HEAT TREATMENT

Heat treatment refers to the heating and cooling operations required to alter the properties
of metals, alloys plastic and ceramic materials.
During heat-treatment of a metal piece, when it is heated to a definite temperature
followed by cooling at a suitable rate, there occur changes in the micro-constituents of the
metal. These changes in the microconstituents of the metal may be in their nature, form,
size and distribution in the metal piece These changes in micro-constituents then control
the changes in physical and mechanical properties of heat treated metal specimen. For
various fabrication and manufacturing operations, heat treatment is a very important
process. The purpose of heat treatment is to achieve any one or more objectives cited as
follows:
(i) To remove strain hardening of a cold worked metal and to improve its ductility.
(ii) To relieve internal stresses set up during cold-working, casting, welding and hot-
working treatments.
(iii) To remove gases from castings, to soften a metal to improve its machinability, and to
increase the resistance to wear, heat and corrosion.
(iv) To improve the cutting ability, i.e., hardness of a steel tool, to improve grain structure
after hot working a metal and to remove effects of previously performed heat-treatment
operations.
(v) To improve magnetization property, especially of steels, for producing permanent
magnets.
(vi) To refine grain structure after hot working a metal.
(vii) To soften and toughen a high carbon steel piece.
(viii) To produce a single phase alloy in stainless steel, and to produce a hard, wear
resistant case on a tough core of a steel part.
(ix) To harden non-ferrous metals and alloys, especially aluminium alloys and to produce a
single phase alloy in stainless steel.
(x) To produce a hard, wear resistant case on a tough core of a steel part and to toughen a
hardened steel piece at the cost of its hardness.

ANNEALING

This is a kind of heat treatment after which a metal or alloy acquires a structure close to the
equilibrium one. A material is exposed to an elevated temperature for an extended time
period and then slowly cooled.
Normally, annealing is carried out to (i) relative stresses (ii) increase softness, ductility and
toughness; and/ or (iii) produce a specific microstructure.
The temperature of heating in annealing depends on the composition of an alloy and the
particular kind of the process; the rate of cooling from the annealing temperature is usually
not high (within 30-200°C/h).
An annealing process consists of three stages: (i) heating to the desired temperature, (ii)
holding or ‘soaking’ at that temperature, and (iii) cooling, usually to room temperature.
The various types of annealing operations are: (i) Full annealing, (ii) Process annealing, (iii)
Spheroidise annealing and (iv) Diffusion annealing.
FULL ANNEALING
This operation removes all structural imperfections by complete recrystallization. This
operation is often utilized in low and medium carbon steels that will be machined or will
experience extensive plastic deformation during a forming operation. This operation
consist of:
(i) Heating the hypoeutectoid steel to about 50-70°C above the upper critical temperature
(for hypoeutectoid steels) and by the same temperature above the lower critical
temperature for hypereutectoid steels until equilibrium is achieved. This ensures that the
metal is heated thoroughly and phase transformation has taken place throughout the whole
volume.
(ii) The alloy is then furnace cooled; i.e., the heat-treating furnace is turned off and both
furnace and steel cool to room temperature at the same rate, which takes several hours.

PROCESS ANNEALING

This is a heat treatment that is used to negotiate the effects of cold work, i.e. to soften and
increase the ductility of a previously strain hardened metal. Process annealing is commonly
utilized during fabrication procedures that require extensive plastic deformation, to allow a
continuation of deformation without fracture or excessive energy consumption. It is the
recrystallization of cold work, i.e., recovery and recrystallization processes are allowed to
occur Process annealing or sub-critical annealing which is done on coldworked low carbon
steel sheet, wire or tubing to relieve internal stresses and to soften the material. The
process is as follows:
(i) The steel is heated to 550-650°C, which is just below the lower critical temperature on
iron-carbon diagram for steel.
(ii) Stresses throughout the metal are relieved and recrystallization causes new grains to
form and grow.
Heating period is followed by slow cooling. Prolonged annealing causes the cementite in
the pearlite to “ball up” or spheroidise. Ferrite grain growth also occurs. Obviously,
annealing time and temperature control is very essential for proper process annealing.

STRESS RELIEF ANNEALING

Internal residual stresses may develop in metal pieces due to: (i) plastic deformation
processes such as matching and grinding; (ii) non uniform cooling of a piece that was
processed or fabricated at an elevated temperature, such as a weld or a casting; and (iii) a
phase transformation that is induced upon cooling where in parent and product phases
have different densities. Distortion and warpage may result in case if residual stresses are
not removed. They can be eliminated by this process-in which the piece is heated to the
recommended temperature, held there long enough to attain a uniform temperature, and
finally cooled to room temperature in air.
In this process, the work pieces are first heated to about their recrystallization temperature
and then these are cooled slowly
Diffusion Annealing

On raising the furnace temperature until the steel reaches its solid phase line state, the
thermal energy level is maintained. After more than 10-hours, but not more than 15-hours,
the steel workpieces is allowed to cool. Having reached room temperature, the chemical
composition of the steel is more consistent than it was before the process. Diffusion work
usually requires a second pass, which is effected as a complete annealing operation or an
alloy normalizing pass.

NORMALIZING
This is used as a finishing treatment for carbon steels giving higher strength than
annealing. There is no serious loss of ductility too. Heating and soaking in this process is
same as in the full annealing but part is allowed to cool in air so that cooling rate is much
faster. An annealing heat treatment called normalizing is used to refine the grains (i.e., to
decrease the average grain size) and produce a more uniform and desirable size
distribution. Fine grained pearlite steels are tougher than coarse-grained ones. The fine
grain structure increases the yield and ultimate strengths, hardness and impact strength.
Normalizing is accomplished by heating at approximately 55 to 85°C above the upper
critical temperature, which is, of course, dependent on composition.
Normalizing often applied to castings and forgings is stress relieving process. To some
extent, it increases strength of medium carbon steel. It improves machinability, when
applied to low carbon steel. Alloy steels in which the austenite a procedure termed
austenizing is very stable can be normalized to produce hard martensitic structure. Cooling
in air produces high rate of cooling which can decompose the austenitic structures in such
steels and martensite is produced. This increases the hardness to great extent.
The advantages of this method are:
(i) In comparison to fully annealed material, normalizing produces stronger material.
(ii) Normalizing refines the grains.
(iii) Normalizing produces homogenised structure.
(iv) Normalizing is used to improve properties of steel castings instead of hardening and
tempering.
(v) Strength and hardness are increased.
(vi) Better surface finish is obtained in machining.
(vii) Resistance to brittle fracture is increased in hot-rolled steel.
(viii) Crack propagation is checked.

SPHERODISING
Tool steels for cutting tools, measuring instruments and cold forming dies have a high
concentration of carbon (07-2%), which provides high hardness and makes these steels
poorly machinable. The hardness of tool steels can be reduced by annealing. Besides,
spheroidizing annealing of hypereutectoid steels prepares their structure to hardening.
This type of heat treatment produces carbide in the form of round or globular (spheroids)
instead of plates as in pearlite. This structure gives: good machinability, high ductility and
improvement in formability.
The hardness of a steel is the lowest when the steel structure consists of granular pearlite
with inclusions of rounded-off (spherical) cementitie grains. From this the name
‘spheroidizing’ annealing transpires. The spheroidizing heat treatment consists of heating
the alloy at a temperature just below the eutectoid phase diagram (line A1 in Fig. 10.1, or at
about 700°C] in the α + Fe3C region of the phase diagram. If the precusor microstructure
contains pearlite, spheroidizing times will ordinarily range between 15 and 25 hours.
During this heat annealing there is coalescence of the Fe 3C to form the spheroid particles.

HARDENING
It is a kind of heat treatment which forms a non-equilibrium structure in an alloy. Non-
equilibrium structures can be produced by heat treatment only in cases when the alloy
being treated undergoes certain transformations in solid solutions, decomposition of a
high-temperature solid solution by eutectoid reaction, etc. To form a non-equilibrium
structure in an alloy, it is heated above the temperature of the phase transformation in the
solid state and then cooled (chilled) quickly; fast cooling is essential for preventing the
equilibrium transformation during cooling.
Structural and tool-making alloys are hardened in order to increase their strength. Alloys
undergoing a eutectoid transformation under the equilibrium conditions can be
strengthened by hardening quite substantially.
Their strength increases either due to the martensitic phase change or due to a reduction of
the temperature of eutectoid reaction; in both cases there forms a fine grained eutectoid
mixture. If the hardening procedure has resulted in that the metal at room temperature
(20-25°C) has the fixed state of hightemperature solid solution, the strengthening effect
immediately after hardening is insignificant; it will be pronounced mainly on a repeated
low-temperature heating or after holding at 20-25°C.
Hardening capacity and hardenability are important characteristics of steels. Hardening
capacity is defined as the surface hardness of a hardened article and depends mainly on the
carbon content of the steel.
We may note that the influence of alloy composition on the ability of a steel alloy to
transform to martensite for a particular quenching treatment is related to a parameter
hardenability

SPECIAL TREATMENTS
In case of large sections where the water quenching may produce cracks, special
treatments are preferred for hardening. The cracks on the surface are caused due to fast
skin cooling and changes into martensite while the inner core cools slowly and transforms
later accompanied by dilation. This dilation causes outer skin to crack. In order to avoid
this type of cracking special treatments have been developed. Prior to their discussion, it
would be proper to have some idea about isothermal transformation.
(i) Isothermal Transformation: Usually austenite is not converted into martensite
instantaneously but the process continues for some time. It is observed that different steels
take different time for full transformation and the time depends upon the temperature
from where cooling begun. Conditions of constant temperature are termed isothermal. The
related phase diagrams are referred to as isothermal transformation diagrams, or
sometimes as time-temperature transformation (or T-T-T) diagrams.
The selected specimen is austenized and then quenched in liquid bath held at temperature
to be investigated. The specimen is held for a different length of time in the bath and then
quenched in the water. One can study the resulting structure under microscope or any
other associated property, e.g. hardness may be studied. It is observed that definite times
are required for the initiation and completion of the transformation and these times vary
with the temperature. The progress of transformation, say for 10%, 50%, or 90% may also
be determined.
Figure 10.10 illustrates complete transformation diagram for eutectoid steel. The
transformation temperature is lowered from A1 temperature to about 550°C, and the
nucleation and completion time decreases and pearlite lamellae becomes finer. The
nucleation and completion time increases from about 550°C to 250°C. The transformation
product is bainite (composed of two equilibrium phases that are ferrite and cementite).
Minimum nucleation time is identified as the nose or knee. The transformation product is
martensite below about 250°C. Although, this forms almost instaneously, but the amount
formed depends upon the temperature. The upper and lower limits of martensite
transformation temperature are represented by Ms and MF respectively. These diagrams
are also referred to as S-curves because of their shape.
(ii) Austempering or Isothermal Quenching: The component or specimen to be hardened is
first austenized and then quenched into a lead or salt bath held at just above the martensite
transformation temperature. The component is kept in the bath until the bainite
transformation is completed. Now, the component is removed from the bath and cooled in
air till the room temperature is reached. The bainite so produced is somewhat softer than
martensite of the same carbon content and distortion is also minimum. Moreover, the
austempered steel has improved shock resistance and low notch sensitivity. Figure 10.11
shows the process of austempering. Molten salts, 45% NaNO3 and 55% KNO3 or molten
alkalies 20% NaOH and 80% KOH are used as quenching medium. Their temperature
is maintained between 150-450°C.

Austempering is often limited to section thickness of 20 mm. This is the only limitation in
austempering, i.e. only small sections are suitable for austempering as big sections cannot
be cooled rapidly to avoid the formation of pearlite. Austempering is applicable to a few
plain carbon steels and requires facility of molten salt bath. One may regard this as a
disadvantage over quenching and tempering.
(iii) Martempering or Steeped Quenching: The sample or the specimen to be hardened is
fully austenized and then quenched into a lead or salt bath held at a temperature just above
that at which martensite starts to form. It is maintained at this temperature until its
temperature becomes uniform throughout, i.e. there remains no difference in outside
and inside temperatures. Then it is water quenched to form complete martensitic structure
and bainite formation is prevented. This process separates successfully the cooling
contraction from the austenite- martensite expansions and thus prevents quenching in
large size articles. The steel can be tempered to low temperature to further refine the
structure Effect of such treatment is to minimise cracking, distortion, and the thermal
shock of the quenching. The hardness and ductility are usually similar to those obtained by
direct quenching to the martensitic state followed by tempering. However, the impact
toughness may be better
SURFACE HARDENING
Surface hardening of articles, like most methods of surface strengthening (chemical heat
treatment, strain hardening, knurling, etc.) offers an additional advantage that large
compressive stresses appear in the surface layers of hardened articles.
A number of components require only a hard surface to resist wear and tear and a tough
core to resist shock loads instead of complete component being made hard. These two
properties do not exist in one steel.
For toughness, one finds that the core should not exceed 0.3% carbon content, also
sometimes it is not desirable to harden complete component. For example, it is undesirable
to have case harden screw threads.
The threads would be brittle and distortion during hardening would need expensive thread
grinding operations to correct the distortions. Surface hardening is classified into two
types:
(i) Selective heating of the surface layers: In this case, the time available to change the
micro-structure of steel is short. Obviously, hardened and tempered steels respond well
but annealed steels do not. Moreover, composition of the steel must be such that the
quenching will produce martensite and so harden the steel Clearly, carbon content to be
0.4% or more.
Flame hardening can be one of the method of selective heating. The surface of a component
is heated to 850°C with an oxyacetylene flame and quenched with cold water immediately.
Flame heating transforms the structure of the surface layers to austenite and quenching
changes the austenite surface layers to martensite resulting into a hard surface. Depth of
hardening depends on the heat supplied per unit time. Flame hardening is mostly used in
case of carbon and alloy steels having carbon content 0.4% to 0.6, e.g. shafts, gears, cylinder
linears, crank shafts bearing journals, etc. Another method of selective heating is induction
hardening. Steel components are placed within a coil through which a high frequency is
allowed to pass. Surface layers of the component are heated between 850-1000°C.
Subsequently cooling transforms the austenite to martensite. The heating coil is often made
of tube perforated with fine spray holes so that it can be used both for heating and
quenching. We may note that the depth of heating produced by this method is related to the
frequency of the alternating current. Higher the frequency of a.c. current, less will be the
hardened depth, but there will be more rapid rise in temperature.
(ii) Case Hardening: In this method C and/or N2 are introduced in the surface layer. In
carburizing the part is surrounded by material or atmosphere rich in carbon and on heating
this carbon is first released and then absorbed in steel. More recently case carburizing is
more effectively performed by heating steel part in the atmosphere of natural gas, coke
even gas, butane or propane or the volatized form of liquid hydrocarbons like terpenes and
benzene or the volatilized form of liquid hydrocarbons like terpenes and benzene.
Volatilized form of alcohol and glycols or ketones have also been used.
In these cases the thickness of hardened layer is proportional to root of the time of
treatment in hour. The depth of hardness depends upon the number of times the process is
repeated. The component is finally raised to a red heat and quenched in water. However,
one will have to take the precaution that the part to be hardened should be covered with
the compound
CARBURIZING
This is another method of surface hardening. The composition of surface layers are
changed. This process is usually carried out on a steel containing less than 0.2% carbon.
Carburizing is usually employed for treating certain types of machine elements which have
to have a wear-resistance working surface and tough core, gear wheels, shafts, pins,
camshafts, cams, worms, etc.
The initial medium for carburizing (carbon saturation) is usually called a carburizer. Two
methods of carburizing are in use: in a solid and in a gaseous carburizer. In both cases,
however, the carburizing process passes through a gaseous phase. The most popular solid
carburizer consists of charcoal with an addition of 20-25% barium carbonate to intensify
the process and of 3-5% of CaCO3 to prevent the carburizer particles from caking. Articles
to be carburized and the carburizer are placed into a container (steel box) and heated in a
furnace to 910-930°C. During heating, charcoal reacts with the oxygen of remaining air

The process of gas carburizing occurs more quickly than that of solid carburizing, since no
time is lost for heating the carburizer box. Besides, gas carburizing can be more easily
controlled and automatized.
By carburizing process hardness can be increased from 200 HB (0.8 carbon content in the
core) to 750 HB (0.7% carbon content in the surface).
Other methods used for carburising are:
Pack Carburizing: The component to be carburised is heated above A3 temperature
between 850°C to 1060°C for about five hours in a sealed metal box containing charcoal
and barium carbonate as mentioned earlier. Oxygen present in the box reacts with the
carbon to produce carbon monoxide. Carbon present in the atmosphere gets diffused into
the surface austenitic layers of the component. When carburising is complete, metal boxes
are allowed to cool down so that they can opened and unpacked. The components are then
cleaned and made available for subsequent heat treatment. This method is mainly used for
large components or where a thick surface layer has to be hardened.
Salt Bath Carburizing: This method involves the component in a bath of suitable carbon
rich salts between 750-850°C. Usually, sodium cyanide is mainly used as a medium. Carbon
from the molten salt diffuses into the component. The advantages and disadvantages of
cyanide salts are:
(i) Cyanide salt is poisonous in nature. Obviously, one will have to take utmost care while
working with such a salt. A few grains of this salt under the fingernails could prove fatal if
transformed to mouth via smoking or food.
(ii) After the treatment, removal of the salt from the hardened surface is more problematic
in case of blind holes or threaded parts.
(iii) In this process heating and carburisation are more uniform with less chance of
distortion.
(iv) The components can be hardened by quenching straight out of cyanide salt without
need for further heat treatment.
Nitriding: This is the process of diffusion saturation of steel surface with nitrogen. The
component is heated in a mixture of ammonia and hydrogen so that nitrogen diffuses into
the surface layers and hard nitride compounds are formed. The process is employed for
increasing the wear resistance and endurance limit of machine elements (crankshafts,
cylinder sleeves, worm gears, shafts, etc.). Prior to nitriding, steel articles are subjected to
hardening and high temperature tempering (improving heat treatment) and finishing. After
nitriding, they are ground and polished.
In a nitriding process, the component is heated in a mixture of ammonia and hard nitride
compounds are formed. Common nitriding is carried out at a temperature of 500-600°C in
a muffle or container through which dissociating ammonia is being passed. This process is
used with those alloys of steel which contain elements that form stable nitrides, e.g.
chromium, molybdenum, tungsten, vanadium, aluminium, etc. It is probable that the
reaction of ammonia dissociation takes place at the steel surface; nitrogen ions are
absorbed by the surface and then diffuse into the depth of the metal. The time taken for
nitrogen to react with the steel surface is about 100 hours.
When nitriding carbon steels, the rate of nitrogen diffusion decreases with an increase of
carbon content and the formation of carbonitride phases becomes possible.
A thin white layer of nitrides is formed on the surface of the component, which should be
removed by mechanical or chemical means as this layer adversely affects the mechanical
properties.
Age Hardening (Precipitation Hardening): One can enhance the strength and hardness of
some metal alloys by the formation of extremely small uniformly dispersed particles of a
second phase within the original phase matrix. However, this must be accomplished by
phase transformations that are induced by appropriate heat treatments. The process is
termed as precipitation hardening, as the small particles of the new phase are termed
“precipitates”. This process is also called as ‘age hardening’, as the strength develops with
time,
or as the alloy ages. The alloys that are hardened by this process are aluminium-copper,
copper, berryllium, copper-tin, and magnesium-aluminium.
Cyaniding[edit]
Cyaniding is a case-hardening process that is fast and efficient; it is mainly used on low-
carbon steels. The part is heated to 871–954 °C (1600–1750 °F) in a bath of sodium
cyanide and then is quenched and rinsed, in water or oil, to remove any residual cyanide.
2NaCN + O2 → 2NaCNO
2NaCNO + O2 → Na2CO3 + CO + N2
2CO → CO2 + C
This process produces a thin, hard shell (between 0.25 and 0.75 mm, 0.01 and 0.03 inches)
that is harder than the one produced by carburizing, and can be completed in 20 to 30
minutes compared to several hours so the parts have less opportunity to become distorted.
It is typically used on small parts such as bolts, nuts, screws and small gears. The major
drawback of cyaniding is that cyanide salts are poisonous.
VACUUM HARDENING
During vacuum hardening, material is heated in the absence of oxygen by convection in the
medium of inert gas (N₂) and / or heat radiation in the underpressure. Steel is hardened
with a stream of nitrogen, whereby cooling rate can be determined by selecting the excess
pressure. Depending on the workpiece shape it is possible also to choose the direction and
time of nitrogen blowing. Optimization of time and steel temperature control are carried
out during process with the use of pilot thermocouples which can be placed on a workpiece
in the heating chamber. Steel that is heat treated in a vacuum furnace obtains the specified
properties of strength and hardness throughout the entire cross-section, without surface
decarburization. Austenitic grain is fine and it complies with international standards.

Plasma nitriding[edit]
Plasma nitriding, also known as ion nitriding, plasma ion nitriding or glow-discharge
nitriding, is an industrial surface hardening treatment for metallic materials.
In plasma nitriding, the reactivity of the nitriding media is not due to the temperature but
to the gas ionized state. In this technique intense electric fields are used to generate ionized
molecules of the gas around the surface to be nitrided. Such highly active gas with ionized
molecules is called plasma, naming the technique. The gas used for plasma nitriding is
usually pure nitrogen, since no spontaneous decomposition is needed (as is the case of gas
nitriding with ammonia). There are hot plasmas typified by plasma jets used for metal
cutting, welding, cladding or spraying. There are also cold plasmas, usually generated
inside vacuum chambers, at low pressure regimes