Metallurgy and Materials Science

MODULE III

a) Solid solution
 Types of solid solutions – Substitutional and Interstitial
 Hume Rothery rules
 Alloys and need of alloying

b) Phase diagrams
 Gibb’s phase rule
 Unary phase diagram
 Binary phase diagram – Isomorphous phase diagram
Eutectic phase diagram
 Invariant reactions
 Iron-carbon phase diagram
 Microstructure changes in eutectoid, hypoeutectoid and hypereutectoid steels
 TTT and CCT diagrams

c) Heat treatment processes and surface hardening methods

d) Hardenability
 Jominy-end quench test
 Factors affecting hardenability

SOLID SOLUTION
A solid solution is a solid that consists of two or more elements dispersed in a single-
phase structure. When two metals are melted and solidified to form a solid phase having a
single crystal structure, such a structure in solid form having two types of atoms is called a
solid solution.

Types of solid solutions – Solid solutions are of two types; substitutional and interstitial.
a) Substitutional solid solution – When there is direct substitution of one type of atom
by another, substitutional solid solutions are formed. Normally, solute atoms are
substituted for parent solvent atoms in a crystal lattice.
Example – Cu-Ni and Al-Cu alloys.
b) Interstitial solid solution – When the solute atoms are much smaller than the solvent
atoms, the solute atoms fit into the spaces between the parent solvent atoms forming
interstitial solid solutions.
Example – carbon in iron (steel)

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HUME ROTHERY RULES

Hume Rothery rules defines the conditions favourable for the formation of
substitutional and interstitial solid solution.
a) Hume Rothery rules for substitutional solid solution –
 Atomic size – The difference in the atomic radius of the two types of atoms
must be less than 15%.
 Crystal structure – The two elements must have the same crystal structure.
 Electronegativity – The two elements must have similar electronegativity
values. Electronegativity is a measure of an atom's ability to attract electrons.
 Valency – The valency of the two types of atoms must be nearly same.
Solid solution of Cu and Ni is an example of substitutional solid solution.
Cu Ni
Atomic radii (nm) 0.128 0.125
Crystal structure FCC FCC
Electronegativity 1.9 1.8
Valency +1 +2

b) Hume Rothery rules for interstitial solid solution –

 Atomic size – Solute atoms must be smaller than the voids in the solvent
atoms.
 Electronegativity – Solute and solvent atoms should have similar
electronegativity.

ALLOYS
An alloy is a combination of two or more metals or metals and non-metals. It may
consist of a single phase or mixture phases, depending only on the composition of the alloy.
Alloying elements are added to the base metal to:
 improve mechanical properties such as hardness, tensile strength and wear resistance.
 enhance corrosion resistance and inertness of the metal to chemical reactions.
 lower the melting point.
 improve electrical and magnetic properties.

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PHASE DIAGRAM
A phase is a homogenous portion of a system of substances, which has uniform
physical and chemical characteristics. A phase diagram is a diagram representing the
relationship between phases in equilibrium as a function of any two parameters among
temperature, pressure and composition.

GIBB’S PHASE RULE

It establishes the relationship between the number of components, the number of
phases and the number of degrees of freedom in a system. Mathematically, it is expressed as
F = C – P +2
where, F is the number of degrees of freedom (temperature, pressure & composition)
C is the number of components
P is the number of phases in the system
When pressure is kept constant, the phase rule gets modified into F = C – P + 1. This
modified form is applicable to all alloy systems involving metals.

For example, consider a system of water in an equilibrium state between solid and liquid
phases. Here, number of components, C = 1 (H2O only)
number of phases in the system, P = 2 (ice and water)
Therefore, number of degrees of freedom, F = 1 – 2 + 2 = 1. That is, only one parameter
(either temperature or pressure) can be varied to create such a system. For creating an
equilibrium state between ice and water, the pressure is directly dependent on the value of
temperature.

UNARY PHASE DIAGRAM

It is a one-component system, in which the composition is held constant. Pressure and
temperature are the variables. The unary phase diagram (also called a pressure-temperature
diagram) is represented as a two-dimensional plot of pressure (y-axis) v/s temperature (x-
axis).
In the phase diagram for water (H2O), the regions of three different phases, namely
solid, liquid and vapour, exist under equilibrium conditions over the temperature-pressure
ranges. At any point on one of the three boundary curves, the two phases on either side of the
curve are in equilibrium with one another. Upon crossing a boundary, one phase transforms
to another. All three of the phase boundary curves intersect at a common point (at a
temperature of 273.16 K and a pressure of 611.2 Pa) called the triple point.

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BINARY PHASE DIAGRAM

Binary phase diagrams are maps that represent the relationships between temperature
and composition of various phases of an alloy at equilibrium. The pressure is held constant,
normally at atmospheric pressure.
The composition (in weight %) is plotted along the x-axis whereas temperature (in
°C) is plotted on the y-axis. In the x-axis, the two components of alloy are represented by the
two extreme sides of the axis. Binary phase diagrams are basically classified into two types
based on the solubility of components in solid states.
a) Isomorphous system – the two components of an alloy are completely soluble in
both liquid and solid states.
b) Eutectic system – the two components are completely soluble in liquid state but has
limited or partial solubility in solid state.
Another type of system in which the two components are completely insoluble in solid
state is called a simple eutectic system.

ISOMORPHOUS SYSTEM
In alloys, when two components are mixed and becomes completely soluble in the
liquid and the solid states, an isomorphous system is produced. The characteristics of an
isomorphous phase diagram are:
 There are three distinct phases which are liquid (L), solid (α) and a two-phase (α+L)
region.
 The boundary between the two-phase region and the liquid region is called the
liquidus curve. The boundary between the two-phase region and the solid region is
called the solidus curve.
Examples of isomorphous system are Cu-Ni, Ag-Cu, Ge-Si, FeO-MgO, etc. The phase
diagram of Cu-Ni alloy is shown below.

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Three kinds of information are available from a phase diagram corresponding to a specific
composition and temperature.
a) the phases present
b) the compositions of these phases
c) the relative percentages of the phases
* refer online class for determining the composition and percentages (using tie-line and
lever rule)

Coring – As an isomorphous alloy solidifies, the centre of a grain will be rich in the
component having higher melting point. The concentration of the element having low melting
point increases with the position from the centre of the grain boundary. This is called coring.

EUTECTIC SYSTEM
Solutions having complete solubility in liquid state but limited solubility in solid state
are known as eutectic systems. Eutectic systems are characterised by a eutectic reaction,
which involves the transformation of a liquid phase into two different solid phases. The
eutectic reaction occurs at a specific composition and temperature called as eutectic
composition and eutectic temperature, respectively.

The solid solutions are formed near both ends of the phase diagram. The curves
showing the solubility limit of these terminal solid solutions are called as solvus lines. An
example of eutectic system (Cu-Ag) is shown below.

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There are six phases in total, which are:

 Three single phases (α, β and L)
 Three two-phase regions (α+L, β+L and α+ β)

The α phase is a solid solution in which Cu is the solvent and Ag is the solute.
In β phase, the solvent is Ag and solute is Cu. The solubility of Ag in Cu is limited in α
phase, while Cu has limited solubility in Ag in β phase. From the phase diagram, maximum
solubility of Ag in Cu is 8.0% and maximum solubility of Cu in Ag is 8.8% (100 – 91.2 =
8.8).

The meeting point of the two liquidus lines (point E in the phase diagram) is the
characteristic of an alloy with the lowest melting point. At this point, eutectic reaction takes
place (at TE = 779°C and CE = 71.9% Ag). At the eutectic point, E the liquid phase is
transformed into two solid phases, α and β on cooling. The eutectic reaction is given by
( ) ( ) ( )

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INVARIANT REACTIONS
Invariant reactions involve three separate phases and according to Gibb’s phase rule
(number of components = 2), the number of degrees of freedom at the invariant point is zero.
The major invariant reactions formed in binary systems are

Reaction Characteristics Representation Examples

Fe-C
Eutectic Cu-Ag
Pb-Sn

Fe-C
Peritectic Cu-Zn
Fe-Ni

Fe-C
Eutectoid Cu-Zn
Al-Cu

Al-Cu
Peritectoid
Al-Ag

Monotectic Cu-Pb

*explain each reaction in separate paragraphs for examination (write the eutectic,
peritectic and eutectoid reactions from the Fe-C phase diagram as examples)

IRON-CARBON (Fe-C) PHASE DIAGRAM

The iron-carbon phase diagram is plotted with the temperature on y-axis and
wt% carbon composition on the x-axis. The maximum % of carbon is taken as 6.67% and is
called as iron carbide (Fe3C). The phase diagram is also called as iron-iron carbide (Fe-
Fe3C) phase diagram when the x-axis is represented by wt% Fe3C instead of wt% C.
Therefore, on the extreme right of the x-axis it would be 100 wt% Fe3C which is equivalent
to 6.67 wt% C.

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Pure iron exist in more than one crystal structure in solid state. There are three
allotropic forms of carbon – α (BCC), γ (FCC), and δ (BCC).
 When liquid iron is cooled down, it crystallizes at 1538°C to δ-phase (BCC) iron
called δ-ferrite.
 Upon further cooling, the crystal structure gets converted to γ-phase (FCC) called
austenite at 1394°C.
 The crystal structure changes to α-phase (BCC) called α-ferrite at 912°C.
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The different phases present in iron-carbon phase diagram are:

1. α-ferrite
 BCC α-ferrite is an interstitial solid solution of carbon in BCC iron. In α-ferrite, only
small concentrations of carbon are soluble; the maximum solubility is 0.022 wt%
carbon at 727°C and at room temperature it is reduced to 0.008%.
 The limited solubility is explained by the shape and size of the BCC interstitial
positions, which make it difficult to accommodate the carbon atoms.
 This particular iron–carbon phase is relatively soft, may be made magnetic at
temperatures below 768°C.

2. Austenite (γ)
 The maximum solubility of carbon in austenite, 2.14 wt% carbon, occurs at 1147°C.
This solubility is almost 100 times greater than the maximum for BCC α-ferrite.
 Austenite is non-magnetic with FCC structure and stable between 912 – 1394°C.

3. δ-ferrite
 δ-ferrite is also an interstitial solid solution of carbon in BCC iron. In δ-ferrite, the
maximum solubility of carbon is 0.09 wt% at 1495°C.
 The limited solubility is also due to the shape and size of the BCC interstitial
positions, which make it difficult to accommodate the carbon atoms.

4. Cementite (Fe3C)
 Cementite forms when the solubility limit of carbon in ferrite is exceeded 0.002%
below 727°C (for compositions within the α+Fe3C phase region).
 Fe3C will also coexist with the phase between 727°C and 1147°C.
 Mechanically, cementite is very hard and brittle; the strength of some steels is greatly
enhanced by its presence.

5. Pearlite (α + Fe3C)
 A laminated structure formed of alternate layers of α-ferrite and cementite with
average composition 0.83% carbon
 Pearly lustre in the microscope.
 It combines the hardness and strength of cementite with the ductility of ferrite and is
the key to the wide range of the properties of steels.
 α-ferrite exists as thick light layers whereas cementite is thin and darker.

6. Ledeburite (γ + Fe3C)
 It is mixture of austenite and cementite formed as a product of eutectic reaction.

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Pearlite Ledeburite

The three invariant reactions in iron-carbon phase diagram are:

1. Eutectic reaction at 1147°C and 4.3 % C

( ) ( )

2. Eutectoid reaction at 727°C and 0.77% C

( ) ( ) ( )

3. Peritectic reaction at 1495°C and 0.18% C

( ) ( )

MICROSTRUCTURE CHANGES IN EUTECTOID, HYPOEUTECTOID AND

HYPEREUTECTOID STEELS
The Fe-C alloys containing 0.008 to 2.14 wt% carbon are generally called steels.
Steels with 0.77% C are called as eutectoid steels, while compositions below 0.77% are
hypoeutectoid steels and those above 0.77% are called hypereutectoid steels.

1. Microstructure changes in eutectoid steels

 Consider, an alloy of eutectoid composition (0.77 wt% C) cooled from a temperature
within the γ phase region, say, 800°C (beginning at point A and moving down the
vertical line XX').
 Initially, the alloy is composed entirely of the austenite phase having a composition
of 0.77 wt% C.
 As the alloy is cooled, there will be no changes until the eutectoid temperature
(727°C) is reached.
 Upon crossing this temperature to point B, the austenite transforms to pearlite
consisting of α-ferrite and cementite (by eutectoid reaction).
 The microstructure of pearlite consists of alternating layers or lamellae of α-ferrite
(thick light layers) and Fe3C (thin darker layers).

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2. Microstructure changes in hypoeutectoid steels

 Consider a composition Co to the left of the eutectoid, between 0.022 and 0.77 wt% C.
Cooling an alloy of this composition is represented by the vertical line YY'.
 At point C, the microstructure will consist entirely of grains of the γ phase.
 In cooling to point D, which is within the α+γ phase region, small α-ferrite particles
will form along the grain boundaries of austenite.
 Cooling from point D to E, just above the eutectoid temperature will produce an
increased fraction of the α phase. The α-ferrite particles will grow larger along the
grain boundaries.
 As the temperature is lowered just below the eutectoid, to point F, all the γ phase that
was present at temperature Te (and having the eutectoid composition) will transform
to pearlite.
 There will be no change in the α phase after crossing the eutectoid temperature. It will
normally be present as a continuous matrix phase surrounding the isolated pearlite
colonies. Thus the α-ferrite phase will be present both in the pearlite and also in the
phase that formed while cooling through the α+γ phase region.
 The α-ferrite present in the pearlite is called eutectoid ferrite, whereas the other that
formed above Te, is termed proeutectoid ferrite.

3. Microstructure changes in hypereutectoid steels

 Consider a composition Cl to the right of the eutectoid, between 0.77 and 2.14 wt% C.
Cooling an alloy of this composition is represented by the vertical line ZZ'.
 At point G, the microstructure will consist entirely of grains of the γ phase.

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 In cooling to point H, which is within the γ+ Fe3C phase region, small cementite
(Fe3C) particles will form along the grain boundaries of austenite. The γ particles will
grow larger along the grain boundaries.
 As the temperature is lowered just below the eutectoid, to point I, all the γ phase that
was present at temperature Te will transform to pearlite.
 The cementite phase will be present both in the pearlite and also in the phase that was
formed while cooling through the γ+ Fe3C phase region.
 The cementite present in the pearlite is called eutectoid cementite, whereas the other
that formed above Te, is termed proeutectoid cementite.

Hypoeutectoid steel Hypereutectoid steel

Pearlite
proeutectoid α proeutectoid Fe3C

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TIME TEMPERATURE TRANSFORMATION (TTT) DIAGRAM

TTT diagram is used to represent the time and temperature dependence of austenitic
to pearlitic transformation. Two solid curves are plotted; one represents the time required at
each temperature for the initiation of the transformation; the other is for the finish of
transformation.

 The curves in TTT diagram are generated from a series of plots of the percentage
transformation versus the logarithm time duration.
 The eutectoid temperature (727°C) is indicated by a horizontal line. At temperatures
above the eutectoid only austenite will exist.
 The austenite to pearlite transformation will occur only if an alloy is cooled below the
eutectoid temperature. The time necessary for the transformation to begin and end
depends on the temperature.
 The start and finish curves are nearly parallel, and close to the eutectoid line. To the
left of the transformation start curve, only austenite (which is unstable) will be
present, whereas to the right of the finish curve, only pearlite will exist. In between,
the austenite is in the process of transforming to pearlite, and thus both austenite and
pearlite will be present. The dashed curve corresponds to 50% of transformation
completion.
 At temperatures just below the eutectoid, long duration of time is required for the
50% transformation, and therefore the reaction rate is very slow. The transformation
rate increases with decreasing temperature.

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 At temperatures just below the eutectoid, relatively thick layers of both α-ferrite and
Fe3C phases are produced. This microstructure is called coarse pearlite.
 At these temperatures, diffusion rates are relatively high, such that during the
transformation carbon atoms can diffuse relatively long distances, which results in the
formation of thick lamellae.
 With decreasing temperature, the carbon diffusion rate decreases, and the layers
become progressively thinner. The thin-layered structure is called fine pearlite.
 Fine pearlite leads to better hardness and strength due to the greater reinforcement and
restriction to dislocation movement.
 In addition to pearlite, bainite consisting of α-ferrite and cementite phases is formed
at temperatures below 520°C till 220°C. Bainite leads to more strength and hardness
compared to pearlite.
 At temperatures just below the nose of the TTT curve, upper bainite having feathery
cementite appearance is formed. At lower temperatures, the cementite grains become
too fine and an acicular needle like pattern is observed. This is lower bainite or
acicular bainite.
 On rapid cooling (quenching) to low temperatures (below 220°C), the austenite
transforms to another microstructure called martensite.
 Martensite forms when the rate of cooling is rapid enough to prevent diffusion of
carbon and hence is called as diffusionless transformation.
 The beginning of this transformation is represented by a horizontal line designated
MS. Two other horizontal and dashed lines, labelled M50 and M90, indicate
percentages of the austenite to martensite transformation.
 Martensite has a body centered tetragonal (BCT) structure and is the strongest and
hardest microstructure of steel.

Uses of TTT diagram –

 TTT diagram indicates the phases existing in steel of a specific composition at various
temperatures and times.
 It is helpful to obtain the desired microstructure in steel and hence to design the
properties of the alloy.

CONTINUOUS COOLING TRANSFORMATION (CCT) DIAGRAM

Steel in most cases is continuously cooled from the austenitic range to room
temperature following different cooling rates. CCT diagram shows the relationship between
transformation temperature and time during continuous cooling. CCT diagrams are used to
represent which types of phase changes will occur in a material as it is cooled at different
rates.
For continuous cooling, the time required for a reaction to start and end is delayed.
From the below figure it is seen that the transformation on continuous cooling starts at lower
temperatures and after longer duration of time as compared to isothermal transformation

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(TTT diagram). The figure also illustrates the superimposed cooling curves corresponding to
fast and slow cooling rates.
 Cooling rate of 140°C/sec promotes the austenite to transform completely to
martensite without entering into the pearlite or bainite regions. This cooling rate is
called critical cooling rate.
 For cooling rates between 35°C/sec and 140°C/sec, the cooling curve crosses the
pearlite start curve but not the pearlite finish curve. Therefore, only a part of austenite
is transformed to pearlite. Other part is transformed to bainite or martensite.
 Cooling rate of 3°C/sec causes 100% fine pearlite.
 Slow cooling rates of 0.01°C/sec causes 100% coarse pearlite.

HEAT TREATMENT PROCESSES

Heating and cooling operations carried out to improve the properties of steel.

To improve - surface hardness

- mechanical properties such as ductility, hardness and strength
- machinability
- wear and corrosion resistance
- to relieve internal stresses
- to refine grain structure
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Types - Process annealing

- Full annealing (annealing)
- Spheroidising
- Normalising

- Hardening
- Tempering

- Austempering
- Martempering
- Ausforming

- Carburising
Surface hardening (by changing surface composition)
- Nitriding

- Flame hardening
- Induction hardening Surface hardening (without changing surface
- Laser hardening composition)
- Electron beam hardening

Steps in heat treatment processes –

i. Heating the steel to a specified temperature
ii. Holding at this temperature for a specific time period
iii. Cooling at a specified cooling rate (or cooling method)

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PROCESS ANNEALING
Purpose - to improve ductility and machinability of steel having less than 0.25% C
- to reduce the effect of strain hardening after cold working
- to reduce hardness

Process - Heating the steel to temperatures around 550 – 650 °C, just below the lower
critical temperature (A1)
- Holding for certain duration
- Cooling in air

FULL ANNEALING (ANNEALING)

 Heating to austenite state followed by very slow cooling.
Purpose - to soften and improve ductility of steel
- to relieve residual stresses
- to remove structural imperfections by recrystallization

Process - Hypoeutectoid steels are heated to temperatures about 50 – 90 °C above the

upper critical temperature (A3)
[Pearlite transforms to austenite - austenitising]
- Holding for certain duration
- Cooling slowly in furnace at cooling rates of 10-20 °C/hr
[Austenite transforms to ferrite and cementite with complete
recrystallization]

- Hypereutectoid steels are heated to temperatures about 50 – 90 °C above the

lower critical temperature (A1)
- Holding for certain duration
- Cooling slowly in furnace
[Austenite transforms to coarse pearlite and cementite forms a brittle
network around pearlite – reduces machinability]
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SPHEROIDISING
 Similar to annealing, done to improve machinability of high carbon or hypereutectoid
steels.
Purpose - To improve machinability of hypereutectoid steels
- To reduce hardness and improve ductility

Process - Hypereutectoid steel is heated to about 30 °C below lower critical

temperature (A1)
[Pearlite transforms to austenite and cementite]
- Holding for certain duration
- Cooling slowly in furnace
[Cementite in pearlite transforms to rounded or spheroidal grains]
 Surface area of cementite grains reduces, thereby reducing hardness.
 Spheroidal grains of cementite are present in soft matrix of ferrite -
improves machinability

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NORMALISING
 Strength of steel is controlled by the fineness of pearlite.
Purpose - To obtain good ductility with sufficient hardness and strength
- To produce uniformly refined grain structure

Process - Hypoeutectoid steel is heated to about 50 °C above upper critical

temperature (A3) and hypereutectoid steel is heated above Acm temperature
[Pearlite transforms to austenite]
- Holding for certain duration
- Cooling in air (faster rate of cooling compared to annealing)
[Austenite transforms to fine lamellae of pearlite]
 Due to faster cooling, diffusion of carbon atoms is less - ductility is
relatively low

HARDENING
 To improve the hardness of steel by formation of martensite.
 For structural components and tool dies, knives, cutting tools.
Purpose - To increase hardness and strength
- To improve wear resistance

Process - Heating hypoeutectoid steels above A3 temperature forms austenite

- Hypereutectoid steels are heated only above A1 temperature since cementite
itself is hard
[Pearlite transforms to austenite and cementite]
- Holding for certain duration to achieve uniform transformation along
thickness
- Rapidly cooling (quenching) in water, oil or brine
[Austenite transforms to martensite]
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 Martensite is formed due to diffusionless transformation

 It has BCT structure with minimum slip planes for dislocation
 Hardness of hypoeutectoid steel depends on the carbon content in
martensite formed
 Hardness of hypereutectoid steel is additionally contributed by
cementite
 Addition of alloying elements like Mn, Cr and Ni suppress the
formation of softer phases of pearlite and bainite

TEMPERING
 Immediately follows hardening process.
Purpose - To reduce brittleness of hardened steel
- To improve toughness by relieving internal stresses developed during
quenching

Process - Reheating the hardened steel below lower critical temperature (A1)
- Holding for short duration
- Cooling slowly in air
 Heating to 150 – 250 °C removes internal stress, increases toughness and ductility
without affecting hardness. Martensite is not transformed.
Applications – cutting tools made of tool steel and low alloy steels.
 Heating to 300 – 450 °C leads to decrease in hardness and strength with increase in
ductility. Microstructure consists of martensite with fine pearlite (troostite).
Applications – springs, axles, hammers and chisels.
 Heating above 450 °C imparts high ductility with adequate hardness and strength.
Martensite transforms to sorbite.
Applications – connecting rods, shafts, gears.

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AUSTEMPERING
 Interrupted quenching process performed at constant temperature (isothermal
hardening).

Purpose - To harden and temper springs and thin sections without distortion
- To obtain uniform hardness
- To achieve adequate ductility and toughness

Process - Heating above austenitising temperature

- Quenched in a molten salt bath maintained at constant temperature (200 –
400 °C)
- Holding at this temperature
[Austenite transforms to lower or acicular bainite]
- Cooling in air

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MARTEMPERING
 Interrupted quenching process performed by slow cooling.
Purpose - To harden and temper steel without distortion and cracking
- To obtain uniform hardness
- To achieve ductility and toughness

Process - Heating above austenitising temperature

- Quenched in a molten salt bath maintained at constant temperature just above
Ms
- Holding at this temperature
- Cooling in air (to prevent large temperature differences between core and
surface)
[Austenite transforms to martensite]
- Followed by tempering to improve ductility and hardness.
 Final microstructure consists of martensite with fine pearlite

AUSFORMING
 Low temperature thermo mechanical treatment (simultaneous application of heat and
deformation)
 Shape is changed with grain refinement.
Purpose - To increase strength without severe effect on ductility and toughness
- To improve fatigue resistance

Process - Heating above austenitising temperature

- Quenched to metastable state in a molten salt bath maintained at constant
temperature just above Ms
- Plastic deformation is carried out at this temperature without transformation
- After 50% deformation it is quenched to room temperature
[Austenite transforms to martensite]
 Applications – undercarriages of aircraft, springs and bolts.
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SURFACE HARDENING METHODS

Industrial areas demand components possessing contradicting or different properties
for the surface and the interior. For example, components like gears, cams, bearings, crank
shafts, etc. require a hard and wear resistance surface (case) with a tough and shock
absorbing interior (core). Storage tanks and chemical processing equipment need a corrosion
resistant surface with reasonable strength and low cost. In order to produce components with
these conflicting properties, surface treatments are carried out.

Surface treatments are classified into two types:

1. Methods which change the surface composition
 Carburising
 Nitriding
Carburising and nitriding are diffusion methods and are called as case hardening
techniques.

2. Methods which do not change the surface composition

 Flame hardening
 Induction hardening
 Laser hardening
 Electron beam hardening
The above four are selective hardening methods in which selected surface areas of the
components can be treated without changing the properties of other surface areas.

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CARBURISING
In this method, carbon particles is diffused into the surface of the steel component to
produce hard and wear resistant surfaces. Components such as pistons, cam shafts, gears and
pins are hardened by this process.
The process involves heating of the steel component in presence of a carbon-rich
substance (carburiser) above critical temperature for long durations. The carbon penetrates
into the steel to form solid solution on its outer surface. On the basis of the carburiser,
carburising is classified into three types – pack or solid carburising, liquid carburising and
gas carburising.

Pack carburising – In this process, solid substances such as coke, coal, charcoal, carbon
black, carbonates of barium, calcium or sodium are used. The steel component is heated in a
steel chamber with the presence of carburiser to a desired temperature. The depth of surface
hardening depends on the time of exposure of the steel to the carbon particles. More the
exposure time, more will the amount of carbon diffused into the steel. Heating is done in a
heat treatment furnace at 870-980°C for 5-10 hours. The rate of diffusion is very slow (0.1
mm/hour) but involves low capital expense.

Liquid and gas carburising – In liquid carburising, the steel component is heated in a
furnace and the heated steel is impinged by jets of a carbon-rich liquid hydrocarbon. The
carbon gets deposited on the steel surface and is further heated to promote diffusion.
In gas carburising, the steel component is heated in the furnace in presence of carbon-
rich gas such as methane, propane, butane or carbon monoxide. Gas carburising is faster and
can be more accurately controlled compared to pack carburising.

NITRIDING
Nitriding is used for hardening the surface of alloy steels containing stable nitride
forming elements such as Al, Cr, Mo, V and W. It is performed on dies, mandrels, gauges,
parts of pumps and engines.
The process involves heating the steel to about 650°C, and holding in an atmosphere
of ammonia for some desired duration of time. Anhydrous ammonia gas is passed into the
furnace, which dissociates into nascent nitrogen and reacts with the alloying elements to form
hard nitrides on the surface. These nitrides diffuse into the steel improving hardness and
corrosion resistance.

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Nitriding offers the hardest case of all surface hardening processes, but is the slowest
of all (0.25 mm/10 hours). Hence it is used for forming very thin cases.

FLAME HARDENING
Flame hardening uses direct heat from oxy-gas flames. The steel is heated to
temperatures to their austenization temperature, causing the surface to change, while the core
remains unchanged and soft. Once the steel surface reaches austenization temperature,
quenching is done immediately by a jet of cooling water. Quenching results in the formation
of martensite, which is a harder surface less susceptible to wear and corrosion.
The depth of the hardened case depends on the temperature of the flame, temperature
of the cooling water, heating time and the time gap between heating and cooling of the
selective region. This process is used for local hardening of gear tooth, cams, machine tool
beds and cutting tools.

Advantages – Flame hardening is rapid and efficient for proving deep cases upto 6 mm. This
method is suitable for hardening large bulky parts which will not fit into a furnace or cannot
be transported due to its weight.
Limitations – Accurate controlling of the depth of hardened layer is not possible. Low
carbon steel cannot be hardened by this method.

INDUCTION HARDENING
This process involves induction heating using various shapes of induction coil made
up of copper wires. A high frequency current is passed through a copper block which acts as
the primary coil of a transformer. This induces an alternating current which produces a
heating effect on the surface of the steel component. The heated surface is immediately
quenched by a jet of water.

Advantages – It is a very fast process with possibility

of accurate controlling of case hardening thickness.
Irregular shapes can be handled easily with this
process. The process also offers excellent resistance to
warpage, distortion, oxidation and scaling.
Limitations – Low carbon steel cannot be hardened
due to low carbon content.

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LASER HARDENING
It is a surface hardening process in which a laser beam is used to heat the surface of a
metal part and then let it quickly cool down in surrounding air. During laser hardening, the
energy from the laser beam is applied directly to the component surface. The surface layer is
heated up to the hardening temperature in a reduced area within a very short period of time.
Laser hardening consists of the rapid heating of a material’s surface by laser beam, a
short hold at the target temperature, and intensive cooling (self-quenching) due to the high
thermal conductivity of the material.
Laser hardening can be used to locally improve the wear resistance and service life of
parts for a wide variety of applications, such as press-forming tools, axle shaft housings,
power steering gear housings and oil-drilling equipment.

Advantages – The amount of heat input is comparatively low, so heat is transmitted into the
base material relatively quickly. Only small dimensional changes and distortions are caused.
Since no water quenching is involved, the process is clean.

ELECTRON BEAM HARDENING

The process involves a heat source
of a beam of high energy electrons which
can be manipulated using electromagnetic
coils. The surface layers of steel
component that are affected by electron
beam are self-quenched, leading to the
formation of martensite. Advantages of
laser hardening are also obtained by this
process.

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HARDENABILITY
Hardenability is a measure of the capacity of a steel to be hardened in depth when
quenched from its austenitizing temperature. It is a qualitative measure of the rate at which
hardness decreases with the distance from the surface of a hardened specimen due to
martensitic content. A material is said to have good hardenability when the decrease in
hardness towards the centre of the steel specimen is very low.
Hardenability is dependent on factors such as amount of carbon content, amount of
alloying elements in the steel, grain size of austenite, etc.

Jominy end quench test – It is a test used to determine the hardenability of steel. The
process is as follows.
 A sample specimen cylinder of 100 mm in length and 25.4 mm in diameter is heated
to a temperature of 800 to 900°C.
 Next, the specimen is rapidly transferred to the test machine, where it is held
vertically and sprayed with a controlled flow of water at one end of the sample. This
cools the specimen from one end.
 Next, the specimen is ground flat along its length to a depth of 0.38 mm to remove
decarburized material. The hardness is measured at intervals along its length
beginning at the quenched end.
 Finally the Rockwell or Vickers hardness values are plotted versus the distance from
the quenched end. The resulting curve is called Jominy curve or hardenability curve.
 After drawing the Jominy curve, a horizontal line is drawn at Rc = 57 to meet the
Jominy curve at a point. This distance is a measure of hardenability and is known as
Jominy distance. Larger the distance, higher the hardenability.

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