Engineering Alloys

Ferrous systems
 Ferrous Alloys

 Allotropy of Fe and its Alloys

 Fe-Fe3C Phase Diagram

 Reactions in Fe-Fe3C Diagram

 Ferrous Alloys

 Classification of Fe-Fe3C Diagram

 Definition of Structures

 Types of Ferrous alloys

Allotropy of Fe and its Alloys

Allotropy
 Multiple crystal structure of the same
chemical composition is called
polymorphism or allotropy.
Example: Iron, Graphite, etc.

 Thedifferent crystal structures exists

at different temperatures and
pressure.
Allotropy of Fe and its Alloys
Liquid

1535
L   iron(BCC)

1400
   iron(FCC)

T°C
910  

 iron(BCC)

Time

Cooling curve of Fe
Allotropy of Fe and its Alloys

 The temperature at which the

allotropic changes takes place in iron
is influenced by alloying elements.

 The most important alloying element

is carbon.

A portion of the Iron-Carbon system

is called Fe - Fe3C diagram.
NEXT
Fe-Fe3C Phase Diagram

NEXT
Reactions in Fe-Fe3C Diagram

 There are three horizontal lines which

corresponds to three isothermal
reactions.

 The first reaction occurs at 1493 ºC is

called Peritectic reaction:

Cooling
Liquid +  iron Austenite ()
Heating
Reactions in Fe-Fe3C Diagram
 The second reaction occurs at 1150 ºC
and 4.3%C is called Eutectic reaction:

Cooling
Liquid Austenite + Cementite
Heating
( ) (Fe3C)
 The eutectic mixture formed is called
ledeburite.

 The mixture is not stable at room

temperature.
Reactions in Fe-Fe3C Diagram

 The third reaction occurs at 725 ºC

and 0.8%C is called Eutectoid
reaction:
Cooling
Austenite Ferrite + Cementite
( ) Heating
() (Fe3C)

 The eutectoid mixture formed is

called pearlite.
NEXT
Classification of Fe-Fe3C Diagram

 Alloyscontaining less than 2%C are

known as steels.

 Steels containing less than 0.8%C is

called hypo eutectoid steels and
greater than 0.8%C is called hyper
eutectoid steels.

 Alloys containing more than 2%C are

called Cast irons. NEXT
 Definition of Structures
1. Ferrite
 Ferrite is an interstitial solid
solution of carbon in BCC Iron.

 It is stable over -273°C to 910 °C in

pure iron.

 The maximum solubility at room

temperature is 0.008wt% and
0.025wt% at 725 °C
 Definition of Structures

 The solubility is limited due to the

size difference between carbon atom
(0.19A°) and the void size(0.17A°).

 Itis the softest phase present in Fe-

Fe3C diagram.
 Definition of Structures
2. Austenite()
 It is an interstitial solid solution of
carbon in FCC Iron.

 It is stable over 910°C to 1410 °C in

pure iron.

 Maximum solubility of carbon is 2wt%

at 1150°C. This is due to the void size
(0.52A°).
 Definition of Structures

3. Cementite
 It is nothing but Fe3C phase. The
crystal structure is orthorhombic.

 The carbon content is 6.67wt%

 It is the hardest phase in the Fe- Fe3C

Diagram.
 Definition of Structures
4. Pearlite
 It is a very fine plate like or lamellar
mixture of ferrite and Cementite.

 Itis the eutectoid mixture containing

0.8wt%C and is formed at 725ºC on
very slow cooling.

 The mixture has good strength and

toughness than soft ferrite and hard
Cementite.
Definition of Structures

Ferrite

Fe3C

Microstructure of Pearlite
 Definition of Structures
5. Martensite
 This is a metastable structure occurs
due to rapid cooling of austenite.

 The crystal structure is BCT (Body

centered tetragonal)

 It is formed through displacive

transformation while cooling from
FCC austenite.
 Definition of Structures
 The microstructure of martensite will
look like needles.

 It is the hardest phase and its

hardness depends on the carbon
content (i.e for higher hardness
higher the carbon content and vice
versa).

NEXT
Types of Ferrous alloys

 STEELS

 CAST IRONS

 WROUGHT IRON
 STEELS

1. Plain carbon (PC) steels

2. Effect of impurities on PC steels

2. Alloy steels
 Classification of Steels
Classification of PC steels

1. Low carbon steels ( 0 - 0.1%C)

2. Mild steels (0.15 - 0.25%C)

3. Medium carbon steels (0.3 - 0.7%C)

4. High carbon steels ( 0.7 - 1.4%C)

 Low carbon Steels
 It has carbon content up to 0.1%

 They are soft, ductile, tough,

machinable, weldable and not
hardenable by heat treatment.

 It is used in the form of cold rolled

sheets.
 Low carbon Steels
 Its microstructure consists of small
amount of pearlite.

 Has Strength between 300 – 370

MPa and %elongation of 28 – 40.

 Used in automobile and refrigerator

bodies, tin cans, corrugated sheets,
nails, welding rods, fan blades, etc.
NEXT
 Mild Steels
 This steel has carbon content
between 0.15 – 0.25%.

 It is used in as rolled and air cooled

conditions.

 Microstructure consists of 25% of

fine pearlite and remaining ferrite.
 Mild Steels
 Strength between 400 - 450 MPa.

 % elongation between 26 – 30.

 Used as structural steels, building

bars, grills, ship hulls, boilers, oil
pipelines, beams, angles, etc.

NEXT
 Medium carbon Steels
 They contains carbon content
between 0.3 – 0.7%.

 They are medium hard, not so

ductile and malleable, medium
tough, slightly difficult to machine
weld and harden.

 They are also called machinery steels.

 Medium carbon Steels

They are used as:

1. Agricultural implements

2. Rail structures

3. Spring steels
 Medium carbon Steels
Agricultural implements
 It has carbon content between 0.3 –
0.5%.

 The agricultural implements are

used in hot forged and air cooled
forms.

 Microstructure consists of fine

ferrite – pearlite mixture.
 Medium carbon Steels
Rail structures
 Carbon content is between 0.5 –
0.65%.

 Microstructure consists of mostly

pearlite structure and is hard,
strong and has good wear
resistance.

 Used as rails, wheels and axels in

railways.
 Medium carbon Steels
Spring steels
 Carbon content is between 0.5 – 0.65%.

 They are quenched and tempered to have

a high yield strength so that resilience
(y/2E) of the steel is increased, because
the elastic modulus cannot be increased.

 Tempering can increase the yield

strength about 1500 MPa. NEXT
 High carbon Steels
 Carbon content between (0.7 –
1.4%C)

 They are hard, wear resistant, brittle,

difficult to machine, difficult to weld
and can be hardened by heat
treatment.

 These steel cannot be cold worked

and are hot worked.
 High carbon Steels

 They are also called tool steels.

 They are used for applications like

forging dies, punches, hammers,
files, drill bits, razor blades, knives,
ball bearings, etc.

NEXT
Effect of impurities in Steels
1. Sulphur

 In commercial steels it is kept below

0.05%.

 Because sulphur combines with

iron to form iron sulfide ( FeS ).
Effect of impurities in Steels
 Iron sulfide forms a low
temperature eutectic with iron
which tends to concentrate on grain
boundaries.

 When steel is hot worked at

elevated temperatures the steel
becomes brittle due to the melting
of the iron sulfide eutectic.This is
called hot shortness.
Effect of impurities in Steels
2. Manganese

 It is kept between 0.03 to 1% in all

commercial P.C steels.

 In the presence of manganese sulfer

tends to form manganese sulfide
(MnS) rather than FeS.
Effect of impurities in Steels
 The MnS may pass out in the slag or
remain as well distributed inclusion
throughout the structure.

 When there is more manganese

present than the amount required to
form MnS, the excess combines
with the carbon to form Mn3C which
is found associated with Fe3C.
Effect of impurities in Steels
3. Phosphorous

 It is generally kept below 0.04%.

 Small quantities dissolves in ferrite

an increasing the strength and
hardness slightly.
Effect of impurities in Steels

 In large quantities, phosphorous

reduces ductility, there by
increasing the tendency of the steel
to crack when cold worked. This is
called cold shortness.
Effect of impurities in Steels
4. Silicon
 Most commercial alloys contain
between 0.05 to 0.3%.

 Silicon dissolves in ferrite,

increasing the strength of the steel
without greatly decreasing ductility.

 It promotes the de-oxidation of

molten steel through the formation
of SiO2 . NEXT
 ALLOY STEELS
 DEFINITION

 REASON FOR ALLOYING

 EFFECT OF ALLOYING ELEMENTS

 STAINLESS STEELS
 ALLOY STEELS
DEFINITION
 Alloy steels are the steels containing
other elements like Ni, Mn, Cr, W, Mo,
etc which are added to plain carbon
steels for enhancement of their one or
more properties.

 They are classified into low alloy

steels ( <10% ) and high alloy steels
( >10%). NEXT
 ALLOY STEELS
REASON FOR ALLOYING

 To increase hardanability.

 To improve mechanical properties

either at low or high temperatures.
 ALLOY STEELS

 Increase wear resistance.

 Improve corrosion resistance.

 Improve magnetic properties, etc.

NEXT
 ALLOY STEELS
EFFECT OF ALLOYING ELEMENTS

1. Solid solution strengthening.

2. Formation of carbides.

3. Formation of intermediate
compounds.
 ALLOY STEELS

4. Formation of inclusion.

5. Influence on critical temperatures

and eutectoid composition.
 ALLOY STEELS
Solid solution strengthening
 Most of the alloying elements are
soluble in ferrite to some extend
and form solid solutions.

 The strengthening effect of P, Si,

Mn, Ni, Mo, V, Cr, etc are in
decreasing order.
 ALLOY STEELS

P Si
Mn Ni
Mo
V
Hardness

Cr

Alloying element(wt%)
NEXT
 ALLOY STEELS
Formation of carbides
 Some of the alloying elements
combine with carbon in steel and
form respective carbides.

 They increase wear resistance.

 In the absence of carbon

considerable amount dissolve in
ferrite.
 ALLOY STEELS

 Mn, Cr, W, Mo and V are examples

of carbide forming elements.

 Chromium and vanadium are

outstanding in hardness and wear
resistance.

NEXT
 ALLOY STEELS
Formation of intermediate compounds

 Some of the elements form

intermediate compounds with iron
like Fe3W2, FeS, etc.

 These phases increases the

brittleness of steel.
NEXT
 ALLOY STEELS
Formation of inclusions

 Some elements may combine with

oxygen and forms oxides when
added to steel

 Example: Si, Al, Mn, Cr, etc.

NEXT
 ALLOY STEELS
INFLUENCE ON CRITICAL TEMPERATURE
AND EUTECTOID CARBON

 Some elements like Ti, Mo, Si, W, Cr,

etc increases the critical temperature.

 Other elements like Ni, Mn reduces the

critical temperature are called austenite
stabilizers.
 ALLOY STEELS

Ti Mo
Si W
Cr
Critical temperature

725°C
Ni Mn
Alloying element(wt%)
 ALLOY STEELS
 Some elements like Mo, Cr, Si tend
to reduce the austenite region as
the amount increases are called
ferrite stabilizers.

 All the alloying elements shift the

eutectoid carbon content to lower
values ( i.e, < 0.8%)
 ALLOY STEELS

19%Cr
Temperature

15% 12%
5%
0%

0 0.8 2
%Carbon
NEXT
 STAINLESS STEELS
 They have high corrosion
resistance in most of the usual
environment conditions, hence the
name stainless steel.

 High corrosion resistance is due to

the presence of Chromium which
forms a passive and self healing
Chromium oxide thin film on the
surface when exposed to oxidation
environments.
 STAINLESS STEELS
 The minimum amount of Cr in solid
solution should be >13% for
sufficient corrosion resistance in
most general environment
conditions.

 When Cr is added to steel it

combines with carbon (17 times the
amount of Carbon) and forms
complex chromium carbides.
 STAINLESS STEELS
 The remaining chromium goes in
the solid solution.

 Therefore the Cr present in the

solid solution form is

= Total Cr – (17 * %C)

 STAINLESS STEELS
Types of Stainless steels

 Martensitic stainless steel

 Ferritic stainless steel

 Austenitic stainless steel

 STAINLESS STEELS
Martensitic stainless steel
 They have Cr content in solid
solution form < 13%
( i.e, %Cr – (17* %C) < 13% )

 These steels show austenitic phase

at high temperatures and hence can
be hardened by martensitic
transformation, hence the name
martensitic stainless steel.
 STAINLESS STEELS
 Therefore, these steels contains 12
-18 %Cr and 0.15 - 1.2 %C.

 They are hard, wear resistant and

magnetic in character.

 Used for springs, ball bearings,

valves, razor blades, surgical
instruments, etc.
NEXT
 STAINLESS STEELS
Ferritic stainless steel
 They have Cr content in solid
solution form > 13%
( i.e, %Cr – (17* %C) > 13% )

 Since Cr is a ferrite stabilizer as the

Cr content increases the ferrite
phase becomes stable over the
entire temperature range and hence
called ferritic stainless steel.
 STAINLESS STEELS
 They cannot be hardened by
martensitic transformation.

 Cold working can be done to

increase the strength and hardness.

 These steels contains 13 - 27 %Cr

and < 0.2 %C.
 STAINLESS STEELS
 They have higher oxidation and
corrosion resistance compare to
martensitic stainless steel.

 They are soft, ductile and magnetic

in character.

 Used for vessels in chemical and

food industries, pans, pipes in
sugar industries, etc.
NEXT
 STAINLESS STEELS
Austenitic stainless steel
 This group contains at least a total of
24% Cr, Ni & Mn and the amount of Cr
alone is at least 18% with the carbon
content between 0.03 to 0.25%.

 The presence of austenitic stabilizers

makes the austenite phase stable at
room temperature and hence called
austenitic stainless steel.
 STAINLESS STEELS
 The equilibrium phases in this steel
is  +  + carbide at room
temperature and homogeneous
austenite above 900°C , however,
due to fast cooling only austenite
phase is present at room
temperature.

 They are soft, ductile and non-

magnetic in character.
 STAINLESS STEELS
 Their corrosion resistance is
superior to other stainless steels.

 They have low thermal conductivity

and high coefficient of expansion.

 Used for food and chemical plants,

utensils, sanitary fittings, etc.
NEXT
 CAST IRON
 Definition

 White cast iron

 Malleable cast iron

 Gray cast iron

 Nodular cast iron

 CAST IRON
Definition

 Cast irons are the alloys of Iron

and carbon with 2 to 6.67% C in it.

 Most commercial alloys contain

carbon only between 2.5 to 4%.
 CAST IRON

 It cannot be forged, rolled, drawn or

pressed into the desired shape.

 They are formed by melting and

casting and hence the name cast
iron.
NEXT
 WHITE CAST IRON
1. White cast iron
 They are hypoeutectic alloys
present in the Fe-Fe3C diagram.

 The fracture surface of the white

cast iron looks white in colour
hence the name white cast iron.

 Carbon is present in the combined

form (Fe3C).
 WHITE CAST IRON
 The microstructure consisting of
dendritic network of Cementite
(Fe3C).

 Due to the presence of large amount

of Cementite, it is hard and wear
resistant but extremely brittle and
difficult to machine.
 WHITE CAST IRON
Liquid

(a) (b)
Primary
-Dendrites
Pearlite Eutectic 
Fe3C

(d) (c)

Microstructural Changes during cooling of a

hypoeutectic white cast iron
 WHITE CAST IRON
 At eutectic temperature, the liquid
undergoes a eutectic reaction to
form ledeburite ( i.e, Austenite +
Fe3C).

 At the eutectoid temperature, all the

austenite, primary( pro-eutectic ) as
well as eutectic, transforms to
pearlite ( i.e, ferrite+ Fe3C).
 WHITE CAST IRON

 Therefore, the final microstructure

consists of dendritic areas of
transformed austenite ( i.e, pearlite)
in a matrix of transformed
ledeburite (Fe3C + pearlite).
 WHITE CAST IRON
Properties & applications
 It is hard, wear resistant, extremely
brittle and difficult to machine.

 Used in high wear resistance

applications such as liners for
cement mixtures, ball mills, etc.

 Used for making malleable cast

iron.
NEXT
 MALLEABLE CAST IRON
2. Malleable cast iron
 They are produced from white cast
iron by a malleablizing heat
treatment.

 The silicon present (1%Si) is low

enough to prevent the formation of
graphite flakes during casting, but
adequate to keep the subsequent
annealing time within reasonable
limit.
 MALLEABLE CAST IRON

 Heat treatment consists of heating

white cast iron to 900- 950°C and
holding at this temperature for a
long time (24 hrs to several days)
followed by cooling to room
temperature.
 MALLEABLE CAST IRON

900°C Cooling
Temperature

Time

Malleablizing Heat treatment Cycle

 MALLEABLE CAST IRON
 At 900°C the structure consists of
austenite and Cementite.

 Cementite being a metastable phase

decomposes to austenite and
graphite with a long holding time.

 The free carbon precipitates in the

form of spheroidal particles called
temper-carbon.
 MALLEABLE CAST IRON
Temper -carbon
Pearlite

Microstructure Malleable Cast Iron

 MALLEABLE CAST IRON
 Therefore, the microstructure at room
temperature consists of temper-
carbon in the matrix of pearlite.

 However, the cooling rate is very slow

(or Si in white cast iron is more), the
Cementite from pearlite may also
decomposes to give a matrix of
temper-carbon in ferrite matrix.
 MALLEABLE CAST IRON
Properties & applications
 The temper carbon doesn’t break up
the continuity of the tough ferrite (or
pearlite) matrix, this results in higher
strength (700MPa) and ductility (10-
15%) than gray cast iron.

 More expensive than gray cast iron.

 Used in automobile crankshafts, pipe

fittings, etc. NEXT
 GRAY CAST IRON
3. Gray cast iron
 Cast irons containing graphite in the
form of flakes are called gray cast irons,
because the fracture surface looks black
(gray) in colour.

 Due to the presence of high silicon

content (2-3%Si), the alloy will form
austenite and graphite(in the form of
irregular elongated and curved flakes) at
the eutectic temperature.
 GRAY CAST IRON

Graphite Flakes Pearlite

or Ferrite

Microstructure Gray Cast Iron

 GRAY CAST IRON
 The microstructure consists of graphite
embedded in a matrix of ferrite or pearlite.

 Gray cast iron is brittle ( ½% elongation)

due to the presence of graphite flakes
which has sharp tips and act like internal
cracks or stress raisers.

 The properties of gray cast iron depends

on the morphology and size of graphite
flakes and matrix.
 GRAY CAST IRON
Properties & applications
 Excellent machinability due to the
presence of graphite flakes.

 It has excellent fluidity and takes

the mould impression quite well.

 The wear resistance of gray cast

iron is very good, as the graphite
flakes acts as lubricant.
 GRAY CAST IRON
 They have excellent damping capacity than
steel due to more internal discontinuities
which favour fast dissipation of vibrational
energy.

 Due to its good compressive strength and

damping capacity it is used as base for
erection of machinery.

 It is also used for cylinder blocks and

pistons of IC engines, pump housings,
gear housing, etc. NEXT
 NODULAR CAST IRON
4. Nodular cast iron

 Spheroidal graphite iron, ductile iron or

nodular iron is the cast iron which
has the graphite present in the form
of tiny balls or spheroids.

 The fairly high silicon content

(2.5%Si) promotes graphitization
during solidification.
 NODULAR CAST IRON

 The modifier (i.e, magnesium and

cerium) makes the growth rate of
graphite to be approximately same in
all directions.

 Thegraphite nodules in this iron is

more spherical than that of temper
carbon.
 NODULAR CAST IRON

Graphite
Pearlite
Spheroids

Microstructure Nodular Cast Iron

 NODULAR CAST IRON
Properties & applications

 Ithas tensile strength of (400-700

MPa) and %elongation between 10-18.

 It is the major engineering material as

it combines the engineering advantage
of steel with the processing
economics of cast iron.
 NODULAR CAST IRON

 Used in agricultural implements,

automotive crankshaft, pistons,
gears, chuck bodies, elevator
buckets in mining, etc.

NEXT
 WROUGHT IRON

 Definition

 Manufacturing process

 Properties & applications

 WROUGHT IRON
DEFINITION

Wrought iron is essentially a two-

component metal consisting of
high-purity iron and slag ( slag is
composed mainly of iron silicate).

NEXT
 WROUGHT IRON
Manufacturing process
i. To melt and refine the base metal.

ii. To produce and keep molten a

proper slag.

iii. To disintegrate the base metal and

mechanically incorporate the slag of
desired amount into the base metal.
 WROUGHT IRON
 In the Byer’s process of manufacturing
consists of the following steps:

 The raw materials such as pig iron,

scrap, etc. are melted in cupolas.

 The pig iron is purified to a highly

refined state in a Bessemer converter
and then transferred to the ladle of the
processing machine.
 WROUGHT IRON
 Iron silicate slag made by melting
together iron oxide and certain
siliceous materials in an open-hearth
furnace is poured into a ladle and
moved directly below the processing
machine.

 The base metal kept at 1535°C is

poured at a predetermined rate into the
ladle containing the molten slag which
is at about 1260°C.
 WROUGHT IRON
 Since the slag is maintained at lower
temperature than the base metal the
metal solidifies rapidly.

 Due to this rapid solidification the

dissolved gases in the liquid is
liberated in the form of small
explosion and this explosion shatters
the metal into small fragments which
settle at the bottom of the slag ladle.
 WROUGHT IRON
 Since the iron is in the welding
temperature the fragments stick
together to form a sponge like ball
of iron globules coated with silicate
slag.

 This globules are passed through

grooved rollers as a result they get
converted into puddle bars.
NEXT
 WROUGHT IRON
Properties & applications

 The carbon content is between 0.02 -

0.03% and slag content between 1-3%.

 It possess high resistance to

corrosion.

 It is never cast, and all shaping is done

by hammering, pressing, forging, etc.
 WROUGHT IRON
 Strength can be increased by cold
working and aging.

 Owing to the nature of slag

distribution the tensile strength and
ductility is greater along the rolling
direction.

 It is used in oil industries, ship

building, under ground service
lines, coal handling plants, etc.