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Nitriding

Nitriding is a surface-hardening heat


treatment that introduces nitrogen into the
surface of steel at a temperature range
(500 to 550°C, or 930 to 1020°F), while it
is in the ferrite condition.
Thus, nitriding is similar to carburizing in that
surface composition is altered, but
different in that nitrogen is added into
ferrite instead of austenite.
Because nitriding does not involve heating
into the austenite phase field and a
subsequent quench to form martensite,
nitriding can be accomplished with a
minimum of distortion and with excellent
dimensional control.
The mechanism of nitriding is generally
known, but the specific reactions that
occur in different steels and with different
nitriding media are not always known.
Nitrogen has partial solubility in iron. It can
form a solid solution with ferrite at nitrogen
contents up to about 6%.
At about 6% N, a compound called gamma
prime (γ’), with a composition of Fe4N is
formed.
At nitrogen contents greater than 8%, the
equilibrium reaction product is ε
compound, Fe3N.
Nitrided cases are stratified.
The outermost surface can be all γ’ and if
this is the case, it is referred to as the
white layer.
Such a surface layer is undesirable: it is
very hard profiles but is so brittle that it
may spall in use.
Usually it is removed; special nitriding
processes are used to reduce this layer or
make it less brittle.
The ε zone of the case is hardened by the
formation of the Fe3N compound, and
below this layer there is some solid
solution strengthening from the nitrogen in
solid solution.
• Principal reasons for nitriding are:
• To obtain high surface hardness
• To increase wear resistance
• To improve fatigue life
• To improve corrosion resistance (except
for stainless steels)
• To obtain a surface that is resistant to the
softening effect of heat at temperatures up
to the nitriding temperature
Nitridable Steels
Nitrided steels are generally medium-carbon
(quenched and tempered) steels that
contain strong nitride-forming elements
such as aluminum, chromium, vanadium,
and molybdenum.
The most significant hardening is achieved
with a class of alloy steels (nitralloy type)
that contain about 1% Al.
When these steels are nitrided the aluminum
forms AlN particles, which strain the ferrite
lattice and create strengthening
dislocations.
Titanium and chromium are also used to
enhance case hardness although case
depth decreases as alloy content
increases.
Of the alloying elements commonly used in
commercial steels, aluminum, chromium,
vanadium, tungsten and molybdenum are
beneficial in nitriding because they form
nitrides that are stable at nitriding
temperatures.
Molybdenum in addition to its contribution
as a nitride former also reduces the risk of
embrittlement at nitriding temperatures.
Other alloying elements such as nickel,
copper, silicon and manganese have little,
if any, effect on nitriding characteristics.
Although at suitable temperatures all steels
are capable of forming iron nitrides in the
presence of nascent nitrogen, the nitriding
results are more favorable in those steels
that contain one or more of the major
nitride-forming alloying elements.
Because aluminum is the strongest nitride
former of the common alloying elements,
aluminum containing steels (0.85 to 1.50%
Al) yield the best nitriding results in terms
of total alloy content.
The following steels can be gas nitrided for
specific applications:
Aluminum-containing low-alloy steels
Medium-carbon, chromium-containing low-
alloy steels of the 4100, 4300, 5100, 6100,
8600, 8700 and 9800 series
Hot-work die steels containing 5% chromium
such as HI1, HI2, and HI3
Low-carbon, chromium-containing low-alloy
steels of the 3300, 8600, and 9300 series
Air-hardening tool steels such as A-2, A-6,
D-2, D-3 and S-7
High-speed tool steels such as M-2 and
M-4
Nitronic stainless steels such as 30, 40,
50, and 60
Ferritic and martensitic stainless steels of
the 400 and 500 series
Austenitic stainless steels of the 200 and
300 series
Precipitation-hardening stainless steels
such as 13-8 PH, 15-5 PH, 17-4 PH, 17-
7 PH, A-286, AM350 and AM355.
Nitriding processes
Process methods for nitriding include:
gas (box furnace or fluidized bed),
liquid (salt bath),
plasma (ion) nitriding.
The advantages and disadvantages of these
techniques are similar to those of carburizing.
However, times for gas nitriding can be quire long,
that is, from 10 to 130 h depending on the
application, and the case depths are relatively
shallow, usually less than 0.5 mm.
Plasma nitriding allows faster nitriding times, and
the quickly attained surface saturation of the
plasma process results in faster diffusion.
Plasma nitriding can also clean the surface by
sputtering.
Gas Nitriding
Gas nitriding is a case-hardening process
whereby nitrogen is introduced into the
surface of a solid ferrous alloy by holding
the metal at a suitable temperature in
contact with a nitrogenous gas, usually
ammonia.
Quenching is not required for the production
of a hard case.
The nitriding temperature for all steels is
between 495 and 565°C.
Because of the absence of a quenching
requirement with attendant volume
changes, and the comparatively low
temperatures employed in this process,
nitriding of steels produces less distortion
and deformation than either carburizing or
conventional hardening.
Some growth occurs as a result of nitriding
but volumetric changes are relatively
small.
Prior Heat Treatment. All hardenable steels
must be hardened and tempered before
being nitrided.
The tempering temperature must be high
enough to guarantee structural stability at
the nitriding temperature: the minimum
tempering temperature is usually at least
30°C (50°F) higher than the maximum
temperature to be used in nitriding.
Single-Stage and Double-Stage Nitriding.
Either a single- or a double-stage process
may be employed when nitriding with
anhydrous ammonia.
In the single-stage process, a temperature
in the range of about 495 to 525°C is used
and the dissociation rate ranges from 15
to 30%.
This process produces a brittle nitrogen-rich
layer known as the white nitride layer at
the surface of the nitrided case.
The double-stage process, known also as
the Floe process, has the advantage of
reducing the thickness of the white nitrided
layer.
The first stage of the double-stage process
is, except for time, a duplication of the
single-stage process.
The second stage may proceed at the
nitriding temperature employed for the first
stage or the temperature may be
increased to from 550 to 565°C;
however, at either temperature, the rate of
dissociation in the second stage is
increased to 65 to 80% (preferably 75 to
80%).
Generally, an external ammonia dissociator
is necessary for obtaining the required
higher second-stage dissociation.
The principal purpose of double-stage
nitriding is to reduce the depth of the white
layer produced on the surface of the case.
Except for a reduction in the amount of
ammonia consumed per hour, there is no
advantage in using the double-stage
process unless the amount of white layer
produced in single-stage nitriding cannot
be tolerated on the finished part or unless
the amount of finishing required after
nitriding is substantially reduced.
To summarize, the use of a higher
temperature during the second stage:
Lowers the case hardness
Increases the case depth
May lower the core hardness depending on
the prior tempering temperature and the
total nitriding cycle time
May lower the apparent effective case depth
because of the loss of core hardness
depending on how effective case depth is
defined.
Operating Procedures.
After hardening and tempering and before
nitriding, parts should be thoroughly
cleaned.
Most parts can be successfully nitrided
immediately after vapor degreasing.
Bright Nitriding
Bright nitriding is a modified form of gas
nitriding employing ammonia and
hydrogen gases.
Atmosphere gas is continually withdrawn
from the nitriding furnace and passed
through a temperature-controlled scrubber
containing a water solution of sodium
hydroxide (NaOH).
Trace amounts of hydrogen cyanide (HCN)
formed in the nitriding furnaces are
removed in the scrubber thus improving
the rate of nitriding.
The scrubber also establishes a predetermined
moisture content in the nitriding atmosphere
reducing the rate of cyanide formation and
inhibiting the cracking of ammonia to molecular
nitrogen and hydrogen.
By this technique control over the nitrogen activity
of the furnace atmosphere is enhanced and
nitrided parts can be produced with little or no
white layer at the surface.
If present, the white layer will be composed of only
the more ductile Fe4N (gamma prime) phase.
Pack Nitriding
Pack nitriding is a process analogous to
pack carburizing.
It employs certain nitrogen-bearing organic
compounds as a source of nitrogen. Upon
heating, the compounds used in the
process form reaction products that are
relatively stable at temperatures up to
570°C.
Slow decomposition of the reaction products
at the nitriding temperature provides a
source of nitrogen.
Nitriding times of 2 to 16 h can be employed.
Pans are packed in glass ceramic or
aluminum containers with the nitriding
compound, which is often dispersed in an
inert packing media.
Ion (or Plasma) Nitriding
Since the mid-1960s, nitriding equipment
utilizing the glow-discharge phenomenon
has been commercially available. Initially
termed glow-discharge nitriding, the process
is now generally known as ion, or plasma,
nitriding.
The term plasma nitriding is gaining
acceptance.
Ion nitriding is an extension of conventional
nitriding processes using plasma-
discharge physics.
In vacuum, high-voltage electrical energy is
used to form a plasma, through which
nitrogen ions are accelerated to impinge
on the workpiece.
This ion bombardment heats the workpiece,
cleans the surface, and provides active
nitrogen.
Metallurgically versatile, the process provides
excellent dimensional control and retention
of surface finish.
Ion nitriding can be conducted at
temperatures lower than those
conventionally employed.
Control of white-layer composition and
thickness enhances fatigue properties.
The span of ion-nitriding applications includes
conventional ammonia- gas nitriding, short-
cycle nitriding in salt bath or gas, and the
nitriding of stainless steels.
Ion nitriding lends itself to total process
automation, ensuring repetitive
metallurgical results.
The absence of pollution and insignificant
gas consumption are important economic
and public policy factors.
Moreover, selective nitriding accomplished
by simple masking techniques may yield
significant economies.
Comparison of Ion Nitriding and
Ammonia-Gas Nitriding
Ammonia-gas nitriding produces a
compound zone that is a mixture of both
epsilon and gamma-prime structures.
High internal stresses result from
differences in volume growth associated
with the formation of each phase.
The interfaces between the two crystal
structures are weak.
Thicker compound zones, formed by
ammonia-gas nitriding, limit
accommodation of the internal stresses
resulting from the mixed structure.
Under cyclic loading, cracks in the compound
zone can serve as initiation points for the
propagation of fatigue cracks.
The single-phase gamma-prime compound
zone, which is thin and more ductile,
exhibits superior fatigue properties.
Reducing the thickness of the ion-nitrided
compound zone further improves fatigue
performance.
Maximization occurs at the limiting
condition, where compound zone depth
equals zero.
Case Hardness. The bulk of the thickness
of the nitride case is the diffusion zone
where fine iron/alloy nitride precipitates
impart increased hardness and strength.
Compressive stresses are also developed,
as in other nitriding processes.
.
Hardness profiles resulting from ion nitriding
are similar to ammonia-gas nitriding but
near-surface hardness may be greater
with ion nitriding, a result of lower
processing temperature
Advantages and Disadvantages of Ion
Nitriding.
Ion nitriding achieves repetitive metallurgical
results and complete control of the nitrided
layers.
This control results in superior fatigue
performance, wear resistance, and hard layer
ductility.
Moreover, the process ensures high dimensional
stability, eliminates secondary operations, offers
low operating-temperature capability and
produces parts that retain surface finish.
Among operating benefits are:
Total absence of pollution
Efficient use of gas and electrical energy
Total process automation
Selective nitriding by simple masking
techniques
Process span that encompasses all sub-
critical nitriding
Reduced nitriding time
The limitations of ion nitriding include high
capital cost, need for precision fixturing
with electrical connections, long
processing times compared to other short-
cycle nitrocarburizing processes, and lack
of feasibility of liquid quenching for carbon
steels.

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