Unit I

Alloys and Phase Diagrams

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HISTORY OF MATERIALS

STONE AGE

IRON AGE COPPER AGE

BRONZE AGE
 METALS

COMPOSITES
PLASTIC
S
TYPE
S

SEMI CERAMICS
CONDUCTORS

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Why should we know about
materials ????

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Mechanical Engineer – Design of
Automobile
Aerospace Engineer – Space shuttle
Chemical Engineer – Plant
Internal structure , properties – for each
application
High temperature resistant material, high
corrosion resistant material

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 ALLOY (Homogeneous Mixture)
 An alloy is a combination of two or more elements ,of
which one of the element should be a metal in major
proportion.
Similar properties-Alloy
VISE VERSA - Composites

Example : Brass Cu-Zn, Steel Fe-C etc…

Classification of alloys:
(i)Pure metal
(ii)Solid Solution
(iii)Intermediate phase
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Solid solutions
 Solid solution is an alloy in which the solute atoms are distributed in
the solvent matrix and has the same structure of the solvent. The
element which is present in larger amount in the alloy is called solvent
and the other element is called solute.
 Solid solutions are of two types namely
◦ Substitutional
 Ordered
 disordered

◦ Interstitial

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 In a substitutional solid solution, the atoms of the solvent
metal are replaced in the crystal lattice by atoms of the solute.
This substitution is either 'ordered' or 'disordered'.
 In the ordered solid solution, the substitution of either atoms in
solvent is by a definite order, while this is not so in a
disordered solid solution. Substitutional solid solution
formation is favoured when the atomic sizes of the two metals
are almost equal. (Au in Cu)

 Interstitial solid solutions are formed only when the atoms of

the solute element are very small compared with those of the
solvent, thus enabling them to fit into the interstices or spaces
in the crystal (C in Steel)
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Hume Rothery’s rules of solid solubility
In the formation of solid solution, the
solubility limit of a solute in the solvent is
governed by certain factors. These factors
are known as Hume Rothery’s rules of
solid solubility
 Relative Size
 Chemical Affinity
 Relative Valency
 Crystal Type

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Relative Size
If the atomic sizes of solute and solvent
differ by less than 15%, conditions are
favorable for the formation of solid
solution
If the atomic size difference exceeds
15%, solid solution formation is
extremely limited

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Chemical Affinity
When two elements have a high chemical
attraction for each other, the greater is
tendency to restrict the solid solution and
to form intermediate phases.
This occurs when one element is
electronegative and the other is
electropositive.
Ex: Cu+ Zn-(possible for solid solution)
◦ Cu+ Pb+ (not Possible)
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Relative Valency
A metal of higher valence dissolves only
a small amount of the lower valence metal
The lower valence metal dissolves greater
amount of the higher valence metal

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Crystal Type
If two metals are of the same crystal
lattice and all the other factors are
favorable , it is possible for complete
solid solubility.

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Intermediate Phases or Compounds
Formed between two dissimilar elements
having widely divergent electrochemical
properties.
Types
 Intermetallic compounds
 Electron compounds
 Interstitial compounds

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Intermetallic Compounds
Obeys the valence law
Formed when one metal (such as Mg)
having chemical properties which are
strongly metallic and other metal such as
Sn, Pb, Bi which are weakly metallic.
They have poor ductility and low
electrical conductivity. (Mg3Bi2,Mg2Sn)

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Electron Compounds
Does not obey valence law
 There is a fixed ratio between the total number of
valence electrons and total number of atoms. There
are three such ratios
 3:2
 21:13
 7:4
e.g.1 Ratio : 3:2 : CuZn
◦ Cu has valence electron 1
◦ Zn has valence electron 2
◦ Total has valence electron 3
◦ No of atoms 2
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e.g.2 Ratio : 21:13 : Cu31Sn8
• Cu has valence electron 1
• Sn has valence electron 4
• Total has valence electron 63
• No of atoms 39
• Ratio = 63:39 or 21:13

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Interstitial compounds
Formed between certain transition (F
block elements in periodic tables- Rare
earth elements) metals and small non
metallic atoms
Have metallic properties and comprise
hydrides, nitrides ,carbides, borides etc ,
and they are very hard
TiC , WC, TiN.

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 THE PHASE RULE
 It was first presented by Gibbs in 1875.
 It is very useful to understand the effect of
intensive variables, such as temperature,
pressure, or concentration, on the equilibrium
between phases as well as between chemical
constituents.
 It is used to deduce the number of degrees of
freedom (f) for a system.

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 THE PHASE RULE
The phase rule is stated as:
If the equilibrium is not influenced by pressure,
temperature and concentration, then the number of
degree of freedom of the system is related to number
of components and number of phases by the
following equation

f=c–p+2
C=No.of components
P=No.of Phase
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 Degree of Freedom
The number of degrees of freedom (f):
Is the minimum number of independent
variable factors such as temperature, pressure and
concentration, which must be fixed in order to
define the system completely
f = 1(Univariant)
f = 2 (bivariant)
f = 3 (trivariant)
f = 0 (invariant)

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 PHASE
A state of matter uniform throughout in
chemical composition and physical state

Number of Phase (P):

Gas or gaseous mixture – single phase
Liquid – One, two or three

miscible liquids – single phase

immiscible liquids – more than one phase
Solids – Every solid constitute a separate phase

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 COMPONENT
Is the minimum number of independent
chemical components needed to form the system
or, in other words, to define all the phases.
Number of Component (C):

1. CaCO3(s) → CaO(s) + CO2(g)

C=2

2. Ice → Water (l) → Vapour (g)

C=1
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When no reaction takes place,
The number of constituents = The number of components

Pure water: a one component system

Water
Mixture of ethanol
and water : a two component system

Ethanol Water

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When reaction takes place,

CaCO3(s) → CaO(s) + CO2(g)

Phase 1 Phase 2 Phase 3

a two component system

CaO CO2

CaO(s) + CO2(g) → CaCO3(s)

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 PHASE DIAGRAM

A phase diagram is a graphical way to summarize

the conditions under which the different states of a
substance are stable
• The diagram is divided into three areas
representing each state of the substance.
• The curves separating each area represent the
boundaries of phase changes.
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 Phase Diagrams
Below is a typical phase diagram. It consists of
three curves that divide the diagram into regions
labeled “solid, liquid, and gas”.

B
.C
pressure

solid liquid

. gas
D A
temperature Engineering Materials and Metallurgy- Unit
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Phase Diagrams
A: Triple Point
The triple point, which is the temperature and pressure
where three phases of a substance exist in equilibrium
C: Critical Solution Temperature & Pressure
The temperature above which the liquid state of a
substance no longer exists regardless of pressure is
called the critical temperature.
The vapor pressure at the critical temperature is
called the critical pressure. Note that curve AC
ends at the critical point, C.

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ONE COMPONENT SYSTEM

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 One component system
If the one component system has one phase
then,
f = c – p + 2 = 1-1+2 = 2, bivariant
If the system has two phase then,
f = c – p + 2 = 1-2+2 = 1, univariant
If the system has two phase then,
f = c – p + 2 = 1-3+2 = 0, invariant

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Water System

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 Water System
Curve AT :
 It is Sublimation curve of
ice.
 It represents equilibrium
between ice and vapour
 The degree of freedom of
the system is one, i.e
univariant

f = c – p + 2 = 1-2+2 = 1
 The equilibrium will
extend upto absolute zero,
where no vapour will exist
only ice will exist
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 Water System
Curve CT :
 It is Fusion curve of ice.
 It represents equilibrium
between ice and water
 The degree of freedom of
the system is one, i.e
univariant
f = c – p + 2 = 1-2+2 = 1

 The line CT is inclined

towards the pressure axis
indicates that the melting
point of ice is lowered by
increase of pressure
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 Water System
Curve TD :
 It is Vapour pressure
curve of water. D

 It represents equilibrium
between water and vapour
 The degree of freedom of
the system is one, i.e
univariant
f = c – p + 2 = 1-2+2 = 1

 The line TD extends as far

as critical solution
temperature of water
(374° C)
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 Water System

Point T: D
 It is Triple Point.
 The curve AT, CT, TD
meet at point T
 It represents equilibrium
between ice, liquid and
vapour
 Invariant

f = c – p + 2 = 1-3+2 = 0

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 Water System
Areas:
 Areas ATC, CTD & ATD represents ice,
water and vapour, respectively.
 The degree of freedom of system is two

f = c – p + 2 = 1-1+2 = 2

 In order to define a system at any point in areas,

it is essential to specify both temperature and
pressure.
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Phase Diagram for pure Mg
For point A:
F=C-P+2
= 1-1+2 = 0

For point :
F=C-P+2
= 1-1+2 = 0

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Application of phase diagram
Alloy making
Zone refining
Softening of refractories
Tempil sticks(Temperature
measurements)
Solder wire
Safety devices
Semiconductor devices

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Binary Alloy Phase Diagrams
Types
(i) Components completely soluble in liquid state
and
(a) completely soluble in solid state ( Isomorphous system)
(b) Partially soluble in solid state(Eutectic Reaction II)
(c) Insoluble in solid state(Eutectic Reaction I)
(d) Peritectic reaction
(ii) Components partially soluble in liquid state and
a) completely soluble in solid state
b) Partially soluble in solid state
(iii) Components completely insoluble in liquid state and Insoluble in
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Transformations in solid state
◦ Eutectoid reaction
◦ Peritectoid reaction

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Isomorphous system:
soluble in liquid state and completely soluble in solid state:
Cu-Ni, Au-Ag, Au-Cu, Au-Ni

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Lever rule
The lever rule is a tool used to determine
weight percentages of each phase in a
binary equilibrium phase diagram.
It is used to determine the percent weight
of liquid and solid phases for a given
binary composition and temperature that is
between the liquidus and solidus.

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The percent weight of element B at the Liquidus is given by wl
The percent weight of element B at the solidus is given by ws.
wo is the percent weight of element B for the given composition

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Eutectic Phase I completely soluble in liquid
state and completely insoluble in solid state
:Bi-Cd, Pb-As, Au-Si

CDFG- Solidus line

CEG- Liquidus curve

It is an reversible, isothermal reaction

of a liquid which transforms two
different solid phase upon cooling.

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Eutectic phase II- Partially soluble in
solid state Ag-Cu, Pb-Sn,Al-Si

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Peritectic reaction: Ag-Pt

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Solid State Reactions:
Eutectoid: Cu-Sn, Zn-Al, Al-Mn
Peritectiod: Ni-Mo, Fe-Nb

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Cooling curve for pure iron

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Iron-Iron Carbide Phase Diagrams

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Microstructures

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Ferrite (α ):
Iron which contains no carbon
Very soft and ductile known as α iron.
Maximum solubility of carbon is 0.02% at 723°
Ferrite (δ ):
Maximum solubility of carbon is 0.1% at 1492°
Austenite(γ) :
 Solid solution of Fe-C which is stable only within a
particular range of composition and temperature.
 Maximum solubility of carbon is 2.08 % at 1147° and
decreases to 0.8% at 723°
 Soft , ductile and malleable phase

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Cementite:
 Carbide of iron
 Extremely hard of low tensile and high compressive
strength
 Fixed carbon of 6.67%

Pearlite:
Alternate layers of ferrite and cementite
Contains about 0.8% carbon
87.5% ferrite and 12.5 % cementite

Ledeburite:
Eutectic mixture of austenite and cementite
Contains 4.3% carbon
Formed at about 1130°
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Martensite:
Brittle mass of fibrous or needle like structures
Normally is a product of quenching
Chief constituent of hardened steel

Toorsite:
Mixture of radial lamellae of ferrite and fine cementite
Produced on tempering below 450°

Sorbite:
Mixture of ferrite and fine cementite
Produced on tempering below 450°

Bainite
Bainite is an acicular microstructure (not a phase) that forms in steels
at temperatures from approximately 250-550°C
A fine non-lamellar structure, bainite commonly consists of cementite
and dislocation-rich ferrite.
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 METALS

NON-
FERROU
FERROU
S
S

CAST
STEELS
IRON
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 STEELS

Plain carbon
steels(low
Alloy steels
alloy
steels )

Medium
Low carbon High carbon
carbon Low alloy High alloy
steels steels
steels

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PLAIN CARBON STEELS
Carbon is the alloying element 1.5%
Magnanese do not > 1.65%
Carbon, silicon must be less than 0.6%
Moderately priced – Absence of large
amount of alloy
Ductile

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Low carbon steels
Less than 0.25% carbon
Mild steels
Relatively soft & weak
Cannot be hardened
Good formability and ductility
Microstructure – ferrite,pearlite
Automobile body, pipelines, bridges,
tincans
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Medium carbon steels
Carbon – 0.25 to 0.6%
Low hardenability
High strength and hardness
Railway wheels, railway trucks, gears,
crankshafts

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High carbon steels
> 0.6%
Hardest, strongest of carbon steels
Least ductile
More wear resistant
Cutting tools, dies, Knives, razors,
hacksaw blades, high strength wire.

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Alloy steels
Other than carbon steels
Mn – 1.65%, Si-0.6%, Cu-0.6%
Alloying element – Chromium, Ni,
Molybdenum, Tungsten, Cobalt, Boron,
Copper and others

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Purpose of alloying
 To increase strength
 To improve hardness, toughness
 To improve the wear resistance
 To improve machinability
 To improve ductility
 To enhance grain size control
 To achieve better electrical, magnetic
properties
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 Alloy
steels

High
low alloy
alloy
steels
steels

AISI HSLA Tool & Stainless

steels steels tie steel steel

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Low alloy steels
3-4% of one or more machine alloying
element
Similar microstructure
Pearlitic alloy steels
AISI – American Iron & steel Institute ,
machine construction
HSLA – high strength low alloy steel

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HIGH ALLOY STEELS
>5% of one or more alloying element
Tool steels – high quality steels, tools &
dies
Stainless steels – Improving corrosion
resistance

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EFFECT OF ALLOYING ELEMENT IN
STEELS
Stainless steel
Tool steels
HSLA steels
Maraging steels

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Stainless steels
Alloys of iron, chromium that resist
corrosion
Corrosion resistant steels or chromium
bearing steels
Austenitic Stainless steel – austenitic
structure

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Austenitic stainless steels
Composition
C-0.03 to 0.15% Mn- 2 to 10%
Si – 1 to 2% Cr – 16 to 26%
Ni – 3.5 to 22%
Highest corrosion resistance
Good strength, Non-Magnetic
Very tough, welded, forged, Rolled
Aircraft industry, Chemical processing, Food
processing, Dairy industry
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Ferritic stainless steel
Ferriticstructure
C – 0.08 to 0.1% Si – 1%
Mn – 1 to 1.5% Cr -12 to 25%
Magnetic, Good ductility, strength,
toughness, welded, forged, rolled,
machined
Pertoleum industry, furnaces, decorative
work, screws, burner parts

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Martensitic stainless steel
C -0.1 to 1.5% Si – 1%
Mn – 1% Cr – 12 to 25%
Good hardness, Ductility, Thermal
conductivity
Toughness and corrosion resistance
Pumps, Valve parts, turbine buckets,
surgical instruments.

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Tool steels
Metals to make tools & dies
Metals are designed to provide wear
resistance, toughness
Good toughness, wear resistance,
machinability, Resistance to softening on
heating
Pneumatic tools, hand chisels, reamers,
brouchers, milling cutters, dies.

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HSLA Steels
High strength – low alloy steels, micro
alloyed steels
Purpose – weight reduction by increasing
strength
Twice the yield strength of plain carbon
steels
Structural materials – bridges, towers,
columns, Automobiles

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Maraging steels
Low carbon high alloy steels
High tensile, impact strength
Ni -18%, Co-7%, C<0.05%
Flexible drive shafts – Helicopters, Die
casting dies, Space vehicle cases
High strength and far superior than
Constructional alloys

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 Classification of steel
Ultimate Tensile
Types Properties Strength Carbon Application
(N/m2)
Dead Mild good formability, very,
320-400 0.05 – 0.15% Chain, rivets, wires ,nails
Steel low strength

Screws, deep drawing parts,

0.15 – 0.20%
Low carbon good formability and pipe, some machine parts
400-600
steels weld ability, low strength
Gears, shafts, levers,
0.20-0.30%
forgings
Connecting rods, shafts,
0.30 – 0.40%
axels
good toughness and
crankshafts, axles, gears,
Medium ductility, relatively good 0.40 – 0.50%
550-850 shafts
carbon steels strength, may be
hardened by quenching Laminated springs, rails,
0.50 – 0.60% wire ropes, heat treated
machine parts

high strength, hardness rolling mills, rope wire,

High carbon
and wear resistance, 650-1400 0.7 – 1.0% screw drivers, hammers,
steels
moderate ductility wrenches, band saws

very high strength, punches, shear blades,

Tool carbon hardness and wear milling cutters, knives,
900-1600 1.0 – 2.1%
steels resistance, poor weld razors, dies, drills, taps, mill
ability low ductility cutters
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Alloying Elements
Metal Percentage
Ni,Cr,C,
Nickel 0.4-0.7%
Silicon 0.3-0.6%
Chromium 0.4-0.6%
Molybdenum 0.15-0.3%
Manganese 0.5-1.0%

Tungsten
Silicon
Copper

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Carbon content and mechanical properties in steel

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Classification of Cast Iron
White cast irons
Grey cast irons
Malleable cast iron
Nodular (ductile) cast irons
Chilled cast Irons

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White cast irons

Chemical composition: C=2.0-3.6 %, Mn=0.2-0.8 %, Si=0.5-

2.0%, Ni+Cu=1.5%, Cr=1%,P=0.15%, S=0.15%, Mo=0.5%
Si content is low (< 1%) in combination with faster cooling rates
 White cast irons – hard and brittle, highly wear resistant cast
irons consisting of pearlite and cementite.
 White cast irons are produced by chilling some surfaces of the
cast mold. Chilling prevents formation of Graphite during
solidification of the cast iron.

Applications of white cast irons: brake shoes, shot blasting

nozzles, mill liners, crushers, pump impellers and other abrasion
resistant parts.

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Micro structure of white cast Irons

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Grey cast irons
Chemical composition: C=2.7-4%, Mn=0.4-1.0%, Si=1.8-3%,
S=0.07% max, P=0.2% max
 Alloying addition of Si (1-3wt.%) is responsible for decomposition
of cementite, and also high fluidity
 Grey cast irons – cast irons, produced at slow cooling and consisting
of ferrite and dispersed graphite flakes.
 Grey cast irons possess high compressing strength, fatigue resistance
and wear resistance. Presence of graphite in grey cast irons impart
them very good vibration dumping capacity.

 Applications of grey cast irons: gears, flywheels, water pipes,

engine cylinders, brake discs, gears.

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Micro structure of gray cast Irons

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Malleable cast iron

Chemical composition: C=2-2.7%, Mn=0.25-1.25%, Si=1-1.75%,

S=0.03-0.18%, P=0.05%max

 Malleable cast iron – cast irons produced by heat treatment of

white cast irons and consisting of ferrite and particles of free
graphite.

 Malleable cast irons have good ductility and machinability. Ferritic

malleable cast irons are more ductile and less strong and hard, than
pearlitic malleable cast irons.

 Applications of malleable cast irons: parts of power train of

vehicles, bearing caps, steering gear housings, agricultural
equipment, railroad equipment.
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Micro structure of malleable cast Irons

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 Nodular (ductile) cast irons

Chemical composition: C=3.5-3.9%, Mn=0.15-0.35%,

Si=2.25-2.75%, S=0.01-0.025%, Mg-.06%, P=0.05%max
 Nodular (ductile) cast irons – grey cast iron, in which
graphite particles are modified by magnesium added to
the melt before casting. Nodular cast iron consists of
spheroid nodular graphite particles in ferrite or pearlite
matrix.
 Ductile cast irons possess high ductility, good fatigue
strength, wear resistance, shock resistance and high
modulus of elasticity.
 Applications of nodular (ductile) cast irons: automotive
engine crankshafts, heavy duty gears, military and
railroad vehicles. Engineering Materials and Metallurgy- Unit
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 Micro structure of Nodular cast Irons

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 Nominal Tensile Elongation Hardness [
Form and
Name composition strength [% (in Brinell scale
condition
[% by weight] [ksi] 2 inches)] ]

Grey cast iron C2.7-4, Si 1.8, Cast 25 0.5 180

Mn 0.5

White cast iron C2.0-3.6 , Cast (as

25 0 450
Si 0.7, Mn 0.6 cast)

C 2-2.7, Si 1.0, Cast

Malleable iron 52 12 130
Mn 0.55 (annealed)

Ductile or nodular C3.5-3.9, P 0.1,

Mn 0.4, Ni 1.0, Cast 70 18 170
iron
Mg 0.06

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Wrought Iron
Wrought iron is an iron alloy with a very low
carbon content, in comparison to steel, and has
fibrous inclusions, known as slag.

0.025 C, 0.13 Mn, 0.10 Si, 0.13 P, and 0.01 S.

 Applications includes rivets, nails, wire, chains

, railway couplings, water and steam pipes,
nuts, bolts, horseshoes, handrails, straps for
timber roof trusses, and ornamental ironwork

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Chilled Cast Iron
 When localized area of a gray cast iron is cooled very
rapidly from the melt, cast iron is formed at the place that
has been cooled. This type of white cast iron is called
chilled iron. A chilled iron casting can be produced by
adjusting the carbon composition of the white cast iron
 Chromium is used in small amounts to control chill depth.
Because of the formation of chromium carbides,
chromium is used in amount of 1 to 4 percent in chilled
iron to increase hardness and improve abrasion resistance.
 Chilled cast iron is used for railway-car wheels, crushing
rolls, stamp shoes and dies, and many heavy-duty
machinery parts.

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Spheroidal Graphite Cast Iron
 The chemical composition of the cast iron is
similar to that of the grey cast iron but with 0.05
wt% of magnesium. All samples are etched using
2% nital(alcohol and nitric acid).
 Spheroidal graphite cast iron usually has a pearlitic
matrix.
 However, annealing causes the carbon in the
pearlite to precipitate on to the existing graphite or
to form further small graphite particles, leaving
behind a ferritic matrix.
 This gives the iron even greater ductility
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Compacted graphite Iron
• Produced when molten iron is desulphurised and
treated at 14000C
• Alloy containing approximate amounts of Mg,Ti
• Sometimes called as Vermicular graphite
• Contains short graphite flakes and have round
edges
• Intermediate between gray and nodular cast iron
• Applications-Gear pumps, fluid and air
cylinders, vehicle brake compounds,engine
blocks, cylinder heads
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Thank You

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