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Surface Hardening Of Steels

Prepared by:-
Hardenability-Why study it?

Having studied hardness, hardenability

comes as an obvious supplement with
it. If we know the hardness number of a
material this concept stands as a waste.
But places such as shafts, gears etc

Hardenability can be defined as the capacity of a

material under a given set of heat-treatment operations to
harden “in depth”. Hardenability as the word itself
suggests decides the hardness of the specimen under
study. The hardness in such cases is not studied and
determined by a single hardness test or a hardness number
but by a specially configured S-A-C hardenability test which
measures the hardness number at two regions basically-
(a)surface (b)core or by plotting the vicker’s /rockwell hardness
as a function of distance from the quenched end.
Hardenability v/s hardness.

Hardenability is with the aim of “penetrating hardness” into the

specimen. This is achieved by dissolving some of the elements into the
original lattice of the specimen. The choice of the added elements has to be
careful as they have to be in synchronization with the original lattice, i.e.
they should be such that they fit into the lattice
without inducing much dislocations, or compressive
and tensile forces which may lead to unexpected
failure of the specimen.

In case of steel(iron-carbon alloy) this has to be done at the austenizing

temperature(temperature at which steel is only austenite).The most suitable
elements for surface-hardening of steels are carbon, nitrogen and
to a small extent boron.
Surface-hardening processes.

• Carburizing in various media.

• Nitriding.
• Flame hardening.
Hardening by
• Induction surface hardening .
It makes use of the fact that carbon will diffuse into iron provided that the latter is
in the FCC(γ) form which exists above 910 0 C

Q. Why only the austenite phase is used for the carburizing process when
carbon is already present in the various other allotropic forms of carbon?
5. Austenite provides a large range of carbon compositions stable with it starting right
from 0.022wt% C to 0.76wt% C.
6. The other phases already have carbon present in combination with iron as a carbide
thus limiting the extent of the carburization process.
7. There are other phases present but they are stable only at higher temperatures
which are difficult to maintain and achieve.

Depending on the carburizing media there are mainly three types of
• Solid
• Liquid
• Gas
Fick’s Law
The rate at which carbon toms diffuse beneath the surface of the
specimen is determined by Fick’s Law which as follows:-

J = amount of carbon passing per unit time across an area S in
a direction
normal to the surface S
(δc/δx) = Concentration gradient of carbon.
D= Diffusion coefficient of carbon in gamma-iron
(Temperature dependent)
Einstein also gave a much simpler law for diffusion as follows:
x=√ 2Dt
‘x’=case depth
Solid carburizing
The process involves packing the work into heat-resisting(25Cr;20Ni) boxes
along with the carburizing material so that there is a space of 50mm between
the components. The boxes are then heated slowly to the carburizing
temperature and maintained at this temperature for according to the depth of
casing required. The reactions occurring inside the boxes are as follows:

2C(charcoal)+O 2 →2CO
At surface of the work it breaks into carbon dioxide releasing
2CO→CO 2 + C
Carbon then dissolves interstitially at the surface of steel.

The rate of carburization is increased by the addition of 10-15% BaCO 3

BaCO 3→ BaO + CO 2

CO 2 + C(charcoal) 2CO
Liquid/salt-bath carburizing
This type of carburizing is carried out in a mixture of salts having
compositions varying from-
20-50% sodium cyanide.
40% sodium carbonate.
Traces of sodium or barium chloride.
The mixture is then heated in ‘calorised’ pots to a the carburizing
temperature and held at the temperature according to the depth
of the casing required.
Q. What are ‘calorised’ pots?
J. Calorised pots are heat-resistant pots developed by a process
called calorising wherein steel is put in a chamber containing
powder and air is purged from it by forcing in argon or nitrogen.
The result is a fine layer of zinc on the surface of the work.
Reactions taking place during liquid carburizing:-
The following reactions are believed to take place

2NaCN + O 2 → 2NaCNO
Sodium cyanate formed decomposes at the surface of steel as follows

8NaCNO→4NaCN + 2Na 2 CO 3 + 2CO + 4N

Dissolves in
2CO→ COsteel
2 + C

Nitrogen released in its elemental form forms nitrides with carbon

in steel and aids in increasing the hardness.
Cyanide fumes are dangerous and a suitable extractor or
filter should be used.

Advantages of liquid over solid carburizing:

The temperature control over the process is much more
satisfactory in a liquid bath.
It produces the specimen of required hardness with
Gas carburizing
In recent years it has become the most popular method of mass
carburizing particularly when thin cases are required.

Q. Why is it the most popular method?

A. (a) It is a more cleaner process.
(b)The required plant size is also compact for a given output.
(c)The carbon content of the case can be most accurately and
easily controlled than in any kind of carburizing.
The work is heated at the carburizing temperature in an environment of
gases which may yield carbon atoms by decomposition at the work
surface. These are generally hydrocarbon alkanes (methane and
propane) which are partially burnt in the furnace or are diluted with a
carrier gas in order to produce an appropriate carbon concentration.
Carrier gases are usually the mixture of hydrogen, nitrogen and
carbon monoxide. The active agent is CO and the following reactions
are believed to take place.

2CO CO 2 + At
C work surface

CH 4 2H 2 + C

CO + H 2 H 2 O +Away
C from work
CO 2 + CH 4 2H 2 + 2CO

Investigational work in ‘plasma carburizing’ is taking place. The

process if successfully developed would lead to big saving of natural gas.
It is claimed that a case of one millimeter
depth would be formed in thirty minutes.
Nitriding is exactly same as carburizing with the only obvious
difference that the function of the agent here is to release nitrogen
after getting adsorbed at it’s surface.

It is possible to nitride many types of steel but the high surface

hardness is obtained with steels such having alloying elements such
as Al,Cr,Mo or V which form nitrides as soon as nitrogen is
dissociated at it’s surface.

Iron dissolves up to 0.1% nitrogen at 5900C and that above this

amount it begins to form hard nitride Fe 4 N. This is where the
difference lies between carburizing and nitriding.

Nitriding has to be performed in the ferritic state at

about 500 0 C while carburizing has to be performed in the
austenitic state at about 900 0 C.
Since it is carried out at low temperatures, nitriding is made the
final operation in the manufacture of the component. The parts are
maintained at 5000C for between 40 and 100 hours in a tight gas
chamber through which nitrogen is made to circulate.The following
reaction has been proved to occur

NH 3 3H + N


Plain carbon steel responds moderately to nitriding as the affinity

of carbon for nitrogen is not high enough thus the diffusing
nitrogen gets dispersed to higher depths reducing the hardness
whereas it is high for steels having chromium, vanadium etc as
they form hard nitrides as soon as they come into contact with

Classification(depending on the state of nitrogen entering the

Ion-/plasma nitriding or ion implantation.
As the name suggests this type of nitriding utilizes nitrogen in the ion

The work is placed in a chamber uniformly surrounded by nitrogen

at near-vacuum conditions and is the cathode. A voltage of 500-
1000 volts is applied due to which N +++ ions are produced. These
move towards the negatively charged
work and infiltrate the casing forming hard nitrides. The collision
of N +++ ions with the work raise the temperature bringing to the
desired temperature(about 590 degree Celsius.)This is evident
from a uniform glow of nitrogen ions around the work.
Advantages of ion-nitriding:-
Ø Since no quenching is required after nitriding, cracking or
distortion are unlikely to occur.
Ø Resistance to fatigue failure is good.
Ø As compared to processes such as salt-bath carburizing where the
work has to be rinsed for removal of toxic salts and the water is to
be disposed of causing harm to the environment ,this is a
clean process
Ø The process is economical when large number of components are
to be produced.

Disadvantages of ion-nitriding:-
Ø The process is profitable only when large number of
components are to be manufactured.
Ø If the work after nitriding is over-heated then all the hardness
would be lost and the work will have to be nitrided again.
As the name suggests in this type of nitriding carbon as well as
nitrogen diffuse into the work-element. Although salt-bath also
achieves the same goal but this process is carried out in
gaseous media.

The gaseous media used consists of carbon

monoxide/hydrocarbon atmosphere with 3-8% ammonia
added. Since carbon diffuses into steel
only at austenitic temperatures this poses an unfavorable
situation for nitrogen(nitrogen dissolves 50 times faster in
ferritic state than in austenitic phase.).Therefore the
temperature is kept at 9000C since the solubility of nitrogen in
austenite falls with increase in temperature.
Localised heat-treatment

Outline of the technique:

The component as a whole is first-treated by quenching
and tempering in order to achieve the necessary core
properties. It’s surface is then austenised by heating locally
and immediately quenched to a hard martensitic structure.
the core structure is tempered martensite and the case is
martensite. Core and Case are separated by a ‘cushion
layer’ of bainite.

The martensite is formed by rapid cooling (quenching) of

austenite which traps carbon atoms that do not have time to
diffuse out of the crystal structure. This martensitic reaction
begins during cooling when the austenite reaches the
martensite start temperature (Ms) and the parent
austenite becomes mechanically unstable. At a constant
temperature below Ms, a fraction of the parent austenite
transforms rapidly, then no further transformation will occur.
When the temperature is decreased, more of the austenite
transforms to martensite. Finally, when the martensite finish
temperature (Mf) is reached, the transformation is

It is a very simple process wherein a flame derived from

gases such as ethyne, propane or natural gas is used
to heat-treat the required area. If the area is quite small
such as tip of a screw driver manually operated torches are
used and as the whole area becomes austenitic the
component is water quenched.

For larger areas torches with built-in water jet

system is used which result in progressive hardening
of the specimen. For symmetrical objects such as
shafts and gears they are spun around at their two
centers in a ring burner. As soon as the area becomes
austenitic the entire component is quenched giving a
hardened surface.
Induction hardening

The process differs only from the previous one that here
the heating is carried out via a current carrying coil.
The material to be hardened is first cast in the form of a bar
and is places within the coil and an alternating current is
passed through it giving rise to a magnetic field. When the
steel bar is introduced in the coil the various magnetic
domains start to align with the increasing magnitude
and direction of current. As the direction and current
starts to decay the various domains start to align in
the opposite direction as indicated by a hysteresis
Thus hysteresis losses as well as heat induced due to
eddy-currents heat the specimen to the austenizing
temperature in a few seconds. The entire array is then
immersed into a water-spray system quenching and
Hardenability tests

Hardenability is determined by the following one test:

Jominy End Quench Test.

Jominy End Quench Test

1st Step:-
First, a sample specimen cylinder either 100mm in
length and 25mm in diameter, or alternatively, 102mm
by 25.4mm is obtained. Second, the steel sample is
austenitised. This is usually at 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 onto one end of the sample.
Because the cooling rate decreases as one moves further
from the quenched end, you can measure the effects of a
wide range of cooling rates that vary from rapid at the
quenched end to air cooled at the far end.
2nd Step(To ground flat the specimen along it’s length)
The specimen is ground flat to a depth of .38mm to remove
decarburised material. The hardness is measured at intervals
along its length beginning at the quenched end. For alloyed steels
an interval of 1.5mm is commonly used where as with carbon
steels an interval of .75mm is typically employed.

3rd Step(To measure and plot Vicker’s and Rockwell hardness)

The Vicker’s and/or Rockwell hardness are plotted versus distance
from the quenched end.