Formations of Alloys,

Phase Diagrams
Chapter 9

1
Automotive Industry

Aluminum foam for

shock absorption

2
 Aerospace Industry

F/A22 Raptor

Single-Crystal
Titanium panels

Pratt and Whitney F119 Engine 3

Formations of Alloys

4
 Phases Formation of Alloys

• PHASE is a homogeneous part of a system

which exhibits uniform physical and chemical
characteristics.
• Phases exist over a range of compositions,
temperatures (and pressures): gas, liquid, solid

• Phase transition - conversion between these

states 5
 Formation of Alloys
Elements (components)
Elements (components)
The elements (or compounds)
are mixed to make an alloy
(Al and Cu)

• The chemical composition is

the concentration of each
Phase α Phase β
element present in an alloy.

Phase
Physically and/or chemically Aluminum atom
uniform and distinct regions Copper atom
in the material.
6
Callister & Rethwisch
 Alloys
Formation of Alloys

Alloying elements (or foreign atoms) have been added

intentionally to impart properties.

• An alloy contains two or more elements.

• Alloys are defined by a chemical composition which
expresses how much of each element is present:

• Mild steel (Fe, 0.4% C, 0.75% Mn)

• 304 stainless steel (Fe, 0.08%C, 19%Cr, 9.25%Ni, 2%Mn)
• 6061 aluminum alloy (Al, 1.2%Mg, 0.6%Si, 0.3%Cu, 0.2%Cr)
• Lead solder (60% Sn, 40% Pb)

7
 Formation of Alloys
Alloys can have more than one phase!

Nature of solid phases in alloys

• Solid solutions
• Intermediate phases

Solid solutions - homogenies phase that contains

two or more elements. Solute atoms are randomly and
uniformly distributed within the solid.

The addition of foreign atoms will result in formation of

a solid solution
- Solute - minor concentration
- Solvent (base)
8
 Formation of Alloys

Solid Solutions
 
Substitutional Interstitial
Solute atoms replace Solute atoms fill the
the matrix atoms holes among matrix atoms
(only small atoms)

9
 Formation of Alloys

Solid Solutions
• Solute (foreign) atoms - atom different than the host
atoms!

Substitutional Interstitial

solid solubility
Al in Cu
Ni in Cu
10
 Formation of Alloys

Substitutional Solid Solutions - rules

• Crystal –structure Factor

• Relative-size Factor
• Chemical-affinity Factor
• Relative-valence Factor

11
 Formation of Alloys
Intermediate Phases

• Intermetallic compounds
A compound of two elements that has distinct formula.
Structure with the simple whole-number fixed ratios of
the component atoms (cementite – Fe3C – 6.67%C)

• Intermediate solid solutions

- Range of compositions, formula
- Brass: Cu (fcc) + Zn (hcp),
- b (bcc) – approximately one Zn atom to one of Cu

12
Phase Diagrams

13
 Characteristics of Phase
ONE COMPONENT PHASE DIAGRAM
• Phase depends on the physical state.

14
Phase diagram of water
 Binary Phase Diagrams
Phase diagram indicates which phases are present at
equilibrium as a function of composition, temperature
and pressure.

➢ In this course we’ll only consider:

• Binary phase diagrams - only 2 elements

(components)

• Systems where the pressure is fixed (1 atm)

15
Experimental method for phase diagrams construction

Cooling curves

Series of cooling
curves in a completely
soluble system.
The dotted line
indicates the form of
the phase diagram.

• DSC – Differential Scanning Calorimeter 16

9.a. Isomorphous phase diagram

• Isomorphous → complete liquid and solid

solubility

• Copper (Cu) – Nickel (Ni) phase diagram

- Cu - FCC, Ni - FCC
- Similar size of atoms
- Approximately ideal solid solution

17
 Cu-Ni Phase Diagram
T(°C) •How many components are
1600 there? What are they?
Cu & Ni
1500 L (liquid)
•How many phases are
1400 there? What are they?

1300 L (liquid)
a (FCC solid solution)
1200 a

1100
(FCC solid •How many phase fields are
there? What are they?
solution)
1000 L
0 20 40 60 80 10 0
Cu wt% Ni L+a
a
Terminology: liquidus, solidus Callister & Rethwisch
18
 Horizontal axis - Composition

20%Ni,
80%Cu 40%Ni, 75%Ni,
60%Cu 25%Cu
60%Ni,
40%Cu

• Chemical composition of an alloy is typically given

as a weight (wt.%) or atomic percent (at.%)
19
Interpreting Phase Diagrams

What phases
are present?
20
 What Phases are Present?

Rule #1: T(°C)

1600

1500
L (liquid)
For any temperature (T)

B(1250,35)
and initial composition 1400
(Co), the phase diagram
indicates: 1300 a
(FCC solid
• How many phases 1200 solution)
are present.
1100 A(1100,60)
• What phases are
present. 1000
0 20 40 60 80 10 0
Cu wt% Ni Ni

Callister & Rethwisch 21

 What Phases are Present?

Examples: T(°C)
1600

• Point A 1500
L (liquid)

B(1250,35)
(1100°C, 60% Ni)
1400
 one phase:
α 1300 a
(FCC solid
1200 solution)
• Point B
(1250°C, 35% Ni) 1100 A(1100,60)
 two phases:
1000
L+α 0 20 40 60 80 10 0
Cu wt% Ni Ni
Callister & Rethwisch
22
Determination of Phase Compositions

What’s the
composition of
each phase?
23
 What is the Composition of Each Phase?
Rule #2:
For any temperature (T) and initial composition (C0), the
phase diagram indicates the composition of each phase
present.

Callister & Rethwisch 24

• The compositions of the solid and the liquid are
fixed at constant temperatures.

• Draw an isothermal (a tie line) through the

given point

• The intersections of the tie line with the

boundaries of the two-phase region determine the
composition of the phases

25
What is the Composition of Each Phase?
Composition determined by the tie line!

•TA - Liquid (L)

CL= C0 = 35% Ni
• TD- Solid (a)
Ca = C0 = 35% Ni
• TB- L and a

Example:
C0 = 35%Ni, 65%Cu

Ca = Csolidus (43 wt% Ni)

CL = Cliquidus (32 wt% Ni)
Callister & Rethwisch
 Take a Breather….

http://www.fly.faa.gov/carf/
27
 Determination of Phase Amounts

How much
(amount)
of each phase is
present? 28
How Much of Each Phase is Present?
Rule #3
For any given T and C0, the phase diagram also indicates
the AMOUNT of each phase present.

29
 Lever Rule
• Sum of phase weight fractions: WL + Wa = 1
• Overall composition: C0 = WLCL + WaCa

Geometrical Interpretation Equilibrating Moments

WLR = WaS
(WL = 1 - Wa)
30
 Lever Rule
Determination of phase amount (weight fraction)
How much of each phase is present?

W. Fraction solid (a) = average composition - composition of liquid

composition of solid - composition of liquid

W. Fraction liquid (L) = composition of solid - average composition

composition of solid - composition of liquid

Solid weight fraction (Wa )+ Liquid weight fraction (WL) = 1

31
32
 Developing a Microstructure
Cooling a Binary Cu-Ni Alloy
• Equilibrium Cooling
• Nonequilibrium Cooling (segregation)
C0 = 35 wt% Ni

• Solidification starts:
1270 oC
CL = 0.35
Ca = 0.46

• Solidification ends:
1220 oC
Cu CL = 0.24
Ca = 0.35
33
Callister & Rethwisch
 Cored vs Equilibrium Structures
Nonequilibrium Cooling (segregation within the dendrites)

Very SLOW rate of cooling: FAST rate of cooling:

Equilibrium structure Cored structure

Uniform Ca: 35 wt% Ni

First a to solidify:
46 wt% Ni
Last a to solidify:
< 35 wt% Ni

34
Callister & Rethwisch
Mechanical Properties of Cu-Ni Alloys
Solute Strengthening!

35
 9.b. Eutectic Phase Digrams
Binary eutectic systems occur when 2 elements completely
dissolve into each other in the liquid state, but have only
limited solubility in the solid state.
Temperature

More than one solid phase

exists in these systems.
a+L b+L
a b Which phases are present
depends, as before, on the
temperature and the
a+b composition of the material.
a+b
A Composition B

36
 Eutectic Phase Diagram
cooling
Liquid a+b
heating Eutectic mixture (E)

Eutectic reaction: two solid phases form

simultaneously from a single liquid phase.

• Eutectic composition – freezes at a lower temperature

than all other compositions
•Eutectic point: three phases in equilibrium at a
constant composition and at a constant temperature

37
Cu-Ag
(jewelry)
a a+L E b+L
b

E+a E+b
a+b
Hypoeutectic
a+b
The alloy cooled from liquid has 25wt.% Ag.
When it cools down:
1. primary (a phase) first,
a
2. E - the remaining liquid phase will go
through the eutectic reaction, forming
E(a+ b).
38
Cu-Ag
(jewelry)
a a+L E b+L
b

E+a E+b

a+b

Hypoeutectic Hypereutectic
b
a+b
a a+b

39
 Determine the chemical composition:

E+a E+b

a+b

Alloy Co = 50%Cu, 50%Ag, Alloy Co = 90%Cu,10%Ag,

T=800oC? T=850oC?
• L: ~68%Ag, 32%Cu • L: ~ 88%Ag, 12%Cu
• a: ~8%Ag, 92%Cu • b: ~ 92%Ag, 8%Cu
40
Pb-Sn (Led-Tin) phase diagram
What is one common
application of Pb-Sn
alloy? SOLDER joint

Are electronics
300
companies in the
T(ºC) L USA allowed to use
a L+ a
200 183 L+b b Pb-Sn alloys? NO!
TE 61.9
a+ E b+ E
100 a+b

0 20 40 60 80 100
Pb Sn
Hypoeutectic: C0 = 50 wt% Sn Hypereutectic
eutectic: C0 = 61.9 wt% Sn

a b
a b
a a b b
a b
a b
175 mm
160 mm
41
Callister & Rethwisch eutectic micro-constituent
 Pb-Sn
Microstructures
L: C o wt%Sn
T(°C)
4 00

• Co - between 2 and L
L
18.3 wt% Sn. 3 00 a
L+ a
a : C o wt%Sn
• The result is: a
2 00
a + b (no eutectic) TE 18.3
a
b
1 00
a+ b a+ b
a+ E
Pb 0 10 20 30
Co wt% Sn
2 18.3

Adapted from Fig. 9.10,

Callister 6e. 42
 Chemical composition Pb-Sn
•Co between 18.3 and 97.8 wt% Sn results in a combination of a phase
& eutectic regions
Just above TE:

T(°C)

300 L
Ca = 18.3 wt% Sn
L+ a
200 a R S L+ b b CL = 61.9 wt% Sn
TE
R S
a+ E b+ E S
100
a+ b Wa = = 50 wt%
R+S
0
0 20 40 60 80 100 WL = (1-Wa) = 50 wt%
18.3 Co 61.9 97.8
Pb Co, wt% Sn
43
Callister & Rethwisch
Chemical composition Pb-Sn
•Co between 18.3 and 97.8 wt% Sn results in a combination of a
phase and eutectic regions.
Just below TE:

Ca = 18.3 wt%Sn

Cb = 97.8 wt%Sn
a+ E b+ E
Wa = S = 73 wt%
R+S

Wb = 27 wt%
Pb
44
Callister & Rethwisch
 Pb-Sn
• Consider an alloy: Co = 40 wt% Sn, 60%Pb at 150oC
• What phases are present?
• What are their compositions?

Answer:
There are 2 phases, a and b. a+ E b+ E

Ca = 11 wt% Sn, 89%Pb

Cb = 99 wt% Sn, 1%Pb Pb

Callister & Rethwisch 45

 Pb-Sn
How much of each phase is present?
• T=150oC, Co= 40%Sn, 60%Pb

Answer:

From the lever rule:

99 - 40 59
Wa = = = 67%
a+ E b+ E

99 - 11 88

Pb
Wb = 1 - Wa = 33%
46
Callister & Rethwisch
 Pb-Sn
How much of primary a, how much eutectic?

• T=150oC, Co= 40%Sn, 60%Pb

Answer:

From the lever rule:

61.9 - 40 21.9 a+ E b+ E
Wa = = = 43%
61.9 - 11 50.9
WE = 1- Wa → 57% Pb

47
Callister & Rethwisch
 Al – Si
•The primary Si has a
cuboidal form.

•The eutectic mixture

is non-lamellar in form
(separate flakes).

Al Si •Coarse flakes of Si in
the eutectic promote
brittleness.

•Most Al-Si alloys used

Si
have a near-eutectic
composition since this
gives a lower melting
point and makes them
cheaper to cast.
48
 Modification
•Adding a small quantity of a
ternary element, Sodium,
causes modification of the
microstructure.
•This addition effectively moves the
eutectic point to a higher Si
concentration and lower temperature.
•This modifies the growth of the eutectic
a silicon.
•The eutectic point has moved far
enough to make the alloy, at this
composition, hypo-eutectic instead of
hyper-eutectic.
Fine fibrous
eutectic mixture •Now primary a forms, rather than
primary Si. 49
 9.c. Peritectic Reaction
L + Solid 1 → Solid2
A liquid and solid phases react isothermally to form
a new solid on cooling.

L+d L
The peritectic region of the
iron-nickel phase diagram

g
L+d=g

50
9.d Eutectoid Reaction

Eutectic-like reaction in a solid state.

Solid1 = Solid2 + Solid3

51
Equilibrium diagram - reactions

52
Phase diagrams having
intermediate phases or
compounds

53
 Intermetallic Compounds

Mg2Pb
Adapted from
Fig. 9.20, Callister &
Rethwisch 8e.

Mg Pb
Note: intermetallic compound exists as a line on the diagram - not an area -
because of stoichiometry (i.e. composition of a compound is a fixed value).
54
 Brass (Cu-Zn)
Narrow two phase region!

Peritectic

Eutectoid
a- solid
solution

Cu Zn
• Application - in the solid Intermediate phases:
solution region (g, d, x , h, h’) 55
 Bronze (Cu-Sn)

Cu Sn
Application - in the Intermediate phases
solid solution region (g, d, x , h, h’)
56
 What Have We Learned?
Key concepts:
• Alloys are derived from 2 or more components.
• They contain one or more phases.

• The essential difference between a component

and a phase.

• A phase diagram indicates equilibrium:

• phases, phase composition, and the relative amount
of each phase.

• How phase diagrams help us understand

microstructures in multi-phase materials.
57