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Metal Heat Treating

Topics of Presentation

What Is Metal Heat Treating?

Where Is It Used?
Why and How It Is Done?
What Processes & Equipment Are Used
for Heat Treating?

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What is Heat Treating ?

Controlled Heating And Cooling of Metal to Change Its
Properties and Performance.


Change in Microstructure

Change in Chemistry or Composition






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A Few Heat Treating Facts

Heat Treating of Metals Represents

Approximately 100 BCF Gas Load
Heat Treaters Use Natural Gas to Supply
About 2/3 of the Energy Used for Heat
Treating (induction, vacuum & commercial
atmospheres main competition).
Current Share of Gas Decisions is about
50 / 50 Between Gas & Electric.

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Why Use Heat Treating ?

In simple Terms.

Soften a Part That Is Too Hard.

Harden a Part That Is Not Hard Enough.

Put Hard Skin on Parts That Are Soft.

Make Good Magnets Out of Ordinary


Make Selective Property Changes Within


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Who uses Heat Treating ?

Aircraft Industry
Defense Sector
Heavy Machinery
Powder Metal
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What Industrial Sectors Use Heat

Treating ?



Steel Mills
Iron and Steel Foundries
Metal Fabrication
Machinery and
Electrical/Electronic Equipment
Transportation Equipment
Commercial Heat Treating
Steel Service Centers

35 & 36
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Types of Heat Treaters

Commercial Heat Treaters
Heat Treating of Parts As Job-shop.
Reported Under SIC Code 3398.
Approx. 10% of All Heat Treating Production Is by Commercial
Heat Treaters.
Usually There Are 4 to 5 Captive Heat Treaters for Each
Commercial Heat Treater Shop.

Captive Heat Treaters

Usually a Part of Large Manufacturing Business.
They Usually Produce Products Rather Than Parts.
Captive Heat Treating Is Scattered Through All Manufacturing
SIC Codes (DEO has over 100 individual SICs for Heat

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Commonly Heat Treated Metals

Ferrous Metals

Cast Iron
Stainless Steel
Tool Steel



Steel Is the Primary Metal Being Heat Treated.

More Than 80% of Heat Treating Is Done for Steel

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Heat Treating Processes

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Steps in Heat Treating Operation


Pre-wash with coalescer
De-phosphate system
Spray rinse

Surface coating
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Soak & diffusion

Quenching (Cooling)

Commonly Used Equipment

for Heat Treating Operations

Metal Cleaning (Wash-Rinse) Equipment

Gas fired furnaces
Direct fired using burners fired directly into a
Indirect fired furnaces: radiant tube, muffle, retort
Molten salt (or lead) bath
Fluidized bed

Electrically heated Furnaces

Induction heating
Electrical resistance heating
Other (i.e. Laser, electron-beam etc.)

Quench or cooling equipment

Material handling system
Testing and quality control laboratory equipment

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Gas Fired Metal Heat Treating Furnaces

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Electrically Heated Equipment for Metal


Electric Atmosphere Furnace

Vacuum Furnace

Induction Equipment
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Types of Heat Treating Furnaces





Bell, Hood, tipup


Vertical Pit


Salt Bath

Lead pot (cont.)
Rolelr hearth
Cont. stripline
Cont. induction



Car Bottom


Fluidized bed


Bell, hood, tip-up




Vertical Pit

Rotary hearth, shaker hearth



Electric beam
Flame heads

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Heat Treating Furnaces

Two Primary Types
Operated at ambient (atmosphere) pressure.
Load is heated and cooled in presence of air
or special gases (process atmospheres), in
liquid baths or in a fluidized bed.

Operated at vacuum or sub-atmospheric
May involve high pressure gas cooling using
special gases.
Includes ion or plasma processing

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Heat Source for Gas Fired Furnaces

Direct Fired Burners *

Radiant Tubes *
Muffle or Retort Heated
by Outside


Hot Oil or Steam Heating


Direct fired muffle furnace

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* These could be directly exposed to the

work or can be outside a muffler a

Nonferrous Heat Treating Furnaces

Types of Furnaces
Coil/foil Annealing Furnaces
Rod/wire Annealing Furnaces
Log Homogenizing Furnaces
Ingot Preheating Furnaces
Aging Furnaces

Indirect Heating
(Radiant Tubes or Electrical Resistance)

Temperature Range 350F to 1150F

Atmosphere With Dew Point Control
May Includes Water Quench or
Controlled Cooling

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Why Use Protective Atmospheres?

To Prevent Oxidation, Loss of Carbon
(Decarburizing), and Avoid Corrosion.
Most Gases Containing Oxygen (i.e. Air, Water
Vapor [H2O], Carbon Dioxide [CO2] React With
Iron, Carbon and Other Elements Present in Steel
and Other Metals.
Reactivity Depends on Temperature and Mixture
of Gases in Contact With Steel.

To Avoid and Eliminate Formation of Flammable

or Explosive Mixtures

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Types of Process Atmospheres

To Protect Metal Parts From Oxidation or Loss of
Carbon and Other Elements From the Metal

To Add Non-metallic (i.e., Carbon, Oxygen,
Nitrogen) or Metallic (i.e., Chromium, Boron,
Vanadium) Elements to the Base Metal.

To Remove Air or Flammable Gases From Furnaces
or Vessels.

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Importance of Protective Atmospheres

in Heat Treating

Proper composition and concentration in a furnace is

required to give the required surface properties for the
heat treated parts.

Loss of atmosphere control can result in

unacceptable parts and result in major economic
penalty - it can cost a lot!

Atmospheres contain potentially dangerous (explosive,

life threatening) gases and must be treated with

New advances in measurement and control of

atmospheres in heat treating allow precise control of
atmospheres to produce quality parts.

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Commonly Used Atmospheres in Heat Treating

Protective and Purging
Endothermic gases
Lean high and low
dew point
Rich - high and low
dew point

Mixture of N2 and
small amount of CO

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Exothermic gases
Mixture (or
individual) of gases:
Hydrogen, CO, CH4,
Nitrogen and other
Dissociated Ammonia
(H2 + N2)

Source of Atmospheres

A Mixture of Gases (CO, H2, CO2, H2O and N2)

That Give the Required Composition for the
Processing Atmosphere.
Natural Gas (Hydrocarbon)
- Air Reaction
Natural Gas - Steam
Ammonia Dissociation or
Ammonia-air Reaction
Mixture of Commercial Gases
(N2, H2 and Hydrocarbons)

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Use of Atmospheres in a

A Mixture of Gases (CO, H2, CO2, H2O and N2)

That Give the Required Composition for the
Processing Atmosphere.
Most plants have an in-house, centrally
located, atmosphere gas generators for
different types of atmospheres required in
the plant
In some cases one or more generators
may be located for each shop or
production area
In many cases other gases (i.e. N2, H2,
NH3) are piped from storage tanks located
within the plant premises and distributed
by a piping system to furnaces.
Gas flow is mixed, measured and
controlled prior to its injection in the
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Annealing, involves heating to a predetermined
temperature, holding at this temperature, and finally
cooling at a very slow rate.
The temperature, to which steel is heated, and the
holding time are determined by various factors such
as the chemical composition of steel, size and shape
of steel component and final properties desired.

Purpose of Annealing
i. Relieve internal stresses developed during
solidification, machining, forging, rolling, or
ii. Improve or restore ductility & toughness;
iii. Enhance machinability
iv. Eliminate chemical non-uniformity;
v. Refine grain size; and
vi. Reduce the gaseous contents in steel.


Annealing treatment can be classified into groups based on the


1. Heat treatment
Full annealing
Partial annealing

2. Phase

3. Specific
Full annealing
Partial annealing

1.1 In full annealing the steel is heated above the critical

temperature(A3) and then cooled very slowly.
1.2 Partial annealing, also known as incomplete annealing
or intercritical annealing, involves heating of steel to a
temp. lying between lower critical temperature(A 1) and
upper critical temperature (A3 or Acm).
1.3 Subcritical annealing is a process in which the
temp. to which is heated is always less than the lower
critical temperature(A1).

Classification based on phase transformation

2.1 First-order annealing is performed on steel with the sole aim of
achieving some properties. Any change in the characteristics of steel
achieved by this type of annealing is not correlated to phase can be performed at a wide range of temperatures
above or below the critical temperatures.

2.2 The second-order annealing differs from the former in the sense
that the end results in the former are essentially due to phase
transformation which takes place during the treatment.

Types of annealing based on specific purpose

3.1 Full annealing

In this, steel is heated to its 50C above the austenitic temperature
and held for sufficient time to allow the material to fully form austenite
or austenite-cementite grain structure. The material is then allowed to
cool slowly so that the equilibrium microstructure is obtained.
The austenitising temp is a function of carbon content of the steel and
can be generalized as:
For hypoeutectoid steels and eutectoid steel
Ac3+(20-40oC) [to obtain single phase austenite]
For hypereutectoid steels
Ac1+(20-40oC) [to obtain austenite+ cementite]

Purpose of full annealing

To relieve internal stresses
To reduce hardness and increase ductility
For refining of grain size
To make isotropic in nature in mechanical aspects
For making the material having homogeneous
chemical composition
For making the material suitable for high machining
To make steel suitable for undergoing other heat
treatment processes like hardening, normalizing etc.

The grain structure has coarse

Pearlite with ferrite or Cementite
(depending on whether hypo or
hyper eutectoid). The steel
becomes soft and ductile.

The formation of austenite destroys all structures

that have existed before heating. Slow cooling
yields the original phases of ferrite and pearlite
in hypoeuetectoid steels and that of cementite
and pearlite in hypereutectoid steels.

3.2 Isothermal Annealing

It is a process in which hypoeutectoid steel is
heated above the upper critical temperature and
this temperature is maintained for a time and then
the temperature is brought down below lower
critical temperature and is again maintained. Then
finally it is cooled at room temperature. This
method rids any temperature gradient.
The prefix isothermal associated with annealing
implies that transformation of austenite takes place
at constant temperature.

The closer the temp of isothermal holding is to A1,

coarser is the pearlite, softer is the steel, but longer
is the time of isothermal transformation.


Improved machinability.
Homogeneous structure and better surface finish.
Time required for complete cycle is comparably less.
The process is of great use for alloy steels as the steels
have to be cooled slowly.


It is suitable only for small-sized components. Heavy

components cannot be subjected to this treatment
because it is not possible to cool them rapidly and
uniformly to the holding temperature at which
transformation occurs. Thus structure wont be
homogeneous mechanical properties will vary across
the cross-section.

3.3 Diffusion Annealing

This process, also known as homogenizing annealing, is employed
to remove any structural non-uniformity like dendrites, columnar
grains and chemical inhomogeneity which promote brittleness and
reduce ductility and toughness of steel.

Steel is heated sufficiently above the upper critical temperature (say,
1000-2000oC), and held at this temperature for 10-20 hours,
followed by slow cooling.
Segregated zones are eliminated, and a chemically homogeneous
steel is obtained by this treatment as a result of diffusion.
Heating to such a high temp. results in considerable coarsening of
austenitic grains & heavy scale formation. The coarse austenite thus
obtained further transforms to coarse pearlite on cooling, which is
not a desirable structure as mechanical properties are impaired.

The main aim of homogenising annealing is to make the

composition uniform, i.e to remove chemical

The impact energy and ductility of the steel increase as

the homogenizing temperature increases and the
hardness, yield strength and tensile strength decrease
with an increase in the homogenizing temperature.

Homogenizing annealing has a few shortcomings as

well. It results in:

Grain coarsening of austenite, thereby impairing the properties

Thick scales on the surface of steels
It is an expensive process

3.4 Partial Annealing

Partial annealing, also known as inter-critical
annealing or incomplete annealing, is a process in
which steel is heated between A1 and Acm and is
followed by slow cooling.
Generally, hypereutectoid steels are subjected to
this treatment. The resultant microstructure
consists of fine pearlite and cementite instead of
coarse pearlite and a network of cementite at grain
As low temperatures are involved in this process, it
is less expensive than full annealing.

Hupoeutectoid steels are subjected to this

treatment to improve machinability. However,
steels with coarse structure of ferrite and pearlite
or with widmansttten structure are not suitable
for this treatment. This is because only a
considerable amount of ferrite remains
untransformed, and only a part of it along with
pearlite transforms to austenite.
This coarse or accicular untransformed ferrite
results in poor mechanical properties.

3.5 Recrystallization
The process consists of heating steel above
the recrystallization temperature, holding at
this temperature and cooling thereafter.
It is used to treat work-hardened parts made
out of low-Carbon steels (< 0.25% Carbon).
This allows the parts to be soft enough to
undergo further cold working without

Recrystallization temp(Tr) is given by:

Tr= (0.3-0.5)Tmp
As little scaling and decarburization occurs in
recrystallization annealing, it is preferred over full
No phase change takes place and the final
structure consists of strain-free, equiaxed grains of
fine ferrite produced at the expense of deformed
elongated ferrite grains.
However It would produce very coarse grains if the
steel has undergone critical amount of deformation.
In such cases, full annealing is preferred.

Aims of Recrystallization Annealing

To restore ductility
To refine coarse grains
To improve electrical and magnetic
properties in grain-oriented Si steels.

3.5 Spheroidization annealing

Spheroidization annealing consists of heating, soaking and
cooling, invariably very slowly to produce spheroidal pearlite
or globular form of carbides in steels.
To improve the machinability of the annealed
hypereutectoid steel spheroidize annealing is applied.
Hypereutectoid steels consist of pearlite and cementite. The
cementite forms a brittle network around the pearlite. This
presents difficulty in machining the hypereutectoid steels.
This process will produce a spheroidal or globular form of a
carbide in a ferritic matrix which makes the machining easy.
Prolonged time at the elevated temperature will completely
break up the pearlitic structure and cementite network. The
structure is called spheroidite.

Spheroidising Process:
Heat the part to a temperature just below the FerriteAustenite line, line A1 or below the AusteniteCementite line, essentially below the 727 C (1340
F) line. Hold the temperature for a prolonged time
and follow by fairly slow cooling. Or
Cycle multiple times between temperatures slightly
above and slightly below the 727 C (1340 F) line,
say for example between 700 and 750 C (1292 1382 F), and slow cool. Or
For tool and alloy steels heat to 750 to 800 C (13821472 F) and hold for several hours followed by slow

All these methods result in a structure in

which all the Cementite is in the form of
small globules (spheroids) dispersed
throughout the ferrite matrix. This structure
allows for improved machining in continuous
cutting operations such as lathes and screw
machines. Spheroidization also improves
resistance to abrasion.

Spheroidizing process applied at a temperature below and above the


Spheroidizing process applied at a temperature below and

above the LCT.

Aims Of Spheroidization Annealing:

minimum hardness
maximum ductility
maximum machinability
maximum softness

Martensite is a very strong phase, but it is normally
very brittle so it is necessary to modify the
mechanical properties by heat, treatment in the
range 150700C.
Essentially, martensite is a highly Supersaturated
solid solution of carbon in iron which, during
tempering, rejects carbon in the form of finely divided
carbide phases.
The end result of tempering is a fine dispersion of
carbides in an -iron matrix which often bears little
structural similarity to the original as-quenched

The normalizing of steel is carried out by
heating above the UCT (Upper Critical
Temperature) to single phase austenitic
region to get homogeneous austenite,
soaking there for some time and then
cooling it in air to room temperature.
The austenitising temperature range are:
For hypoeutectoid steels and eutectoid steel
Ac3 + (40-60oC)
For hypereutectoid steels
Acm + (30-50oC)

During normalising we use grain refinement

which is associated with allotropic
transformation upon heating
Parts that require maximum toughness and
those subjected to impact are often
When large cross sections are normalized,
they are also tempered to further reduce
stress and more closely control mechanical
The microstructure obtained by normalizing
depends on the composition of the castings
(which dictates its hardenability) and the
cooling rate.

Figure below shows the normalizing temperatures

for hypoeutectoid and hypereutectoid steels


To produce a harder and stronger steel than

full annealing
To improve machinability
To modify and/or refine the grain structure
To obtain a relatively good ductility without
reducing the hardness and strength
Improve dimensional stability
Produce a homogeneous microstructure
Reduce banding
Provide a more consistent response when
hardening or case hardening





The metal is heated to a higher temperature and then removed
from the furnace for air cooling in normalizing rather than furnace
In normalizing, the cooling rate is slower than that of a quenchand-temper operation but faster than that used in annealing.
As a result of this intermediate cooling rate, the parts will possess
a hardness and strength somewhat greater than if annealed.
Fully annealed parts are uniform in softness (and machinability)
throughout the entire part; since the entire part is exposed to the
controlled furnace cooling. In the case of the normalized part,
depending on the part geometry, the cooling is non-uniform
resulting in non-uniform material properties across the part.
Internal stresses are more in normalizing as compared to
Grain size obtained in normalizing is finer than in annealing.
Normalizing is a cheaper and less time-consuming process.

Comparison of temperature
ranges in annealing and

Comparison of time-temperature cycles

for normalizing and full annealing

The slower cooling of annealing results in higher temperature transformation

to ferrite and pearlite and coarser microstructures than does normalizing.

effect of annealing and normalizing on

ductility of steels
Annealing and normalizing do not present a significant
difference on the ductility of low carbon steels. As the
carbon content increases, annealing maintains the %
elongation around 20%. On the other hand, the ductility of
the normalized high carbon steels drop to 1 to 2 % level.

effect of annealing and normalizing

on the tensile strength AND YIELD
POINT of steels
The tensile strength and the yield point of the
normalized steels are higher than the
annealed steels.
Normalizing and annealing do not show a
significant difference on the tensile strength
and yield point of the low carbon steels.
However, normalized high carbon steels
present much higher tensile strength and
yield point than those that are annealed. This
can be illustrated from the figures.

effect of annealing and normalizing on the

hardness of steels
Low and medium carbon steels can maintain similar
hardness levels when normalized or annealed. However,
when high carbon steels are normalized they maintain
higher levels of hardness than those that are annealed.


Better mechanical properties
Lesser time-consuming
Lower cost of fuel and operation
Greater softness
Complete absence of internal stresses
which is a necessity in complex and
intricate parts

It is the process of heating the steel to
proper austenitizing temperature , soaking at
this temperature to get a fine grained and
homogeneous austenite , and then cooling
the steel at a rate faster than its critical
cooling rate.

The aims of hardening are:
1. Main aim of hardening is to induce high hardness. The
cutting ability of a tool is proportional to its hardness.
2. Many machine parts and all tools are hardened to induce
high wear resistance higher is the hardness , higher is the
wear and the abrasion resistance .For example ,gears, shaft.
3. The main objective of hardening machine components made
of structural steel sis to develop high yield strength with
good toughness and ductility to bear high working stresses.

Austenising Temperature for Pearlitic Steels

The steel is first heated to proper austenising temperature
to obtain a homogeneous and fine grained austenite. This
temperature depends on the composition(carbon as well
as alloying elements).
The austenitising temperature of plain carbon steels
depends on the carbon content of the steel and is
generalised as :
For hypo-eutectoid steels :Ac3 + (20 40C)
For hyper-eutectoid steels and eutectoid steel:Ac1 + (20

Austenising Temperature for Pearlitic Steels

Austenising Temperature for Pearlitic Steels

Hypereutectoid steels, when heated in above temperature
range, to obtain homogeneous and fine-grained austenite
which on quenching transforms to fine-grained (very fine
needles/plates), and hard martensite as is desired to be
Heating these steels only up to critical range (between Ac3 and
Ac1) is avoided in practice.
Steel then has austenitic and ferrite.
On quenching, only austenite transforms to martensite, and
ferrite remains as it is, i.e., incomplete hardening occurs .
The presence of soft ferrite does not permit to achieve high
hardness, if that is the objective.

Austenising Temperature for Pearlitic Steels

If the aim is to get high strength by the process of
tempering ferrite does not permit this as it has low tensile
and yield strengths .
In fact, ferrite forms the easy path to fracture.
Quenching of hypoeutectoid steels from temperatures
much above the proper temperatures , when austenite
has become coarse, results in coarse acicular form of
Coarse martensite is more brittle, and a unit or two lower
in hardness. It lowers the impact strength even after
tempering, and is more prone to quench-cracking.

Austenising Temperature for Pearlitic Steels

Hypereutectoid steels, when heated in the above range, i.e., just
above Ac1 have fine grains of austenite and proeutectoid
On quenching austenite transforms to fine martensite and
cememtite remains unchanged.
As the hardness of cementite ( 800 BHN) is more than that of
martensite (650-750 BHN), its presence increases the
hardness, wear and abrasion resistance as compared to only
martensitic structure.
If temperature of austenitisation is much higher than Ac1 but still
below Acm temperature, a part of proeutectoid cementite gets
dissolved to increase the carbon content of austenhlc(> 0.77%)

Austenising Temperature for Pearlitic Steels

On quenching as-quenched hardness is less,

because :
1. Lesser amount of proeutectoid cementite is
2. Larger amount of soft retained austenite is
obtained as the dissolved carbon of cementite has
lowered the Ms and Mf temperature.
3. A bit coarser martensite has lesser hardness .

Austenising Temperature for Pearlitic Steels

Heating hypereutectoid steels to a temperature higher
than Acm results in 100% austenite . It is very coarse
austenite as very rapid grain-growth occurs due to
dissolution of restraining proeutectoid cementite .
The as-quenched hardness is low because of:
1) Absence of harder cementite.
2) As more carbon has dissolved in austenite, more retained
austenite is obtained.
3) Coarser martensite is a bit less hard and more brittle.

Thus, these temperatures are avoided in carbon steels

When a heated steel object (say at 840C) is plunged into a
stationary bath of cold it has three stages as:
Stage A -vapour-blanket stage:

Immediately on quenching, coolant gets vapourized as the

steel part is at high temperature, and thus, a continuous
vapour- blanket envelopes the steel part.
Heat escapes from the hot surface very slowly by radiation and
conduction through the blanket of water vapour.
Since the vapour-film is a poor heat conductor, the cooling rate
is relatively low (stage A in fig ). This long stage is undesirable
in most quenching operations.


Stage B-Intermittent contact stage (Liquid-boiling stage):
Heat is removed in the form of heat of vaporization in this
stage as is indicated by the steep slope of the cooling curve.
During this stage, the vapour-blanket is broken intermittently
allowing the coolant to come in contact with the hot surface
at one instant, but soon being pushed away by violent
boiling action of vapour bubble.
The rapid cooling in this stage soon brings the metal surface
below the boiling point of the coolant.


The vaporization then stops. Second stage corresponds

to temperature range of 500 to 100c , and this refers
to nose of the CCT curve of the steel , when the steel
transforms very rapidly ( to non martensite product ).
Thus, the rate of cooling in this stage is of great
importance in hardening of steels.

Stage C-Direct-Contact stage (Liquid-cooling stage):

This stage begins when the temperature of steel
surface Is below the boiling point of coolant.
Vapours do not form. The cooling is due to convection
and conduction through the liquid. Cooling is slowest

As the aim is to get martensite, the coolant should have
quenching power to cool austenite to let it transform to martensite.
The following factors effect the quenching power of the coolant :
The cooling rate decreases as the temperature of water and brine
increases, i.e., it increases stage A, i.e., helps in persistence of
the vapour blanket stage.
The increased temperature brings it closer to its boiling point, and
thus, requires less heat to form vapour, specially above 60C.
Good range of temperature for water as coolant is 20-40C.
Oils in general, show increased cooling rates with the rise of
temperature, with optimum cooling rates in range 5080C.

In oils, the increase of temperature increases the persistence of vapourblanket, but this resulting decrease in the cooling rate is more than
compensated by the decrease of viscosity (with the rise in temperature)
to result in increase of rate of heat removal through the oil.
If the boiling point of a coolant is low, vapours form easily to increase
the A stage of cooling. t is better to use a coolant with higher boiling
point. A coolant with low specific heat gets heated up at a faster rate to
form vapours easily.
A coolant with low latent heat of vapourisation changes into vapour
easily to promote A stage, i.e., decreases the cooling rate.
A coolant with high thermal conductivity increases the cooling rate.
Coolants with low viscoity provide faster cooling rates and decrease the
A stage.

A coolant should be able to Provide rate of cooling fast
enough to avoid transformation of austenite to pearlite and
bainite . Plain carbon steel invariably require ooling in water
or brine. Whereby alloy steels are quenched normally in oils.
But milder the cooling medium , lesser the internal stresses
developed , and thus lesser the danger of distortion , or
cracks . An ideal quenching medium is one which is able to
provide very fast cooling rate near the nose of the curve ( 650
-550C)and at the same time it should provide very
considerable slower rate if cooling within the range of
martensitic transformation( 300 - 200C) to minimize internal
stresses .

The oldest and still the most popular quenching medium, water meets the
requirements of low cost ,general easy availability, easy handling and safety.
The cooling characteristics change more than oil with the rise of temperature,
specially there is a rapid fall in cooling capacity as the temperature rises
above 60C, because of easy formation of vapour-blanket.
The optimum cooling pover is when water is 2O-4OC.
Thc cooling power of water is between brine and oils.
Water provides high cooling power to avoid the transformation of austenite to
pearlite/bainite, but the major draw back is that it also provides high cooling
rate in the the temperature range of martensite formation.
At this stage, the steel is simultaneously under the influence of structural
stresses (non-uniform change in structure) and thermal stresses which
increase the risk of crack formation.

Sodium chloride aqueous solutions of about 10% by weight are widely
used and are called brines.
The cooling power is between 10% NaOH aqueous solution and water.
These are corrosive to appliances.
The greater cooling efficiency of brines, or other aqueous solutions is
based as :
In brine heating of the solution at the steel surface causes the
deposition of crystal of the salt on hot steel surface .
This layer of solid crystals disrupts with mild explosive violence, und
throws off a cloud of crystals. This action destroys the vapour-film from
the surface, and thus permits direct contact of the coolant with the
steel surface with an accompanying rapid removal of heat.
Brines are used where cooling rates faster than water arc requited.

Oils have cooling power between water at 40C to water at 90C.
In oil-quench, considerable variation can be obtained by the use of animal,
vegetable, or mineral oil, or their blends.
Oils should be used at 50- 80C when these are more fluid, i.e less
VISCOUS, which increases the cooling power.
As the oils used generally have high boiling points, moderate increase of
temperature of oil does not very much increase the vapour blanket stage.
However, oils in contrast to water, or brine, have much lower quenching
power .
Its this relatively slow cooling rate in the range of martensitic formation is
atlvantageous as it helps in minimsing the danger to crack formation.
Oils with high viscosity are less volatile, and thus have decreased vapourblanket stage (increase thecooling rate). As lesser volatile matter is lost,
their cooling power is not affected much with use.

polymer quenchants cool rapidly the heated steel to Ms
temperature, and then rather slowly when martensite is
forming .
Polymer quenchants are water-soluble organic
chemicals of high ,molecular weights, and are generally
polyalkylene glycol-based, or polyvinyl pyrolidenebased.
Widely different cooling rates can be obtained by varying
the concentration of Organic additives in water; higher
the additions, slower is the cooling rate of solution.
There are little dangers of distortions and cracks.

It is an ideal quenching medium for a steel of
not very large section but with good
Addition of O.3-O.5% water almost doubles
the cooling capacity. Normally holding time is
2-4 minutes/cm of section thickness.
Salt baths used for austenitising keep the
steel clean.


internal stresses are produced due to non-uniform plastic deformation.
In quenching of steels ,this may be caused by thermal stresses,
structural stresses, or both, or even premature failure of part in service.
Cooling during quenching lakes place non-uniformly, i.e., causes
temperature gradient across the section.
Surface layers contract more than the central portion.
Contraction of surface is resisted by the central portion, and this puts
the central portion under the compressive stresses, and the surface
layers in tension .
If the magnitude of stress becomes more than the yield stress of steel
(at that deformation occurs.
These stresses that develop in a quenched part as a result of unequal
cooling are called thermal stresses.


Structural stresses are the stresses which develop due to due to phase
change (mainly austenite to martensite), and at different times.
Structural stresses are developed due to two main reasons:
1. Austenite and its transformation products have unequal specific
volume i.e. change in volume occurs when transformation occurs.
2. Phase changes occur at different times in the surface and in centre.
Under right conditions, both types of stresses get superimposed to
become larger than the yield strength to cause warping. but when the
tensile internal stresses become larger than the tensile strength cracks
If an austenitised steel is quenched, it contracts thermally till Ms
temperature is attained .



figure(a) illustrates this in stage 1 As surface cools faster than
centre, i.e., contracts more than centre distribution of stresses
across the section is illustrated in fig (b), i.e, the surface is under
tensile nature of stress, while centre is under compressive
Only thermal Stresses are produced in stage 2 , surface having
attained Ms temperature, transforms to martenSite, and thus
expands, while the centre is still contracting as it is getting cooled.
In stage Il, centre may get plastically deformed ,as it is still ductile
In stage 3, martensite of surface and austenite of centre continue
contracting leading to slight increase in stress levels.


In stage IV, centre has attained M5 temperature, and begins
to expand as it forms martensite, while surface is still
The centre, as it expands, puts the surface in higher stress
levels .
The surface has little deformation as it consists of brittle
It is during this stage, the greatest danger of cracking exists.
Thus, stress levels are highest not in the beginning of the
quench, but when the centre is transforming to martensite.


However, higher is the Ms temperature of the
steel, lesser is the expansion, there is reduced
danger of quench-cracking.
Increase of carbon and alloying elements lower
the Ms temperature making the steel more prone
to quench cracking.

Martensitic transfomiation is essentially an athermal transformation.
Austenite begins to transform to martensite at Ms, and the amount of
martensite formed increases as the temperature decreases to complete at
Mf temperature.
Less than 1 % of austenite may not transform because of unfavourable
stress conditions.
The Ms and Mf temperatures are lowered as the amounts of carbon content
and alloying elements(except cobalt and aluminium) increase in the steel.
In a quenched steel, the amount of martensite formed depends on the
location of Ms and Mf and the temperature of the coolant (which is normally
room temperature. As long as room temperature lies between Ms and Mf
temperatures, austenite does not transform completely to martensite as it
has not been cooled below Mf temperature.
This untransformed austenite is retained austenite.


10% retained austenite is normally desirable as its

ductility relieves some internal stresses developed
during hardening. This reduces the danger to distortion
or cracks.
The presence of 30-40% retained austenite makes
straightening of components possible after hardening.
Non distorting tools owe their existence to retained
austenite . It tries to balance transformational volume
changes during heating as well as cooling cycles of heat
treatment to produce little overall change in size of the

1) The presence of soft austenite decreases the
hardness of hardened steels.
2) As retained austenite may transform to lower
bainite, or martensite later in service ,increase in
dimensions of the part occurs.
3) This creates problems in precision gauges or
4) Stresses may develop in the part itself as well as
in adjacent pans. Grinding-cracks are mainly due
to retained austenite transforming to martensite.
5) Austenite is non-magnetic, decreases the
magnetic properties of the steels.


Retained austenite is generally undesirable. It is eliminated by one of
the methods:
1. Sub-Zero treatment (cold treatment):
It Consists of cooling the hardened steel (having retained austenite) to
a temperature below 0C or its Mf temperature.
There is no reason to cool a steel much below its Mf temperature.
Sub-zero treatment is more effective if it is done immediately after the
quenching operation (normally done to room temperature).
Sub-zero treatment is done in a low temperature-cooling unit, which
consists of double-walled vessel.
The interior is made of copper in which the parts to be deep-frozen are
kept, and the exterior is made of steel provided with good heatinsulation.


The space in between the vessels is filled with some
The sub-zero coolants could be, dry ice (Solid CO2)
+ acetone ( 78C); Ice + NaCl (23C); liquid air
(183C); liquid N2 ( 196C); Freon ( 111C).
Total time of cooling in this unit is 1/2 to 1 hour.
As this treatment transforms austenite to martensite,
steels after sub-zero treatment have high hardness,
wear and abrasion resistance, and have no danger
of grinding-cracks.


The stresses are increased further and thus, tempering should
be done immediately after sub-zero treatment.
Carburised steels, ball-bearing steels, highly alloy tool steels,
are normally given cold treatment.
2. Tempering:
The second stage of tempering eliminates the retained
austenite in most steels.
In high alloy steels, multiple tempering is able to eliminate the
retained austenite during cooling from the tempering

The main defects produced during hardening are:
1. Mechanical properties not up to specifications:
The common defect in hardened tools, or component is too low a
One or more of the followings could be the cause of such a
Insufficient fast cooling due to overheated or even polluted
coolant could be responsible for a defect.
The presence of scale, or oil, etc. on the surface also decreases
the cooling rate.
Circulation of coolant, or agitation of component may also result
in such defect.

A shorter austenitising time can also cause such a defect. Lower
austenitising temperature can also result in such a defect.
Decarburisation can also result in low surface hardness. If too
high temperature had been used, which produces larger amount
of retained austenite can result in low surface hardness.
2. Soft Spots:
Soft areas on the hardened surface are called soft spots.
The adhering scale, or decarburisation of some areas or
prolonged vapour-blanket stage due to overheated coolant or
insufficient agitation or circulation of coolant, or rough surface
could cause presence of soft spots surface.


3. Quench Cracks:
Quench cracks form as a result of internal stresses developed of tensile
nature exceeding the tensile strength of the steel.
Steel with lower Ms temperature due to higher contents of alloying elements
are more prone to quench cracks. Higher carbon also results in more brittle
Quench cracks can form if there is more time lag between the process of
quenching and tempering.
Overheating of steel or a wrong coolant which gave much faster rate of
cooling, or there is faulty design of the component with sharp corners and
sharp transition between sections, or a wrong steel has been chosen.
Presence of large amounts of retained austenite causes grinding cracks.
The other defects could be distortion and warpage; change in dimensions;
oxidation and decarburisation

Tempering of plain carbon steels

In the as-quenched martensite structure,the laths
or plates are heavily dislocated to an extent that
individual dislocations are very difficult to observe
in thin-foil electron micrographs.
A typical dislocation density for a 0.2 wt% carbon
steel is between 0.3 and 1.0 x 1012 cm cm-3. As
the carbon content rises above about 0.3 wt%,
fine twins about 510 nm wide are also observed.

Often carbide particles, usually rods or small

plates, are observed (Fig. 9.1).

Tempering of plain carbon steels

These occur in the first-formed
martensite, i.e. the martensite formed
near Ms, which has the opportunity of
tempering during the remainder of the
This phenomenon, which is referred to
as aut-tempering, is clearly more
likely to occur in steels with a high Ms.

Stages of Tempering

Stages of Tempering
On reheating as-quenched martensite, the tempering
takes place in four distinct but overlapping stages:
Stage 1, up to 250C precipitation of E-iron carbide;
partial loss of tetragonality in martensite.
Stage 2, between 200 and 300C decomposition of
retained austenite .
Stage 3, between 200 and 350C replacement of
&iron carbide by cementite; martensite loses
Stage 4, above 350C cementite coarsens and
spheroidizes; recrystallization of ferrite.

Tempering stage 1
Martensite formed in medium and high carbon steels
(0.31.5 wt% C) is not stable at room temperature
because interstitial carbon atoms can diffuse in the
tetragonal martensite lattice at this temperature.
This instability increases between room temperature
and 250C, when -iron carbide precipitates in the
martensite (Fig. 9.2).
This carbide has a close-packed hexagonal structure,
and precipitates as narrow laths or rodlets on cube
planes of the matrix with a well-defined
orientation relationship .

Tempering stage 1
At the end of stage 1 the martensite still possesses a tetragonality,
indicating a carbon content of around
0.25 wt%.
It follows that steels with lower carbon contents are unlikely to
precipitate -carhide.
This stage of tempering possess an activation energy of between
60 and 80 kJ mo1, which is in the right range for diffusion of carbon
in martensite. The activation energy has been shown to increase
linearly with the carbon concentration between 0.2 and 1.5 wt% C.
This would be expected as increasing the carbon concentration also
increases the occupancy of the preferred
interstitial sites, i.e. the octahedral interstices at the mid-points of
cell edges, and centres of cell faces, thus reducing the mobility of C

Tempering stage 2
During stage 2. austenite retained during quenching is
decomposed usually in the temperature range 230300C.
In martensitiC plain carbon steels below 0.5
carbon. the retained austenite is often below 2%, rising
to around 6 % at 0.8 wt C and over 30 % at 1.25 wt C.
The little available evidence suggests that in the range
230-300C, retained austenite decomposes to bainitic
ferrte and cementite, but no detailed comparison
between this phase and lower bainite has yet been

Tempering stage 3
During the third stage of tempering, cementite flrst
appears in the microstructure as a Widmanstatten
distribution of plates which have a well-defined
orientation relationship with the matrix which has now
lost its tetragonality and become ferrite.
This reaction commences as low as 100C and is fully
developed at 300C, with particles up to 200 nm long
and 15 nm in thickness.
Similar structures are often observed in lower carbon
steels as quenched, as a result of the formation of
Fe3C during the quench.

Tempering stage 3
During tempering, the most likely sites for the
nucleation of the cementite are the -iron carbide
irterfaces with the matrix (Fig 9.2) and as the Fe3C
particles grow, the -iron carbide particles gradually
The twins occurring in the higher carbon martensites
are also site for the nucleation and growth of
cementite which tends to grow along
the twin boundaries forming colonies of similarly
oriented lath shaped particles (Fig. 9.3) which can
be readily ditinguished from the normal
Widmanstatten habit.

Tempering stage 3
A third site for the nucleation of cementite is the grain
boundary regions (Fig, 9.4)of both the interlath boundaries
of martensite and
the original austenite grain b0unjaries.
The cementite can form as very thin films which are
difficult to detect but which gradually
sp1eroidise to give rise to welI-defined particles of Fe3C in
the grain boundary regions.
There is some evidence to show that these.
boundary cementite films can adversely affect
ductility.However it can be modified by addition of
alloying elements.

Tempering stage 3
During the third stage of tempering , the
tetragonality of thc matrix disappears and it
is then, essentially, ferrite, not
supersaturated with
respect to carbon.
Subsequent changes in the morpriology of
cementite particles occur by process where
the smaller particles dissolve in the matrix
providing carbon for the selective growth of
the larger particles.

Tempering stage 3
During the third stage of tempering ,
the tetragonality of thc matrix
disappears and it is then, essentially,
ferrite, not supersaturated with
respect to carbon.
Subsequent changes in the morpriology
cementite particles occur by process
where the smaller particles dissolve in
the matrix providing carbon for the

Tempering stage 4
It is useful to define a fourth stage of tempering in which the
cementite particles undergo a coarsening process and
essentially lose their crystallographic morphology, becoming
It commences between 300 and 400C, while
spheroidizatiun takes place increasingly up to 700C.
At the higher end of this range of tempera.
ture the martensite lath boundaries are replaced by more
equi-axid frrite grain boundaries by a process which is best
described as recrystallization.
The final result is an equi-axed array of ferrite
grains with coarse spheroidized particles of Fe3C (Fig. 9.5),
partly, but not exclusively, by the grain boundaries.

Tempering stage 4
The spherodisation of the Fe3C is encouraged by the resulting
decrease in surface energy.
The particles which preferentially grew and spheroidize are
located mainly at interlath boundaries and prior
austenite boundaries, although some particles remain in the
The boundary sites are preferred because of the greater ease of
diffusion in these regions. Also, the growth of cementite into
ferrite is associated with a decrease in density so vacancies are
required to accommodate the growing cementite.
Vacancies will diffuse away from cementite particles which are
redissolving in the ferrite and towards cementite particles which
are growing, so that the rate controlling process is likely to be
the diffusion of vacancies.

Tempering stage 4
The original martensite lath boundaries remain stable up to
about 600C, but in the range 350600C. there is
considerable rearrangement of the dislocations within the laths
and at those lath boundaries which are essentially low angle
This leads to a marked reduction in the dislocation density and
to lath-shaped ferritic grains closely related to the packets of
similarly oriented laths in the original
This process, which is essentially one of recovery, is
replaced between 600 and 700C by recrystallization which
results in the formation of equi-axed ferrite grains with
spheroidal Fe3C particles in the boundaries and within the

Tempering stage 4
This process occurs most readily in carbon
At higher carbon content, the increased
density of cementite particles is much
more effective in pinning the ferrite
boundaries, so recrystallisation is much
more sluggish.
The final process is the continued
coarsening of the cementite particles and
gradual ferrite grain growth.

Role of carbon content

Firstly, the hardness of the as-quenched martensite is
largely influenced by the carbon content,as is the morphology
of the martensite laths which have a up to 0.3 wt% C, changing
at higher carbon contents.
The Ms temperature is reduced as the carbon content
increases, arid thus the probability of the occurrence of autotempering is less.
During fast quenching in alloys with less than 0.2 wt % C, the
majority (up to 90%) of the carbon segregates to dislocations
and lath boundaries, but with slower quenching some
precipitation of cementite occurs.
On subsequent tempering of low carbon steels up to 200C
further segregation of carbon takes place. but no precipitation
has been observed.

Role of carbon content

Role of carbon content

Under normal circumstances it is difficult to
detect any tetragonality in martensitic in
steels with less than 0.2 wt% C, a fact which
can explained by the rapid segregation of
carbon during quenching.
The hardness change; during tempering are
also very dependent on carbon content, as
shown in figurefor steels up to 0.4 wt% C.
Above this concentration, an increase in
hardness has been observed in temperature
range 50150C, as -carbide precipitation
strengthens the martensite.
However, the general trend is an overall
softening, as the tempering temperature is

Mechanical properties of tempered plain carbon steels

The absence of other alloying elements means that the

hardenability of the steels is low, so a fully martensitic structure
is only possible in thin sections.
However, this may not be a disadvantage where shallow
hardened surface layers are all that is required.
Secondly, at lower carbon levels, the Ms temperature is rather
high, so autotempering is
likely to take place.
Thirdly, at the higher carbon levels the presence
of retained austenite will influence the results.
Added to these factors, plain carbon steels can exhibit quench
cracking which makes it difficult to obtain reliable test results.
This is particularly the case at higher carbon levels, i.e. above
0.5 wt% carbon.

Tempering of alloy steels

The addition of allying elements to a steel has a
substantial effect on the kinetics of the y
transformation, and also of the pearlite reaction.
Most common alloying elements move the TTT curves
to longer times, with the result that it is much easier to
miss the nose of the curve during quenching.
This essentially gives higher hardenability, since
martensite structures can be achieved at slower
cooling rates and, in practical terms, thicker specimens
can be made fully martensitic.
Alloying elements have also been shown to have a
substantial effect in depressing the Ms temperature.

The effect of alloying elements

on the formation of iron carbides
It is clear that certain elements, notably silicon
can stabilize the -iron carbide to such an extent
that it is still present in the microstructure after
tempering at 400C in steels with 1-2 wt% Si,
and at even higher temperatures if the silicon is
The evidence suggests that both the nucleation
and growth of the carbide is slowed down and
that silicon enters into the -carbide structure.
It is also clear that the transformation of -iron
carbide to cementite is delayed considerably.

The effect of alloying elements

on the formation of iron carbides
While the tetragonality of martensite
disappears by 300C in plain carbon
steels, in steels containing some
alloying elements, e.g. Cr, Mo, W V, Ti,
Si, the tetragonal lattice is still observed
after tempering at 450C and even as
high as 500C .
It is clear that these alloying elements
increase the stability of the
supersaturated iron-carbide solid
In contrast manganese and nickel
decrease the stability.

The effect of alloying elements

on the formation of iron carbides
Alloying elements also greatly influence
the proportion of austenite retained on
Typically a steel with 4% molybdenum,
0.2%C, in the martensitic state contains
less than 2% austenite, and about 5% is
detected in a steel with 1% vanadium
and 0.2%C.
The austenite can be revealed as a fine
network around the martensite laths, by
using dark field electron microscopy.

The effect of alloying elements on

the formation of iron carbides
On tempering each of the above steels at
300C, the austenite decomposes to give thin
grain boundary
films of cementite which, in the case of the
higher concentrations of retained austenite, can
be fairly continuous along the lath boundaries.
It is likely that this interlath cementite is
responsible for tempered embrittlement
frequently encountered as a toughness
minimum in the range 300350C, by leading
to easy nucleation of cracks, which then
propagate across the tempered martensite

The effect of alloying elements on the

formation of iron carbides
Alloying elements can also restrain the coarsening of
cementite in the range 400-700C, a basic process
during the fourth stage of tempering.
Several alloying elements, notably silicon, chromium.
molybdenum and tungsten, cause the cementite to
retain its fine Widmanstatten structure to higher
temperatures, either by entering into the cementite
structure or by segregating at the carbide-ferrite
Whatever the basic cause may be, the effect is to
significantly the softening process during tempering.

The effect of alloying elements

on the formation of iron carbides
This influence on the cementite dispersion has
other effects, in so far as the carbide particles,
by remaining finer, slow down the
reorganization of the dislocations inherited
from the martensite, with the result that the
dislocation substructures refine more slowly.
In plain-carbon Steel cementite particle begin
to coarsen in the temperature range 350
-400C and addition of chromium, silicon,
molybdenum or tungsten delays the
coarsening to the range 500-550C.
It should be emphasized that up to 500C the
only carbides to form are those of iron.

The formation of alloy carbides Secondary Hardening

A number of the familiar alloying elements in
steels form carbides, nitrides and borides which
are thermodynamically more stable than
It would therefore be expected that when strong
carbide elements are present in a steel in
sufficient concentration, their carbides would be
formed in preference to cementite.
Nevertheless during the tempering of all ahoy
steels, alloy carbides do not form until the
temperature range 500-600C , because below
this the metallic alloying elements cannot diffuse
sufficiently rapidly to allow alloy carbides to

The formation of alloy carbides Secondary Hardening

The metallic elements diffuse substitutionally, in
contrast to carbon and nitrogen which move
through the iron interstitially.
With the result that the diffusivities of carbon and
nitrogen are of several orders of magnitude
greater in iron than those of the metallic alloying
Consequently higher temperatures are needed for
the necessary diffusion of the alloying elements.
It is this ability of certain alloying elements to
form fine alloy carbide dispersions in the range
500600C, which remain very fine even after
prolonged tempering, that allows the development
of high strength levels in many alloy steels.

The formation of alloy carbides Secondary Hardening

Indeed, the formation of alloy carbides
between 500 and 600C is accompanied by
a marked increase in strength, often in
excess to that of the as-quenched

This phenomenon, which is referred to as

secondary hardening, is best shown in
steels containing molybdenum, vanadium,
tungsten, titanium, and also in chromium
steels at higher alloy concentrations.

The formation of alloy carbides Secondary Hardening

This secondary hardening process is a type
of age-hardening reaction, in which a
relatively coarse cementite dispersion is
replaced by a new and much finer alloy
carbide dispersion.
On attaining a critical dispersion
parameter, the strength of the steel
reaches a maximum, and as the carbide
dispersion slowly coarsens, the strength

The formation of alloy carbides Secondary Hardening

The process is both time and temperature
dependent, so both variables are often
combined in a parameter:
P = T(k + log t)

T is the absolute temperature and
t the tempering time in hours,
while k is a constant which is about 20 for
alloy steels, usually referred to as the
Holloman-Jaffe parameter.

Interrupted quench from the


Delay cooling just above

martensitic transformation for

a length of time to equalize T
throughout the piece
Reduce thermal gradient
btw surface & center
Minimize distortion, cracking,
and residual stress.

Low carbon steels cannot be hardened
by heating due to the small amounts of
carbon present.
Case hardening seeks to give a hard
outer skin over a softer core on the
The addition of carbon to the outer skin
is known as carburising.

Different stages of Case Hardening

Case hardening or surface hardening is the process of hardening

the surface of a metal object while allowing the metal deeper
underneath to remain soft, thus forming a thin layer of harder metal
(called the "case") at the surface. For steel or iron with low carbon
content, which has poor to no hardenability of its own, the case
hardening process involves infusing additional carbon into the case
Case hardening is usually done after the part has been formed into its
final shape, but can also be done to increase the hardening element
content of bars to be used in a pattern welding or similar process. The
term face hardening is also used to describe this technique, when
discussing modern armour
Because hardened metal is usually brittler than softer metal, throughhardening (that is, hardening the metal uniformly throughout the piece)
is not always a suitable choice for applications where the metal part is
subject to certain kinds of stress. In such applications, case hardening
can provide a part that will not fracture (because of the soft core that
can absorb stresses without cracking) but also provides adequate
wear resistance on the surface

Case Hardened Chisel

- cutting edge is hard and wear-resistant
- tang is tough and elastic
If the chisel would be hard throughout, it could
break when the hammer is striked onto it!

Figure - Cut through a hardened chisel - 1 cutting edge

(hard), 2 twig (tough)


The highest hardness of a steel is obtained when its carbon
content ishigh, around 0.8 weight % C (Figure 1). Steels with
such high carbon content are hard, but also brittle, and
therefore cannot be used in machine parts such as gears,
sleeves and shafts that are exposed to dynamic bending and
tensile stresses during operation. A carbon content as high as
1% C also makes the steel difficult to machine by cutting
operations such as turning or drilling. These shortcomings can
be eliminated by using a low carbon content steel to machine a
part to its final form and dimensions prior to carburizing and
hardening. The low carbon content in the steel ensures good
machinability before carburizing. After carburizing and
quenching the part will have a hard case but a softer core that
will assure wear and fatigue resistance. The martensitic case
attains a hardness corresponding to its carbon content. The
case is typically 0.11.5 mm (0.004- 0.060 inches) thick. The
core of the part maintains its low carbon concentration and
corresponding lower hardness.

A carburizing atmosphere must be able to

transfer carbon and also nitrogen in the
case of carbonitriding to the steel
surface to provide the required surface
hardness. To meet hardness tolerance
requirements this transfer must result in
closely controlled carbon or nitrogen
concentrations in the steel surface. The
carbon concentration, as indicated in
Figure 3, can be controlled by the ratio (vol
% CO)2/(vol% CO2) in the furnace
atmosphere. The atmosphere nitrogen
activity, which plays an important role in

The gas-carburized (carbonitrided) part can
be said to consist of a composite material,
where the carburized surface is hard but
the unaffected core is softer and ductile.
Compressive residual stresses are formed
in the surface layer upon quenching from
the carburizing temperature. The
combination of high hardness and
compressive stresses results in high fatigue
strength, wear resistance, and toughness.

Maximum hardness for unalloyed steels is

obtained when the carbon concentration is
about 0.8%C, as was shown. Above that carbon
concentration the hardness decreases as the
result of an increased amount of retained
austenite. The hardness curve therefore often
exhibits a drop in hardness close to the
surface, where the carbon concentration is
highest. Carbon, nitrogen and almost all
alloying elements lower the Ms-temperature
(see reference [2] for the definition of Ms
temperature). This leads to a retained
austenite concentration gradient that increases

To compensate for this effect, the surface carbon

concentration after carburizing that provides
maximum surface hardness has to be lowered as
the alloy content of the steel increases. Carbide
forming elements, such as chromium and
molybdenum, can counteract this effect and raise
the surface carbon concentration that provides
maximum hardness. This is because the formation
of carbides leads to a lowered carbon
concentration in the austenite, although the
average carbon concentration is high. Table 1
gives some examples of the relation between
maximum hardness and carbon concentration for
different types of steels. Mo-alloyed steels obtain
the highest surface hardness and Ni-alloyed steels

Case and Carburizing depth

According to European standards [6], the case
depth is abbreviated to CHD (case hardened
depth) and defined as the depth from the
surface to the point where the hardness is
550HV, as shown . Sometimes a hardness
other than 550HV is used to define the case

Attained case depth depends not only on

carburizing depth, but also on the hardening
temperature, the quench rate, the
hardenability of the steel and the dimensions
of the part. This is illustrated in the schematic
CCT diagrams. The hyperbolic temperature/
time-dependent parts of the transformation
curves depict the transformation from
austenite to ferrite/pearlite. For a high
hardenability steel these curves are located far
to the right in the diagram, ensuring that the
cooling curves do not cross the ferrite/pearlite

Hardenability increases not only with

base steel alloy content but also with
increased carbon and nitrogen
concentrations. The carburized or
carbonitrided case therefore has higher
hardenability than the base steel

In Figure a the cooling curves for both

surface and center cross the
transformation line for the base steel, the core.
This means that the core will transform to
ferrite/pearlite upon cooling from hardening
temperature. If the cooling curves are related
to the case instead, it can be seen that the
cooling line for the surface passes to the left of
the ferrite/pearlite transformation curve. Thus
thesurface cooling line first crosses the Ms
(case) line, meaning that the austenite will
transform to martensite, as is the intention in
case hardening. The hardenability of steel
number 1 in Figure b is too low to result in

In Figure c carbonitriding is a method for

achieving high enough hardenability to form a
martensitic case. (The surface cooling line
passes to the left of the carbonitrided
transformation curve.) Carbonitriding is a way
to make water-quench steels become oil
hardening steels.
In Figure d schematically shows the effect of
part dimensions on cooling rate. The bigger
the dimensions, the slower the cooling rate.
Therefore there is a certain maximum
diameter for a certain steel grade that can be
hardened to form a martensitic case. When a
martensitic case is formed the case depth will

Carburizing depth is not standardized but is

nevertheless used in practice, and is defined as
the depth from the surface to the point
corresponding to a specified carbon
concentration. As a guideline, the case depth
(CHD) for common steels and part dimensions
is approximately equal to the carburizing depth
to the point where the carbon concentration is
about 0.35%. The carburizing depth depends
on treatment time and temperature. With
prolonged carburizing time carbon can diffuse
to a greater depth into the steel. Increasing the
temperature increases the rate of diffusion and
thus increases the carburizing depth


Carbon itself is solid at case-hardening

temperatures and so is immobile.
Transport to the surface of the steel was
as gaseous carbon monoxide, generated
by the breakdown of the carburising
compound and the oxygen packed into the
sealed box. This takes place with pure
carbon, but unworkably slowly. Although
oxygen is required for this process it is recirculated through the CO cycle and so
can be carried out inside a sealed box

The sealing is necessary to stop the CO

either leaking out, or being oxidised to
CO2 by excess outside air.
Adding an easily decomposed
carbonate "energiser" such as
barium carbonate breaks down to BaO
+ CO2 and this encourages the reaction
C (from the donor) + CO2 <> 2 CO

Increasing the overall abundance of CO and

the activity of the carburising compound.[1] It is
a common knowledge fallacy that casehardening was done with bone, but this is
misleading. Although bone was used, the main
carbon donor was hoof and horn. Bone
contains some carbonates, but is mainly
calcium phosphate (as hydroxylapatite). This
does not have the beneficial effect of
encouraging CO production and it can also
introduce phosphorus as an impurity into the
steel alloy.

Carbon transfer from gas to

Possible carbon transfer reactions are
CH4 C + 2H2
It has been shown that the last of these
reactions,is by far the fastest and is therefore
the rate-determining reaction in carburizing
atmospheres with CO and H2
as major gas components . The slowest
carburizing reaction is from methane, with a
rate that is only about 1% of the rate of
carburizing from CO+H2

Interaction between Furnace Atmosphere and

In the above reaction, carbon monoxide (CO) and
hydrogen(H2) react so that carbon (C) is deposited on
the steel surface and water vapor (H2O) is formed. The
furnace atmosphere must contain enough carbon
monoxide and hydrogen to allow the carburizing
process to proceed in a uniform and reproducible
fashion. The supply of fresh gas must compensate for
the consumption of CO and H2. A higher gas flow is
required in cases where the furnace charge area is
high, resulting in a high rate of carbon transfer from
gas to surface. In the initial part of a carburizing cycle,
there is also a high carbon transfer rate, which may be
compensated for by increasing the gas supply.

According to the fundamental principles of chemistry, the

equilibrium condition for the carburizing reaction 1 is described by
an equilibrium constant expressed by:
K1 = (ac PH2O)/(PCO PH2)
The value of K1 is dependent on the temperatureand can be
calculated from the relationship:
log K1 = 7.494 + 7130/T
where T is the absolute temperature in Kelvin. ac is termed carbon
activity and is a measure of the carbon content of the gas. We
see that ac can be calculated if K1 and the gas composition are
known. When the carbon activity of the gas, acg, is greater than
that of the steel surface, acs, there is a driving force to transfer
carbon as expressed by the following equation:
dm/dt = k (acg acs)
dm/dt = k (ccg ccs)
where: m designates mass, c concentration per unit volume, t

The gradient dc/dx has its highest value at the

beginning of the cycle when carbon has only diffused
to a thin depth. This results in a high driving force for
carbon flux by diffusion into the steel. The rate of the
carbon transfer from gas to surface will therefore
initially be the limiting step. At the start of a
carburizing cycle, the term ccg ccs has its highest
value, and accordingly the driving force for carbon
transfer from gas to steel has its highest value. The
surface carbon Concentration ccs will increase with
increasing carburizing time. The driving force for
carbon transfer, ccg ccs, will thus decrease. The carbon
concentration gradient, dc/dx, will decrease
concurrently as carbon diffuses into the steel. In
conclusion, these limitations will lead to a continuous

Carburizing Atmospheres
A carburizing atmosphere can be achieved
by means of incomplete combustion of
propane or methane with air in accordance
with one of the reactions:
C3H 8 + 7.2 air 5.7 N2 + 3CO + 4H2
CH4 + 2.4 air 1.9 N2 + CO + 2H2
The mixing and combustion of fuel and air
takes place in special endothermicgas

Nitrogen/Methanol Atmospheres
Introducing nitrogen and methanol directly into the
furnace chamber is a common way of creating the
furnace atmosphere. Upon entering the furnace,
methanol cracks to form carbon monoxide and
hydrogen in accordance with the following reaction:
CH 3 OH CO + 2H 2
complete cracking of methanol into CO and H 2 only
occurs if the temperature is above 700-800C (12921472F),which is why methanol should not be
introduced into a furnace at a lower temperature. The
cracking of methanol into CO and H2 requires energy.
This energy is taken from the area surrounding the
point of methanol injection. There must therefore be
sufficient heat flux towards the injection point to

A high gas flow is desirable in the following

At the beginning of a cycle when the
furnace is originally airfilled or has been
contaminated with air after a door opening.
The higher the gas flow is, the faster the
correct gas composition will be obtained.
When carbon demand is great, i.e. at the
beginning of a process or in cases with a
large charge surface area.

Low gas flow can be used in the

following cases:
When the furnace is empty.
When the carbon demand is low,
i.e. at the end of a process or in
cases with a small charge surface

Purging of a furnace with inert gas.

Solid or pack carburising
Liquid carburising
Gas carburising

Pack carburising
The component is packed
surrounded by a carbon-rich
compound and placed in
the furnace at 900 degrees.
Over a period of time
carbon will diffuse into the
surface of the metal.
The longer left in the
furnace, the greater the
depth of hard carbon skin.
Grain refining is necessary
in order to prevent

The gas-carburizing process

In gas carburizing the workpieces are heated in
contact with carbon containing gases such as
the hydrocarbons, methane, ethane, and
propane. The carburizing gases are diluted with
an endothermic carrier gas which consists
mainly of nitrogen (N2) and carbon monoxide
(CO) along with smaller amounts of carbon
dioxide (CO2), hydrogen (H2), and water (H2O).
Of these gases, N2 is inert and acts only as a
dilutent. The carrier gas serves to control the
amount of carbon supplied to the steel surface
and prevents the formation of soot residue.

The reactions involved in carburizing are as below. First, the

methane or propane enrichment of the carburizing-gas mixtures
provides the primary source for the carbon for carburizing by slow
reactions such as
CH4 + CO2 2CO + 2H2 (14-1)
CH4 + H2O CO + 3H2 (14-2)
These reactions decrease the concentrations of CO2 and H2O and
increase the amounts of CO and H2. Then the CO breaks down to
deposit and allow the carbon to diffuse into the steel surface by
the following overall reversible reactions:
2CO C (in Fe) + CO2 (14-3)
CO + H2 C (in Fe) + H2O (14-4)
The carbon-potential control during carburization is attained by
maintaining a steady flow of the carrier gas and varying the flow
of the hydrocarbon enrichment gas

Induction: Why Induction Heat Treatment?

Greatly shortened


Highly energy


heat treatment cycle




Practical Problems
Lack of systematic heating time and temperature distribution control inside WP.
Nonlinear effect of material properties.
Lack phase transformation data inside WP for hardness and residual stress determination.
Evaluate combination effect of AC power density, frequency and gap on final hardness pattern.
Trial and error, cost and design period.

Research content: FEM based electromagnetic/thermal analysis

Numerical modeling
may provide better

+ quenching analysis + hardening analysis

Research objective: (1) Provide T field, time history inside WP

(2) Determine formed content of martensite, pearlite and bainite.
(3) Determine hardness distribution in WP.
(4) Guidance for induction system design.

Introduction: Induction Hardening Process

Induction heating:
metal parts heated to
austenite Phase

Fast quenching
process transforms
austenite to
martensite phase

content determines
the hardness
structure is the
most hardest



Joule heat
c field


freq. AC

Principle: Electromagnetic and

Thermal Analysis
Electromagnetic Analysis



Thermal Analysis with

finite element model

Input AC power
to coil
Calculation of
magnetic vector potential (A)
Calculation of
magnetic flux density (B)
Calculation of
magnetic field intensity (H)
Calculation of
electric field intensity (E)
Calculation of
electric field density (D)

0 I


(Gauss Law for
magnetic field)



(Faradays Law)


QE t






Calculation of
Inducting heat (Qinduction)

Qinduction = E J = J2/

Circuital Law)




(c) Interior element

Calculation of
current density (J)

Heat generation Qinduction in WP

(b) FEA model

(a) WP geometry

(d) Surface element

Heat conduction


k 2T Qinduction

k 2T Qinduction A F T 4 Tair4 A h T Tair

Induced Joule heat

Heat radiation

Heat convection

Case Study: Complex Surface

Material: Carbon
Steel, AISI 1070
Automotive parts from
Delphi Inc.,

Concave and convex on

surface of workpiece make
the heating process not easy
to control.


Real spindle to be hardened

Geometry Model

ANSYS system is employed

for the analysis.
Mesh should be much finer
at locations of convex and
concave in both coil and

FEA model and B.C.

Mesh generated by ANSYS

Case Study: Material Properties -- AISI

(a) Electromagnetic Properties

WP relative


(b) Thermal Properties



Case Study: Magnetic Field Intensity Distribution

Effect of current density distribution

Constant current distribution in
coil can not result in good heating
pattern, especially at concaves of
Better hardened pattern
resulted from modification of
Finer coil mesh and enhanced
coil current density at area
neighboring to surface concaves
of workpiece.

(a1) Constant current distribution in coil

(a2) heated pattern

(b1) Adjusted current distribution in coil

(b2) heated pattern

Enhanced coil current density

suggests utilization of magnetic
controller at those area in coil
design process. Physically this
can be fulfilled by magnetic

Case Study:Temperature Variation with Time in Induction

Heating Process
Total heating time
th = 7.05s
J=1.256e6 A/m2



Case Study: Heating Curves

A finite element method based modeling system is developed to
analyze the coupled electromagnetic/thermal process in induction
heating and implemented in ANSYS package, with following
Provide electrical and magnetic field strength distribution.
Provide instantaneous temperature field data in workpiece.
Provide Temperature history at any location in heating process.
Provide guidance for inductor/coil design based on adjustment of

Quenching of carburized
Carburized parts are usually quenched
from the austenitic condition to produce
a hard case with a martensitic structure,
as shown

Most gas-carburized parts are directly

quenched from the carburizing
temperature of about 925C or from
about 845C without being cooled to
room temperature. The decrease in
temperature from about 925 to 845C
can be accomplished by allowing the
temperature of the carburizing to
decrease, moving the workpiece to a
lower temperature zone of the furnace,
or by transferring the workpiece to
another furnace

Tempering of carburized

Many carburized and hardened parts are placed into

service without tempering, especially if the
applications for the parts are not critical with respect
to cracking and chipping. On the other hand, many
hardened carburized parts are given a lowtemperature temper treatment, usually in the 150 to
190C range, since in this temperature range,
hardening is not greatly reduced and toughness and
resistance to cracking is slightly increased


The diffusion of nitrogen into the surface layers of low

carbon steels at elevated temperature. The formation of
nitrides in the surface layer creates increased
mechanical properties.



Benefits of Nitriding
Types of Nitriding
Future of Nitriding
Process Determination
CVD Reaction
Deposition Process
Diffusion Depth
Process Results

Principal Reasons for Nitriding are:


Obtain High Surface Hardness

Obtain a Resistant Surface
Increase Wear Resistance
Increase Tensile Strength and Yield
Improve Fatigue Life
Improve Corrosion Resistance
(Except for Stainless Steels)



Improves Mechanical Properties

Surface Hardness
Corrosion Resistance
Chemical Reaction
Nitrogen & Iron
Core Properties Not Effected
Temperature Range
495 - 565 C
Below Tempering Temperature
White Layer By-Product
Hard Iron Nitride

Process methods for nitriding
***Lots of more nitriding methods for
specific applications***

Gas Nitriding
Gas methods:
Case-Hardening Process
Nitrogen Introduction
Surface of a Solid Ferrous Alloy
Suitable Temperature
Between 495 and 565C (for Steels)
Nitrogenous Gas

Liquid Nitriding
Liquid nitriding:
Thermo-chemical Diffusion Treatment
Hardening Components With
Salt Bath, at Less Critical
Preserves Dimensional Stability
Corrosion Protection
Exhibit Long-Term Resistance to Wear,
Seizure, Scuffing, Adhesion and

Plasma Nitriding
Vacuum Chamber
Pressure = 0.64 Pa


t- Pre-Heat Cycle

Surface Cleaning
Ion Bombardment
Control Gas Flow
N, H, CH4


Ionization by Voltage

Blue-Violet Glow
Wear Resistant Layer

Mechanism of Nitriding
Fe- N equilibrium diagram can be used to study
nitriding process.
The solubility limit of nitrogen in iron is temperature
dependent, and at 450 C the iron-base alloy will
absorb up to 5.7 to 6.1% of N.
Beyond this, the surface phase formation on alloy
steels tends to be predominantly -phase.
This is strongly influenced by the C-content of the
steel; the greater the carbon content, the more
potential for the phase to form
As the temperature is further increased to the
gamma prime (-nitride) phase temperature at 490
C , the window or limit of solubility begins to
decrease at a temperature of approximately 680 C.

Effect of alloying elements

Plain carbon steel form Iron nitride
(brittle & low hardness) on nitriding due
to absence of nitriding forming
Strong nitriding elements- Al, Mo, Cr, Ti,
V etc form nitrides causes internal
precipitation of nitrides resulting high
surface hardness.
Steel containing several alloying
elements have higher hardness than by
a single element

Effect of alloying element on hardness after nitriding


The Future of Nitriding

Replacing Liquid Nitriding
Environmental Effects
Ease of Control
More Complex Substrates
Performed at Lower
Creates Higher Residual Stress

Problem Statement
Gas Nitriding
How do the variables of nitriding steel affect
the process and the mechanical properties of
the surface?
The following variables were investigated:
Gas Velocity
Develop Process Model

CVD Equations


CVD Process


CVD Reaction


CVD Process

The FollowingComposition
Variables Were Used
in The Calculation of C surface








Case Depth


Case Depth


Case Depth

Time Effects
Increase Diffusion Depth
Temperature Effects
Surface Composition
Deposition Efficiency
Diffusion Rate
Diffusion Depth
Gas Velocity Effects
Surface Composition
Replenishes Nitrogen Gas
Minimizes Stagnant Layer Thickness

Microstructural Effects
Processing Temperature
Surface Microstructure
Mechanical Property Effects
Surface Hardness
Wear Resistance
Corrosion Resistance
Fatigue Life
Yield Strength
Fracture Toughness


It is an expensive process.
Much more time is required to develop
the requisite case depth (due to low
Expensive gas ammonia is used in
Expensive alloy steels can only be
nitrided and are used.
Nitriding is more expensive than
carburising and carbonitriding

Carbonitriding of Steels
Carbonitriding is a modified form of carburizing and is not a
form of nitriding. The modification in carbonitriding consists
of adding ammonia (NH3) to the carburizing gas so that
nitrogen diffuses in the steel case along with carbon.
Carbonitriding is usually carried out at a lower temperature
and for a shorter time than gas carburizing, and so a thinner
case is usually produced than by carburizing. Carbonitriding
is principally used to produce a hard, wear-resistant case in
steels, normally from 0.075 to 0.75 mm thick. Nitrogen
increases the hardenability of steel, and so a carbonitrided
case has higher hardenability than a carburized case on the
same steel. Also, since nitrogen is an austenite stabilizer,
high nitrogen levels can result in retained austenite,
particularly in alloy steels. Maximum hardness and less
distortion can be attained by carbonitriding since less
drastic oil quenching than for carburizing can be used.

Laser Hardening

LASER beams are invisible electromagnetic
radiation in infra-red portion of spectrum.
Used for surface hardening of ferrous material
Laser used for hardening:
YAG- Solid state type
CO2 Gas type

CO2 Laser is commonly used for surface

hardening when the power required is more
than 500W.

Hardening Mechanism-Hypoeutectoid
Consider the microstructure of a hypoeutectoid
steel containing 0.35% carbon. It consists of
pearlite colonies surrounded by proeutectoid
On heating,
Pearlite Austenite (dissolution of the cementite),
Growth of the Austenite transformation front into
regions of high carbon concentration, at a rate
controlled by carbon diffusion between the lamellae.
Ferrite transforms by nucleation and growth of austenite
at internal ferrite grain boundaries, (rate controlled by
carbon diffusion

The phase diagram shows that under equilibrium

conditions, pearlite begins to transform to
austenite at 723C(Ac1), and that transformation
of ferrite is complete at about (Ac3) temperature.
The high heating rate experienced during laser
heating (on the order of 1000 K s1) results in
superheating of Ac1 and Ac3, typically by about
30 and 100C, respectively.
The heat is conducted to the bulk at a very fast
rate which results in surface quenching and
martensitic hardening.

By selecting power density and the

speed of the laser spot a desired case
depth can be hardened.
Case depth also depends on hardening
response of ferrous material (not more
than 2.5mm)

Why LASER Hardening?

Local surface hardening exactly where
Low distortion and no rework
Short wavelength enabling superior absorption
Closed-loop temperature control
Highest process efficiency of all laser types
Extremely reliable for production processes
Highest level of process safety and

Advantages of LH vs other hardening


Selective areas hardened without affecting surrounding material

Possible automation and integration with other in-line production


Quick turn-around time

Treatment depth accurately controlled and highly reproducible due to
direct temperature control

Superior hardness can be obtained compared to conventional processes

(typically 20% higher hardness)
No external quenching required eliminates complex quench equipment
Minimal heat input limited distortion no need for post treatment
machining final machined components for laser hardening

Phase transformation + volume expansion residual compressive

stresses into surface improves mechanical properties, e.g. wear and
fatigue resistance, lowers crack sensitivity

Laser hardening applications

Steering gear assemblies

Turbine blades
Cutting edges and edges of dies for sheet metal forming
Cam followers, Gear teeth and Shafts
Rim geometries, e.g. Piston rings
Plastic injection moulds at highly loaded areas on the surface
Cylinder liners in diesel engines
Heavy duty and ball bearing steels
Tool steels

High initial cost
Laser use 10% of the input energy
Depth of case is very limited
Working cost is high
Difficult to surface harden high alloy
Extra care is needed to avoid fusion


TOOL STEEL are high quality steels made to
controlled chemical composition and processed to
develop properties useful for working and shaping
of other materials.
The Carbon content in them is between 0.1 -1.6% .
Tool steel also contain alloying elements like,
Chromium, Molybdenum and Vanadium.
Tool steel offers better durability, strength,
corrosion resistance and temperature stability,
as compared to the Construction & Engg. Steel.
These are used in applications such as Blanking,
die forging, forming, extrusion and plastic molding

To obtain a desired microstructure and
properties suitable for machining or cold
To release residual stresses accumulated
during previous thermal and mechanical
To homogenize the microstructure with
globular carbides by a spheroidization
To dissolve by a normalizing treatment the
intergranular carbides that are detrimental

Require special heat treatment
Higher cost than alloy steels.
Better hardenability than most carbon
and alloy steels.
Higher heat resistance.
Easies to heat treat.

Carbides in Tool steels



High Carbon, High








Carbon content = 0.5-0.6%. Alloying elements Cr,
W , Mo.
These are characterized by good toughness,
hardness and improved hardenability. These steels
are generally, water or oil- hardened.
Low temperature Tempering is carried out where,
toughness and hardness of the tool steel are of
prime importance, otherwise High temperature
Tempering is preferred.
Silicon-manganese steels (0.55% C, 2.0% Si, 1.0 %
Mn) are included in this group. Due to their high Sicontent, decarburization and grain coarsening takes
place in these type of steels.

HEAT TREATMENT PROCEDURE (in general) : Annealing : Slow & uniform heating in the
range of 790-800C followed by furnace cooling
at rate of 8-15C/hr.
Stress relieving : Heat to 650- 675C and
furnace cooling.
Hardening :
Preheating warming to about 650C &
holding for 20 minutes/ 25mm.
Austenitizing heating to 900-950C &
holding again for 20minutes/25mm.


Pneumatic chisels
Shear blades
Scarring Tools
River sets
Driver bits.




Carbon content = 0.3-0.5% . These steels are used for
high temperature metal forming operation (except
cutting), where the temperature is around 200-800C.
These are characterized by high hot yield strength, high
red hardness , wear resistance, toughness, erosion
resistance, resistance to softening at elevated
temperatures, good thermal conductivity
These are divided into 3 groups depending on the
principle alloying elements:
Chromium based [H11- H19]
Tungsten based [H20- H26]
Molybdenum based [H41- H43]

Contains Chromium (>=3.25%), and small amounts of
Vanadium, Tungsten and Molybdenum.
These are characterized by high red hardness & high
Oil quenching is reqd. when dimensional stability is not
of prime importance. Tempering temperature for these
steels varies from 550-675C.
Hot dies for extrusion, forging, mandrels,
Highly stressed structural parts of supersonic
Hot work steels.

Contains tungsten (=9.00%) & Chromium (2.0
-12.0%), and low Carbon %.
These are characterized by resistance to high
temperature softening.
Tempering temperature for these steels varies
from 550-675C.
Punches .
Mandrels .
Extrusion dies for Brass, Steel & Nickel alloys.

Contains Molybdenum (8.00%) &
Chromium (4.0 -12.0%), and some
tungsten and Vanadium.
These are characterized by high toughness
& high heat check resistance.
Tempering temperature for these steels
varies from 550-650C.

Microstructure of

Microstructure of
Annealed H-13 TOOL


These steels are used for making tools for cold
work applications, when the tool surface
temperature does not rise more than 200c.
These are characterized by high abrasion & wear
resistance, higher toughness and high impact
These steels are also called Non- distorting
Steels, as they show little change in dimension
during heat treatment.
These are divided into 3 groups:
Oil hardening Steels [GRADE O]
Air hardening Steels [GRADE A]
High Carbon, High Chromium Steels


These are hardened by oil-quenching & contain
high carbon with manganese, chromium &
These are characterized by high machinability,
wear resistance & non-distorting properties.
Tempering temperature for these steels varies from
Taps .
Blanking & forging dies.
Threading dies.
Expansion reamers.


These are hardened by air-quenching and contain
Carbon (1.0%) with manganese, chromium &
molybdenum & tungsten.
These are characterized by high wear resistance &
high hardenability, fair red hardness, good
toughness & resistance to decarburization.
Tempering temperature for these steels varies from
Knives .
Blanking & trimming dies.
Coining dies.


These are hardened by oil- or air- hardening &

contain Carbon (1.4-2.3%) & Chromium (12-14%),
with molybdenum, cobalt, vanadium.

Vanadium prevents these steels form showing

Grain coarsening (upto 1040C). Chromium imparts
non-deforming properties. Tempering of these
steels results in high hardness, wear & abrasion

Tempering temperature for these steels varies from


Mandrel for tube rolling by Pilger rolls .
Blanking & piercing dies, Coining dies,

Microstructure of
As-Tempered COLD



High Speed Tool Steels

These are high alloyed tool steels developed
initially to do high speed metal cutting. Now, they
used in a wide variety of machining operations.
These are characterized by high hardness (60-65
HRC at 600-650C), high red hardness, wear
resistance, reasonable toughness and good
They contain 0.6 % carbon, 4% Chromium, 5-12%
Carbon imparts hardness of at-least 60 HRC of
martensite formed. Chromium increase
hardenability & corrosion resistance. Cobalt
increases the thermal conductivity, melting point,

These are divided into two groups depending upon the

principal alloying elements & the composition:
Molybdenum High speed steel [GRADE M]
(contain Molybdenum, Tungsten, Chromium,
Vanadium & sometimes cobalt).
Tungsten High Speed steels [GRADE T]
(contain high amount of tungsten with chromium,
vanadium and some cobalt.)
Applications :
End mills, drills, lathe tools, planar tools.
Punches, reamers,
Routers, taps, saws.
Broaches, chasers, and hobs.



(1 hr)


(1 hr)

Typical heat treatment cycle for


Microstructure of
oil- quenched HSS

Microstructure of
oil- quenched
18-4-1 type HSS


Water hardened tool steels

These steels contain carbon in the range of 0.91.0% along with Cr, V, Mo.
These are characterized by high tensile strength
& hardness levels but low ductility & toughness
In order to improve machinability, these steels
are given Spheroidizing annealing treatment.
Presence of Cr improves both hardness &
hardenability and Vanadium checks the tendency
of grain coarsening.
Tempering temperatures are in the range 170-

Applications :

Heavy forging hammers, hand hammers.

Forging dies, bending dies, cutting dies.
Large blanking tools, boring tools.ENGRAVING
Chisels, scissors, knife blades.
Milling cutters, lathe centre.
Watch makers tools.
Engraving tools.



High strength low alloy steels

Conventional low carbon steels have low yield strength but
good weldability.
However when carbon content is increased to increase
strength, toughness and weldability decreases.
Microalloyed steels are mild steels with carbon content
between 0.03-0.15 % , manganese content around 1.5 % and
less than 1% of niobium,
Titanium, vanadium and also aluminium, which have been
given controlled rolling and controlled cooling.
Hence we obtain ultra fine ferrite grains of size below 5 and
attain yield strength of 290-550 Mpa along with tensile
strength of 415-700 Mpa.
The alloying elements are intended to change the
microstructure of carbon steels from a pearlite mix to that of
an almost pure ferrite having fine dispersion of carbides.
Presence of low carbon i.e. no pearlite with ultra fine ferrite
grains induces high strength and toughness and also good
Precipitation strengthening plays a minor role also in

strength and elongation of


Currently, high strength steel

products whose microstructure
is reinforced for greater
strength have been used.
(DP steel, TRIP steel)

Conventional high strength sheet

steel for automobiles used to be
solid solution-hardened steel or
precipitation-hardened steel with
micro-alloy added.

Microstructure of a cold rolled HSLA 340 steel;

Courtsey -

entional thermo-mechanical processing technique diag

High Strength Low Alloy Steel (HSLA)

(Precipitation strengthened/Grain refined
Addition of micro-alloysteel)
(carbide, nitride or carbonitride forming elements) such as Nb, V, Ti in
structural steel and strip steel grades, the materials
are known as High Strength Low Alloy (HSLA) steel
At slab soaking temperature ~ 1200 C
- undissolved particles (such as TiN, NbC and AlN)
restricts the size of austenite grain (affect to inhibit
recrystallization during hot rolling produces fine
austenite grain size induces fine ferrite grain size)
- a proportion of micro-alloys are dissolved to
solid solution (affect to precipitate in later process in
form of fine carbide/carbonitride/nitride at austeniteferrite interface on cooling to room temperature)

High Strength Low Alloy Steel (HSLA)

(Precipitation strengthened/Grain refined
Hot rolled materials can
be strengthened by
separate mechanisms of grain refine &
precipitation strengthening
Magnitude of effects depend on:
- type and amount of elements added
- base compositions
- soaking temperatures
- finishing and coiling temperatures
- cooling rate to room temperature
Strength increment up to 300 N/mm2 and Y.S. ~
500-600 N/mm2 can be produced in hot rolled

High Strength Low Alloy Steel (HSLA)

(Precipitation strengthened/Grain refined
steel) Precipitate Ti growth
austenite > 1250 C
Precipitate Nb growth austenite
1150 C
Precipitate Al growth austenite
1100 C
Precipitate V growth austenite
1000 C

HSLA steel precipitation strengthening

ferrite grain refining

High Strength Low Alloy Steel (HSLA)

(Precipitation strengthened/Grain refined

High Strength Low Alloy Steel (HSLA)

(Precipitation strengthened/Grain refined

High Strength Low Alloy Steel (HSLA)

(Precipitation strengthened/Grain refined
steel) (PTT)
Diagram Nb(CN) austenite 50%

Nb(CN) dynamic
precipitation ~
900 C
%Mn precipitation
(shift PTT curve
Ps : Precipitation
Pf : Precipitation

High Strength Low Alloy Steel (HSLA)

(Precipitation strengthened/Grain refined
steel) (PTT)
Diagram Ti(CN) austenite

precipitation ~
1025 C Norecrystallization
temperature (Tnr)
%Mn precipitation
(shift PTT curve
HSLA steel Nb)

High Strength Low Alloy Steel (HSLA)

Recystallization-Time-Temperature (RTT) Diagram
Nb microalloyed steel plain carbon steel
a) recystallization rate Nb
microalloyed steel plain
carbon steel
b)Nb solute atom (solute effect only)
ecystallization rate (recystallization
plain carbon steel

c) precipitation Nb(CN) recystallization

Rs: Recystallization start, Rf: Recystallization finish
Ps: Precipitation start, Pf: Precipitation finish
(C): for plain carbon steel
(S): for Nb microalloyed steel (solute effect only)
(Nb): for Nb microalloyed steel (precipitation effect)

High Strength Low Alloy Steel (HSLA)

(Precipitation strengthened/Grain refined steel)

temperature; Tnr)

Grain size refinement

Fine grain sizes in HSLA steels are possible by control of austenite grain
size by the
precipitation of carbonitrides during hot rolling as the temperature of the
steel falls.
The austenite grains may recrystallize several time during during hot
controlled rolling resulting in marked refinement of austentite grains
until transformation temperature.
Fine precipitation of carbonitrides must occur in rolling range of 1300
C - 925 0C when the recrystallization of austenite could occur and the
volume of the precipitates formed must be large.
It is essential to use high soaking temperatures to dissolve as much of
the elements niobium, vanadium, titanium so that these could
precipitate later during rolling while the temperature continuously
A fine grain boundary precipitate of TiN does not dissolve completely at
the highest soaking temperature(1200-1300 0C) and controls austenite
grain growth.
Main refinement during hot rolling is achieved in range of 1300 925
C when the temperature continuously falls and fine carbonitrides are
precipitated from austenite.
Niobium effectively precipitates carbides and carbonitrides during hot

Refining the ferrite grain

(Grain size effect)

Refining the ferrite grain size (Grain size


Effect of microalloying on recrystallization temperatur

Effect of micro-alloying on austenite grain coarsenin

Controlled Rolling
Controlled hot rolling is done to obtain ultra fine grains of ferrite and
precipitation hardening.
Fine austenite grains or very thin unrecrystallized grains of austenite
before transition is a prerequisite to obtain fine ferrite grains.
Presence of TiN and Nb(C,N) during hot rolling of austenite at high
temperatures does some refinement.
This demands heavy deformation and low finishing temperatures below
950 0C so that austenite is unable to recrystallize.
Heavy reductions (more than 50 %) is done during the finishing stages in
no- recrystallization range of austenite to obtain, thin, elongated and
flattened austenite grains.
Normally finishing temperature is above the transition temperature
and nature of transformation is changed by using water sprays during
rolling to enhance cooling rate.
The subcritical transformation produces still finer ferrite grains and this
may produce widmanstatten ferrite with still higher dislocation density.

Controlled rolling/Thermo-mechanical
processing (TMCP)
1. Outline process
SRT ~ 1200-1250 C
FT ~ 1000 C

Roughing rolling

normalizing ~ 920 C

No-recystallization temperature (Tnr)

Finishing rolling
(Below Tnr)

Austenite-elongated grain
(pancake structure)

Controlled rolling/Thermo-mechanical
processing (TMCP)
2. Slab Reheating
Importance of slab reheating stage
- control amount of micro-alloying element taken
into solution
- starting grain size
Re-solution temperature of micro-alloy
- VC: complete solution ~ 920 C (normalizing
- VN: at somewhat higher temperature
- Nb(CN), AlN and TiN: around 1150-1300 C
- TiN (most stable compound) little dissolution at
normal slab reheating temperature (SRT)

Controlled rolling/Thermo-mechanical
processing (TMCP)
2. Slab Reheating
Un-dissolved fine carbo-nitride (CN) particles
- maintain fine austenite grain size at slab
reheating stage
Micro-alloying elements taken into solution
(which can be influence in later stage in process)
- control of recrystallization
- precipitation strengthening
Multiple micro-alloy additions for above dual

Controlled rolling/Thermo-mechanical
processing (TMCP)

3. Rolling

Three distinct stages during controlled rolling.

- Deformation in the recrystallization (austenite
phase) temperature range just below SRT
- Deformation in temperature range between
recrystallization temperature and Ar3
- Deformation in 2 phase (austenite-ferrite)
temperature range between Ar3 & Ar1
At temperature just below SRT
- rate of recrystallization is rapid
- provided the strain per pass exceeds a minimum
critical level
- recrystallization is retarded by presence of solute
atom Al, Nb, Ti, V (solute drag) strain induced
precipitation form fine carbonitride during rolling

Controlled rolling/Thermo-mechanical
processing (TMCP)

3. Rolling

- rolling temperature decrease, recrystallization

more difficult and reach a stage recrystallization
stop temperature (Trs or No-recrystallization
temperature; Tnr) (the temperature at which
recrystallization is complete after 15 s. after
particular rolling sequence)
- Nb is powerfull retardation effect which depend on
solubilities in austenite
- Nb lease soluble
- largest driving force for precipitation
- creating greater effect in increasing of
recrystallization temperature than Al and V
At temperature between recrystallization
temperature & Ar3

Controlled rolling/Thermo-mechanical
processing (TMCP)

3. Rolling

- strain induced precipitation of Nb(CN) or TiC is

sufficient rapid to prevent recrystallization before
the next pass (deformed-austenite providing
nucleation sites of carbo-nitride precipitation and
pins the substructure which inhibits
- finishing rolling below recystallizaion stop
- can be obtain elongated-pancake morphology in
the austenite structure
At temperature between Ar3 & Ar1
- further grain refinement
- mixed structures of polygonal-ferrite (transformed
from deformed-austenite) and deformed-austenite
during rolling process

Controlled rolling/Thermo-mechanical
processing (TMCP)

4. Transformation to ferrite

Mean ferrite grain size relate to:

- thickness of pancake-austenite grain
- alloying elements depress the austenite to ferrite
transformation which decrease ferrite-grain size
- cooling rate from austenite or austenite-ferrite
region (accelerate cooling)
increase strength
achieve strength level by lower alloy content
- direct quenching
refine ferrite-grain
formation of bainite and martensite (required

Controlled rolling/Thermo-mechanical
processing (TMCP)

Controlled rolling/Thermo-mechanical
processing (TMCP)

ches of microstructural changes in low-carbon steels that develo

tion of finishing temperature in austenite and cooling to initiate

Precipitation Hardening

Precipitate strengthening occur by those particles that form :In austenite at low temperatures at low temperatures.
At the interface at low temperatures.
In ferrite during further cooling.
Main contribution to precipitation strengthening is due to precipitation of carbide
Ti, V which occurs during transformation of austenite to ferrite progressively at
boundaries called interphase precipitation.
It occurs on a very fine scale between 850 650 0C with size about 5 nm.
Solid solution strengthening due to presence of elements like Mn, Si, and even u
N takes place.
The most effective factor is the ultra fine ferrite grain size as ferrite size is 5-10
plates though a size of 1-2 has been obtained under laboratory conditions.

Yield strength as a function of grain size in various low carbon steels.

Advantages of HSLA steels

HSLA steels are designed to handle large amount of stress and
possess a good strength to weight ratio. They are usually 2030 % lighter than a carbon steel of same strength.
HSLA steels are also more resistant to rust then most carbon
steels. Although the material quickly becomes covered with
surface rust, this is superficial and rust takes a long time to
threaten the integrity of a structure made from the material.
Good formability at room temperature. Hot forming requires
careful control to avoid strength degradation.
Good weldability with most conventional welding methods and
lower preheat requirements.
They are further characterised by a good resistance to fatigue
and impact.

Uses of HSLA steels

HSLA steels are used in sectors such as :
Automotive: pressed chassis and reinforcement
parts, beams or
welded tubes.
Seats: tubes, rails and mechanical elements.
Industrial vehicles, tractors, trailers and skips as
chassis components (resistance to fatigue).
Lifting and handling equipment (cranes, fork lifts,
platforms, warehouse shelves, lifts).
The agricultural sector for chassis and protective
Roll bars, buildings, containers, urban lighting
masts, concrete

Uses of HSLA steels

Dual phase steels

Dual phase steels have microstructures consisting of islands of
martensite (normally 10-20 %), or dispersion of martensite in a
ferrite matrix.
DPS starts as a low or mediumcarbon steeland is quenched from
a temperature above A1but below A3on acontinuous cooling
This results in amicrostructureconsisting of a soft ferrite matrix
containing islands of martensite as the secondary phase
(martensite increases thetensile strength).
The soft ferrite phase is generally continuous, giving these steels
excellent ductility.
When these steels deform, strain is concentrated in the lowerstrength ferrite phase surrounding the islands of martensite,
creating the unique high work-hardening rate exhibited by these
The desire to produce high strength steels
withformabilitygreater thanmicroalloyed steel led the
development of DPS in 1970s.
Dual phase steels are gaining importance among auto makers as

(a) Dual phase 600

(b) Dual phase 980 Y700

Methods of obtaining DP steels

A normalized steel is heated to intercritical temperature
(e.g. 790 0C) and held there for several minutes till
equilibrium amounts of austenite and ferrite are obtained.
On quenching it ( or air cooling it if it has been alloyed
with 0.2-0.4 % Mo and 1.5 % Mn), austenite transforms to
fine martensite.
Nowadays this extra reheating is avoided. The required
structure is obtained during cooling itself after controlled
Such steels normally have 0.4 % Mo and 0.5 % Cr.
The hot rolling is completed at around 870 0C when the
steel has around 80 % ferrite on the water cooled run out
tables from the mills.
This steel is cooled bypassing the pearlitic nose to 550620 0C, where the steel is cooled ,when it is in metastable
On subsequent cooling, transformation of austenite

ron-Carbon phase diagram with thermal treatment for dual phase steel

TTT diagram for obtaining dual phase steel

Advantages of DP steels
Low cost of manufacturing.
Excellent formability.
High strength (500-700 MN/m2).
Low yield stress (300-350 MPa).
Rapid rate of work hardening.
No yield point elongation.
A high strain rate sensitivity (the faster it is crushed the more
energy it absorbs).

Good fatigue resistance.

son between dual phase and hsla steel mechanical pr

Dual Phases (DP) Steel

Dual Phases (DP) Steel

Maraging steels
Maraging steels, a portmanteau of martensitic and aging, are iron alloys,
are a special class of low carbon ultra high strength steels which derive
their strength not from carbon, but from precipitation of inter metallic
The maraging steels offer a good combination of strength and ductility
with a yield strength as high as 400 MPa and an elongation of 6 %.
These are essentially high alloy steels with C < 0.03 %, upto 25 % Ni, 710 % Co, 3-5 % Mo,1.75 % Ti & 0.2 % Al.
Presence of Ni in large amount is necessary to form ductile and soft
martensite based on Fe-Ni system.
The soft ductile and tough martensite is strengthened by precipitation
hardening resulting in a fine dispersion of Ni3(X,Y) intermetallic phases
along dislocations left by martensitic transformation, where X and Y
aresoluteelements added for such precipitation.
Maraging steels have good weldability and can be cold rolled to 80-90 %
before aging.
Maraging steels also have good machinability and undergo little
dimensional changes onheat treatment.
Due to the higher cost maraging steels are mainly used for rocket
casings and other aerospace applications.
They are suitable for engine components, such as crankshafts and gears,

Properties of maraging steels

Maraging steels
A series of iron base alloys capable of attaining
yield strengths upto 300,000 psi.
in combination with excellent fracture toughness.
Low carbon (0.03%),
18-25 % Nickel and other hardening elements.
Yield strength: The stress at which a material exhibits a
specified deviation from proportionality of stress and
Fracture toughness:resistance to crack propagation.

Maraging steels
As annealed, these steels are martensitic.
They achieve high strength on being aged in the
annealed or martensitic condition.

This martensite is soft and tough as compared to the

hard and brittle martensite formed in conventional low
alloy steels.

This ductile martensite has a low work hardening rate

and so can be cold worked to a high degree.

Maraging steels
There are two groups, based on hardening element
1.The 18% nickel grades use cobalt molybdenum
2.The 20% nickel grades use titanium-aluminiumcolumbium additions.

Maraging steels
1 hr

18% Nickel
Heated to 1500 deg F , held for
1 hour .
3 hrs

Soaked to anneal austenite and

dissolve hardening elements Co
and Mo.




52 RC

Air cooled to 100 deg F, forms

martensite of 28 32 RC
Reheated to 900 deg F, held for
3 hrs- aged to harden.
stress relief also occurs at the
same time.

Deg F

Hardness of 52 RC can be

Maraging steels
18% Nickel
The interest is in achieving high strength at room
Simple heat treatment carried out at moderate
temperature is enough to achieve good properties.
Section size, heating and cooling rates are not
Very low in carbon content and so no problem of
Protective atmosphere is not required.
Low aging temperatures means less distortion.

Maraging steels
Effect of additives on maraging
strength development
Solution treated 110,000 psi
After maraging 300,000 psi


Iron nickel martensite 25Rc

A weak response to maraging is
seen after addition of 7% cobalt.


The addition of molybdenum alone

gives a slight increase in annealed
hardness and good maraging

Rockwell C


%Mo or %Co


When Mo is added in presence of 7%

Cobalt, an increase in hardness
greater than the combined effect of
both the elements is seen.

Maraging steels
Largely austenitic after annealing.
The conversion to martensite is done by ausaging or
cold working.
Ausaging-conditioning treatment at 1300 deg F.
Reduces the stability of austenite by causing nickel
titanium compounds to precipitate from the austenitic
solid solution.
It raises the Ms temperature so that martensite will
start forming at room temperature.
Cold worked to 25% to start the transformation to
martensite and is completed by refrigeration at
minus100 deg F.

Maraging steels
20% Nickel
Lower alloy content
Freedom from cobalt and molybdenum. Useful in
certain environments and applications.
Compared to the 25% grade, this does not require a
conditioning treatment to become martensite.
Ms temperature is above room temperature.
Lower in
toughness, resistance to stress corrosion cracking and
in dimensional stability during heat treatment.

Maraging steels
Applications for maraging steels
Hulls for hydrospace vehicles
Pressure vehicles
Motor cases for missiles
Mortar and rifle tubing
Hot extrusion dies
Low temperature structural parts
Cold headed bolts
(Complex shapes that need to be strong after shaping)



1913, Sheffield, U.K.

Harry Brearley experimenting with alloy

steels for gun barrels
Samples with 14% chromium were
discarded as they proved to be unsuitable
for this application
Some months later he noticed that low
alloyed samples had rusted
The chromium alloyed samples were still

In general terms we can say that a

stainless steel is an alloy with:

a minimum 12% Cr

Stainless steel are versatile for the following
Good corrosion and oxidation resistance

Cr2O3 protective layer formed

Good creep strength
High resistance to scaling and oxidation at
elevated temperatures
Wide range of strength and hardness
High ductility and formability
Excellent pleasing appearance
Good weldability and machinability
Good low temperatur properties


Stainless steels contain large amounts of chromium,
and an important starting place to understand the
phase relationships and microstructures in stainless
steels is the iron-chromium (Fe-Cr) equilibrium phase
Phase diagrams of importance are FeCr, FeNi, CrNi,
FeMo, FeTi, NiTi, FeNb, FeMn, FeSi, FeCrNi and
FeCrMo ternary diagrams and the quaternary FeCr
three main features of the FeCr diagram which are
relevant to stainless steels, are the ferrite-stabilizing
character of Cr and the presence of sigma () and
alpha prime () phases
The FeNi diagram clearly shows the strong austenitestabilizing effect of Ni. The intermetallic compound
Ni3Fe is not normally observed in stainless steels. Also

The FeMo diagram shows that Mo is a strong ferrite

stabilizer and also that it forms four intermetallic
compounds with iron. Of these, the sigma () phase and
the Laves phase, Fe2Mo, often occur in stainless steels.
The mu () phase, Fe7Mo6, occurs less frequently in
stainless steels
In the FeTi diagram one can also see the very strong
ferrite-stabilizing character of the Ti and also the
presence of a Laves phase, Fe2Ti, that can occur in
stainless steels, particularly in those in which the
relationship Ti:C is high, the so-called over-stabilized
The NiTi diagram shows the presence of the Ni3Ti that
can be used to produce precipitation strengthening in Nicontaining stainless steels. The FeNb diagram shows the
ferrite-stabilizing character of the Nb and also the

As to the FeMn diagram the most relevant

characteristic is the austenite-stabilizing character of
Mn. Finally, the FeSi diagram shows a strong ferritestabilizing effect of Si but none of the five
intermetallic compounds is found in commercial
stainless steels.
The ternary FeCrNi diagram is the basic diagram
for stainless steels. It shows the presence of only
three solid phases: austenite, ferrite, and sigma
phase. For a high Cr/Ni ratio delta ferrite may occur
during solidification and sigma phase may occur
during aging at temperatures between 550oC and
The FeCrMo diagram shows the presence of six
phases: (Fe,Cr)=solid solution; (Cr,Mo)=solid

Binary ironchromium equilibrium

diagram. (From J.R. Davis (Ed.): ASM
Speciality Handbook: Stainless Steels,
ASM International, Materials Park, OH,

Gamma loops formed in various binary

systems of iron

Three-dimensional view of the FeCrNi

equilibrium diagram

The Fe-Ni phase diagram

Projections of the liquidus

and solidus surfaces of the
Fe-Cr-Ni ternary system

The Schaeffler constitution

diagram (1949) for stainless
steel weld metal

The Delong constitution

diagram (1974) with Welding
Research Council ferrite
number system for weld metal

Austenitic Stainless Steel


Basic composition of it is 16-25% Cr & sufficient

amount of austenite stabilisers
Austenite at room temperature
Most commonly used stainless steel
Austenite is the primary phase
These are not hardenable by heat treatment
These have high ductility, low yield strength,
relatively high ultimate tensile strength
Basic crystal structure is FCC

As austenitic steels have FCC structure
magnetic in nature
tough at low
temperatures as no ductile brittle transition good
ductility with elongation about 50%
Excellent corrosion resistance in organic acid , industrial
& marine environment
Excellent formability, fabricability, cleanability and
hygiene characteristics
Cr/Ni austenitic steels are resistant to high temperature
Excellent weldability since single phase materials
Austenitic steels do not have 475o C embrittlement but
show reduced ductility and toughness due to formation of
brittle intermettalic compounds called sigma phase.
Sigma phase increaseswith increase in chromium amount
& presence of Mo, Ti & Si. Manganese helps reduce the

These steels are not strong materials because these

are single phase materials. Austenitic steels are not
hardenable by heat treatment but they are hardened
cold work
solid solution strengthening

Cold work
Work hardening rate is high due to low stacking fault energy of
0.002 J/m2
Upon cold working by 60% increases yield strength from 240
Mpa to 1035 Mpa & tensile strength of 585 Mpa gets doubled
Loss of strength at temperatures above 600 OC & also in HAZ of
a weld

solid solution strengthening

Substitutional solids show little increase of strength but
interstitial solutes are very effective

Microstructure of austenitic

Microstructure of annealed type 316L austenitic stainless

steel. Etched in 20% HCl, 2% NH4FHF,
0.8% PMP

Microstructure of annealed type 316L austenitic

stainless steel. Etched in waterless Kallings reagent

There are two limitations of austenitic stainless steel
Cracking due to stress corrosion
Intergranular corrosion

Stress corrosion
Austenitic stainless steel is prone to stress corrosion
cracking in the presence of chloride ions even
present in ppm levels
Failure can occur due to the presence of small
stresses or even residual stresses
Fracture ids transgranular with little or no plastic
Can reduced inhigh nickel (>30%Ni) austenitic steels
or reduce the stress or eliminate chloride ions

Intergranular carbides in austenitic stainless steel

Austenitic steels on being heated in the range of 500 OC to 800
cfor any reasonable time leads to the chromium present in
stainless steel to react with carbon to form Cr23C6 . This reduces
the the Cr available(below 12 %) to provide the passive film &
leads to preferential corrosion which can be severe. This is also
known as sensitization.

Microstructure of type 304 stainless steel with

chromium carbide
precipitation on grain boundaries. ASTM A262
Practice A oxalic
acid etch. Scanning electron micrograph

Grain boundary M23C6 precipitates in an

austenitic stainless steel observed using
electron microscopy ISIJ International

High-angle grain boundaries are preferred sites for

precipitation and diffusion because of the relatively
high atomic disorder where grains of different
orientations meet. Thus, M23C6 particles readily
nucleate and grow, severely depleting the adjacent
austenite of chromium, from 19 wt% to about 10 wt
Twin boundaries have much better atomic matching
than most high-angle boundaries and therefore are
not as favourable for nucleation and growth of M23C6
particles. The carbides are largest on the high-angle
grain boundaries, quite small on the incoherent twin
boundaries, and absent on the coherent twin

Chromium depletion as a
function of distance from
various types
of grain boundaries in type 304
stainless steel. Courtesy of M.G.
Burke, Westinghouse Electric
Corp., Pittsburgh

Chromium carbide precipitation on various

types of boundaries
in type 304 stainless steel. Arrows in upper
left point to large
carbides on a high-angle grain boundary, and
IT and CT refer to incoherent and
coherent twin boundaries, respectively.
Transmission electron micrograph

M23C6 carbide precipitation

kinetics in type 304 stainless steel
containing 0.05% C and originally
quenched from 1250 C
(2282 F)

Heat Treatment in Austenitic


Main thermal treatments and

transformations that occur in austenitic
stainless steels
between room temperature and the
liquid state ISIJ International (Japan)

Solution Annealing
main objective of this treatment is to dissolve the phases that
have precipitated during the thermo mechanical processing of
the material, especially the chromium-rich carbides of the
M23C6-type where M =Cr, Fe, Mo
lower temperature limit for solution annealing should be over
900 oC
Carbides should be completely dissolved but they dissolve
slowly. Grain growth limits the maximum solution-annealing
abnormal grain growth, also known as secondary
recrystallization, must be avoided
Cooling from heat treatment temperatures should be sufficiently
fast to avoid chromium carbide precipitation. On the other hand,
too fast cooling rates cause component distortions
During solidificationor welding, the formation of d-ferritemay
occur, whichmay be difficult to eliminate completely during the
thermomechanical treatment and itmay be present before the

In the case of non stabilized grades such as AISI 201, 202,

301, 302, 303, 304, 305, 308, 309, 316, and 317, if
distortion considerations permit, water quenching may be
utilized. In the case of the AISI 309 and 310 types that
contain maximum allowed carbon content and are
susceptible to carbide precipitation, water cooling is
mandatory. In the case of stabilized AISI 321, 347, and
348 types, water cooling is not needed and air cooling is
sufficient to avoid sensitization. Molybdenum-containing
steels, such as AISI 316, 316L, 317, and 317L, present an
intermediate tendency toward sensitization when
compared to non stabilized conventional and the
stabilized types, i.e., they do not require water cooling
from the solution-annealing temperature
In the case of molybdenum-containing steels, such as AISI
316, 316L, 317, and 317L types, long exposure times at
temperatures in the 650 to 870 8C (1200 to 1600 8F)

Grain boundary M23C6 precipitates

in an austenitic stainless steel
observed using transmission
electron microscopy

Optical micrograph showing secondary

recrystallization start in a titanium-stabilized
austenitic stainless steel after solution
annealing. Etched with V2A-Beize

Stabilize Annealing
Stabilize annealing is used for stabilized austenitic stainless
steels in order to assure maximum intergranular corrosion
After the solution-annealing treatment, only part of the carbon
is bound in the form of primary phases, such as carbides, MC,
carbo-nitrides, M(C,N), nitrides MN, or carbo-sulfides M4C2S2,
where M=Ti, Nb, or V. The remaining carbon stays in solid
solution and may precipitate as secondary carbides MC or
M23C6 at lower temperatures, since the carbon solubility in
austenite under 900 oC is very low
exposing the steel, after solution annealing, to temperatures in
the 845 to 955 oC temperature range for up to 5 h (depending
on component size), favors MC precipitationin detriment to
M23C6. Furnace atmosphere control, avoiding carburizing or
excessively oxidizing conditions, should be employed and the
sulfur content in oil- or gas-fired furnaces should be kept at low

Stress Relief Annealing

cool the component slowly from the solution annealing
temperature. during slow cooling, some M23C6 precipitation
may occur with consequent sensitization. On the other
hand, fast cooling may reintroduce residual stresses and
make the component susceptible to stress-corrosion
cracking (SCC). In general, a small amount of intergranular
corrosion is preferable to a failure in few weeks due to SCC.
Moreover, the selection of a low carbon or of a stabilized
steel would be a more appropriate solution. The selection of
a lower working temperature range, say in the 925 to 1010
C range, would allow longer time exposure without
significant grain growth.
stress relieve at a lower temperature range, between 425
and 550 oC where M23C6 precipitation is very slow, allowing
the material to be exposed for some hours without
sensitization occurrence. This treatment may not be very

Bright Annealing

All austenitic stainless steel types can be

bright annealed in a pure hydrogen or
dissociated ammonia atmosphere,
provided that its dew point is kept below
508 oC and that the components are dry
and clean before entering the furnace. If
the dew point is not kept sufficiently low,
some thin green oxide film may be
formed, which will be difficult to remove.

Martensite Formation
Austenite in stainless steel is generally not a stable
In the solution-annealed condition, the Ms temperature
is normally below room temperature. For the majority
of these steels, the Md temperature (the temperature
below which martensite will form under deformation) is
above room temperature.
Two kinds of martensite can occur in stainless steels:
(bcc, ferromagnetic) and (hcp,nonferromagnetic).
The transformation of austenite to martensite can be
also induced in austenitic stainless steels by cathodic
charging with hydrogen.
Typical lattice parameters are
=0.2872nm &
a =0.2532nm C =0.4114nm

Transformation during cooling

many steels when cooled to cryogenic
temperatures,will form alpha prime (a) martensite.
The ability to form alpha prime (a) martensite
becomes more significant during cooling after
sensitization. M23C6 precipitation at grain boundaries
causes depletion of chromium, carbon, and other
alloying elements in the vicinity of the grain
boundaries. This leads to a higher Ms temperature,
making the material more susceptible to the
formation of alpha prime (a) martensite close to
grain boundaries during cooling
formation of epsilon (e) martensite increases with a
decrease in the stacking fault energy of austenite
Ms ( C) =1302-42 (% Cr)-61 (% Ni)-33 (% Mn)-28 (%
Si)-1667 (% [C+N])

Residual nitrogen contents of austenitic stainless

steel are usually in the range of 300 to 700 ppm
(0.03 to 0.07 wt%) and thus when combined with
carbon may have a strong effect on stabilizing
austenite with respect to martensite formation
The epsilon martensite forms on close-packed (111)
planes in the austenite and, except for size, is
morphologically very similar to deformation twins or
stacking fault clusters, which also form on (111)
planes. The martensite forms as plates with (225)
habit planes in groups bounded by faulted sheets of
austenite on (111) planes. The nucleation of
martensite and its relationship to martensite has
been difficult to resolve; evidence for formation
directly from austenite and with as an intermediate

Strain Induced Transformation

Strain-induced martensite forms at higher temperatures than
does martensite, which forms on cooling, and the parameter
Md, the highest temperature at which a designated amount of
martensite forms under defined deformation conditions, is used
to characterize austenite stability relative to deformation
Carbon and nitrogen have a very strong effect on austenite
stability, and the extra-low carbon grades are quite sensitive to
strain-induced martensite formation, a characteristic that may
render them susceptible to reduced performance in highpressure hydrogen
Deformation-induced martensite, however, significantly
enhances strength generated by cold work, and types 301 and
302 stainless steels are designed to have lower chromium and
nickel contents in order to exploit this strengthening
The extent of strain-induced transformation of austenite to
martensite is dependent on temperature, strain rate, and
strain, in addition to composition. Large amounts of martensite

The strong effect of strain-induced martensite formation at

lower temperatures is marked by noticeable inflections in the
stress-strain curves. The strain hardening associated with these
inflections produces very high ultimate tensile strengths, and
as the strain-induced transformation decreases, the ultimate
tensile strength also decreases.

Stress-strain curves for types

304 and 301 austenitic

Strain-induced martensite formation as a

function of strain at various temperatures.
Solid lines are original data of Angel,
dashed lines are data of Hecker et al., and
dotted extrapolations are from Olsons

Engineering stress-strain
curves for type 304 stainless
steels at
various temperatures

Ferritic Stainless Steel

Chromium content is usually between 17 to 26%
Carbon content is kept as low as 0.08 to 0.2% to improve
toughness and reduce sensitization
Ferrite stainless steel follow relationship of (Cr-17xC)>12.7
They have ferritic structure upto melting point
They have slightly high yield strength but lower strain
These have BCC crystal structure & are less ductile than
austenitic steels
These are not hardenable by heat treatment

Body Centred Cubic

Basic Properties
Moderate to good corrosion resistance increases with Cr
Not hardenable by heat treatment and always used in the
annealed condition
Magnetic in nature
Formability not as good as the austenitic stainless steel
Moderate ductility - not easy to deep draw 20%
Low impact strength - brittle at low temperatures
Poor weld ductility due to grain growth in HAZ
Moderate strength
These steels work harden less
Yield strength is 275-415 Mpa ,tensile strength is 500600Mpa &yield elongation is 30%

Advantages of ferritic stainless


Ferritic stainless steels are cheaper than austenitic

stainless steels because expensive nickel is not used
High corrosion resistance, increases with increase in Cr
Immune to chlorides hence no failure due to stress
Reasonable cold formability
Excellent hot ductility
Cr rich ferritic steelshave good oxidation resistance at
high temperatures .thus used as furnace components
Good machinability, higher thermal conductivity lower
thermal expansion
Magnetic in nature

Limitations of ferritic steels

These steels get corroded in Cl- & SO42- containing industrial
and marine atmospheres. These are less corrosion resistant
than austenitic stainless steels in reducing atmospheres
Grain refinement is difficult because no phase change occurs
on heating. Grain growth is rapid on heating as diffusion is
faster in BCC structure. Grains start coarsening at 600oC.
Due to its BCC structure, they show ductile to brittle transition
& it is considerably higher for mild steel due to embrittlement
effect of Cr . Presence of coarse grains raises the transition
Also due to its BCC structure ,these steels have lower general
ductility and higher yield strength
These show stretcher strains during drawing or stretching
These steel suffer from two types of embrittlement effects
other than the natural brittleness
Suffer from intergranular corrosion in the HAZ of the weld due
to precipitation of chromium carbides. Sensitisation occurs
rapidly in ferritic as diffusion is faster due to bcc structure.

Microstructure of ferritic steels

Microstructure of annealed ferritic

stainless steel (E-Brite 26-1
containing 26% Cr and 1% Mo).
Etched electrolytically in 60%

Intermetallic Phases
Various phases found are SIGMA Phase ,CHI phase &
Various intermetallic phases form by the arrangement of
iron, chromium, molybdenum, and other transition metal
atoms into crystal structures that accommodate atomic
size and electronic differences that limit the lowtemperature solid solubility of alloying elements in the
bcc ferritic structure
The formation of the intermetallic phases follows C
curve kinetics, which are influenced by alloy composition
The C curves are useful in that they define temperature
ranges that can be used to dissolve the intermetallic
phases and through which specimens must be rapidly
cooled to avoid reprecipitation of the phases. The C
curves also identify operating temperatures that should
be avoided for application of ferritic stainless steels.

Estimated time-temperaturetransformation curves for ferritic


Treischke and Tamman studied the FeCr system and
proposed the existence of an intermetallic
compound containing Cr in the 30 to 50 wt% range.
In 1927, Bain and Griffiths studied the FeCrNi
system and observed a hard and fragile phase,
which they called constituent B, from brittle. In 1936,
Jett and Foote called it sigma()phase and in 1951,
Bergmann and Shoemaker determined through
crystallography its structure in the FeCr system.
The precipitation of sigma phase in stainless steels
can occur in the austenitic, ferritic, and ferritic
austenitic phases with duplex structure types. The
precipitation of this FeCrMo intermetallic, of
tetragonal structure with 30 atoms per unit cell,

Intermetallic Phase ie. ( Sigma)



No - Sigma Phase



Cooling Curve


Sigma Phase Formation



Cooling Curve

Sigma Phase
Sigma Phase


In the austenitic steels, precipitation generally requires

hundreds or even thousands of hours and the precipitated
volumetric fraction is generally smaller than 5 vol% [58].
Precipitation can be represented by a common precipitation
reaction: * + where * is a chromium- and molybdenumdepleted austenite, if compared to the original austenite.
Precipitation occurs predominantly at grain boundaries,
especially at triple points.
In the case of duplex stainless steels, precipitation can be
complete in a few hours and consumes all ferrite of the
microstructure [59]. Precipitation in this case can be
represented by a eutectoid-type reaction: * + where * is
a chromium- and molybdenum-depleted austenite if compared
to a non transformed austenite. Precipitation starts at the ag
interface and moves into the ferrite grain.
The quantity, speed, and probably the mode of the sigmaphase precipitation in ferritic stainless steels strongly depend
on the steel composition, especially on the chromium and
molybdenum contents. Increasing chromium and molybdenum

Microstructures of ferritic stainless steel containing

24.5% Cr, 3.54% Mo, 3.90% Ni, 0.17% Nb,
and 0.32% Al annealed at 850 C (1560 F). (a) Annealed
100 min. Arrow points to chi phase. (b)
Annealed 300 min. Dominant second phase (etched gray)
is sigma

Sigma-phase precipitation in aged

samples (8508C for 30 h) of a
superferritic stainless
steel X 1 CrNiMoNb 28 4 2 (W.
Nr. 1.4575). Etched with V2ABeize

Chi Phase
Chi (x) phase was identified, for the first time, by Andrews in
1949 in residues extracted from the CrNiMo steel. Later,
Kasper synthetically produced the chi (x) phase with the
Fe36Cr12Mo10 composition and studied its crystal structure in
Chi ( x) phase, for example, may occur also in austenitic,
ferritic, and duplex (ferritic austenitic) stainless steels and its
precipitation is associated with negative effects on properties.
While sigma phase is present in the binary FeCr system, chi
phase appears only in the FeCrMo ternary and in the FeCr
NiMo and FeCrNiTi quaternary systems. Still in comparison
with the sigma phase, chi ( x) phase is richer in molybdenum
and poorer in chromium.
The occurrence of (x)-phase in ferritic stainless steels is
conditioned to a minimum in the molybdenum content

Effect of molybdenum on the sigma (s)- and chi (x)-phase formation in the Fe28 wt% Cr
Mo system

The 475 oC Embrittlement

It is caused by the presence of the alpha prime phase in the
300 to 550 oC temperature range. This phase contains mainly
chromium and iron, richer in chromium than in iron, as shown
in the FeCr The alpha prime phase has a bcc structure and is
coherent with ferrite. The alpha prime precipitates are small, in
the range of 20 to 200 A . They have a high coarsening
resistance, even for long exposure times. The alpha prime
precipitates contain essentially chromium and iron. These two
atoms show very similar atomic sizes, x-ray, and electron
scattering amplitudes
Hardness, yield, and tensile strength are increased, while
elongation and impact resistance are decreased by the
presence of alpha prime. Ferrite without alpha prime presents
wavy glide lines because of the numerous gliding systems in
the bcc structure and its high stacking fault energy facilitating
dislocation cross-slip. The presence of alpha prime changes this
situation, it makes the dislocation movement difficult,
restricting slip to a few crystal planes. This causes some
straight slip lines, typical of fcc and low stacking fault energy

Alpha prime containing ferrite predominantly deforms by

twinning and that the straight deformation lines mentioned
above are, in reality, deformation twins. Ferrite embrittled due
to the presence of alpha prime, in general, presents a cleavage
type brittle fracture at room temperature.
Corrosion resistance is also affected by the presence of alpha
prime. Bandel and Tofaute observed that the presence of alpha
prime significantly reduced the corrosion resistance in a
solution of boiling nitric acid. Pitting corrosion resistance,
determined by cyclic polarization tests, in a solution of 3.5 wt%
NaCl, is also significantly reduced by the presence of alpha
prime. It is important to remember that super ferritic stainless
steels have as one of their main features an excellent
resistance to pitting corrosion in seawater.
The magnitude of the effects of alpha prime on the properties
depends chiefly on the chromium content of the alloy and it
increases with an increase in chromium content

Martensitic Stainless Steel

Main alloying elements are Cr(12-17%),Mo(0.21%),no Ni except for two grades & 0.1-1.2%C
Follows relationship %Cr-17%(C)<=12.7%
These steels are austenite at a temp of 950-1000 oC
but transform to martensite on cooling
Increasing the C content increases the strength &
hardness but decreases ductility & toughness

Basic Properties
Less resistant to corrosion in comparison to the other
grades of steel
Can be hardened by heat treatment
High strength & hardness levels can be achieved
Poor weldability
Magnetic in nature
Yield strength of 550-1860Mpa
Poor machinability
As Cr content increases hardenability increases
Have improved toughness

Microstructure of annealed martensitic stainless steels. Fine particles are

spheroidized carbides. (a) Type 403 stainless steel etched in 4% picral-HCl.
(b) Type 416 stainless steel etched with Vilellas reagant. Arrows point to
sulfide particles for machinability

Projection of the ternary

FeCrC diagram on the
temperature x% Cr (in wt
%) plane

Influence of nickel on the

extent of the g-loop in
ternary FeCrNi alloys (in

Effect of carbon and nitrogen on

gamma loop in Fe-Cr alloys

Martensitic stainless steels may be subdivided into

three subgroups:
(a)low-carbon steels for turbines
(b) medium-carbon steels for cutlery
(c) high-carbon wear-resistant steels
The microstructure of each group is also characteristic
(a) Martensitic needle-like microstructure
(b)Very fine martensitic microstructure
(c) Ultrafine martensitic microstructure containing
primary carbides,

Low Carbon High Strength

C content is kept low ~ 0.1% to give good weldability,
formability & impact strength
Quenched in oil or air from around 1050 oC when fully
austenitic & then tempered. The tempering temperature is kept
low for high tensile as well as yield strength with low
Tempering range of 440-540 oC is avoided as it causes
reduction in impact strength
Petrochemical & chemical plant construction
Gas turbine engines
Turbine blades
Electrical generation plants
Compressor & discs
Aircraft structural & engine applications
Propeller shafts in ships sailing in fresh water

High carbon High Strength

Strength & hardness can be increased by increasing
the C content of steels but decreases weldability,
toughness & even corrosion resistance
Increasing C increases the amount of carbides &
thus higher austenising temperatures
Knives, needle valves, gears, razor blades
Surgical instruments
Ball bearings for high temperature applications
Stainless steel bearings

AISI 410 martensitic stainless steel,

quenched and tempered to 20 HRC.
Microstructure of tempered martensite
with fine-carbide precipitates

AISI 420 martensitic stainless steel.

Microstructure of tempered martensite with
intergranular and intragranular precipitates.
Scanning electron microscopy using secondary
electrons. Etched with Villela.

Duplex Stainless Steel

Main alloying elements Cr(23-30%) & Ni(2.5-7%) ,Mo
(2.5-4%) & Ti
These steels contain ferrite and austenite in its
microstructure. Thus combining the toughness &
weldability of austenite with strength & resistance to
localized corrosion of ferrite.
Austenite phase as islands surrounded by ferrite
On melting it solidifies from liquid phase to a
completely ferritic structure
At room temperature microstructure has roughly
50% of ferrite & asutenite each

Basic Properties
Stronger than austenitic steels due to
two phase structure
presence of delta ferrite causes grain refinement causing
refinement in grain structure due to thermo-mechanical
Good corrosion resistance
Freedom from transgranular stress corrosion cracking
Good weldability but micro duplex structure destroyed in HAZ
which decreases strength as well as stress corrosion resistance
Duplex steels have ductile brittle transition temperature due
the presence of ferrite
Suffer from embrittlement effect

Duplex Applications

Chemical & Petrochemical industry

Pharmaceutical industry

Pulp & paper industry

On/offshore industry

Food & Beverage Industry

Architecture, Building, Construction

Marine chemical tankers

Combining Ferrite & Austenite

forms the Duplex structure




Solidification of DSS

Correct balance of Ferrite &



Microstructure of duplex steels

Ferrite (F) and austenite (A) grains in

duplex stainless steel Al 2205 (UNS
531803). Transmission electron

Three-dimensional composed micrograph of

rolled duplex stainless steel. Optical microscopy.
Ferrite is the darker phase. Etched with Behara II.

Embrittlement Effects
Duplex stainless steels are susceptible to three types
of embrittlement :
1. Embrittlement caused by the presence of a
carbide network, particularly in the austenite, in alloys
with higher carbon content
2. Embrittlement caused by precipitation of the phase, 475 oC embrittlement of ferrite
3. Embrittlement caused by precipitation of the phase, particularly in the ferrite

In the case of duplex steels with higher carbon content, the first
phase that solidifies is also ferrite. The residual liquid enriched in
carbon solidifies forming austenite and a chromiumrich M23C6type carbide network. This carbide network within the austenite
leads to an improved wear resistance. During cooling, austenite
islands can also form in the ferrite grains.Some secondary carbide
may also precipitate in austenite in the solid state. With the
application of mechanical stresses, these carbides initiate
fractures and cracks that propagate along the carbide network

Crack propagation along carbide

network in the high-carbon duplex
stainless steel

The schematic TTT diagram shows the regions in which alpha

prime ( ) and sigma ( ) precipitation can occur. These
precipitates increase the hardness and decrease ductility and the
toughness. It must be pointed out that -phase precipitates within
the ferrite . In comparison to austenitic and ferritic stainless
steels, precipitation of -phase in duplex alloys occurs at shorter
times, at higher temperatures and larger volume fractions may be

Schematic TTT diagram showing

precipitation of sigma (), alpha
prime (), and other phases in
duplex stainless steels

Sigma phase precipitation in duplex

stainless steels observed using scanning
electron microscopy with secondary
electrons. Etched with V2A-Beize.
Aaustenite; F=ferrite; S=sigma phase.
(a) Low-carbon duplex stainless steel (b)
High-carbon duplex stainless steel

Influence of Nitrogen on Sigma





600 C


Too slow cooling rate

Risk for intermetallic phase formation
Reduces pitting and impact properties

The role of Nitrogen

Nitrogen is a very important alloying element in DSS
Improves corrosion resistance
Improves austenite reformation

During TIG welding operation, the loss of nitrogen is

compensated for by using Ar + 1 - 2%N2 as a
shielding gas

Phase Imbalance
High ferrite (> 70%):
low ductility
loss of corrosion
H2 cracking susceptibility
High austenite (> 80%):
low SCC resistance
low strength

Avoid imbalance

The importance of the Duplex


Must stay on the

road !!!

Intermetallics when Welding

Sigma Phase formation will occur as a result of the

interpass temp exceeding its limit of 150 C - 250 C for

prolonged periods.
Secondary Austenite is a result of TIG HOT pass - second
layer over heating the root weld
This will result in loss of corrosion resistance & lowers
ductility in the weld

Chrome Nitrides
Result from rapid cooling
Can result in excessive ferrite content and
chromium nitrides
Which will reduce pitting resistance

Chromium Nitrides

Precipitation Hardenable Steels

Precipitation hardenable stainless steel is
the special class Martensitic or austenitic type,
modified by addition of alloying elements like
Al to form hard intermetallic compound during
Can be supplied in a solution treated condition in
which they are machinable & can be hardened
Used for high strength to weight ratio applications
Matrix in precipitation hardenable stainless steel
could be austenite or martensite
Hardening is obtained after adding one or more
alloying elements

Types of precipitation hardenable


Types of steels
martensitic ,semi-austenitic & austenitic

Lath martensite microstructure of

hardened type 403 stainless
steel. 4% picral-HCl etch

Solution-treated and aged

microstructure of martensitic
precipitation- hardening stainless
steel PH 13-8 Mo. Etched in Frys

Microstructure of 17-7 PH. (a) Surface tilting caused

by martensite formation on refrigeration to-730C
(100 F). (b) Refrigerated and aged at 4800C (896 F).
Electropolished and etched in chrome acetic acid

Fine, disc-shaped precipitates in

an aged austenitic precipitationhardening stainless steel

Martensitic alloys
Predominantly austenitic structure at annealing
temperature of around 1040-1065 0C. Upon cooling to room
temperature austenite changes to martensite

Semi Austenitic alloys

These are soft enough to be cold worked. They retain their
austenitic structure at room temperature but will form
martensite at very low temperature.

Austenitic alloys
Retain their austenite structure after annealing & hardening
by ageing. Precipitate hardening phase is soluble. Hardness
is lower than the other two & remain non magnetic

Typical P-H Stainless Steel

17-7 Stainless Steel.
Low carbon (<0.09%C).
17% Cr. 7% Ni.
Quenched and Aged.
Sometimes Cold-worked
Yield: 1590 Mpa. 231
UTS: 1650 Mpa, 239 Ksi.
Ductility: %EL = 1%.
Uses: High strength high
temperature applications.
Chemical processing

Grade 630 martensitic precipitation

hardening stainless steel has a combination of
high hardness and strength after suitable heat
treatment. It also has similar corrosion and heat
resistance to Grade 304. The terms "Type 630"
and "17-4PH" refer to the same grade.
The great benefit of this grade (and of other
precipitation hardening grades of stainless steel)
is that they are generally supplied in the solution
treated condition, in which they are just
machinable, and then can be age hardened to
achieve quite high strengths. This aging
treatment is so low in temperature that there is
no significant distortion. These grades are
therefore well suited to production of long
shafts, which require no re-straightening after

Mechanical properties as a function of tempering temperature of type 410 stainless steel. Data on left is for
specimens austenitized at 925 C (1697 F) and data on right is for specimens austenitized at 1010 C (1850
F). All specimens oil quenched between 65 and 95 C (149 and 203 F), stress relieved at 175 C (347 F), and
tempered for 2 h

The effect of adding alloying

Interstitial Elements
C, N, B etc.



Influence of Alloying Elements

Carbon - C - austenite () former
Low carbon (<0.03%) improves weldability
High affinity with Chromium - Forms chrome
carbides (Cr23C6) resulting in risk of
intergranular corrosion
Improves creep strength in high temperature
alloys (this can also be achieved with
In martensitic stainless steels high C (0.151.20%) makes them hardenable

Chromium - Cr - Ferrite () former

Main alloying element in Stainless Steel

>12% for self healing passive oxide
Improves pitting resistance
risks formation of sigma (d) phase

Nickel - Ni - Austenite () former

>8% Nickel in a Chromium steel, structure usually
becomes austenitic
Great effect on
mechanical properties - toughness
Improves resistance to
general corrosion
stress corrosion cracking
Beneficial for strength at high temperatures

Molybdenum - Mo - Ferrite () former

Greatly improves the resistance to general
corrosion in most media
Greatly improves resistance to pitting

PRE = %Cr + (3.3 x %Mo) + (16 x %N)

Beneficial for strength at elevated
Promotes formation of sigma () phase

Titanium - Ti, Niobium - Nb - Ferrite ( formers

Stabilising elements (5 x %C for Ti, 10 x C for
Higher affinity with C than Cr
Obstructs formation of Cr carbides
T321 - Ti, T347 - Nb, T316Ti

Copper - Cu - Austenite () former

Reduces Hardness and Ultimate Tensile
Lowers rate at which austenite hardens with
cold work & and the temperature to soften it.
In Molybdenum alloyed steels, improves
general, pitting and crevice corrosion
Improves resistance to sulphuric &
phosphoric acids

Nitrogen - N - Austenite () former

Added in contents of 0.15%-0.3%
Improves strength and corrosion resistance of
austenitic and duplex stainless steels
Improves pitting resistance
Reduces tendency to form sigma phase
Duplex (weldability) and high temperature alloys
Reduces grain growth in high temperature alloys
(4C54) at elevated temperatures

Silicon - Si - Ferrite () former

Positive effect on resistance to high
temperature corrosion
Increases the tendency to form sigma
()phase embrittlement
Increases risk of hot cracking during welding
In welding improves the fluidity of the

Manganese - Mn - Austenite () former

Little influence on corrosion resistance
Improves dissolution of N2 (in steelmaking)
Combines with sulphur to form Manganese
Sulphide (MnS)
MnS improves chip forming properties in
free machining grades e.g. T303
MnS has a negative effect on pitting

Sulphur - S

Phosphorus - P

Usually below 0.03%

Increases risk of hot
cracking during welding
Improves machinability
- refer Manganese

Usually below 0.040%

Increases risk of hot cracking
during welding

Aluminium - Al - Ferrite () former

Improves oxidation resistance at high
Sanicro 31HT, Kanthal APM, Inconel 601
Forms aluminium carbonitrides in
precipitation hardening steels to increase
hardness and tensile at elevated

Rare Earth Metals

Cereium - Ce, Lanthanum - La
Increase oxide strength and oxidation
Strong affinity with sulphur
Refines grain boundary structure by
removing sulphur and dissolved gases
Improves resistance to high temperature
sulphur containing atmospheres forming oxysulphides instead of Ni-NiS (650oC)
Causes arc instability during welding

Tungsten - W - Ferrite () former

Strong carbide forming tendency
Strong tendency to form sigma phase
embrittlement in super duplex stainless
steels (Zeron 100)
Contributes significantly to hardenability and
high temperature creep strength

Stress strain curves

Austenite, ferrite and duplex
duplex (2205)

Stress [MPa]













Strength at

Impact Resistance

The objective of this lecture is to describe the
relationship between precipitation and
hardness as an example of a key
microstructure-property relationship.


Age Hardening Curves

The most quoted age
hardening curve is that
for Al-Cu alloys
performed in the late
40s. Keep in mind that
age hardening was
known empirically (Alfred
Wilm) as a
technologically useful
treatment from the early
days of aluminum alloys.
Higher Cu contents result
in higher maximum
hardnesses because
larger volume fractions
of precipitate are


Al-Cu precipitation sequence

The sequence is:
a0 a1 + GP-zones a2 + q a3 +
q a4+ q
The phase are:
an - fcc aluminum; nth subscript
denotes each equilibrium
GP zones - mono-atomic layers of Cu
on (001)Al
q - thin discs, fully coherent with
q - disc-shaped, semi-coherent on
(001)q bct.

Al-Cu ppt

GP zone structure

Al-Cu microstructures
This tableau shows which of the different
ppt types are associated with which part
of the hardening curve.
GP zones


Al-Cu driving forces

Each precipitate has a different free energy curve
w.r.t composition. Exception is the GP zone, which
may be regarded as continuous with the alloy
(leading to the possibility of spinodal decomposition,
discussed later).
P&E fig. 5.27 illustrates the sequence of successively
greater free energy decreases and also successively
greater G*.
P&E fig. 5.28 illustrates the point that the nucleation
barriers are much smaller for each individual
nucleation step when the next precipitate nucleates
heterogeneously on the previous structure.

Al-Cu phase relationships

The explanation of age hardening
depends on understanding the
metastable phases that can appear.


Nucleation sites, reversion

The nucleation sites vary depending on circumstances.
q most likely nucleates on GP zones by adding additional
layers of Cu atoms.
Similarly, q nucleates on q by in-situ transformation.
However, q can also nucleate on dislocations, see P&E fig.
The full sequence is only observable for annealing
temperatures below the GP solvus. Any of the intermediate
precipitates can be dissolved, reverted, by increasing the
temperature above the relevant solvus, fig. 5.32.


Al-Ag: example 2
The age hardening curve has the same
double peak as for the Al-Cu series, but
the separation is more pronounced.



Al-Ag, contd.
GP zones are spherical (Ag atom is larger than Al).
g is hcp with OR (0001)g//(111)a and [1120]g //[110]a;
heterogeneously nucleated on the stacking faults of
dislocations which provide sites of local hexagonal packing.
g is also hcp with the same OR; forms plate-like precipitates. A
cellular mechanism can also occur.



Age hardening in steel: example


It is important to understand that age hardening occurs in

almost any system in which the solid solubility decreases
appreciably with decreasing temperature. Ferrite has a very
low solubility for carbon and therefore age hardening (also
called quench hardening) occurs here too. To avoid it, the
soluble carbon levels must be reduced, which is a common
objective of the IF or interstitial-free steel grades. These have
additions of carbide formers such as Ti or Nb to sequester the



Particles impede dislocations.
Ex: Al-Cu system
--Pt A: solution heat treat
(get solid solution)
--Pt B: quench to room temp.
--Pt C: reheat to nucleate
small crystals within

Other precipitation

Adapted from Fig.

11.22, Callister 7e.






0 B 10






wt% Cu

composition range
needed for precipitation hardening

Adapted from Fig. 11.24, Callister 7e. (Fig. 11.24 adapted from
J.L. Murray, International Metals Review 30, p.5, 1985.)

Pt A (soln heat treat)

Pt C (precipitate
Pt B




Solution Treat






2014 Al Alloy:
%EL reaches minimum
with precipitation time.



pr wer
ov ecip lar
era ita ge
ge tes
%EL (2 in sample)

sol n-eq
id uil
sol .
pr ny s
eci m
pit all
ag ates

tensile strength (MPa)

TS peaks with
precipitation time.
Increasing T accelerates


1h 1day 1mo 1yr
precipitation heat treat time




1h 1day 1mo 1yr
precipitation heat treat time

Adapted from Fig. 11.27 (a) and (b), Callister 7e. (Fig. 11.27 adapted from Metals Handbook:
Properties and Selection: Nonferrous Alloys and Pure Metals, Vol. 2, 9th ed., H. Baker (Managing
Ed.), American Society for Metals, 1979. p. 41.)


After quenching, there is thermodynamic
motivation for precipitate to form.
Precipitates initiate and grow due to diffusion,
enhanced by higher temperatures.
To get significant strengthening the precipitate
should be coherent
When the precipitates get too large, they lose
coherence and strengthening decreases





Cutting versus Bowing

At small sizes, the dislocation cuts through the particle at a
lower stress than the Orowan bowing stress (and so this is what
is observed). Larger particles mean higher cutting stresses.
At large sizes, the dislocation bows around the particle more
easily than it cuts through it (so no cutting is observed). Larger
particles mean fewer particles (via coarsening) hence lower
flow stresses.

Particles becoming stronger

Fewer and fewer particles,

further apart


Breaking Angle: fc

Gb c

L 2

Strong Obstacles: ~ 0

463 ~ 180
Weak Obstacles:

Hardness -microstructure
In order to understand the relationship between
microstructure and hardness, we need to delve into the
subject of hardening mechanisms.
The central concept is that the strength of a ductile
material is governed by dislocation flow past obstacles.
Therefore strength can be designed by controlling the
density and nature of the obstacles to dislocation motion.
Most technological (metallic) alloys rely on precipitation
hardening in one form or another to achieve high
strengths. Ceramics, on the other hand, are intrinsically
harder and therefore the main objective of strengthening
is to increase their fracture toughness and thereby
increase their (reliable) load carrying capacity. The
objective of this discussion is therefore to bring your
attention to a number of ways in which we can
understand and predict the contributions to strength
different types of obstacle.

Strengthening Methods
Microstructural Feature:
strength dependence.
Dislocations: strain/work hardening
(discussed in 301): (dislocation spacing)1/2.
Internal Boundaries: grain boundaries can
have a strong strengthening effect, i.e. the
Hall-Petch effect (discussed in 301): (grain
Dislocation Boundaries (low angle
boundaries): (subgrain size)-1.
Second Phase Particles: particle spacing.
Solutes: (concentration)1/2.

Mechanisms of particle

1) Coherency Hardening: differences in density between the particle

and the matrix give rise to elastic stresses in the vicinity of the
2) Chemical Hardening: creation of new surface when a particle is
sheared increases the area of the interphase boundary, which
increases the energy associated with the interface and hence an
additional force must be exerted on the dislocation to force it
through the particle.
3) Order Hardening: passage of a dislocation through an ordered
particle, e.g. Ni3Al in superalloys, results in a disordered lattice and
the creation of antiphase boundaries.
4) Stacking-fault Hardening: a difference in stacking fault energy
between particle and matrix, e.g. Ag in Al, increases flow stress
because of the different separation of partial dislocations in the
two phases.
5) Modulus Hardening: a large difference in elastic modulus results
in image forces when a dislocation in the matrix approaches a
particle. Consider, e.g., the difference between silver particles

A re-statement of the governing equation
for strength controlled by obstacle
M 0 Gb /






crss versus density



Dislocation Boundaries
At large strains and higher temperatures, low angle
boundaries appear as a subgrain network forms. We
distinguish this microstructural feature from the first
two categories because the [lattice] misorientations
are much smaller (2-5) than grain boundaries
(15+) and they are distinct from statistically stored
dislocations. This strengthening method is most
important at high temperatures where other
microstructural features such as solutes are weak.
The contribution to the flow strength is typically
found to be proportional to (grain size)-1; this is in
contrast to the 1/d dependence of the Hall-Patch

Solutes in a crystal act as obstacles to
dislocation motion through their elastic
and/or chemical interactions with
dislocations. Most solutes are weak
hardeners except for the
(technologically) important class of
interstitial solutes that induce anisotropic
distortions of the lattice, e.g. tetragonal
distortions of C in Fe.

Substitutional solutes
Most Solutes have only a rather weak effect on strength. In
other words, even if you put several per cent of a soluble
atom into another element, you will not see a dramatic
increase in flow stress. These remarks can be quantified by
going back to the Orowan equation, i.e. the force balance
between the forward motion and the resisting force:
tcrss = b/l.
For substitutional solutes, the numerator in the RHS, i.e. the
reaction force from the solute atoms is of order Gb2/120,
which is a small number. This is so because the small
differences in size between solute and matrix atoms results
in a small interaction energy with dislocations. Thus they
are weak obstacles and dislocations remain nearly straight
when interacting with solutes (weak obstacles,
before this).

Interstitial solutes
Interstitials in bcc, however, can exert forces on the
order of Gb2/5 to Gb2/10, which are large values. In
this case, the dislocations bow out significantly
between the atoms, and the breaking angle deviates
significantly from 180. In this case, the concentration
dependence is easy to obtain. The spacing between
interstitials is inversely proportional to the (square root
of the) concentration, and so we can insert a spacing
into the standard (Orowan bowing) formula to get the
following, where A is a constant of order unity:
t = AGb(c/b) = AGc.


Strength vs. solute content:

solutes in
l solutes

Second Phase Particles

Whether introduced as insoluble particles in powder
compaction, or as precipitates in a solid state reaction, second
phase particles are generally the most potent strengthening
agent in practical high strength engineering materials. Ironbase, aluminum, nickel, titanium alloys all employ second
phases to achieve high strength.
Quantitative relationships: from previous stereological analysis
(301 - lecture 4):

1 VV( )
; L3
( )

4r 1 VV( ) 4r1 f 4r

3 VV

Coherency hardening
Differences in density between the particle and the matrix give
rise to elastic stresses in the vicinity of the particle. This has
been analyzed on the basis of the elastic stresses that exist in
the matrix adjacent to a particle that has a different lattice
parameter than the matrix. Ignoring differences in modulus for
now, and setting a parameter, e, that approximates a strain to
characterize the magnitude of the effect. For
e = (aparticle amatrix )/ amatrix
t = 7|e|3/2 G(rf/b)1/2
This mechanism applies to the early stages of precipitation,
e.g. strengthening by GP zones.


Chemical hardening
Cutting through a particle with a dislocation displaces one half
relative to the other by b, thereby creating new interfacial energy
of 2rbg, where g is the interfacial energy between the matrix
and the particle. The distance over which this energy has to be
created occurs at the entry and exit points and so the
characteristic distance is of order b. Thus the force is dE/dx, or,
F = 2rbg/2b = rg


Chemical hardening, contd.

If the dislocations are straight, we can approximate the spacing
between particles as L=2r/f. Dividing the force by bL to find the

t = fg/2b.
A more realistic approach produces the following relationship.

t = 2G{g/Gr}3/2(fr/b)1/2
Courtney defines a chemical hardening parameter, ech = g/Gr,
related to the interfacial energy, modulus and particle size. This
parameter is precisely analogous to the same parameter used,
e.g. in APB hardening. Chemical hardening applies only in the
early stages of precipitation.

Order Hardening
The hardening depends on the product of the antiphaseboundary energy (APBE) and the area swept by a dislocation in
a particle. Thus the increase in flow stress is given by:

t = f{APBE}/2b
In general, low values of the APBE not only predict small
increments in hardness, but also the result that the dislocations
can move through the particles independently of one another.
A more detailed analysis, not presented here, shows a square
root dependence on volume fraction, with particle size,

t = 0.7 Ge3/2 (fr/b)

eord= APBE/Gb
Important for
Ni-based superalloys

Modulus hardening
The line length in the particle is 2r and the change in tension is
(Gparticle-Gmatrix)b2/2, assuming the same Burgers vector in matrix
and particle. Multiplying the two together and dividing by the
distance, i.e. the radius, we get:
F= b2(Gparticle-Gmatrix) = Gb2e,
where e = (Gparticle-Gmatrix)/Gmatrix, a measure similar to that used in
solution hardening.
More realistic estimates of modulus hardening lead to the
following formula:
t = 10-2 G e3/2 {fr/b}
Think of modulus hardening as being caused by a temporary
increase in dislocation line energy while it resides within a


Ability to form martensite

Jominy end quench test to measure hardenability.
(heated to
phase field)
24C water

flat ground
Rockwell C
hardness tests

Hardness, HRC

Hardness versus distance from the quenched end.

Distance from quenched end

Why Hardness Changes with

Hardness, HRC

The cooling rate varies with position.


distance from quenched end (in)







t e ar
rli Pe
lite ea +
ar P i t e
Pe ine ens
ar ite
M en s

0 M(finish)




Time (s)

Hardenability vs Alloy


80 %M





2 Cooling rate (C/s)



"Alloy Steels"
(4140, 4340, 5140,
--contain Ni, Cr, Mo
(0.2 to 2wt%)
--these elements
shift the "nose".
--martensite is
easier to form.


Hardness, HRC

Jominy end quench

results, C = 0.4 wt


0 10 20 30 40 50
Distance from quenched end (mm)




0 -1

shift from
A to B due
to alloying

103 105 Time (s)

Equivalent distance and Bar diameter



Radial hardness profile