HEAT TREATMENT

TECHNOLOGY
 Unit 3: Ferrous metals and Designation

What is steel?
Steel is a interstitial solid solution of
iron and carbon containing 0.008 to
2% carbon by weight
COOLING CURVE OF PURE Fe

δ - Fe

γ - Fe

α - Fe
 Phases in Steel

α-ferrite
Interstitial solid solution of carbon dissolve in
α-iron having BCC structure.
Maximum solubility of carbon in α-iron is
0.02% (at 7270C)
At room temperature solubility is 0.008%
 Phases in Steel

Properties of α-ferrite
Soft and ductile phase
Ferromagnetic upto curie temperature(7680C)

Tensile Strength 40,000psi (276 Mpa)

Elongation 40% (2in GL)
Hardness 80 BHN
Toughness Low
 Phases in Steel

Microstructure of α-ferrite
 Phases in Steel

Austenite (γ)
Interstitial solid solution of carbon dissolve in
γ-iron having FCC structure.
Maximum solubility of carbon in γ-iron is 2.%
(at 11470C)
Stable only above 7270C
 Phases in Steel

Properties of Austenite
Soft and ductile phase
Non magnetic
It can be extensively worked at the temperature
of its existence.

Tensile Strength 1,50,000psi (1034 Mpa)

Elongation 10% (2in GL)
Hardness Rc 40
Toughness High
 Phases in Steel

Microstructure of Austenite
Why Solubility of Carbon in Austenite is Very High?

Austenite, being FCC have four atoms per unit cell

Ferrite, being BCC have two atoms per unit cell
Empty space in FCC Austenite=25%
Empty space in BCC Ferrite=32%
This means Austenite have much denser packing of
atoms than ferrite.
Still Solubility of Carbon in Austenite (2%) is very
high compare to Ferrite (0.02).
Why Solubility of Carbon in Austenite is Very High?

(c) tetrahedral interstices

in bcc structure,
(d) octahedral interstices
in bcc structure
(e) and (f) octahedral interstices
in bcc and fcc iron
Why Solubility of Carbon in Austenite is Very High?
It is interesting that the fcc structure, although more closely packed,
has larger holes than the bcc structure. These holes are at the centres of
the cube edges, and are surrounded by six atoms in the form of an
octagon, so they are referred to as octahedral holes
Why Solubility of Carbon in Austenite is Very High?

Reason:
The largest interstitial sphere that would just fit in
BCC cell has radius of 0.36 x 10-8cm

The largest interstitial sphere that would just fit in

FCC cell has radius of 0.52x10-8cm
Why Solubility of Carbon in Austenite is Very High?

α-ferrite
BCC
Radius
=0.36x 10- 8 cm
Why Solubility of Carbon in Austenite is Very
High?

Radius
Austenite =0.52 x 10- 8 cm

FCC
 Phases in Steel

δ-ferrite
Interstitial solid solution of carbon dissolve in
δ-iron having BCC structure.
Maximum solubility of carbon in δ-iron is
0.1% (at 14920C)
Stable only above 14000C
 Phases in Steel

Iron Carbide (Cementite)

Intemetallic compound of iron and carbon
with fixed carbon content of 6.67% and having
orthorhombic structure.
Chemical formula Fe3C
Metastable phase
Free Energy Unstable

Metastable

Stable
 Phases in Steel

Properties of Iron Carbide

(Cementite)
Extremely hard and brittle phase
Ferromagnetic upto 2100C
Tensile Strength 5000psi (35 MPa)
Elongation 1%
Hardness 900-1200 VHN
Toughness Very Low
Compressive Strength Very High
 Transformations
 Peritectic reaction:
S1 + L S2

 Eutectic reaction:

L S1 + S2

 Eutectoid reaction:

S1 S2 + S3

9-5
 Transformations
Peritectic reaction:
General Reaction:
S1 + L S2

Reaction in steel: 14920C

Liquid + δ Cooling γ
0.55%C 0.1% C 0.18% C
BCC FCC

9-5
 • GEN FORM: S1 + L -> S2, AT
PERITECTIC CONST. TEMP. 1492°
REACTION • δ + L C γ
(0.1%C) (0.55%C) (0.18%C)
δ+L L • PERITECTIC TRANS RANGE:
0.1 % - 0.55 % C
γ+ • STEELS WITH (0.1 < C <
Fe3C 0.18%), hypoperitectic steels
• STEELS WITH
(0.18 < C < 0.55%), are called
hyperperitectic steels
• PRACTICALLY OF NO USE AS
“BURNING OF STEEL”
 Transformations
Eutectic reaction:
General Reaction:
L S1 + S2
Reaction in steel:

Liquid 11470C γ + Fe3C

4.3%C Cooling 2% C 6.67% C
FCC Orthorhom

9-5
EUTECTIC • GEN FORM: L -> S1 + S2, AT
CONST. TEMP.
REACTION
• L 1147° γ + Fe3C
C
(4.3%C) (2.0%C) (6.67%C)
• EUTECTIC MIXTURE OF ( γ +
Fe3C) CALLED AS LEDEBURITE
• AT LOW TEMP, γ NOT STABLE;
727° TRANFORMED TO PEARLITE
C
• AT ROOM TEMP, STR HAS
(PEARLITE + CEMENTITE)
CALLED AS TRANFORMED
LEDEBURITE (HARD,BRITTLE)
 Transformations
Eutectoid reaction:
General Reaction:
S1 S2 + S3
Reaction in steel:

γ 7270C α + Fe3C
0.8%C Cooling 0.02% C 6.67% C
FCC BCC Orthorhombic

9-5
 • GEN FORM: S1 -> S2 + S3, AT
EUTECTOID
REACTION CONST. TEMP.
• γ 727
°C
α + Fe3C

(0.8%C) (0.025%C) (6.67%C)

γ γ + Fe3C FCC BCC O’RHOMBIC
• EUTECTOID MIXTURE OF
(α+Fe3C) CALLED AS “pearlite”
• PEARLITE HAS ALTERNATE
α+ LAMELLAE OF α AND Fe3C
Fe3C
 Eutectoid reaction:
γ 7270C α + Fe3C
0.8%C Cooling 0.02% C 6.67% C
FCC BCC Orthorhombic
This eutectoid mixture is called Pearlite due to its pearly
appearance under microscope.

Pearlite: It is a eutectoid mixture of alpha ferrite

and cementite formed from austenite containing
0.8%C while cooling at 7270C

9-5
 Phases in Steel

Properties of Pearlite
Good Hardness and T.S.
magnetic

Tensile Strength 1,20,000psi (825 Mpa)

Elongation 20% (2in GL)
Hardness Rc 20 (250 BHN)
Toughness High
 Phases in Steel

Microstructure of Pearlite
 Phases in Steel

Microstructure of Pearlite
Microstructure of Pearlite
 Phases in Steel

Microstructure of Pearlite
Laminar (Platelike) or Fingerprint Microstructure

Ferrite (white)

Cementite
(dark)
Fe-C EQUILIBRIUM DIAGRAM
34
Cooling of Eutectoid Steel (0.8% C)
 Off Eutectoid Steels

Steels with compositions

between 0.008 to 0.8 wt% Carbon
are hypoeutectoid steels.

Steels with compositions

between 0.8 to 2 wt% Carbon are
hypereutectoid steels
 Cooling of Hypoeutectoid Steel (0.8% )
T(°C)
1600
d
1400 L
g g g +L
g g 1200
g
1148°C L+Fe3C

Fe3C (cementite)
(austenite)
g g
g g 1000
g + Fe3C
a
ag g 800 727°C
g ag a
600
a + Fe3C
400
a 0 1 2 3 4 5 6 6.7
(Fe)C0
0.76

C, wt% C
pearlite

Hypoeutectoid Steels 37
 Cooling of Hypoeutectoid Steel (0.8% )
Proeutectoid α-ferrite
• Formed before the eutectoid
• Ferrite that is present in the pearlite is called eutectoid ferrite.
• The ferrite that is formed above the Teutectoid (727°C) is proeutectoid.

38
 Cooling of Hypereutectoid Steel (0.8% )
T(°C)
1600
d
1400 L
g g g g +L
g g
1200 1148°C L+Fe3C

Fe3C (cementite)
(austenite)
g g 1000
g g g +Fe3C
Fe3C
g g 800
g g a
600
a +Fe3C
400
0 1 2 3 4 5 6 6.7
0.8

(Fe) C, wt%C
pearlite

Hypereutectoid Steels
Cooling of Hypereutectoid Steel (0.8% )

Proeutectoid Cementite
 Hypereutectoid Steel

Microstructure of Hypereutectoid Steel

COOLING OF HYPO / EUTECOID /
HYPEREUTECTOID STEELS
 Critical Temperatures in
Iron-Iron Carbide Equilibrium Diagram
S. Critical Temp Significance During Heating
N. Points
1 A0 210 0C Cementite becomes
paramagnetic
2 A1 727 0C Perlite Austenite
3 A2 768 Ferrite becomes
paramagnetic
4 A3 727- Completion of
9100C Ferrite Austenite
5 Acm 727- Completion of
11470C Cementite Austenite
 Critical Temperatures in
Iron-Iron Carbide Equilibrium Diagram
S. Critical Temp Name of Critical
N. Points Temperature
1 A0 210 0C Curie Temperature of Fe3C
2 A1 210 0C Lower Critical Temperature
3 A2 768 Curie Temperature of Ferrite
4 A3 727- Upper Critical Temperature
9100C for Hypoeutectoid Steel
5 Acm 727- Upper Critical Temperature
11470C for Hypereutectoid Steel
Numerical Examples
Ex.1:For eutectoid steel determine amount of
alpha ferrite and cementite just below the
eutectoid temperature
 Numerical Examples
Ex.2:For peritectic steel determine amount of
delta ferrite and austenite just below the
peritectic temperature

Ex.3:For eutectic cast iron determine amount of

austenite and cementite just below the
eutectic temperature
Ex.4: Find the maximum amount of
proeutectoid cementite in any steel.
 Numerical Examples
Ex.5:For 0.40 % C steel at a temperature just
below the eutectoid, determine the
following
a) Amount of pearlite and proeutectiod ferrite
(a)
b) the amount of cementite
 Numerical Examples
Ex.5:For 1.1 % C steel under equilibrium
conditions determine the following:
a) Amount of austenite and proeutectiod
cementite just above eutectoid temp.
b) Amount of pearlite and proeutectiod
cementite and total cementite at room
temperature.
 Numerical Examples
Ex.6:A slowly cooled steel contains 10% proeutectoid
ferrite at room temperature. Determine the
amount total ferrite and cementite present in the
alloy.
Ex.7:A slowly cooled steel contains 60% ferrite and
40% pearlite at room temperature. Determine the
amount of pearlite, total ferrite and cementite
present in the alloy at the temperature just below
eutectoid temperature.
Property Variation With Microstructure
Mechanical properties are structure sensitive
Mech Properties= f (Types of phases, amount of
phases and morphology of
structure)
Morphology means distribution of phases
For two phase alloy with α-β structure, the property on an
average can be expressed as(when morphology is
insignificant):

Average property=
Amount of α x property of α
+ Amount of β x property of β
Property Variation With Microstructure

Since hardness is less sensitive to morphology.

For hypoeutectoid steels:
Hardness (BHN) =
Amount of α-ferrite x Hardness of of α-ferrite
+ Amount of pearlite x Hardness of pearlite

= Amount of α-ferrite x 80 BHN

+ Amount of pearlite x 230 BHN
Property Variation With Microstructure

Since hardness is less sensitive to morphology.

For hypereutectoid steels:
Hardness (BHN) =
Amount of Fe3C x Hardness of of Fe3C
+ Amount of pearlite x Hardness of pearlite

= Amount of Fe3C x 900 +

Amount of pearlite x 240
Property Variation With Microstructure
Many of the mechanical properties like T.S., ductility,
toughness are very sensitive to morphology. Hence,
unless the distribution of phases are not known
correctly, property prediction can not be done
accuratly.
For hypoeutectoid steels:
Since phases are well distributed in
hypoeutectoid steels T.S. is less sensitive to
morphology.
T.S. (psi)
= Amount of α-ferrite x 40000 psi
+ Amount of pearlite x 1,20,000 psi
Property Variation With Microstructure

For hypoeutectoid steels:

T.S. (kg/mm2)
= Amount of α-ferrite x 28 kg/mm2
+ Amount of pearlite x 84 kg/mm2
= (1- %C/0.8) x 28 kg/mm2
+ ( %C/0.8) x 84 kg/mm2
T.S. of hypoeutectoid steel increases by
7kg/mm2 for every 0.1%C rise.

T.S. (kg/mm2)= 0.36 X BHN

 Property Variation With Microstructure

T.S.
Property

84 kg/mm2
350 BHN
40%
Hardness
230 BHN

28 kg/mm2

10%
80 BHN
Ductility
0.4 0.8 1.2 2.0

%C
Non Equilibrium Cooling of Steels
Non Equilibrium Cooling of Steels
Non-equilibrium cooling means cooling faster
than equilibrium cooling.
Faster cooling lowers all transformation
temperatures
Eutectoid point shift towards left side for
hypoeutectoid steel and towards right for
hypereutectoid steel
Amount of proeutectoid phase decreases and
amount of pearlite increases
Pearlite becomes finer.
 WIDMANSTATTEN STRUCTURE

• DURING COOLING OF STEELS, PROEUTECTOID

PHASE SEPERATES IN GRAINS ALONG CERATIN
CRYSTALLOGRAPHIC PLANES & DIRECTIONS
• SEPERATING PROEUTECTOID FERRITE OR
CEMENTITE HAS A DEFINITE ORIENTATION
RELATIONSHIP WITH PRIOR AUSTENITE PHASE
• STRUCTURE SHOWS TYPICAL GEOMETRIC
PATTERN UNDER THE MICROSCOPE i.e. W’ STR
WIDMANSTATTEN STRUCTURE
 WIDMANSTATTEN STRUCTURE

• DEPENDS ON
1. COMPOSITION OF STEEL: HIGHER THE
PROEUTECTOID PHASE, MORE ARE CHANCES OF
FORMATION OF W’STR AS PROEUTECTOID
PHASE WILL SEPARATE INSIDE THE GRAINS
ITSELF INSTEAD OF AT GRAIN BOUNDARY
2. GRAIN SIZE OF AUSTENITE: LARGER THE GRAIN
SIZE, MORE CHANCES OF FORMATION OF
W’STR, AS HIGHER DISTANCE HAS TO BE
COVERED TOWARDS GRAIN BOUNDARY REGION
 WIDMANSTATTEN STRUCTURE

3. COOLING RATE: FASTER COOLING RATE, NO

SUFFICIENT TIME FOR MIGRATION OF
PROEUTECTOID PHASE TO GRAIN BOUNDARY
• W’STR SHOWN BY STEELS CONTAINING LESS
THAN 0.6% C & MORE THAN 1% C WHEN
COOLED AT HIGHER COOLING RATE
• FOR HYPOEUTECTOID STEEL: LOW
TOUGHNESS,DUCTILITY SO NOT BENEFICIAL
• FOR HYPEREUTECTOID STEELS: BETTER
PROPERTIES
 INTRODUCTION

What is Heat Treatment

A combination of heating and cooling
operations, timed and applied to a metal or
alloy in solid state in a way that will produce
desired properties
 Unit 4: Heat Treatment of Steels

Objectives of Heat Treatments

To increase hardness, wear and abrasion resistance
and cutting ability of steels
To resoften the steel after it has been hardened by
heat treatment or cold working.
To adjust its other mechanical, physical or chemical
properties such as hardness, T.S., ductility,
electrical and magnetic properties, microstructure
or corrosion resistance
 Unit 4: Heat Treatment of Steels

Objectives of Heat Treatments

To reduce or eliminate internal residual stresses.
Internal stresses lead to premature and brittle
failures of the components. They also reduce
corrosion resistance and hence are not desirable
To induce controlled residual stresses; e.g.
compressive stresses on the surface sharply
increase the fatigue life of components
To stabilize the steel so that it does not show
changes in dimensions with time. This property is
highly essential for precision gauges and
measuring instruments
 Unit 4: Heat Treatment of Steels

Objectives of Heat Treatments

To decrease or increase the grain size of steels
To produce special microstructures to increase
machinability or corrosion resistance
To eliminate gases, particularly hydrogen, which
embrittles the steel. If the steel is held at some
elevated temperature for a short time, these gases
gets diffuse into atmosphere
To change the composition of the surface by
diffusion of C,N etc so as to increase wear
resistance, fatigue life or corrosion resistance
 Simple Heat Treatment Cycle

Soaking
Temperature

Heating
Cooling

Time
Annealing

Types
Conventional Annealing (Full Annealing)
Bright Annealing
Box Annealing
Isothermal Annealing
Spheroidise Annealing
Subcritical Annealing
Stress Relief Annealing
Recrystallization Annealing
Process Annealing
Conventional Annealing
(Full Annealing)

Purpose
To relieve the internal stresses induced due to cold
working,welding etc.
(Internal stresses are not desirable because they lead to
premature, sudden, and brittle failures of the components.
They also decrease the corrosion resistance)
To reduce hardness and to increase ductility
Conventional Annealing
(Full Annealing)

Purpose
To increase the uniformity of phase distribution
and to make the material isotropic in respect of
mechanical properties
To refine the grain size
To make the material homogeneous in respect of
chemical composition
To increase machinability
To make the steel suitable for subsequent heat
treatment like hardening
Conventional Annealing
(Full Annealing)

Process
The process consists of heating the steel to above A3
temperature for hypoeutectoid steels and above A1
temperature for hypereutectoid steel by 30-500C,
holding at this temperature for a definite time period
and slow cooling to room temperature in furnace
Conventional Annealing
(Full Annealing)
Conventional Annealing
(Full Annealing)

Why hyperetectoid steels are not annealed

from the temperature above Acm?
 If slowly cooled from above Acm temperature, a
proeutectoid cementite separates along the grain
boundaries of pearlite.
 This forms a brittle cementite network along the grain
boundaries of pearlite.
 Due to this the dislocations get blocked at cementite
regions are not able to move from one pearlite region to
another
 This increases brittleness of steel, departing from the aim
of annealing
Conventional Annealing
(Full Annealing)
Conventional Annealing
(Full Annealing)

Why hyperetectoid steels are not annealed

from the temperature above Acm?
 This is also undesirable condition if machining is to be done

Moreover
 Acm temperature is high and therefore, heating to above
Acm results in more oxidation and decarburization of steel
 Heavy grain coarsening of austenitic grain occurs above
Acm. This leads to deterioration of mechanical properties.
Bright Annealing

Annealing of steel components is carried out using some

protective medium to prevent oxidation and surface
discolouration.

Such a type of annealing keeps the surface bright a hence

is called bright annealing.

The surface protection is obtain by the use of an inert gas

such as argon or nitrogen or by using reducing
atmospheres like hydrogen gas or dissociated NH3.
Box Annealing

Here annealing, is carried out in a sealed

container under conditions that minimise oxidation.

The components are packed with cast iron chips,

charcoal or clean sand and annealed in a way
similar to full annealing.

It is also called black annealing, close annealing

or pot annealing
Spheroidize Annealing
Used on steels with carbon contents
above 0.5%
Applied when more softness is
needed for machinability
Cementite transforms into globes, or
spheroids
These spheroids act as chip-breakers
– easy machining
Spheroidize Annealing
A spheroidizing anneal is
designed to improve:

- cold formability

- machinability of
hypereutectoid and tool steels
Spheroidize Annealing

Holding at just below A1

Thermal cycling around A1

Hardening and high

temperature tempering

Divorced Eutectoid
Transformation
 Spheroidize Annealing
Holding at just below A1
1. Heat to just below Lower Critical
Temperature. (about 650-700 deg C)
2. Cool very slowly in the furnace
3. Structure will now be spheroidite, in
which the Iron Carbide has ‘balled up’
4. Used to improve the properties of
medium and high carbon steels prior to
machining or cold working.
Spheroidize Annealing
Driving force for the cementite
spheroidization is the reduction in
surface free energy of the system.
The spheroidization process, i.e.
transformation of cementites from
lamellar morphology to spherical
shapes, decreases the interface area
between cementite and ferrite
phases, reducing surface free energy
of the system. The energy reduction
associated with the spheroidization,
The microstructure of in general, is not large enough to
spheroidite, with Fe3C particles drive the process at a high rate,
dispersed in a ferrite matrix making the process time consuming
Spheroidize Annealing

There are two steps to the spheroidization process. In the

first step any carbides with high aspect ratios (such as
cementite lamellae in pearlite) are broken into many small,
spherical carbides. The spherical particles have lower surface
area to volume ratios than the elongated structures.

These small spherical particles are then coarsened by

Ostwald ripening into large particles thus further decreasing
the total surface area to volume ratio. The kinetics of both
stages of spheroidization is controlled by the diffusion of
carbon and other alloying elements through the ferrite or
austenite matrix.
Spheroidize Annealing

1040 steel - 21 hours @ 700°C 1040 steel - 200 hours @ 700°C

Spheroidize Annealing
Thermal cycling around A1

A typical heat treatment cycle of thermal cycling

Spheroidize Annealing
Thermal cycling around A1
Due to thermal cycling in a narrow
temperature interval around A1, cementite
lamellae from pearlite become spheroidal

During heating above A1, cementite or

carbides try to dissolve and during cooling
they try to form

This repeated action spheroidises the

carbide particles
Spheroidize Annealing
Hardening and high
temperature tempering
Due to tempering of hardened steels at 650-
700oC for a long time, cementite globules
are formed in the matrix of ferrite from
martensite.

Martensite Cementite (in globuler form) + Ferrite

Spheroidize Annealing
Spheroidize Annealing and SPD

One of the effective methods noted to increase the

spheroidization speed is to introduce defects in the cementite
via severe plastic deformation.

This increased speed of spheroidization has been attributed to

the dissolution of carbon in ferrite matrix and the introduction
of defects such dislocations, nonstoichiometry, as well as kinks
and ledges to the cementite during the plastic deformation
Annealing

Subcritical Annealing
Stress Relief Annealing
Recrystallization Annealing
Process Annealing
Stress Relief Annealing

Stresses may result from:

Plastic deformation (cold work, machining)
Non-uniform heating (ex. welding)
Phase transformation (quenching)
Stress Relief Annealing

In this process, cold worked steel is heated to a

temperature between 500 and 550°C i.e. below its
recrystallization temperature ( 600°C)
Kept at this temperature for 1 - 2 hours and
cooled to room temperature in air.
Due to this, internal stresses are partly relieved
without loss of strength and hardness i.e. without
change of microstructure.
Stress Relief Annealing

It reduces the risk of distortion in machining, and

also increases corrosion resistance.
Since only low carbon steels can be cold
rolled/worked, the process is applicable to
hypoeutectoid steels containing less than 0.4%
carbon.
Stress relief annealing is also carried out on
components in which internal stresses are
developed from other sources like rapid cooling
and phase changes.
Recrystallization Annealing

This is done below A1 temperature i.e. at

temperature between 625 and 675°C.
The cold worked ferrite recrystallizes and
cementite tries to spheroidise during this
annealing process.
Not only internal stresses are eliminated but also
the steel becomes soft and ductile.
Refinement in grain size is also possible by
control of degree of cold work prior to annealing or
by control of annealing temperature and time
Recrystallization Annealing
Process Annealing

In this method, cold worked metal is

heated to above its recrystallization
temperature

This is also accomplished by the

formation of strain free equiaxed grains

This is given to metals to soften them

during mechanical processing so as to
continue the cold working process without
cracking of metals
Process Annealing

It mayor may not involve full

recrystallization of the cold worked metal.

In principle, process annealing and

recrystallization annealing are same

Both the processes involve

recrystallization and formation of new stress
free equiaxed grains from strained and
distorted cold worked grains.
Process Annealing

A process anneal is
designed to restore the
ductility of a steel
between processing
steps.

facilitates further cold

working

Prevents cracking
during hot working

Softens for shearing or

straightening

Promotes ease of
machining
Normalising
Process:
The normalizing of steel is carried out by
heating approximately 30-50°C above the
upper-critical-temperature (A3 or Acm)line
holding long enough at this temperature
for homogeneous austenitization and
followed by cooling in still air to room
temperature.
Normalising
Normalizing
Normalising Temperature Range
Normalising

Purpose:
The purpose of normalising is almost
same as that of annealing.
However,normalizing is aimed to
produce a harder and stronger steel than
full annealing so that for some
applications normalizing may be a final
heat treatment.
Normalising
Purpose:
 For hypereutectoid steels, the process is used to
eliminate the cementite network that may have
formed due to slow cooling in the temperature range
from Acm to A1
 Used to improve machinability.
 Modify and refine cast dendritic structures
 Refine the grain
 Homogenize the microstructure in order to
improve the response in hardening operations.
Normalising
 Normalising involves non equilibrium cooling
 The increase in cooling rate due to air cooling as
compared with furnace cooling affects the
transformation of austenite and the resultant
microstructure in several ways.
 There is less time for the formation of the
proeutectoid phase hence there will be less
proeutectoid ferrite in normalized hypoeutectoid
steels and less proeutectoid cementite in
hypereutectoid steels as compare with annealing
Normalising
The faster cooling rate in normalizing will
also affect the temperature of austenite
transformation and the fineness of the
pearlite.
In general,the faster the cooling rate, the
lower the temperature of austenite
transformation and the finer the pearlite.
Normalising
The difference in spacing of the cementite plates
in the pearlite obtained after annealing and
normalizing is shown schematically

Ferrite is very soft, while cementite is very hard, with

the cementite plates closer together in the case of
normalized pearlite, they tend to stiffen the ferrite so it
will not yield as easily, thus increasing hardness of
steel
Normalising
Nonequilibrium cooling also shifts the
eutectoid point toward lower carbon
content in hypoeutectoid steels and toward
higher carbon content in hypereutectoid
steels.
The net effect is that normalizing produces
a finer and more abundant pearlite
structure than is obtained by annealing,
which results in a harder and stronger steel.
Normalising
• Hypereutectoid steels are usually normalised from above
Acm temperature. This is because due to air cooling from
above Acm the proeutectoid Fe3C separates in the form
of needles in the grains of austenite which transform to
pearlite at A1
• The microstructure at room temperature shows
innumerable needles of Fe3C in the matrix of pearlite
(Widmanstatten structure).
• Thus for hypereutectoid steels, normanzing will reduce
the continuity of the proeutectoid cementite network,
and in some cases it may be suppressed entirely.
• Such structures are less brittle because the dislocation can
move via certain regions avoiding these needles.
Normalising

Normalized 0.90 percent carbon steel, 100X. Bright

proeutectoid cementite in dark pearlitic matrix.
Annealing Vs Normalising

S. Annealing Normalising
N
.
1 Furnace Cooling Air Cooling
(Equilibrium Cooling) (Non equilibrium Cooling)
2
Annealing Vs Normalising

S. Annealing Normalising
N
.
3 Slightly less hardness, T.S. Slightly more hardness, T. S. and
and toughness. toughness.
4 For plain carbon steels, Microstructure shows more
microstructure shows pearlite than observed in
pearlite almost in annealed components
accordance with the Fe-C
equilibrium diagram
5 Pearlite is coarse and Pearlite is fine and usually
usually gets resolved by appears unresolved with optical
the optical microscope. microscope.
Annealing Vs Normalising

S. Annealing Normalising
N
.
6 Less internal stresses are More internal stresses are
produced produced

7 Cementite network is No Cementite network is

produced in produced in hypereutectiod
hypereutectiod steels steels

8 More time required hence Less time required hence more

less economical economical
Heat treatment Temperature Ranges
Heat treatment Temperature Ranges
Hardening
 Under slow or moderate cooling rates, the carbon
atoms are able to diffuse out of the austenite
structure. The iron atoms then move slightly to
become b.c.c. (body-centered cubic).
 This gamma-to-alpha transformation takes place
by a process of nucleation and growth and is time-
dependent.
 With a still further increase in cooling rate,
insufficient time is allowed for the carbon to
diffuse out of solution, and although some
movement of the Iron atoms takes place, the
structure cannot become b.c.c. while the carbon is
trapped In solution.
Hardening
 The resultant structure called martensite,is a
supersaturated solid solution of carbon trapped in
a body-centered tetragonal structure. Two
dimensions of the unit cell are equal, but the third
is slightly expanded because of the trapped
carbon.
 The axial ratio c/a increases with carbon content
to a maximum of 1.08
 This highly distorted lattice structure is the prime
reason forthe high hardness of martensite. Since
the atoms of martensite are less densely packed
than in austenite, an expansion occurs during the
transformation.
Hardening
Transformations of austenite into pearlite: g → P
pearlite
Diffusional transformations
1) At slightly lower T below 727 ℃ :
• Coarse pearlite
: nucleation rate is very low.
: diffusion rate is very high. 655 ℃ 600 ℃

2) As the Tt (trans. temp.) decreases

to 500 ℃
• Fine pearlite
: nucleation rate increases.
: diffusion rate decreases.
534 ℃ 487 ℃
Hardening
Diffusionless Transformations -
Martensitic transformation
When the austenite is quenched to temp.
below Ms
g → a’ (martensite)
Instead of the diffusional migration of carbon atoms to
produce separate a and Fe3C phases, the matensite
transformation involves the sudden reorientation of C
and Fe atoms from the austenite (FCC) to a body
centered tetragonal (bct) solid solution.
Hardening
 Martensitic transformation (contd.)

BCT unit cell of g (austenite)

c
 2  1.414
a
BCT unit cell of a’ (martensite)

c
Expand
 1.00  1.08
a
~ 12%
Contract
0% C (BCC) 1.2 % C
~ 20%
Hardening
Hardening
• Austenitizing : heating the
steels to a high enough
temperature until they
convert to austenite.
• Quenching: Media – brine
(salt water), fresh water,
oil,polymers and air
• Tempering – Reheat to 200
- 700°C, to decrease internal
stresses, hardness, and
regain ductility and
toughness.
Hardening
Purpose
(i) To harden the steel to the maximum
level by austenite to martensite
transformation. (Due to increase in
hardness, brittleness also increases)

(ii) To increase the wear resistance and

cutting ability of steel.
Hardening
Process
The conventional hardening process consists of
heating the steel to above A3 temperature for
hypoeutectoid steels and above A1 temperature
for hypereutectoid steels by 50°C, austenitising
for a sufficient time and cooling with a rate just
exceeding the critical cooling rate of that steel to
room temperature or below room temperature.
Due to this, the usual diffusion transformations
are stopped and the austenite transforms to
martensite by a diffusionless process.
Hardening
Temperature Range for Hardening

Hardening
Hardening
Hypoeutectoid steels are hardened from
above A3 temperature.
• They are not hardened from temperatures between A1
and A3
• This is because the phases which exist at this
temperature are austenite and proeutectoid ferrite and
only austenite gets transformed to martensite with no
change in ferrite.
• Such steels show free ferrite in their microstructures and
since ferrite is a soft phase, the hardness of hardened
steel gets reduced.
Hardening
Hypereutectoid steels are always hardened from
temperatures between A1 and Acm
(i.e. from above A1)
At this temperature, austenitization is not
complete and some proeutectoid Fe3C will exist
along with austenite at the temperature of
heating.
Such steels after hardening show free Fe3C along
with martensite in their microstructures.
Hardening
Hypereutectoid steels are always hardened from
temperatures between A1 and Acm
(i.e. from above A1)
Since Fe3C being a hard phase, the hardness of
hardened steels does not get reduced
 Moreover, this free Fe3C does not increase the
brittleness of steels because usually it is fine,
well distributed and partially spheroidised. Also,
the grain size remains fine because the Fe3C
particles do not allow to coarsen the austenite.
Hardening
Hypereutectoid steels are always hardened from
temperatures between A1 and Acm
(i.e. from above A1)
However, if these steels are hardened from
above Acm temperature, the following
drawbacks are observed.
(i) Since Acm line is steep, higher temperatures
are required to cross the Acm line. Due to this and
absence of Fe3C above Acm temperature, heavy
grain coarsening occurs during austenitization and
results in coarse grained martensite which is
extremely brittle.
Hardening
Hypereutectoid steels are always hardened from
temperatures between A1 and Acm
(i.e. from above A1)
However, if these steels are hardened from
above Acm temperature, the following
drawbacks are observed.
(ii) Quenching from such a high temperature results in
more distortions and may lead to cracking of the
components.
(iii) Due to higher temperatures, oxidation and
decarburization is more.
(iv) The amount of retained austenite increases because of
higher thermal stresses.
Microstructure of Martensite

The needle-like structure of martensite, the

white areas are retained austenite.
Microstructure of Martensite
Microstructure of Martensite

(a) Lenticular martensite in an Fe–30% Ni alloy.

(b) Lenticular (thermoelastic) martensite in Cu–Al–Ni alloy.

Microstructure of Martensite
• Lath martensite(strip like or rod like):
Less than 0.6% C
Plate martensite(neddle like): More than
1.0% C
Microstructure of Martensite
•

Lath type Plate type

Microstructure of Martensite
•
Salient Features of Martensitic
Transformation
The transformation is diffusion less

There is no change in chemical composition

 Austenite transform to martensite by a

shear mechanism
Salient Features of Martensitic
Transformation
Athermal Transformation
The transformation proceeds only during
cooling and ceases if cooling is interrupted.
Therefore, the transformation depends only
upon the decrease in temperature and is
independent of time.
A transformation of this type is said to be
athermal,in contrast to one that will occur at
constant temperature (isothermal
transformation)
Salient Features of Martensitic
Transformation
Athermal Transformation
• Koistenen and Marburger equation which describes the progress of
transformation below Ms:

Vα′ is the fraction of martensite and Tq

the temperature below Ms, to which
the sample is cooled. This athermal
character is a consequence of very
rapid nucleation and growth, so rapid
that the time taken can be neglected.
Instead, thefraction transformed
depends only on the number of
nucleation sites triggered,
with the less potent sites contributing
at higher undercoolings.
Salient Features of Martensitic
Transformation
Athermal Transformation
From Koistenen and
Marburger Equation, it is
evident that some austenite
remains untransformed
when T is set to room
temperature. This is referred
to as retained austenite.
It is also clear that there is no
martensite-finish
temperature,Mf but for
convenience, the latter is
frequently defined at the point
where 95% of the martensitic
transformation is completed.
Martensitic
transformation never
goes to 100% completion
Salient Features of Martensitic
Transformation
Transformation proceeds at a speed close to
the speed of sound

The amount of martensite formed with decreasing temperature

is not linear. The number of martensite needles produced at
first are small; then the number increases, and finally, near the
end, it decreases again .
Salient Features of Martensitic
Transformation
Characteristics Temperatures Ms and Mf
 The temperature of the start of martensite
formation is known as the Ms temperature and
that of the end of martensite formation as the Mf
temperature.
 The Ms and Mf temperatures are function of
chemical composition only.
Ms (OC)= 539 - (423 x % C)- (30.4 x % Mn)- (17.7x % Ni)
- (12.1 x % Cr)- (7.5 x % Mo)
Salient Features of Martensitic
Transformation
Characteristics Temperatures Ms and Mf
 The influence of carbon on the Ms and Mf temperatures is
shown in Fig
 The Mf temperature line is shown dotted because it is
usually not clearly defined
 Theoretically, the austenite to martensite transformation is
never complete, and small amounts of retained austenite
will remain even at low temperatures
 The transformation of the last traces of austenite becomes
more and more difficult as the amount of austenite
decreases.
Salient Features of Martensitic
Transformation
Characteristics Temperatures Ms and Mf
Salient Features of Martensitic
Transformation
The martensitic transformation of given
alloy cannot be suppressed changing cooling
rate.
Martensite is metastable phase
 Martensite is never in a condition of real
equilibrium
 Although it may persist indefinitely at or near room
temperature.
 The structure can be considered as a transition
between the unstable austenit phase and the
stable ferrite
Salient Features of Martensitic
Transformation
The most significant property of martensite
is its potential of very great hardness.
 Extreme hardness are possible only in steels that
contain sufficient carbon.
 The high hardness of martensite is result of the
severe lattice distortions produced by its
formation, since the amount of carbon present is
many times more than can be held solid solution.
 The maximum hardness obtainable from a steel in
the martensitic condition is function of carbon
content only
Salient Features of Martensitic
Transformation
The most significant property of martensite
is its potential of very great hardness.
 The hardness of martensite increases rapidly at first
with increase in carbon content, reaching about 60
Rockwell C at 0.40 percent carbon
 Beyond that point the curve levels off, and at the
eutectoid composition (0.80.percent carbon), the
hardness is about Rockwell C 65.
 The leveling off Is due to the greater tendency to
retain austenite in higher carbon steels.
Salient Features of Martensitic
Transformation
The most significant property of martensite
is its potential of very great hardness.
Salient Features of Martensitic
Transformation
Orientation relationships
The habit plane
• The habit refers to the interface plane
between austenite and martensite For
unconstrained transformations this
interface plane is flat, but the need to
minimize strains introduces some
curvature when the transformation is
constrained by its surroundings.
Any process that contributes to the formation of martensite
cannot rely on assistance from thermal activation. There
must, therefore, exist a high level of continuity across the
interface between martensite and austenite. The interface
must be coherent or semicoherent; in the latter case, the
dislocations in the interface must be able to glide as the
martensite grows.
Salient Features of Martensitic
Transformation
Orientation relationships
Why the shape of martensite is lenticular?
Salient Features of Martensitic
Transformation
Orientation relationships
Why the shape of martensite is lenticular?
Salient Features of Martensitic
Transformation
Orientation relationships
The formation of martensite involves the coordinated movement of atoms. It
follows that the austenite and martensite lattices will be intimately related. All
martensitic transformations therefore lead to a reproducible orientation
relationship between the parent and product lattices.
1.Low carbon steel:
Habit plane: {111}g
Kurdjumov-Sach relation: {111}g || {110}a ' ,  1 1 0 g || 1 1 0 a '
Refered as Lath Martensite
2. Medium carbon steel
Habit plane: {111}g
Kurdjumov-Sach relation
Refered as Acicuar Martensite
3.High carbon steel
Habit plane: {111}g
Nishiyama-Wasserman relation {111} || {110} ,  112  || 1 1 0  '
g a' g a
Salient Features of Martensitic
Transformation
Shape deformation
During martensitic transformation, the pattern in which the atoms in the
parent crystal are arranged is deformed into that appropriate for martensite,
there must be a corresponding change in the macroscopic shape of the crystal
undergoing transformation.
Salient Features of Martensitic
Transformation
Shape deformation
The dislocations responsible for the deformation are in the α′/γ interface, with Burgers
vectors such that in addition to deformation they also cause the change in crystal
structure.
Salient Features of Martensitic
Transformation
Shape deformation
Evidence that the transformation involves large shears can easily be obtained
by polishing a surface, or better two surfaces at right angles, prior to transformation.
Any scratches present prior to transformation are themselves displaced.
Salient Features of Martensitic
Transformation
Shape deformation
Salient Features of Martensitic
Transformation
Shape deformation

Dislocations Twins

TEM images of (a) Lathe martensite showing dislocations (b) plate

martensite showing twins
Salient Features of Martensitic
Transformation
Thermodynamics of Martensitic transformation

(a) Free energy-temperature diagram for fixed composition (Co) of

steel (b) Free energy-composition diagram of steel as Ms
Salient Features of Martensitic
Transformation
Thermodynamics of Martensitic transformation

(a) Iron carbide phase diagram with To (b) TTT diagram for steel with Co
carbon %
Salient Features of Martensitic
Transformation

Strength of Martensite
Several possible strengthening mechanisms:
(a) substitutional and interstitial solid solution;
(b) dislocation strengthening, i.e. work hardening;
(c)Fine twins
(d) Grain size
(e) Segregation of carbon atoms
(f) Precipitation of carbides
Salient Features of Martensitic
Transformation
Numerical Example:
Calculate the change in volume in 0.6% C steel
when austenite transforms to martensite using
Bain Model
Given:
For austenite: a=3.548+0.044 (%C) in A
For martensite: a=2.861-0.013(%C) in A
c=2.861+0.116(%C) in A
Ans: 4.28%
Quenching Media
Quenching is done by using the following
mediums:
Brine (cold water + 5 to 10% salt)
(The salt may be sodium chloride, sodium
hydroxide or calcium chloride)
Cold water
Water + soluble oil
Oil
Fused salts
Air
Quenching Medium

Vapor Blanket

Vapor Transport

Liquid Cooling
Quenching Medium
Quenching Medium
Mechanism of Heat Removal During
Quenching
 The structure, hardness, and strength resulting
from a heat-treating operation are determined by
the actual cooling rating obtained by the quenching
process.
 If the actual cooling rate exceeds the critical cooling
rate, only martensite will result.
 If the actual cooling rate is less than the critical
cooling rate, the part will not completely harden.
Quenching Medium
Mechanism of Heat Removal During
Quenching
 The greater the difference between the two cooling rates
the softer will be the transformation products and the lower
the hardness.
 Liquid cooling media remove the heat from the component
through the following stages

Vapour blanket stage

Vapour transport stage
Liquid cooling stage
Quenching Medium
Vapour blanket stage
 The temperature of the steel is so high that the
quenching medium is vaporized at the surface of
the metal and a thin stable film of vapor surrounds
the hot metal
 This vapour blanket does not allow to extract the
heat and reduce the cooling rate.
 Cooling is by conduction and radiation through the
gaseous film, and since vapor films are poor heat
conductors, the cooling rate is relatively slow
through this stage
Quenching Medium
Vapour transport stage
 This stage starts when the metal has cooled to a
temperature at which the vapor film is no longer
stable
 The vapour blanket breaks and the liquid comes in
contact with the surface of hot component
 Wetting of the metal surface by the quenching
medium take place and violent boiling occur
 Heat is removed from the steel very rapidly as the
latent heat of vaporization
 This is the fastest stage of cooling
Quenching Medium
Liquid cooling stage
This occurs when temperature of the
component reaches boiling point of
quenching medium
Vapor no longer forms, so cooling is by
conduction and convection through the
liquid
The rate of cooling is the lowest in this stage
Quenching Medium

The factors determining the

actual cooling rate are
The type of quenching medium
The temperature of the quenching
medium
 The surface condition of the part
The size and mass of the part
Quenching Medium
The type of quenching medium
Quenching Medium

Types of Quenching Medium

Quenching Boiling Duration Duration
Medium Point of Vapor of Vapor
(OC) Blanket Transport
Stage (sec) Stage (sec)
Brine 105 1 10
Cold 100 3 15
Water
Oil 378-505 5-13 15-22
Quenching Medium

Types of Quenching Medium

Propertites of quenchant which affect quenching
speed:
1. Boiling point
2. Specific heat of quenchant
3. Latent heat of vapourisation
4. Thermal conductivity of quenchant
5. Viscosity
Quenching Medium
The type of quenching medium
Brine
 This quenching medium has a very short vapor stage
lasting about 1 s
 And then drops quickly into the boiling stage, where
the cooling rate is very rapid
 It finally goes into the third stage at about 10s
Quenching Medium
The type of quenching medium
Water
The vapor stage is slightly longer than for
brine
It drops into the boiling stage after about 3 s
The cooling rate during this stage, while very
rapid, is not quite so fast as that for brine
The third stage is reached after about 15 s
Quenching Medium
The type of quenching medium
Fused Salt
The fused salt has a very short vapor stage
approximately equal to that of brine.
However,the cooling rate during the boiling
stage is not so rapid as that for brine or water
It reaches the third stage at about 10 s.
Quenching Medium
The type of quenching medium
Oil
They both show a relatively long vapor stage
Enters the boiling stage after about 7 s
The third stage is reached after about 15 s
Air
 Never get out of the vapor stage and therefore
shows a very slow cooling rate over the entire range
Quenching Medium
Temperature of Quenching Medium
 Generally, as the temperature of the medium rises,
the cooling rate decreases
 This is due to the increase in persistence of the
vapor blanket stage
 Since the medium is closer to its boiling point, less
heat is required to form the vapor film
 This is particularly true of water and brine.
Quenching Medium
Temperature of Quenching Medium
Quenching Medium
Temperature of Quenching Medium
 In the case of oil, there are two opposing factors to
be considered.
 As the temperature of the oiI rises there is a
tendency for the cooling rate to decrease due to the
persistence of the vapor film.
 However, as the temperature of the oil rises it also
becomes more fluid, which increases the rate of
heat conduction through the liquid
Quenching Medium
Surface Condition
 When steel is exposed to an oxidizing atmosphere,
because of the presence of water vapor or oxygen in
the furnace a layer of iron oxide called scale is
formed
 A thin layer of scale has very little effect on the
actual cooling rate, but a thick layer retards the
actual cooling rate
 Many methods are used Industrially to minimize the
formation of scale
• Copper Plating
• Protective Atmosphere
• Cast-iron Chips
Quenching Medium
Size and Mass
 Since it is only the surface of a part which is in
contact with the quenching medium, the ratio of
surface area to mass is an important factor in
determining the actual cooling rate.
 This ratio is a function of the geometric shape of the
part and is largest for a spherical part
 Thin plates and small-diameter wires have a large
ratio of surface area to mass and therefore rapid
cooling rates.
Quenching Medium
Size and Mass

Specimens
quenched in
oil (125oF)

Effect of size of steel specimen on cooling rate during quenching

Quenching Medium
Ideal Quenching Medium: Polymer Quenchant
•These are water soluble organic chemicals of higher
molecular weight
•They are generally polyalkylene glycol based or
polyvinyl pyrolidene based polymers
•Inverse solubility is a unique characteristics of these
quenchant
Quenching Medium
Ideal Quenching Medium: Polymer Quenchant
Advantages
1. Desired Cooling rate can be achieved by varying
concentration of polymer
2. Less tendency for cracking
3. Less distortion
4. No fire hazards
5. No solute drag effect
Tempering
Purpose
 To relieve the internal stresses
(Stresses are developed due to rapid cooling
of
steels during hardening process (i.e.
austenite
to martensite transformation) and due to
volume changes occurring in the above
transformation, to reduce brittleness. )
 To reduce hardness, and to increase ductility and
toughness
 To eliminate retained austenite.
 To obtained spheroidized Cementite
Tempering
Process
Tempering

Process
After hardening, heating and holding steel
below A1 line and slow cooling (usually in air)
to room temperature
Done in the range 100-700˚C
Tempering
 After hardening heat treatment, steel
contains martensite and retained
austenite.
 In some steels like hypereutectoid
steels and alloy steels, carbides are
also present.
 Martensite and austenite are not
stable phases and try to transform to
more stable phases during heating.
 Martensite is a supersaturated solid
solution of carbon trapped in a body-
centered tetragonal structure.
Tempering

 This is a metastable phase, and as

energy is applied by tempering, the
carbon will precipitated as cementite
and the martensite becomes b.c.c
aplha ferrite

a   
 a  Fe3C
tempering
Tempering
Tempering is classified in the following
types
Low temperature tempering
(100-200°C)
Medium temperature tempering
(200-500°C)
High temperature tempering
(500-700°C )

9-17
Tempering
Low temperature tempering (100-200°C)
During low temperature tempering the original
as-quenched martensite is beginning to lose its
tetragonal crystal structure by the formation of
a hexagonal close-packed transition carbide
(epsilon Carbide, Fe2.4C) and low-carbon
martensite.

α’ Low carbon α’ + ε-carbide

Tempering
Low temperature tempering (100-200°C)
The precipitation of the transition
carbide may cause a slight increase in
hardness, particularly in high carbon
steels
There is no appreciable change in the
retained austenite.
The brittleness of steel decreases due to
sharp decrease the internal stresses.
Tempering
Medium temperature tempering
(200-500°C)
 Heating in the range from 200 to 500°C changes
the epsilon carbide to orthorhombic cementite
(Fe3C) The low-carbon martensite becomes b.c.c.
ferrite
 Retained austenite is transformed to lower bainite
or decomposes and form cementite and
martensite
 This transformation of austenite to martensite is
due to increase Ms temperature because of
decrease in carbon content of austenite
Tempering
Medium temperature tempering
(200-500°C)
 These changes in microstructure result in decrease
of hardness with increasing tempering
temperature
 The decrease in hardness is gradual upto 350°C
and rapid thereafter, reaching to almost a
minimum value at about 500°C.
 These changes are accompanied by simultaneous
increase in toughness and ductility.
Tempering
High Temperature tempering
(500-700°C)
 During this stage of tempering, cementite
particles become coarse.
 Except this, there is no other change in the structure.
 When the particles are resolvable by optical
microscope, they appear to be spheroidal in shape
 The structure is called tempered martensite
Tempering
High Temperature tempering
(500-700°C)
 Coarsening of particles results in a slight decrease in
hardness and toughness.
 Since the coarsening rate is very less, the decrease in
properties with time is also very less.
 Spheroidized structures can be machined with high
speeds because of their excellent machinability.
 Some of the steels which are difficult to machine like
high carbon steels and few of the alloy steels can be
machined easily after spheroidising.
Tempering

Tempering
Temperature Structure
100-200 0C Epsilon Carbide+Low carbon α’+RA

200 – 5000C
Cementite+Ferrite +Cementite+
Bainite/Martensite

500 – 7000C
Cementite(Spheroidite)+Ferrite
Structural Changes during Tempering
A number of basic phenomena that occur during the decomposition of martensite have
been identified. These are as listed next and tend to occur in the order presented.
However, many of the phenomena tend to overlap to some degree.
(1) A redistribution of the carbon atoms in the martensite. This occurs roughly
between room temperature and 100°C. There are several ways that this
redistribution may occur:
(i) A segregation of the carbon atoms to lattice defects such as dislocations
and twin boundaries.
(ii) A clustering of the carbon atoms, which in turn can occur in several ways
and involve spinodal decomposition and ordering.
(2) The precipitation of a transition carbide or carbides. The most generally
identified transition carbide is epsilon carbide. However, in many cases this
carbide is not well resolved and it is sometimes referred to as (ε/η) carbide, that
is, epsilon or eta carbide. The primary difference is that epsilon carbide is hcp
and eta carbide is orthorhombic. The precipitation of the transition carbide
leaves a matrix of iron still containing the carbon atoms that were segregated to
the dislocations.
Structural Changes during Tempering
(3) The decomposition of retained austenite into a mixture of
ferrite and cementite. This structure has often been called bainite
or secondary bainite.
(4) The conversion of the transition carbide and segregated carbon
into small rod shaped cementite particles.
(5) Spheroidization of the rod-shaped cementite to reduce the
surface energy of the particles.
(6) Recovery of the ferrite structure.
Structural Changes during Tempering
(7) Recrystallization of the ferrite structure.
(8) Ostwald ripening of the cementite. In this process, the larger
cementite particles grow at the expense of the smaller particles.
This further reduces the surface energy and is accomplished by the
diffusion of carbon atoms through the iron matrix.
 Structural Changes during Tempering
Stage Temp (oC) Structural Changes Micrograph
First 25-250 Carbon segregation to
Stage dislocations and boundaries; pre-
precipitation, clustering and ordering of
transition-carbide (diam.2 nm). Carbides
may be η (Fe2C) or ε (Fe2.4C)

ε (Fe2.4C) Carbide

η (Fe2C) Carbide
 Structural Changes during Tempering
Stage Temp (oC) Structural Changes Micrograph
Second 200-300 Retained austenite transforms to ferrite
Stage and cementite

Third 200-350 Lath-like Fe3C precipitation Segregation of

Stage impurity and alloying elements
Recovery of dislocation substructure. Lath-
like Fe3C agglomerates to form spheroidal
Fe3C

Cementite at twinned
boundaries

Cementite at grained
boundaries
 Structural Changes during Tempering
Stage Temp (oC) Structural Changes Micrograph
Fourth 350-700 Recovery of dislocation substructure.
Stage Lath-like Fe3C agglomerates to form
spheroidal Fe3C. Formation of alloy
carbides. (secondary hardening),
Recrystallization and grain growth;
coarsening of spheroidal Fe3C
Fe–0.17C water-quenched from
900◦C and tempered 5 h at 650◦C.

microstructure of lath martensite in

an iron-0.2% carbon alloy after
tempering at 700°C for 2h.
Structural Changes during Tempering

426oC 593oC 675oC

1hr 1hr 1hr
Structure of tempered martensite in a steel with
0.75 percent carbon. Electron microscope.
15,000 X
Structural Changes during Tempering

Spheroidized cementite in a 1.1 percent carbon

steel. Light microscope. 1000 X
 Structural Changes during Tempering
High Carbon Steel Low Carbon Steel
1 Redistribution of the carbon atoms Redistribution of the carbon atoms
(Autotempering)
2 Precipitation of a transition carbide or Precipitation of a transition
carbides carbide or carbides
3 Decomposition of retained austenite Decomposition of retained
austenite
4 Conversion of the transition carbide Conversion of the transition
carbide
5 Spheroidization of the rod-shaped Spheroidization of the rod-shaped
cementite cementite
6 Recovery of the ferrite structure Recovery of the ferrite structure
7 Recrystallization of the ferrite structure. Recrystallization of the ferrite
structure.
8 Ostwald ripening of the cementite Ostwald ripening of the cementite
Effect of Tempering on Mechanical
Properties

The hardness of low and medium iron-carbon martensite

tempered for 1 hour between 100°C and 700°C. (From Speich, G. R.,
TMS-AIME, 245 2553 [1969].)
Effect of Tempering on Mechanical
Properties
Variation in properties with tempering
temperature