Phase Diagrams

EEAQ 2118 –
INTRODUCTION
TO MATERIALS
SCIENCE
Ferrous Alloys
 Phase Diagrams

A phase in a material is a region that differ in its microstructure and

or composition from another region

Al2CuMg

Al H2O(solid, ice) in H2O

(liquid) ⇒ 2 phases

• homogeneous in crystal structure and atomic arrangement

• have same chemical and physical properties throughout
• have a definite interface and able to be mechanically separated from its
surroundings

Additional resources: Callister, chapter 9 and 10 Chapter 8 1

 Phase diagram and “degrees of freedom”
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 T, p, and compositions
• “equilibrium” is important: phase diagrams are determined by using slow cooling
conditions ⇒ no information about kinetics

Degree of freedom (or variance) F is the number of variables (T, p, and

composition) that can be changed independently without changing the phases of
the system

Chapter 8 2
Phase diagram of CO2
Phase Diagram of Water
3 phases: solid,
liquid, vapour
Triple point:
4.579 Torr
(~603Pa),
0.0098oC

• Field – 1 phase
• Line – phase coexistence, 2 phases
• Triple point – 3 phases

Chapter 8 3
 Gibbs Phase Rule
Gibbs' phase rule describes the possible # 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)

F+P=C+2
F is # of degrees of freedom or
variance
P is # of phases
C is # of components

Component is the minimum # of

species necessary to define the
composition of the system
H2O C=1
(i) P=1, F=2;
(ii) P=2, F=1;
(iii) P=3, F=0
4
 How to construct phase diagrams? -
Cooling curves

Cooling curves:
• used to determine phase transition temperature
• record T of material vs time, as it cools from its molten state through solidification
and finally to RT (at a constant pressure!!!)

The cooling curve of a pure metal

BC: plateaue or region of

thermal arrest; in this region
material is in the form of
solid and liquid phases
CD: solidification is
completed, T drops

5
 Cooling curve for pure iron @ 1atm

As T ⇓: melted iron (liquid) ⇒ bcc Fe, δ (solid) ⇒ fcc Fe, γ (solid) ⇒ bcc Fe, α (RT)

6
 Binary systems (C = 2)
F+P=C+2=4 ⇒ F=4-P
Degrees of freedom (F): At p = const (or T=const)
p, T, composition
p T F=3-P

0 weight % of B 100%
composition 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)
7
 Binary Isomorphous Alloy System (C=2)
Isomorphous: Two elements are completely soluble in each other in solid and liquid
state; substitutional solid state solution can be formed; single type of crystal str. exist
Reminder: Hume-Rothery rules: (1) atoms have similar radii; (2) both pure materials have
same crystal structure; (3) similar electronegativity (otherwise may form a compound instead);
(4) solute should have higher valence

Example: Cu-Ni phase diagram (only for slow cooling conditions)

Liquidus line: the line connecting
Ts at which liquid starts to solidify
under equilibrium conditions
Solidus: the temperature at which
the last of the liquid phase
solidifies
Between liquidus and solidus: P =2

8
 53 wt% Ni – 47 wt% Cu at 1300oC

P=1
F=3–P=2

P=2;F=3–P=1
• contains both liquid and solid phases ⇒ neither of these phases can have
average composition 53 wt% Ni – 47 wt% Cu

• draw a tie line at 1300oC ⇒ from the graph: composition of liquid phase wL =
45% and solid phase wS = 58% at 1300oC
9
 The Lever Rule
The weight percentages of the phases in any 2 phase region can be
calculated by using the lever rule
Consider the binary equilibrium phase diagram of elements A and B that are
completely soluble in each other

Co
Mass fraction of B
Let x be the alloy composition of interest, its mass fraction of B (in A) is Cο
Let T be the temperature of interest ⇒ at T alloy x consists of a mixture of liquid (with
CL - mass fraction of B in liquid) and solid (CS - mass fraction of B in solid phase)
10
Q.: A Cu-Ni alloy contains 47 wt % Cu and 53% of Ni and is at 1300oC. Use Fig.8.5 and
answer the following:
A. What is the weight percent of Cu in the liquid and solid phases at this temperature?
B. What weight percent of this alloy is liquid and what weight percent is solid?

12
Nonequilibrium Solidification of Alloys

⇐ constructed by using very slow

cooling conditions

Atomic diffusion is slow in solid state; as-cast

microstructures show “core structures” caused
by regions of different chemical composition

As-cast 70% Cu – 30% Ni alloy 13

showing a cored structure
 Nonequilibrium Solidus

Solidification of a 70% Ni-30%Cu alloy Schematic microstructures at T2 and T4

Fig. 8.9, Smith Fig.8.10, Smith

• each core structure will have composition gradient α1-α7

• additional homogenization step is often required (annealing <T7)
14
 Binary Eutectic Alloy System

• Components has limited solid solubility in each other

• Example: cooling 60%Pb – 40%Sn system

Liquid ⎯eutec
⎯ tic
⎯_⎯T → a solid solution + b solid solution

This eutectic reaction is called an invariant

reaction ⇒ occurs under equilibrium conditions
at specific T and alloy composition
F=0
at eutectic point

15
 Solubility Limit: Water-Sugar
• Changing T can change # of phases: path A to B.
• Changing Co can change # of phases: path B to D
B (100,70) D(100,90)
1 phase 2 phases
10 0

80 L
(liquid)
Temperature (°C)

60 +
L
S
(liquid solution (solid
40 i.e., syrup) sugar)
20 A(70, 20 )
2 phases
0
0 20 40 60 70 80 10 0
C o =Composition (wt% sugar) Adapted from Callister
16
Binary Eutectic Alloy System

Figure 8.13, Smith 17

Q: A lead-tin (Pb – Sn) alloy contains 64 wt % proeutectic (α) and 36% eutectic α+β at
183oC – ∆T. Using Figure 8.13, calculate the average composition of this alloy.

18
 Binary Peritectic Alloy System

The melting points of the two components are quite different

A liquid phase reacts with the solid phase to form a new and different
solid phase
Liquid + α → β

19
Binary Peritectic Alloy System (cont.)

20
 Binary monotectic systems
Monotectic reaction: a liquid phase transforms into a solid phase and another
liquid phase
L1 → α + L2

Chapter 8 21
 Invariant Reactions
To summarize:
5 invariant reactions (F = 0)
1. Eutectic Liquid → α+β
2. Eutectoid α → β+γ
3. Peritectic Liquid + α → β
4. Peritectoid α+β → γ
5. Monotectic L1 → α + L2

The eutectic and eutectoid reactions are similar in that they both involve the
decomposition of a single phase into two solid phases. The –oid suffix indicates
that a solid, rather than liquid, phase is decomposing.

Chapter 8 22
Phase Diagrams with Intermediate Phases
and Compounds

Terminal phase: a solid solution of one component in another for

which one boundary of the phase field is a pure component
Intermediate phase: a phase whose composition range is between
those of terminal phases

23
 Ti-Si-O system

• Experiment (700-1000oC)
Ti + SiO2 → Ti5Si3 and TiOy

• At equilibrium the system will be in

TiSix – TiOy – SiO2 three phase
region (from calculations)

• Ti5Si3 – TiO – SiO2 three phase

region determined experimentally
and remaining tie lines can be
inferred

24
 TernaryPhase Diagram

F+P=C+2
For p = 1atm, T = const (isoterms)

Cr-Fe-Ni alloy
stainless steel

Chapter 8 25
 Three and four component system
AB + AC = 2A + BC
∆G = (2GA + GBC) – (GAB + GAC)

If ∆G <0, there is tie line between A and BC

The remaining tie lines cannot cross
A
AB + AC + AD = 3A + BCD
∆G = (3GA + GBCd) – (GAB + GAC + GAD)

AB AC • Two phase equilibrium is represented

by a tie line
• If ∆G <0, there is a tie line between A
and BCD;
• otherwise plane connects AB-AC-AD

B BC C Chapter 8 26
 The Ti-Si-N-O quaternary phase diagram
• Entire phase diagram can be
calculated by taking into account all
possible combinations of reactions and
products
• 4 ternary diagrams of Ti-Si-N, Ti-N-O,
Ti-Si-O and Si-N-O were evaluated
• additional quaternary tie lines from
TiN to SiO2 and Si2N2O
• stable metallization bilayer of TiN and
TiSi2 in contact with SiO2

A.S.Bhansali, et al., J.Appl.Phys. 68(3) (1990) 1043

Z.Chen, et al., Phys.Stat.Sol.B 241(10) (2004) 2253

Chapter 8 27
FERROUS
ALLOYS
 Metal Alloys

Adapted from Fig.

Ferrous Nonferrous 11.1, Callister &
Rethwisch 8e.

Steels
Steels Cast Irons
Cast Irons
<1.4 wt% C
<1.4wt%C 3-4.5wt%C
3-4.5 wt% C

T(ºC) microstructure: ferrite,

1600 graphite/cementite
d
1400 L
g+L Adapted from Fig. 9.24, Callister &
1200 g 1148ºC L+Fe3C Rethwisch 8e. (Fig. 9.24 adapted from
austenite Binary Alloy Phase Diagrams, 2nd ed., Vol.
Eutectic: 1, T.B. Massalski (Ed.-in-Chief), ASM
1000 4.30
International, Materials Park, OH, 1990.)
g+Fe3C
a800 727ºC Fe3C
ferrite Eutectoid: cementite
600 0.76 a+Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe)
Co , wt%
C
Iron-Carbon Phase Diagram

 a - Ferrite (Alpha iron)

 g - Austenite (Gamma
iron)
 d - Ferrite (Delta iron)
 Fe3C – Cementite
(Iron Carbide)

Figure: Phase diagram

for iron-carbon system,
up to about 6.67% carbon.
 Explanation on Iron-Carbon Phase Diagram
• Vertical line (y-axis) – temperature from 0oC ~ 1538oC
• Horizontal line (x-axis) – carbon content from 0% ~ 6.67%
• At 723oC :-
- where pure iron, steel and cast iron looses their
magnetism
- Plain carbon steel up to 0.86%C changes from ferrite
and pearlite to austenite and ferrite
- Plain carbon steel with 0.86%C changes from pure
pearlite to austenite
- Other steel or cast iron with more than 0.86%C
changes from pearlite and cementite to austenite and
cementite
Solubility Limits of Carbon in Iron

• Ferrite phase can dissolve only about 0.022%

carbon at 723C (1333F)
• Austenite can dissolve up to about 2.1% carbon at
1130C (2066F)
– The difference in solubility between alpha and
gamma provides opportunities for strengthening by
heat treatment
• Pure Iron melt at 1536oC
• Cast Iron melt at 1145oC
Eutectic and Eutectoid Compositions

Eutectic

• FIGURE : The iron-iron-

carbide phase diagram.
Eutectoid Because of the
importance of steel as an
engineering material,
this diagram is one of
the most important
phase diagrams.
 Constituents in Steel

1. Ferrite

• a and -phase with

the BCC lattice
 2 Austenite

• The g-phase with the

FCC lattice.
3. Cementite

• Name given to iron carbide

• having fixed composition Fe3C.
• Cementite is a hard and brittle
substance, influencing on the properties
of steels and cast irons
 4. Pearlite
• fine mixture of ferrite and
cementite structure
• forming as a result of
decomposition of austenite
at slow cooling conditions
• the black lamellae are the
Fe3C parts; their thickness is
a few µm.
• The name comes from the
pearl-like luster of this
material. Microstructure of pearlite in 1080 steel, formed from austenite
of eutectoid composition. In this lamellar structure, the lighter
regions are ferrite, and the darker regions are carbide.
Magnification: 2500X.
 5. Martensite
• In steel, under rapid cooling, so that
equilibrium is prevented, austenite
transforms into a nonequilibrium phase
called martensite, which is hard and brittle
• A unique phase consisting of an iron-carbon
solution whose composition is the same as
the austenite from which it was derived
• Face-centered cubic (FCC) structure
of austenite is transformed into
body-centered tetragonal (BCT)
structure of martensite
• The extreme hardness of martensite results
from the lattice strain created by carbon
atoms trapped in the BCT structure, thus
providing a barrier to slip
 Classification of Ferrous Alloys
Low Alloy High Alloy
low carbon Med carbon high carbon
<0.25wt%C 0.25-0.6wt%C 0.6-1.4wt%C

heat
Name plain HSLA plain
plain tool stainless
treatable
Cr,V Cr, Ni Cr, V,
Additions none none none Cr, Ni, Mo
Ni, Mo Mo Mo, W
Example 1010 4310 1040 4340 1095 4190 304, 409
Hardenability 0 + + ++ ++ +++ varies
TS - 0 + ++ + ++ varies
EL + + 0 - - -- ++
Uses auto bridges crank pistons wear drills high T
struc. towers shafts gears applic. saws applic.
sheet press. bolts wear dies turbines
vessels hammers applic. furnaces
blades Very corros.
resistant
increasing strength, cost, decreasing ductility

Based on data provided in Tables 11.1(b), 11.2(b), 11.3, and 11.4, Callister & Rethwisch 8e.
Effects of Carbon

How hard steel is depends on the how much

carbon is inside.
Effects of Carbon

Hardness and tensile strength increases as carbon

content increases up to about 0.85% C!
 Low Carbon Steel
Also known as mild steel
Contain 0.05% -0.32% carbon

Tough, ductile and malleable

Easily joined and welded
Poor resistance to corrosion
Often used a general purpose material

Nails, screws, car bodies,

Structural Steel used in the construction industry
 Medium Carbon Steel
Contains 0.35% - 0.5% of carbon

Offer more strength and hardness BUT

less ductile and malleable

Structural steel, rails and garden tools

 High Carbon Steel
Also known as ‘tool steel’
Contain 0.55%-1.5% carbon

Very hard but offers Higher

Strength Less ductile
and less malleable

Hand tools (chisels, punches)

Saw blades
 Cast Iron
Contains 2%-4% of carbon

Very hard and brittle

Strong under compression
Suitable for casting [can be pour at a relatively
low temperature]

Engine block, engineer vices, machine parts

 Cast Iron
White:
Hard and brittle, good wear resistance
Uses: rolling & crunching
Equipment

Grey:
Good compressive & tensile strength, machinability,
and vibration-damping ability
Uses: machine bases, crankshafts, furnace doors,
Engine Blocks
 Cast Iron
Ductile:
High strength and ductility Uses: engine and machine parts

Malleable:
Heat-treated version of white cast iron

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 Stainless Steel
Steel alloyed with
chromium (18%), nickel (8%), magnesium (8%)
Hard and tough
Corrosion resistance
Comes in different grades
Sinks, cooking utensils, surgical instruments
Stainless Steels
Main types:

Ferritic chromium:
very formable, relatively weak;
used in architectural trim, kitchen range hoods, jewelry,
decorations, utensils Grades 409, 430, and other 400

Austentitic nickel-chromium:
non-magnetic, machinable, weldable, relatively weak;
used in architectural products, such as fascias, curtain
walls, storefronts, doors & windows, railings; chemical
processing, food utensils, kitchen applications.
series. Grades 301, 302, 303, 304, 316, and other 300
series.
Martensitic chromium:
High strength, hardness, resistance to abrasion; used in
turbine parts, bearings, knives, cutlery and generally
Magnetic. Grades 17-4, 410, 416, 420, 440 and other
400 series

Maraging (super alloys):

High strength, high Temperature alloy used in structural
applications, aircraft components and are generally
50
magnetic. Alloys containing around 18% Nickel.
 High Speed Steel
Medium Carbon steel alloyed with
Tungsten, chromium, vanadium

Very hard
Resistant to frictional heat even at high temperature
Can only be ground

Machine cutting tools (lathe and milling)

Drills
Desirable Mechanical Properties