Materials For Engineering 20ME11T Unit V - HEAT TREATMENT PROCESSES

Vidya Vikas Education Trust ®
Viday Vikas Polytechnic College

Department of Mechanical (General)
Materials for Engineering [20ME11T]

Unit V- HEAT TREATMENT PROCESSES
Notes
5.0 Concept of phase
5.1 Gibbs phase rule
5.2 Equilibrium phase diagram
5.3 Phase diagram of a pure metal
5.4 Phase diagram of alloy
5.5 Phase diagram of Solid solution
5.6 Iron–carbon equilibrium diagram indicating various phases
5.7 Critical temperature and its significance
5.9 Reactions on Iron carbon equilibrium diagram of Mild steel
5.9 Heat treatment
5.10 Purpose of heat treatment
5.11 Mechanism of heat treatment
5.12 Types or Classification of Heat Treatment Processes
5.12.1.1 Annealing
5.12.1.2 Normalizing
5.12.1.3 Hardening
5.12.1.4 Tempering
5.12.1.5 Nitriding
5.12.1.6 Cyaniding
5.12.1.7 Carburising
5.12.1.8 Case Hardening or Surface Hardening
Mr. THANMAY J S Be, M-Tech, H.O.D Mechanical (General), Vidya Vikas Polytechnic College, Mysore Page 1
5.0 Concept of phase
A phase can be defined as a homogeneous portion of a system that has uniform physical and
chemical characteristics i.e. it is a physically distinct from other phases, chemically
homogeneous and mechanically separable portion of a system.
A component can exist in many phases.

E.g.: Water exists as ice, liquid water, and water vapor. Carbon exists as graphite and diamond.
When two phases are present in a system, it is not necessary that there be a difference in both
physical and chemical properties; a disparity in one or the other set of properties is sufficient.
 A solution (liquid or solid) is phase with more than one component; a mixture is a material
with more than one phase.
 Solute (minor component of two in a solution) does not change the structural pattern of the
solvent, and the composition of any solution can be varied.
 In mixtures, there are different phases, each with its own atomic arrangement.
 It is possible to have a mixture of two different solutions.
5.1 Gibbs phase rule

The phase rule, first announced by J. Willard Gibbs in 1876, relates the physical state of a
mixture to the number of constituents in the system and to its conditions. It was also Gibbs who
first called each homogeneous region in a system by the term "phase."
In a system under a set of conditions, number of phases (P) exist can be related to the number of
components (C) and degrees of freedom (F) by Gibbs phase rule.
Degrees of freedom refers to the number of independent variables (e.g.: pressure, temperature)
that can be varied individually to effect changes in a system.
Thermodynamically derived Gibbs phase rule:
In practical conditions for metallurgical and materials systems, pressure can be treated as a
constant (1atm.). Thus Condensed Gibbs phase rule is written as:
5.2 Equilibrium phase diagram
A diagram that depicts existence of different phases of a system under equilibrium is termed as
phase diagram. It is actually a collection of solubility limit curves. It is also known as
equilibrium or constitutional diagram. Equilibrium phase diagrams represent the relationships
between temperature, compositions and the quantities of phases at equilibrium. These diagrams
do not indicate the dynamics when one phase transforms in to another.
Useful terminology related to phase diagrams: liquidus, solidus, solvus, terminal solid solution,
invariant reaction, intermediate solid solution, inter-metallic compound, etc.
Phase diagrams are classified according to the number of component present in a particular
system. Important information’s, useful in materials development and selection, obtainable from
a phase diagram
-It shows phases present at different compositions and temperatures under slow cooling
(equilibrium) conditions.
-It indicates equilibrium solid solubility of one element/compound in another.
-It suggests temperature at which an alloy starts to solidify and the range of solidification.
-It signals the temperature at which different phases start to melt.
-Amount of each phase in a two-phase mixture can be obtained.
The phase diagram is a crucial part of metallurgy - it shows the equilibrium states of a
mixture, so that given a temperature and composition, it is possible to calculate which phases
will be formed, and in what quantities. As such it is very valuable to be able to construct a phase
diagram and know how to use it to predict behavior of materials.
The main theory behind phase diagrams is based around the latent heat that is evolved when a
mixture is cooled, and changes phase. This means that by plotting graphs of temperature against
time for a variety of different compositions, it should be possible to see at what temperatures the
different phases form.
It is relatively easy to produce a rough binary phase diagram, as will be shown later in the
package, but although it is quick to take readings for the top part of a phase diagram, it takes
longer, and hence more sensitive equipment to monitor the changes that take place when a solid
changes phase. A typical simple binary phase diagram is as follows:
Where L stands for liquid, and A and B are the two components and α and β are two solid phases
rich in A and B respectively. The blue lines represent the liquidus and solidus lines, which are
relatively simple to measure. The red lines involve a solid-to-solid transition, and so require
much more sensitive equipment.
However, there is also a lot of thermodynamic theory behind phase diagrams, which allows more
problematic or more complex systems to be predicted, and this can lead to faster creation of
phase diagrams, as it can take a long time to pick up all the stable phases in experiments, and
there is not always the time available for such practical work.
A crucial point to remember is that a phase diagram should always display the equilibrium
phases, and so with cooler temperatures, these are hard to attain due to kinetic problems. Even at
higher temperatures, there may be problems of having enough time for the solid to fully
equilibrate as the system is cooling.
5.3 Phase diagram of a pure metal

Phase diagram of a pure metal or a substance is a graphical representation of the domain in
which a given state is stable. For example it gives the range of temperature and pressure over
which it exists as solid (S), liquid (L) or gas G). Figure shown below gives a typical phase
diagram of a pure metal. A schematic phase diagram of a pure metal indicating the, pressure,
temperature domain where it can exist as solid, liquid or gas. The line indicates boundary
between two phases. On any point on the line two phases are equally stable. There is a point
where three lines meet. This is a critical point (triple point) where three phases can coexist.
Apply phase rule. This gives F=0 meaning that it has no degree of freedom. Three phases can
coexist only at a fixed temperature & pressure. For water the triple point is at 0.006atmosphere
0.01°C. The caption of fig 2 describes the main features of the phase diagram. It has a horizontal
line drawn at 1 atmosphere pressure. It intersects the S/L boundary at its melting point and L/G
boundary at its boiling point. The slopes of these lines are positive indicating that both melting
and boiling points increase with increasing pressure.
5.4 Phase diagram of alloy

Phase Rule. When pressure and temperature are the state variables, the rule can be written as
follows:
f=c-p+2
Where f is the number of independent variables (called degrees of freedom), c is the
number of components, and p is the number of stable phases in the system.
The phase rule says that stable equilibrium between two phases in a unary system allows one
degree of freedom (f= 1 - 2 + 2).
This condition, called uni-variant equilibrium or mono variant equilibrium, is illustrated
as lines 1, 2, and 3 separating the single phase fields in Figure below. Either pressure or
temperature may be freely selected, but not both. Once a pressure is selected, there is only one
temperature that will satisfy equilibrium conditions, and conversely.
The three curves that issue from the triple point are called triple curves: line 1,
representing the reaction between the solid and the gas phases, is the sublimation curve; line 2 is
the melting curve; and line 3 is the vaporization curve. The vaporization curve ends at point 4,
called a critical point, where the physical distinction between the liquid and gas phases
disappears.
5.5 Phase diagram of Solid solution

A solid solution describes a family of materials which have a range of compositions
and a single crystal structure. Many examples can be found in metallurgy, geology
and solid-state chemistry. The word "solution" is used to describe the intimate mixing
of components at the atomic level and distinguishes these homogeneous materials
from physical mixtures of components.
The solid solution phase diagram explains the behavior of chemical solid solution
series, such as the transition from high temperature, calcium-rich plagioclase to low
temperature sodium-rich plagioclase, or the transition from high temperature
magnesium-rich to low temperature iron-rich crystals in ferro-magnesium minerals
(e.g. olivine, pyroxene).
Solid solutions have important commercial and industrial applications; as such mixtures often
have superior properties to pure materials. Many metal alloys are solid solutions. Even small
amounts of solute can affect the electrical and physical properties of the solvent.
The binary phase diagram in Fig. 2 shows the phases of a mixture of two substances in varying
concentrations, A and B. The region labeled "α" is a solid solution, with B acting as the solute
in a matrix of A. On the other end of the concentration scale, the region labeled "β" is also a solid
solution, with A acting as the solute in a matrix of B. The large solid region in between
the α and β solid solutions, labeled "α + β", is not a solid solution. Instead, an examination of
the microstructure of a mixture in this range would reveal two phases—solid solution A-in-B and
solid solution B-in-A would form separate phases, perhaps lamella or grains.
5.6 Iron–carbon equilibrium diagram indicating various phases

A study of the constitution and structure of all steels and irons must first start with the
iron-carbon equilibrium diagram. Many of the basic features of this system influence the
behavior of even the most complex alloy steels.
A study of the constitution and structure of all steels and irons must first start with the iron-
carbon equilibrium diagram. Many of the basic features of this system (shown in Figure below)
influence the behavior of even the most complex alloy steels. For example, the phases found in
the simple binary Fe-C system persist in complex steels, but it is necessary to examine the effects
alloying elements have on the formation and properties of these phases. The iron-carbon diagram
provides a valuable foundation on which to build knowledge of both plain carbon and alloy
steels in their immense variety.
It should first be pointed out that the normal equilibrium diagram really represents the metastable
equilibrium between iron and iron carbide (cementite). Cementite is metastable, and the true
equilibrium should be between iron and graphite. Although graphite occurs extensively in cast
irons (2-4 wt % C), it is usually difficult to obtain this equilibrium phase in steels
(0.03-1.5 wt %C). Therefore, the metastable equilibrium between iron and iron carbide should be
considered, because it is relevant to the behavior of most steels in practice.
The much larger phase field of γ-iron (austenite) compared with that of α-iron (ferrite) reflects
the much greater solubility of carbon in γ-iron, with a maximum value of just over 2 wt % at
1147°C. This high solubility of carbon in γ-iron is of extreme importance in heat treatment, when
solution treatment in the γ-region followed by rapid quenching to room temperature allows a
supersaturated solid solution of carbon in iron to be formed.
The α-iron phase field is severely restricted, with a maximum carbon solubility of 0.02 wt% at
723°C (P), so over the carbon range encountered in steels from 0.05 to 1.5 wt%, α-iron is
normally associated with iron carbide in one form or another. Similarly, the δ-phase field is very
restricted between 1390 and 1534°C and disappears completely when the carbon content reaches
0.5 wt% (B). There are several temperatures or critical points in the diagram, which are
important, both from the basic and from the practical point of view.
5.7 Critical temperature and its significance
 Upper critical temperature (point) A3 is the temperature, below which ferrite starts to
form as a result of ejection from austenite in the hypoeutectoid alloys.
 Upper critical temperature (point) ACM is the temperature, below which cementite
starts to form as a result of ejection from austenite in the hypereutectoid alloys.
 Lower critical temperature (point) A1 is the temperature of the austenite-to-pearlite
eutectoid transformation. Below this temperature austenite does not exist.
 Magnetic transformation temperature A2 is the temperature below which α-ferrite
is ferromagnetic.
5.8 Reactions on Iron carbon equilibrium diagram of Mild steel

1. Peritectic Reaction:
A peritectic reaction, in general, can be represented by an equation:
Where, L represents a liquid of fixed composition, S1 and S2 are two different solids of fixed
composition each. As illustrated in the peritectic region of Fe-Fe3C diagram.
2. Eutectic Reaction:
A eutectic invariant reaction in general can be represented by an equation:
Where, L represents liquid of eutectic composition and, S1 and S2 are two different solids of
fixed composition each. As illustrated in the eutectic region of Fe-Fe3 C diagram.
3. Eutectoid Reaction:
The eutectoid invariant reaction is a solid state version of eutectic reaction and, in general, can be
represented by an equation:
Where, S1, S2 and S3 are three different solids each of fixed composition. As illustrated in the
eutectoid region of Fe-Fe3C diagram.
5.9 Heat treatment
Heat treatment is defined as an operation involving the heating and cooling of a metal or an
alloy in the solid-state to obtain certain desirable properties without change composition.
The process of heat treatment is carried out to change the grain size, to modify the structure of
the material, and to relieve the stresses set up the material after hot or cold working.
 The heat treatment is done to improve the machinability.

 To improve magnetic and electrical properties.
 To increase resistance to wear, heat and corrosion, and much more reason.
Heat treatment consists of heating the metal near or above its critical temperature, held for a
particular time at that finally cooling the metal in some medium which may be air, water,
brine, or molten salts. The heat treatment process includes annealing, case hardening, tempering,
normalizing and quenching, nitriding, cyaniding, etc.
The process of heat treatment involves heating of solid metals to specified (re-crystallization)
temperatures holding them at that temperature and then cooling them at suitable rates in order to
enable the metals to acquire the desired properties to the required extents. All this take place
because of the changes in size, form, nature and the distribution of different constituents in the
micro-structure of these metals. All heat treatment processes, therefore, comprise the following
three stages of components:
1. Heating the metal to a predefined temperature.
2. Holding it at that temperature for sufficient time so that the structure of the metal becomes
uniform throughout.
3. Cooling the metal at a predetermined rate in a suitable media so as to force the metal to
acquire a desired internal structure and thus, obtain the desired properties to the required extent.
5.10 Purpose of Heat Treatment

Metals and alloys are heat treated in order to achieve one or more of the following objectives:
1. To relieve internal stresses set up during other operations like casting, welding, hot and
cold working, etc.
2. To improve mechanical properties like hardness,toughness, strength, ductility, etc.
3. To improve machinability
4. To change the internal structure to improve their resistance to heat, wear and corrosion.
5. To effect a change in their grain size.
6. To soften them to make suitable for operations like cold rolling and wire drawing.
7. To improve their electrical and magnetic properties.
8. To make their structure homogenous so as to remove coring and segregation.
9. To drive out trapped gases.
5.10 Mechanism of heat treatment
5.12 Types or Classification of Heat Treatment Processes

Various heat treatment processes can be classified as follows:
1. Annealing
2. Normalizing
3. hardening
4. Tempering
5. Nitriding
6. Cyaniding
7. Carburising
8. Case Hardening or Surface Hardening
5.12.1 Annealing
Annealing is one of the most important processes of heat treatment. It is one of the most widely
used operations in the heat treatment of iron and steel and is defined as the softening process.
Heating from 30 – 50°C above the upper critical temperature and cooling it at a very slow rate by
seeking it the furnace. The main aim of annealing is to make steel more ductile and malleable
and to remove internal stresses. This process makes the steel soft so that it can be easily
machined.
Purpose of Annealing
 It softens steel and to improve its machinability.

 To refine grain size and remove gases.
 It removes the internal stresses developed during the previous process.
 To obtain desired ductility, malleability, and toughness.
 It modifies the electrical and magnetic properties.
Depending on the carbon content, the steel is heated to a temperature of about 50° to 55°C above
its critical temperature range. It is held at this temperature for a definite period of time depending
on the type of furnace and nature of work. The steel is then allowed to cool inside the furnace
constantly.
Application of Annealing
 It is applied to castings and forgings.
Different type of annealing processes can be classified as follows:
1. Full annealing.
2. Process annealing.
3. Spheroidise annealing.
4. Diffusion annealing.
5. Isothermal annealing.
5.12.2Normalizing
The main aim of normalizing is to remove the internal stresses developed after the cold working
process. In this, steel is heated 30 – 50°C above its upper critical temperature and cooling it in
the air. It improves mechanical and electrical properties, machinability & tensile strength.
Normalizing is the process of heat treatment carried out to restore the structure of normal
condition.
Purpose of Normalizing
 Promote uniformity of structure.

 To secure grain refinement.
 To bring about desirable changes in the properties of steel.
The steel is heated to a temperature of about 40° to 50°C above its upper critical temperature. It
is held at this temperature for a short duration. The steel is then allowed cool in still air at room
temperature, which is known as air quenching.
Application of Normalizing
 It is applied castings and forgings to refine grain structure and to relieve stresses.
 It is applied after cold working such as rolling, stamping and hammering.
5.12.3 Hardening
Hardening: The main aim of the hardening process is to make steel hard tough. In this process,
steel is heated 30° – 40°C above the upper critical temperature and then followed by continues
cooling to room temperature by quenching in water or oil. It is the opposite process of annealing.
Purpose of Hardening
 By hardening, it increases the hardness of steel.

 To resist to wear
 Allows the steel to cut other metals
The steel is heated above its critical temperature range. It is held at that temperature for a definite
period of time. The steel is then rapidly cooled in a medium of quenching. The quenching
medium is selected according to the degree of hardness desired. The air, water, bring, oils and
molten salts are used as quenching mediums. A thin section, such knife blades are cooled in air.
Water is widely used medium but it results in the formation of bubbles on the surface of the
metal. Hence brine solution is used to prevent this. Oil is used when there is a risk of distortion
on cracks and is suitable for alloy steels. The molten salts are used to cool thin section to obtain
crack-free and impact-resistant products.
Application of Hardening
It is applied for chisels, sledgehammer, hand hammer, centre punches, taps, dies, milling cutters,
knife blades and gears.
5.12.4 Tempering
Tempering: When the hardening process hardens a steel specimen, it becomes brittle and has
high residual stress. It is an operation used to modify the properties of steel hardened by
quenching for the purpose of increasing its usefulness. Tempering or draw results in a reduction
of brittleness and removal of internal strains caused during hardening. Steel must be tempered
after the hardening process. The tempering is divided into three categories according to the
usefulness of steel required.
 Low-temperature tempering.
 Medium temperature tempering.
 High-temperature tempering.
Purpose of Tempering
 To relieve internally stressed caused by hardening.

 To reduce brittleness.
 Improve ductility, strength and toughness.
 To increase wear resistance.
 To obtain desired mechanical properties.
The steel after being quenched in the hardening process is reheated to a temperature slightly
above the temperature range at which it is to be used, but below the lower critical temperature.
The temperature here varies from 100°C to 700°C. The reheating is done in a bath of oil or
molten lead or molten salt. The specimen is held in the bath for a period of time till attains the
temperature evenly, the time depends on the composition and desired quality of steel. Now the
specimen is removed from the bath and allow to cool slowly in still air.
Application of Tempering
It is applied to cutting tools, tools, and gears, which are hardened by the hardening process.
5.12.5 Nitriding
Nitriding is the process of the case or surface hardening in which nitrogen gas is employed to
obtain hard skin of the metal. In this process, steel is heated in the presence of ammonia
environment. Due to this, a nitrogen atom is deposited and makes material hard. Induction
hardening and Flame hardening objects are heated by an oxy-acetylene flame.
Purpose of Nitriding
 To harden the surface of the steel to a certain depth.

 Increase resistance to wear and fatigue.
 To increase corrosion resistance.
It is done in the electric furnace where temperature varying between 450° and 510°C is
maintained. The part is well machined and finished and placed in an airtight container provided
with outlet and inlet tubes through which ammonia gas is circulated. The container with the part
is placed in the furnace and ammonia gas is passed through it while the furnace is heated. During
the process of heating nitrogen gas is released from ammonia in the form of atomic nitrogen,
which reacts with the surface of the part, and forms iron nitrate. The depth of entrance depends
upon the length of time spent at the nitriding temperature. The part is taken out and it does not
require any quenching or further heat treatment.
Application of Nitriding
 It is applied for hardening the surface of medium carbon alloy steels.
5.12.6 Cyaniding
Cyaniding: In this process, steel is heated in the presence of sodium cyanide environment. Due to
this, carbon and nitrogen atoms are deposited on the surface of steel and make it hard.
Purpose of Cyaniding
 This method is effective for increasing the fatigue limit of medium and small-sized parts such
as gears, shafts, wrist pins etc.
 To increase surface hardness.
 Increase wears resistance.
 To give the clean, bright and pleasing appearance to the hardened surface.
The part to be treated is dipped in a molten cyanide salt bath maintained at a temperature of
950°C. The molten salts used are sodium chloride, sodium carbonate, sodium cyanide and soda
ash. The immersed article is left in the molten cyanide salt at a temperature of 950°C for about
15 to 20 minutes. The decomposition of sodium cyanide yield nitrogen and carbon from carbon
monoxide, which is diffused into the surface resulting in hardening the surface. The part is then
taken out of the bath and quenched in water or oil.
Application of Cyaniding
 It is applied to small articles like gears, bushing, screws, pins and small hand tools, which
require a thin and hard wear-resisting surface.
5.12.7 Carburising:
Carburising: In this process, steel is heated in the presence of carbon environment. Due to
this carbon atoms are deposited on the metal surface and make it hard.
5.12.8 Case Hardening or Surface Hardening
The main aim of this process is to make the only external surface of steel hard and inner core
soft. It is the process of carburization i.e., saturating the surface layer of steel with carbon, or
some other process by which case is hardened and the core remains soft.
Purpose of Case Hardening

 To obtain a hard and wear resistance to machine parts.
 By case hardening, it obtains a tough core.
 To obtain a higher fatigue limit and high mechanical properties in the core.

Materials For Engineering 20ME11T Unit V - HEAT TREATMENT PROCESSES

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Vidya Vikas Education Trust ®

Viday Vikas Polytechnic College

Materials for Engineering [20ME11T]

A component can exist in many phases.

5.1 Gibbs phase rule

Thermodynamically derived Gibbs phase rule:

5.3 Phase diagram of a pure metal

5.4 Phase diagram of alloy

5.5 Phase diagram of Solid solution

5.6 Iron–carbon equilibrium diagram indicating various phases

5.8 Reactions on Iron carbon equilibrium diagram of Mild steel

 The heat treatment is done to improve the machinability.

5.10 Purpose of Heat Treatment

5.10 Mechanism of heat treatment

5.12 Types or Classification of Heat Treatment Processes

 It softens steel and to improve its machinability.

 Promote uniformity of structure.

 By hardening, it increases the hardness of steel.

 To relieve internally stressed caused by hardening.

 To harden the surface of the steel to a certain depth.

 It is applied for hardening the surface of medium carbon alloy steels.

Purpose of Case Hardening

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