ENGINEERING MATERIALS &

METALLURGY

UNIT II
HEAT TREATMENT

2. 11
Definition – Full annealing, stress relief, recrystallisation and spheroidizing –normalising, hardening and
Tempering of steel. Isothermal transformation diagrams – cooling curves superimposed on I.T. diagram
CCR - Hardenability, Jominy end quench test – Austempering, martempering – case hardening,
carburising, nitriding, cyaniding, carbonitriding – Flame and Induction hardening.
INTRODUCTION

Ø In engineering applications it is desirable to have materials (ball bearings,

razor blade, etc.) with a hardened surface, so as to resist any wear and tear.

Ø At the same time it is also necessary that the materials should not be
brittle, and its interior should have a medium value of hardness, so that it
is able to absorb shocks.

Ø This can be achieved in any specimen by hardening the surface layer

alone, while the rest of it is left unaffected.

Ø There are two types of surface hardening methods and each type includes
a variety of techniques. They are

v Diffusion methods

v Non-diffusion methods (Thermal methods)

SURFACE HEAT TREATMENT BY DIFFUSION METHODS

Ø Diffusion methods involve heating the entire sample to a particular

temperature, in a suitable atmosphere,

Ø The absorption of foreign atoms and consequent diffusion take place.

Ø The diffusion of foreign atoms is limited only to the surface of a few

hundred microns depth, surface hardening alone is achieved.

These methods are called chemical hardening processes. Different diffusion

methods are

ü Carburizing

ü Nitriding

ü Cyaniding

ü Carbonitriding

These methods change the CHEMICAL COMPOSITION,

Ø CARBURISING by the addition of CARBON,

Ø NITRIDING by the addition of NITROGEN,

Ø CYANIDING by the addition of both CARBON AND NITROGEN.

 Ø CARBONITRIDING by the addition of both CARBON AND
NITROGEN.

CARBURIZING: PROCESSING PRINCIPLES

This is the oldest and one of the cheapest methods of

hardening.

Low-carbon steel, usually about 0.20 percent carbon or lower,

is placed in an atmosphere that contains substantial amounts of
carbon monoxide.

Carburizing is most frequently performed between 850 to

950°C,

Higher temperatures are used to reduce cycle times and/or

produce deeper depths of the high-carbon surface layer

Two important processes influence the introduction of carbon into austenite

during carburizing.

ü One is the environmental reaction that causes carbon to

be absorbed at the surface of the steel.

ü The rate at which carbon can diffuse from the surface to

the interior of the steel.

One of the most important carburizing reaction is

Fe+2CO—* Fe(C) +C0

v Where Fe(C) represents carbon dissolved in austenite.

v Very quickly a surface layer of high carbon (about 1.2 percent) is built up.

v The core is of low carbon content, the carbon atoms will diffuse inward
trying to reach equilibrium.

v At a given temperature, the rate of diffusion of carbon in austenite is

dependent upon the diffusion coefficient and the carbon-concentration
gradient.

v After diffusion has taken place for the required amount of time depending
upon the depth desired, the part is removed from the furnace and cooled.

v After cutting when the cut cross-section it is examined microscopically,

the carbon gradient can be realized in the gradual change of the structure.
 v At the surface is the hypereutectoid zone consisting of PEARLITE with a
white cementite network.

v Following that is the eutectoid zone of only PEARLITE.

v Next one can observe HYPOEUTECTOID zone of PEARLITE and

FERRITE.

v The amount of FERRITE gradually increases until the core is reached.

v The case depth may be measured microscopically with a micrometer

eyepiece. By machining small trace of the sample can be removed and
chemically analysised to measure the carbon

Carbon-concentration gradient in a car- burized steel

ADVANTAGES OF CARBURIZING
v Free from oxidation and sooting problems
v Uniform case depth and carbon content
v Rapid rate of penetration
v Carburizing temperature is reached by steel quickly because of higher thermal
conductivity of the bath
DISADVANTAGES

v Parts must be thoroughly washed after treatment to prevent rusting

v Bath composition has to be adjusted to obtained uniform case depth
v Cyanide salts are poisonous and require careful attention to safety.

POST-CARBURIZING HEAT TREATMENTS

Ø After carburizing, the grain structure of the steel is usually coarse throughout the
cross- section.
Ø Coarse grained steel, if quenched directly from the carburizing temperature, tends
to harden in the core as well.
Ø It leads to brittleness and distortion.
Ø Two separate heat treatments may be necessary to obtain the optimum properties
of the core and the case.

Post-carburizing heat treatment cycle is represented along with Equilibrium Diagram.

Post-carburizing heat treatments

I) direct quenching
2) Core refining
3) Case refining
4) Core and case refining
APPLICATIONS
v Fatigue resistance may be improved in some alloys by carburizing.
v In some applications, it is necessary to harden the surface of steel (or iron- carbon
alloy) above that of its interior.
v In the process carburizing, increase of surface concentration of carbon results in
this.

NITRIDING
v Nitriding is a surface hardening heat treatment that introduces nitrogen into the
surface of steel while it is in the ferrite condition.
v This is a process for case hardening of alloy steel in an atmosphere consisting of a
mixture in suitable proportions of ammonia gas and dissociated ammonia.
v Pure ammonia decomposes to yield nitrogen which enters the steel:

v The solubility of nitrogen in ferrite is small.

v Most of the nitrogen that enters the steel forms hard nitrides (e.g. Fe, Aluminum,
chromium and molybdenum) form very hard and wear resistant nitrides.
v The parts lobe nitrided are placed in an airtight container through which the
nitriding atmosphere is maintained continuously while the temperature is held
between
v 500—590°C.
v The nitriding cycle is quite long, depending upon the case depth desired.
v A 60 h cycle gives a case depth of approximately 0.6 mm at 525°C.
v A nitrided case consists of two distinct zones.
v In the outer zone the nitride-forming elements, including iron, have been
converted to nitrides.
v This region; which varies in thickness up to a maximum of about 0.05 mm is
commonly
v known as the white layer because of its appearance under microscope.
v This layer is very brittle and tends to crack.
v In the zone beneath this white layer, alloy nitrides only have been precipitated.
v The depth of nitride case is determined by the rate of diffusion of nitrogen from
the white layer to the region beneath.
v In order to maintain the white layer thickness, the nitriding medium should
contain only sufficient active nitrogen.
v The concentration of active nitrogen on the surface of the steel, which determines
the depth of the white layer, is fixed by the degree of dissociation of the ammonia.
v In the single-stage nitriding process this dissociation is held between 15 and 30
percent by adjusting the rate of flow keeping the temperature in the 500 to 525°C
range.
v In the double-stage process, the ammonia dissociation is held at 20 percent for a
period of 5 to 10 h at 525°C in the first stage.
v During the period the white layer is established, and the useful nitride starts to
form by diffusion of nitrogen out of it.
v In the second stage the ammonia dissociation is increased to 83 to 86 percent
maintaining the temperature in the 550 to 565°C range.
v This process maintains a thin white layer on the finished part.
v Thicker white layers produced by the single-stage process must be removed by
grinding or lapping after nitriding.
v If the double-stage process is used, grinding or other finishing operations may be
omitted.
v The very thin white layer obtained by this method, usually from 0.05 to 0.1 mm in
depth, does not chip or pit.
v The frictional characteristics of such surfaces are excellent.
v This layer also has good wear-in properties with improved corrosion resistance.
v Hardest cases are obtained with aluminum alloy steels known as Nitralloys.
v These are medium-carbon steels containing also chromium and molybdenum.
v Medium- carbon standard steels are used in some applications where lower
hardness is acceptable.
v Nitriding has also been applied to stainless steels and tool steels for certain
applications.

Depth of nitrided case Vs time at 525°C

ADVANTAGES:
Ø An extremely hard surface is formed
Ø The treatment is conducted at comparatively low temperatures, minimizing
cracking and distortion
Ø No subsequent heat treatment is necessary.

CYANIDING
v Cases that contain both carbon and nitrogen are produced in liquid salt
baths in cyaniding.
v While cyaniding is done in a liquid bath of NaC with the concentration
varying between 30 and 97%,
v Carbon and nitrogen enter the steel via the following reactions

ü In cyaniding, the proportion of nitrogen and carbon in the case

produced by a cyanide bath depends on both composition and
temperature of the bath.
ü The carbon content of the case developed in the cyanide bath
increases with an
ü increase in the cyanide concentration of the bath.
ü The temperature used for cyaniding is in the range of 800
Nitrogen content is higher in baths operating at the lower end
of the temperature range than those operating at the upper end
of the range.
ü A bath operating at 845°C and containing about 30 percent
cyanide will develop a
ü 0.125 mm case on the surface of 0.65 percent carbon steel in 45
minutes.

CARBONITRIDNING

v This is a case-hardening process in which a steel is heated in a gaseous

atmosphere of such composition that carbon and nitrogen are absorbed
simultaneously.
v This process is also known as dry cyaniding or gas cyaniding or nicarbing.
v It is the gas carburizing process modified by the addition of anhydrous ammonia.
v The atmospheres used generally comprise a mixture of carrier gas, enriching gas,
and ammonia.
v The carrier gas is usually a mixture of nitrogen, hydrogen, and carbon monoxide.
v At the furnace temperature, the added ammonia NH breaks up or dissociates to
provide the nitrogen to the surface of the steel.
v A typical gas mixture consists of 15% NH 5% CH. and 80% of neutral carrier gas.
 v The temperature used is 750—900°C. With increase of temperature, a greater
proportion of carbon enters the steel.
v This process also has the same applications as that of cyaniding.

SURFACE HEAT TREATMENT BY THERMAL (NON-DIFFUSION) METHODS

Ø Thermal methods are non-diffusion.

Ø These methods do not change the composition and consists of hardening
the surface by heating and then subsequently cooling.

Different non-diffusion methods are:

Flame hardening
Induction hardening
Electron beam hardening and
Laser hardening.

POSSIBLE TRANSFORMATION DURING HEAT TREATMENT

Ø Suppose that each of a number of steel specimens under study are all of the same
composition.
Ø On cooling from a temperature above eutectoid temperature different
transformations are possible involving the decomposition of austenite depending
on the cooling rate.
Ø If it is slow or moderate cooling, it allows diffusion of carbon resulting in the
formation of ferrite and cementite phases.
Ø The martensitic transformation occurs when the quenching rate is rapid enough to
prevent carbon diffusion.
Ø During martensitic transformation, large numbers of atoms experience slight
displacement relative to its neighbors.
Ø This occurs in such a way that the FCC austenite experiences a polymorphic
transformation to a body centered tetrogonal (BCT) martensite.
Ø All carbon atoms remain as interstitial impurities in martensite.
Ø They constitute a supersaturated solid solution that is capable of rapidly
transforming to other structures if heated to temperatures at which diffusion rates
become appreciable. Many steels and other systems that are characterized by
diffusion less transformation retain their martensitic structure almost indefinitely
at room temperature.
Ø Cooling transformation diagram also represents the above transformations
graphically.
 FLAME HARDENING

v Flame hardening consists of heating the selected areas of steel into the austenite
range with an oxyacetylene or oxyhydrogen torch and immediately quenching it
to form martensite.
v Therefore, it is necessary to start with steel which is capable of being hardened.
v It is in the range of 0.30 to 0.60 percent carbon.
v In flame hardening, heat may be applied by a single oxyacetylene torch, or it may
be part of an elaborate apparatus which automatically heats, quenches, and
indexes the parts. Depth of the hardened zone may be controlled by the
adjustment of the flame intensity, heating time and/or speed of traverse.
v Skill in required in adjusting and handling manually operated equipment to avoid
overheating the work because of high flame temperature.
v Overheating can result in cracking after quenching and excessive grain growth in
the region just below the hardened zone.
Four methods are in general use for flame hardening.

LOCALIZED OR SPOT HARDENING may be performed by directing a stationary

flame head to an area of a stationary work piece.

PROGRESSIVE HARDENING methods the torch travels over the work piece or the
work piece travels under a stationary torch.

SPINNING METHODS in which the work piece is rotated within an array of torches are
often used for small rounds.

PROGRESSIVE-SPINNING METHOD, the torch moves over a rotating work piece,

which is used to harden the surface of the long circular parts such as shafts and rolls.

ADVANTAGES OF FLAME HARDENING

v Adaptability and portability of the flame hardening equipment

v Feasibility of treatment of localized area
v No limitation on the size of the component to be treated
v Ability to treat components after surface finishing since there is little scaling,
decarburization, or distortion.

DISADVANTAGES

Ø Possibility of overheating and thus damaging the part and

Ø Difficulty in producing hardened zones less than 1 mm in depth.

INDUCTION HARDENING

v When high-frequency alternating current passes through the work coil, a high-
frequency magnetic field is set up.
v This magnetic field induces high-frequency eddy currents and hysteresis currents
in the metal to be hardened.
v Heating results from the resistance of the metal to passage of these currents.
v The high-frequency induced currents tend to travel only at the surface of the
metal.
v It is possible to heat a shallow layer of the steel without heating the interior.
v The depth of heating produced by induction related to the frequency of the
alternating current.
v The higher the frequency, the thinner or more shallow the heating
v Deeper case depths and hardening are produced by using lower frequencies.
v A wide variety of heating patterns maybe established by induction heating
depending on the shape of the coil, the number of turns of the coil, the operating
frequency, and the alternating current power input.
v Fig shows examples of the heating patterns produced by various types of coils.
 v As in flame hardening, induction heating does not change the composition of
steel, and therefore a steel selected for induction hardening must have sufficient
carbon content and alloying for the desired surface hardness distribution.

ELECTRON BEAM HARDENING

v Electron beam hardening is used to obtain shallow case hardened depths (0.5 mm
or less). The demand for high performance and durability in automobiles has
recently increased.
v Strenuous efforts have been made to improve the wear resistance of engine parts
by hardening their surfaces.
v Quite a lot of studies have been carried out on surface modifications of case iron
by high energy beams such as laser beam and electron beam.
 v An electron beam has an energy range from 50 to 200 KeV,
v It usually requires a vacuum chamber.
v This is one of the major limitations of electron beam hardening.
v The depth of the hardened surface layer is proportional to the electron penetration
depth. Using electron beam a layer depth of about 1 mm can be hardened.
v To harden a broad area, the scanning width of an electron beam can be easily
controlled up to several tens of centimeters by changing the magnetic field.

LASER SURFACE HARDENING

v The laser has some unique properties for surface heating

v .The laser beam is absorbed within the first few atomic layers of opaque
materials, such as metals.
v The applied energy can be directed precisely on the surface only where it is
needed.
v Thus it is a true surface heater and a unique tool for surface engineering.

Common ADVANTAGES OF LASER SURFACING compared to alternative processes

are:
• Chemical cleanliness
• controlled thermal penetration and therefore negligible distortion
• controlled thermal profile and therefore less heat affected zone
• After machining is not required
• Non-contact processing
• Relatively easy to automate

Currently the processes which use lasers in surface treatment include:

• Surface heating for transformation hardening or annealing

• Surface melting for homogenization, microstructure refinement, generation of rapid
solidification structures and surface sealing
• Surface alloying for improvement of corrosion, wear or cosmetic properties
• Surface cladding for similar reasons as well as changing thermal properties such as
melting point or thermal conductivity
• Surface texturing for improved paint appearance
• Plating by Laser Chemical Vapour Deposition (LCVD), Laser Physical Vapour
Deposition (LPVD)
Some processes such as transformation hardening and laser chemical vapour deposition
require low power density of laser while processes involving surface melting require
higher power densities.
The initial goal of laser heat treatment was selective surface hardening for wear
reduction;
It is now used to change metallurgical and mechanical properties also.
PRACTICAL USES OF LASER HEAT TREATMENT
Ø Hardness increase
Ø Strength increase
Ø Reduced friction
Ø Wear reduction
Ø Increase in fatigue life
Ø Surface carbide creation
Ø Selective tempering