metals, Materials Park, OH, 1985.)

Adapted from Fig. 9.11, Callister 8e.

Microstructures in Eutectic Systems-IV

18.3wt%Sn < Co < 61.9wt%Sn
Result: a crystals and a eutectic

microstructure

Pb-Sn
system

Just above TE:

Ca = 18.3wt%Sn
CL = 61.9wt%Sn
Wa = S =50wt%
R+S
WL = (1-Wa) =50wt%

Just below TE:

Ca = 18.3wt%Sn
Cb = 97.8wt%Sn
Wa = S =73wt%
R+S
Wb = 27wt%
Adapted from Fig. 9.14, Callister 8e.

H2ONaCl phase diagram

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Primary and Eutectic fractions

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EQUILIBRIUM DIAGRAMS HAVING INTERMEDIATE PHASES

OR COMPOUNDS

Terminal solid solutions, exist over composition ranges near

the concentration extremities of the phase diagram.
Eg. The eutectic coppersilver and leadtin phase diagrams
Intermediate solid solutions (or intermediate phases) may
be found at other than the two composition extremes.
Eg. The copperzinc system
-there are some invariant points and reactions
-there are six different solid solutionstwo terminal ( and
) and four intermediate (, , , and )
The commercial brasses are copper-rich copperzinc alloys; Eg.
Cartridge brass :70 wt% Cu30 wt% Zn and a microstructure
consisting of a single phase

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Intermetallic compounds

For some systems, discrete intermediate compounds rather than

solid solutions may be found on the phase diagram, and these
compounds have distinct chemical formulas; for metalmetal
systems, they are called intermetallic compounds.
For example, magnesiumlead system

The compound Mg2Pb exists by itself only at 19 wt% Mg81 wt% Pb

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EUTECTOID AND PERITECTIC REACTIONS

Eutectic: liquid transforms to two solid phases
Eutectoid: one solid phase to two other solid phases
Peritectic: liquid and one solid phase transform to a second
solid phase
In all cases, three phases are at equilibrium.

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Eutectoid reaction

Peritectic reaction

Phase transformations for which there are no compositional

alterations are said to be congruent transformations.
Eg. Allotropic transformations, pure substance transformations
Incongruent transformations, at least one of the phases will
experience a change in composition.
Eg. Isomorphous and eutectic transformations
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THE GIBBS PHASE RULE

This rule represents a criterion for the number of phases that
will coexist within a system at equilibrium, and is expressed
by the simple equation:
P+F=C+N
Where: P is the number of phases
F is the degree of freedom or the no. of externally
controlled variables
C is the number of components in the system
N is the number of non-compositional variables

F is the number of variables that can be changed

independently without altering the number of phases that
coexist at equilibrium.

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Binary T-C PDs

P+F=2+1=3
Single phase fields
F=3-1=2
Two phase fields
F=3-2=1
Three phases at Eq.
F=3-3=0

The phase rule helps in analyzing for

non-equilibrium conditions.
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The most important Phase Diagram

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