CHAPTER-03

B.TECH. 3RD SEM.

BRANCH- METALLURGICAL & MINING ENGG.
SUBJECT- MATERIALS ENGINEERING

METALLIC MATERIALS
DR. S. HEMBROM
ASSISTANT PROFESSOR
DEPARTMENT OF METALLURGICAL ENGINEERING
B.I.T. SINDRI, DHANBAD,JHARKHAND
 ALLOTROPIC TRANSFORMATIONS OF IRON

Iron is an allotropic metal, which means that it can exist in more than one type of
lattice structure depending upon temperature. A cooling curve for pure iron is
shown below:
 Iron – Cementite Phase Diagram
The Fe-C (or more precisely the Fe-Fe3C) diagram is an important one.
Cementite is a metastable phase and ‘strictly speaking’ should not be included in
a phase diagram. But the decomposition rate of cementite is small and hence can
be thought of as ‘stable enough’ to be included in a phase diagram. Hence, we
typically consider the Fe-Fe3C part of the Fe-C phase diagram.

A portion of the Fe-C diagram – the part from pure Fe to 6.67 wt.% carbon
(corresponding to cementite, Fe3C) – is technologically very relevant.

Cementite is not a equilibrium phase and would tend to decompose into Fe and
graphite. This reaction is sluggish and for practical purpose (at the
microstructural level) cementite can be considered to be part of the phase
diagram. Cementite forms as it nucleates readily as compared to graphite.

Compositions up to 2.1%C are called steels and beyond 2.1% are called cast
irons. In reality the classification should be based on ‘castability’ and not just on
carbon content.

Heat treatments can be done to alter the properties of the steel by modifying the
microstructure .
 IRON CARBON DIAGRAM

Reacti Peritectic L Eutectic L = γ Eutectoid γ = α

+δ=γ + Fe C + Fe3C
 Three Phase Reactions
Peritectic, at 1493°C, with low wt% C alloys (almost no engineering importance).
Eutectic, at 1147°C, with 4.3wt% C, alloys called cast irons.
Eutectoid, at 723°C with eutectoid composition of 0.8wt% C, two-phase mixture
(ferrite & cementite). They are steels.

The diagram shows three horizontal lines which indicate isothermal

reactions (on cooling / heating):
❖ First horizontal line is at 1493°C, where peritectic reaction takes place
Liquid + δ ↔ Austenite(γ)

❖ Second horizontal line is at 1147°C, where eutectic reaction takes

place
Liquid ↔ Austenite(γ) + Cementite

❖ Third horizontal line is at 723°C, where eutectoid reaction takes place:

Austenite ↔ Pearlite (mixture of ferrite & cementite)
 Ferrite(α)

It is an interstitial solid solution of a small amount of carbon dissolved in a iron.

The maximum solubility is 0.025%C at 723ºC and it dissolves only 0.008%C at
room temperature. It is the softest structure that appears on the diagram.
Ferrite is ferromagnetic at low temperatures but loses its magnetic properties with
the rise of temperatures with major loss at curies temperatures, 768ºC and above
this temperature, it becomes non magnetic (paramagnetic).
The crystal structure of ferrite (a) is B.C.C
Tensile strength – 245 Mpa,
Yield strength 118 Mpa
Elongation – 40-50% in 2 in.
Hardness - 95 VPN

α (Ferrite) –
90X

α(Ferrite)
contains
B.C.C structure
 CEMENTITE
Cementite or iron carbide, chemical formula Fe3C, contains 6.67%C by weight and
it is a metastable phase.
It is typically hard and brittle interstitial compound of low tensile strength (35 Mpa)
but high compressive strength and high hardness ~800VPN.
It is the hardest structure that appears on the diagram.
It has a complex orthorhombic crystal structure with 12 iron atoms and 4 carbon
atoms per unit cell.
It is slightly ferromagnetic up to 210ºC and paramagnetic above it. Melting point
around 1227ºC.

network
Cementite
 Pearlite (α+Fe3C)
Pearlite is the eutectoid mixture containing 0.80 %C and is formed at 723ºC on
very slow cooling.
It is very fine plate like or lamellar mixture of ferrite and cementite. The fine
finger print mixture called pearlite is shown in below figure.
The weight % of these two phases are thus in ratio 8:1
Tensile strength – 120,000 psi or 825 Mpa
Elongation – 20 percent in 2 in.
Hardness – HRC 20, HRB 95-100, or BHN 250-300

Fine Pearlit Coars

e e
 Austenite (γ)

It is an interstitial solid solution of a small amount of carbon dissolved in γ iron

and has FCC crystal structure. The maximum solubility is 2.1%C at 1147ºC.
Austenite is soft, ductile tough and malleable (FCC structure) and non magnetic
(paramagnetic).
Steels are commonly rolled and forged above about 1100ºC when they are in
austenite state due to its high ductility and malleability, which is also due to its
FCC structure.
Tensile strength – 150,000 psi or 1035 Mpa
Elongation – 10% in 2 in.
Hardness - 395 VPN and Toughness is high.

F
e
 Ledeburite (γ+Fe3C)
❖Ledeburite is the eutectic mixture of austenite and cementite. It contains 4.3%C
and is formed at 1147ºC
❖ Structure of ledeburite contains small islands of austenite are dispersed in the
carbide phase.
❖ Not stable at room temperature.
 Ferrite (δ)

❖Interstitial solid solution of carbon in iron of body centered cubic crystal structure. (δ
iron ) of higher lattice parameter (2.89Å) having solubility limit of 0.09 wt% at 1495°C
with respect to austenite. The stability of the phase ranges between 1394-1539°C.
❖It is a high temperature phase and is a high temperature manifestation of a ferrite.
❖This is not stable at room temperature in plain carbon steel. However it can be
present at room temperature in alloy steel specially duplex stainless steel.

δ-Ferrite
 Limitations on Fe—Fe3C phase diagram

❖Fe-Fe3C diagram represents behavior of steels under equilibrium conditions, whereas

the actual heat treatments of steels are normally under non-equilibrium conditions.
❖ The diagram does not indicate the character of transformation of austenite such as to
bainite, or martensite.
❖ The diagram does not indicate the presence of metastable phases like martensite, or
bainite.
❖ It does not indicate the temperature of start of martensite Ms or bainite B.
❖ It does not indicate the kinetics of the transformation of austenite to martensite,
bainite or even pearlite.
❖ It does not indicate the possibilities of suppressing the pearlitic or bainitic
transformations.
❖ It does not indicate the possibilities of suppressing the pearlitic or bainitic
transformations.
 Time Temperature Transformation (TTT) Diagram:

❖ TTT diagram is a plot of

temperature versus the
logarithm of time for a steel
alloy of definite composition.

❖ It is used to determine when

transformations begin and end
for an isothermal heat
treatment of a previously
austenitized alloy.

❖ TTT diagram indicates when a

specific transformation starts
and ends and it also shows what
percentage of transformation of
austenite at a particular
temperature is achieved.
 Time Temperature Transformation (TTT) Diagram:
❖ Depending on the type of heat treatment, time and temperature, final microstructure
of the steel, or any Iron carbon will be changed and so does the properties.

Martensite
T Martensite

STRENGTH

DUCTILITY
Bainite
Fine Pearlite
Coarse Pearlite
Spheroidite

General Trends
 Time-Temperature-Transformation (TTT) Diagrams
❖The temperature of transformation controls the nature of decomposed product (of
austenite) which in turn decides the resultant properties of steel.
❖ The kinetics of austenitic transformation can be studied best at a constant
temperature rather than by continuous cooling.
❖ The constant temperature transformation is also referred to as isothermal
transformation.
❖ Davenport and Bain were the first to develop the TTT diagram of eutectoid steel.
They determined pearlite and bainite portions whereas Cohen later modified and
included Ms and Mf temperatures for martensite.
❖ There are number of methods used to determine TTT diagrams. The most popular
method is salt bath techniques combined with metallography and hardness
measurement with addition of this we have other techniques like dilatometry,
electrical resistivity method, magnetic permeability, in situ diffraction techniques
(X-ray, neutron), acoustic emission,thermal measurement techniques, density
measurement techniques and thermodynamic predictions.
❖TTT diagrams, also called as Isothermal (temperature constant) Transformation
diagrams.
❖ For every composition of steel we should draw a different TTT diagram.
 Determination of TTT diagram for eutectoid steel
❖For the determination of isothermal transformation (or) TTT diagrams, we consider molten salt
bath technique combined with metallography and hardness measurements.
❖ In molten salt bath technique two salt baths and one water bath are used.
❖Salt bath I is maintained at austenising temperature (780°C for eutectoid steel).
❖Salt bath II is maintained at specified temperature at which transformation is to be determined
(below A, typically 700-250°C) for eutectoid steel.
❖ Bath III which is a cold water bath is maintained at room temperature.
❖ In bath I number of samples are austenite at A1 +20-40°C for eutectoid, A3 +20-40°C for
hypo-eutectoid steel and ACm +20-40°C for hyper-eutectoid steels for about an hour.
❖ Then samples are removed from bath I and put in bath II and each one is kept for different
specified period of time say t1, t2, t3, t4,…..........,tn etc.
❖ After specified times, the samples are removed and quenched in cold water.
❖ The microstructure of each sample is studied using metallographic techniques. The type, as
well as quantity of phases, is determined on each sample.
❖ Transformation of austenite to ferrite-cementite mixtures occurs after a definite time (say
t).This time during which transformation does not proceed is known as incubation period.
❖ The magnitude of incubation period provides a qualitative idea about the relative stability of
supercooled austenite. Smaller incubation period corresponds to lesser stability of austenite.
Determination of TTT diagram for eutectoid steel

Eutectoid section of the iron - carbon diagram

TTT curve of austenite to pearlite for 1080 steel

 TTT DIAGRAM
Example :
❖ Iron-carbon alloy with
eutectoid composition.
❖ Specify the nature of the final
microstructure (% bainite,
martensite, pearlite etc) for the
alloy that is subjected to the
following time–temperature
treatments:
❖ Alloy begins at 760°C and has
been held long enough to
achieve a complete and
homogeneous austenitic
structure.
Treatment :
(i) Rapidly cool to 350°C,
Hold for 104 seconds, Quench
to room temperature.
 TTT DIAGRAM
Example :
❖Iron-carbon alloy with
eutectoid composition .
❖ Specify the nature of the final
microstructure (% bainite,
martensite, pearlite etc) for the
alloy that is subjected to the
following time–temperature
treatments:
❖Alloy begins at 760°C and has
been held long enough to achieve
a complete and Homogeneous
austenitic structure.
❖Treatment :
(i) Rapidly cool to 250 °C
(ii) Hold for 100 seconds
(iii) Quench to room temperature
HEAT TREATMENT
 OBJECTIVE

Heating and cooling a solid metal or

alloy in a way so as to obtain specific
conditions and/or properties
Physical
Mechanical
Electrical
Magnetic
CLASSIFICATION OF HEAT TREATMENT
 Objectives
To increase strength, hardness and wear resistance (bulk hardening, surface
hardening)
To increase ductility and softness (Tempering, Recrystallization Annealing)
To increase toughness (Tempering, Recrystallization annealing)
To obtain fine grain size (Recrystallization annealing, Full annealing,
Normalizing)
To remove internal stresses induced by differential deformation by cold working,
non- uniform cooling from high temperature during casting and welding (Stress
relief annealing)
To improve machinability (Full annealing and Normalizing)
To improve cutting properties of tool steels (Hardening and Tempering)
To improve surface properties (surface hardening, high temperature resistance-
To improve surface properties (surface hardening, high temperature resistance
precipitation hardening, surface treatment)
To improve electrical properties (Recrystallization, Tempering, Age hardening)
To improve magnetic properties (Hardening, Phase transformation)
 ANNEALING PROCESS
Annealing involves heating the material to a predetermined temperature and hold
the material at the temperature and cool the material to the room temperature
slowly.
The Steps involves:
1) Heating of the material at the elevated or predetermined temperature.
2) Holding the material (Soaking) at the temperature for longer time.
3) Very slowly cooling the material to the room temperature.
 ANNEALING PROCESS

The various purpose of these heat treatments is to:

1) Relieve Internal stresses developed during solidification, machining, forging, rolling

or welding.

2) Improve or restore ductility and toughness.

3) Enhance Machinability.

4) Eliminate chemical non-uniformity.

5) Refrain grain size, &

6) Reduce the gaseous contents in steel.

Full Annealing:

The steel is heated above A3 (for hypo-eutectoid steels) , A1 (for

hyper-eutectoid steels) →(hold) →then the steel is furnace cooled
to obtain Coarse Pearlite .

Coarse Pearlite has ↓ Hardness, ↑ Ductility.

Not above Acm →to avoid a continuous network of proeutectoid

cementite along grain boundaries (→path for crack propagation)
 NORMALIZING PROCESS
Heat above A3 /Acm→Austenization →Air cooling →Fine Pearlite ((Higher
hardness)
Normalizing is similar to full annealing, except steel is generally cooled in still air.
The normalizing consists of heating steel to about 40-550C above critical temperature (Ac3or
Acm), and holding for proper item and then cooling in still air or slightly agitated air to room
temperature.
In some special cases, cooling rates can be controlled by either changing air temperature or
air volume.
❖After normalizing, the resultant micro-structure should be pearlitic. Since the
temperature involved in this process is more than that for annealing , the
homogeneity of austenite increases and it results in better dispersion of
ferrite and Cementite in the final structure.
❖ The grain size is finer in normalized structure than in annealed structure.
Normalized steels are generally stronger and harder than fully annealed steels.

Steels are soft in annealed condition and tend to stick during machining. By
normalizing, an optimum combination of strength and softness is achieved, which
results in satisfactory level of Machinability in steels.

Normalizing is the effective way to eliminate the carbide network.

Normalized treatment is frequently applied to steel in order to achieve any

one or more of the objectives, namely:
1.To refine the grain structure.
2. To obtain uniform structure.
3. To decrease residual stresses.
4. To improve Machinability.
 HARDENING PROCESS
Heat above A3/Acm→Austenization →Quench (higher than critical cooling rate)
❖Hardening and Hardness are two different things. One is a process of heat
treatment and other is a extrinsic property of a material.
❖ Hardening is a heat treatment process in which steel is rapidly cooled from
austenitising temperature. As a result of hardening, the hardness and wear
resistance of steel are improved.
❖ Hardening treatment generally consists of heating to hardening temperature,
holding at that temperature, followed by rapid cooling such as quenching in oil or
water or salt baths.
 The high hardness developed by this process is due to the phase transformation accompanying
rapid cooling. Rapid cooling results in the transformation of austenite at considerably low
temperature into non equilibrium products.
The hardening temperature depends on chemical composition. For plain carbon steels, it
depends on the carbon content alone. Hypoeutectoid steels are heated to about 30–50 0C above
the upper critical temperature, whereas eutectoid and hyper eutectoid steels are heated to about
30 – 500C above lower critical temperature.
Ferrite and pearlite transform to austenite at hardening temperature for hypoectectoid steel.
This austenite transforms to martensite on rapid quenching from hardening temperature. The
presence of martensite accounts for high hardness of quenched steel.
❖Hardening is applied to cutting tools and machine parts where high hardness and wear
resistance are important.
The Process Variables:
1. Hardening Temperature:The steel should be heat treated to optimum austenitising
temperature. A lower temperature results lower hardness due to incomplete transformation t
austenite. If this temperature is too high will also results lower hardness due to a coarse
grained structure.
2. Soaking Time: Soaking time at hardening temperature should be long enough to transform
homogenous austenite structure. Soaking time increases with increase in section thickness and
the amount of alloying element.
3. Delay in quenching: After soaking, the steel is immediately quenched. Delay in quenching
may reduce hardness due to partial transformation of austenite.
Hardening :
The main purpose of hardening tool steel is to develop high hardness.This enables
tool steel to cut other metals. High hardness developed by this process also
improves wear resistance. Gears, shafts and bearings.Tensile strength and yield
strength are improved considerably hardening structural steels.

Because of rapid cooling, high internal stresses are developed in the hardened
steel. Hence these steels are generally brittle. Hardening in general is followed by
another treatment known as tempering which reduces internal stresses and makes
the hardened steel relatively stable,
 TEMPERING PROCESS
Hardened steels are so brittle that even a small impact will cause fracture.
Toughness of such a steel can be improved by tempering. However there is small
reduction in strength and hardness.
Tempering is a sub-critical heat treatment process used to improve the toughness
of hardened steel.
Tempering consists of reheating of hardened steel to a temperature below
Lower critical temperature and is held for a period of time, and then slowly
cooled in air to room temperature.
At tempering temperature, carbon atoms diffuses out and form fine cementite and
softer ferrite structure left behind. Thus the structure of tempered steel consists of
ferrite and fine cementite.
Thus tempering allows to precipitate carbon as very fine carbide and allow the
microstructure to return to BCC.
The temperatures are related to the function of the parts. Cutting tools are tempered
between 230 – 3000C . If greater ductility and toughness are desired as in case of
shafts and high strength bolts, the steel is tempered in the range of 300 – 600 0C.
Tempering:
Tempering temperatures are usually identified by the colour. Tempering
temperatures for tools and shafts along with temper colors.
Depending on temperatures, tempering processes can be classified as:
1) Low- tempering temperature (150 – 2500C)
2) Medium – tempering temperature (350 – 4500C )
3) High – tempering temperature (500 – 6500C)
Tempering:
The hardened steel is not readily suitable for engineering applications. It
possesses following three drawbacks.
Martensite obtained after hardening is extremely brittle and will result in failure
of engineering components by cracking.
Formation of martensite from austenite by quenching produces high internal
stresses in the hardened steel.
Structures obtained after hardening consists of martensite and retained
austenite. Both these phases are austenite. Both these phases are metastable and
will change to stable phases with time which subsequently results in change in
dimensions and properties of the steel in service.
Tempering helps in reduce these problems. Tempering is the process of heating
the hardened steel to a temperature maximum up to lower critical temperature
(A1), soaking at this temperature, and then cooling, normally very slowly.
 SURFACE HARDENING - CARBURISING
❖Carburising is carried out on a steels containing carbon less than 0.2%. It involves
increasing the carbon contents on the surface layers upto 0.7 to 0.8%.
❖ In this process, the steel is heated in contact with carbonaceous material from
which it absorbs carbon. This method is mostly used for securing hard and wear
resistance surface with tough core carburising is used for gears, cams, bearings and
clutch plates.
2 CO C + CO2
❖ The Following methods are used to diffuse carbon into surface layers:
(1) Pack (solid) Carburising, (2) Gas Carburising,
(3) Liquid Carburising.

Gas Carbusing process

Liquid Carburising
Process
 NITRIDING PROCESS
❖ Nitriding involves diffusion of nitrogen into the product to form nitrides. The
resulting nitride case can be harder than the carburized steel. This process is used
for alloy steels containing alloying elements (Aluminum, Chromium and
Molybdenum) which form stable nitrides.
❖ Nitriding consists if heating a component in a retort to a temperature of about 500
to 6000C. Through the retort the ammonia gas is allowed to circulate. At this
temperature the ammonia dissociates by the following reaction.
2 NH3 2N + 3H2
❖ The atomic nitrogen diffuses into steel surface, and combines with the alloying
elements (Cr, Mo, W, V etc) to form hard nitrides. The depth to which nitrides are
formed in the steel depends on the temperature and the time allowed for the
reaction. After the nitriding the job is allowed to cool slowly. Since there is no
quenching involved, chances of cracking and distortion of the component are less.
❖ Nitriding : The depth of nitrided case ranges from 0.2 to 0.4 mm and no
machining is done after nitriding.
❖ Nitriding increase wear and corrosion resistance and fatigue strength of the steel.
Since nitriding is done at low temperature, it requires more time than carburising,
and also the capital cost if the plant is higher than carburising.
 HARDENABILITY
Hardenability:
❖ The responsibility of a steel to a
given hardening treatment is indicated
by the property known as
Hardenability.
❖ It is an index of the depth to which
the martensite can be formed in a
given steel as a result of a given
hardening treatment.
❖ The term Hardenability is used to
measure the depth of hardness
achieved i.e. martensite introduced
into the steel section by quenching the
steel from austenite state.
❖ Greater the depth of hardness below
the surface, higher will be the
Hardenability of steel.
•Engineering Materials
• Metals
• Ferrous
•Steel

•Alloy steel
•Cast iron
•Wrought iron

•Non-Ferrous
•Copper & Alloys

•Aluminium& Alloys
•Lead & Alloys

•Tin

•Nickel & Alloys

❖ Effect of the alloy materials on cast iron-:

1. Silicon -: It also helps to produce ,sound casting free from blow-holes.

2. Sulphur -: It makes the cast iron hard and brittle.

3. Manganese -: It may be present in cast iron upto 0.75%.It makes the cast
iron white and hard.

4. Phosphorus-: It’s content in cast iron varies between 0.05 to 1.00%.

5. Carbon -: If carbon is present in combined form, it makes the iron hard

and strong.
Steels -:
In alloy of carbon and iron with carbon content usually ranges from 0.08 to
1.5 %. These steels are called plain carbon steels or simply carbon steels.
Steels generally contain small amounts of sulphur , phosphorous , silicon
,and manganese in addition to carbon.

The carbon steels can be classified on the basis of their carbon content as -:

(i) Low carbon steel

( ii) Medium carbon steel

(iii) High carbon steel

 ALLOY STEEL :

❖ Alloy steel may be defined as steels to which elements other than carbon
are added in sufficient amounts to produce improvements in properties. In
general ,alloy steels can give better strength, ductility,and toughness than
plain carbon steels. The commonly added elements include nickel,
chromium,silicon ,manganese ,tungsten molybdenum, copper,cobalt,
aluminium,etc.

Main types of alloy steels used in practice are -:

(i) Stainless steels
(ii) Heat resisting steels
(iii) High speed steels
(iv) Spring steels
EFFECT OF THE ALLOYING ELEMENTS ON ALLOY STEEL:

1. Silicon -: The amount of steel usually ranges from 0.05 to 0.30%.

2. Manganese -: It commonly ranges from 0.30 to 1.00%.

3. Sulphur -: It contains in steel either as iron sulphide or manganese sulphide.

4. Phosphorus -: The phosphorus content should not exceed 0.05% in good

quality steels.

5. Nickel -: It increases the strength and toughness of the steel.

6. Chromium -: It imparts corrosion-resisting properties to steels.

7. Tungsten -: It forms hard abrasion resistant particles,increases strength and

high elastic limit.
 • NON-FERROUS MATERIALS -:
• The non-ferrous metals are those which contain a metal other than iron as
their chief constituent. They are usually used in industry due to the
following characteristics.

(i) Ease of manufacturing

(ii) Resistance to corrosion
(iii) Electrical and thermal conductivity
(iv) Weight

❖ IMPORTANT NON-FERROUS METALS ARE ALUMINIUM,

COPPER, LEAD,TIN,NICKEL,ZINC,ANDTITANIUM.
 ALUMINIUM AND ITS ALLOYS-:

❖ Aluminum is silvery-white and lighter in weight than steel and copper.

❖ It has high corrosion resistance.
❖ Low density (1.7 g/cc), low melting point (6600C), high ductility(Even room
temp.)
❖ High electricity and high conductivity.
❖ Aluminium has good machinability,formability and castability.
❖ Duralumin and Y-alloy are the important aluminium alloys.

❖ Application-: These are widely used in air craft and automobile industry,
food and chemical handling etc,.
• COPPER AND ITS ALLOYS-:

• Copper is one of the most widely used non-ferrous metals in industry. It is a

soft, malleable, good conductor of electricity.

Following are the main alloys of copper:

(1) Brass (2) Bronze

APPLICATION-: Copper is largely used in making electric cables and wires

for electric machinery and appliances,refrigerators etc.
• LEAD AND ITS ALLOYS-:

• Lead is the heaviest and softest among all common metals. It is corrosion
resistant and having good lubricating properties.

Application -: It is extensively used for making solder, as a lining for acid

tanks ,water pipes, batteries ,bearings,etc.
• NICKEL AND ITS ALLOYS -:

• Nickel is an important alloying element and widely used in

engineering industry on account of their high mechanical strength
properties , corrosion resistance, etc.

Application -:
A large percentage of nickel is used for production of stainless
steels. these are used in making propellers, condenser tubes etc.
 ASSIGNMENT-03
1. Draw the Iron –Carbon equilibrium diagram and level the various phases
present in it and also writes the various invariant reactions that takes
place at different temperatures.

2. Write short notes on the following.

(a) Annealing (b) Aluminium alloys
(c) Nitriding (d) Copper alloys
(e) Normalizing. (f) Cyaniding
3. Draw a neat sketch of the T T T diagram for a eutectoid steel and label the
regions.
4. What are δ-iron and Austenite?
5. Define the term heat treatment .why are the steels heat treated?
6. Differentiate between Hardness and Hardenability. Draw hardness and
hardenability curves for steel.