Nitriding

Nitriding process is a chemical-heat treatment consists in introducing nitrogen into metallic

materials to improve their surface hardness, fatigue life, wear and corrosion resistance. In
engineering the depth of nitriding is generally about 0.3-0.4mm; this thin harder surface layer
may cause surface layer spall from matrix because of high-applied load or great stress gradient in
surface layer. During nitriding, two different structures are formed from surface to core, known
as the compound layer and diffusion region. [14]

Nitriding results in a considerable increase of hardness and the formation of compressive

residual stress. [14]

Nitriding is a ferritic thermochemical method of diffusing nascent nitrogen into the surface of
steels and cast irons. [15]

Nitriding often is applied to low-alloy steels to “harden” the steel and improve corrosion
resistance. [15]

It was used in applications that required: high torque, high wear resistance, abrasive wear
resistance, corrosion resistance, high surface compressive strength. [15]

Several factors helped nitriding to gain acceptance:

- Compared to other case hardening methods, nitriding is a relatively low-temperature process.

- Nitriding is relatively easy to control in terms of process parameters.

- It produces enhanced corrosion resistance in low-alloy and low-carbon steels.

-Core hardness is not significantly affected, due to prehardening and tempering.

- No quenching is required, thus reducing distortion. [15]

Nitriding is a relatively low-temperature process and produces a shallower case than does
carburizing. Most importantly, no quench is involved.[15]

The amount of growth is influenced by time,Temperature, Steel chemistry, Gas flow, Gas
dissociation, Steel surface condition prior to the nitriding process, Surface metallurgy
(compound layer thickness), and Total case depth [15]
The higher the temperature, the faster and deeper the nitrogen diffusion.[15]

The compound layer can have greatly improved wear and corrosion resistance [16].

The hardened diffusion zone is responsible for a considerable enhancement of the fatigue
endurance. [16]

Nitriding minimizes distortion and deformation of the heat treated parts [16].

According to the medium used to provide the nitrogen, the nitriding process can be classified as
gas nitriding, plasma nitriding, pack nitriding, and salt bath nitriding. [16]

Gas nitriding (GN) is a typical thermochemical treatment used to improve the surface hardness,
corrosion property and wear resistance of mechanical components [1–3]. In recent years, GN has
become one of the most widely used surface engineering techniques owing to its simple
operation and excellent applicability to a wide range of steel grades, aswell as the small
dimensional changes of nitrided work pieces. [17]

GN process is mainly dependent on the interface reaction between NH3 gas and the workpiece
surface as well as the effective diffusion of N atoms into the workpieces thus increasing the
driving force of the interface reaction and accelerating internal diffusion are essential
for a rapid GN process. [17]

Up to now, many technologies have been developed to improve GN efficiency, such as the
activated GN by adding ammonia chloride, the surface nanocrystallization pretreatment , as well
as the cathode sputtering pretreatment Although these methods can accelerate GN process to
some degree, they all have to rely on either special pretreatment or higher vacuum conditions
[17]
Gas Nitriding

As described in Chapter 1, the patent for gas nitriding was first applied for by Adolph Machlet
and was for the nitrogenization of iron and steel in an ammonia gas atmosphere diluted by
hydrogen. [15]

Examples of process parameters for gas nitriding include; Furnace Temperature, process
temperature, process control, time, gas flow, gas activity control, process chamber maintenance.
[15]

Controlled nitriding, which is a further development of traditional gasnitriding in which all the
process parameters are computer controlled. [15]

Gas nitriding has a considerable effect for wear resistance. [14]

The surface hardening due to the gas nitriding processes can be associated to complex and
competitive mechanisms like 1) Precipitate dispersion-hardening: hard insoluble nitrogen
precipitates are incorporated into the matrix; 2) Solid solution: nitrogen in solid solution that
creates a Cottrell atmosphere that locks the dislocation; 3) Surface residual stress. [14]

It is possible to obtain the desired compound of hardness, structure and thickness of the
compound layer leading to optimal wear resistance of the 42CrMo4 steel reported here, by
controlling the gas nitriding time. [14]
For example, gas nitriding increases the surface roughness of gray cast iron. Proper identification
of the advantages and disadvantages of these two methods could significantly improve their use.
[13]

The gas-nitriding mechanism using ammonia is less controversial and has been considered as a
catalytic reaction of ammonia with iron which leads to the formation of the active nitrogen atoms
in statu nascendi and their chemisorption according to the reaction [13]

gas nitriding can produce a compound zone (white layer) of practically any thickness by
controlling the nitriding potential using hydrogen or oxygen sensors and modern automatic
methods. Also, gas nitriding can be used for hardening parts having small holes, such as those in
diesel injector plungers, and nitriding the entire surface of any product. [13]

The authors observed that gray cast iron dies become rougher after gas nitriding and require
more finishing than the plasma-nitrided dies, which has a high possibility of being a result of
differences in the nitriding mechanisms of the two methods. [13]

Ammonia molecules in gas nitriding enter all of the confined spaces at first and then generate
active nitrogen atoms during collisions with the solid (walls of the cavities). Therefore, they have
a longer lasting effect, and by penetrating deeply, produce very significant roots of the
compound zone below the surface. Those processes increase specific volume of the near-surface
layer, and by causing local plastic deformation of the material, lead to local bulging of the
surface, thus increasing its roughness. [13]

On the other hand, gas nitriding, because of its ability to penetrate deeply into those materials,
cannot be used easily in such applications. [13]

The process represents one of the most efficient among the various methods of improving the
surface properties of engineering components, especially the parts with complicated shapes
requiring homogeneous hardening of the surface [16].

Gas nitriding is an important thermochemical surface treatment that is used to improve the wear
and corrosion resistance as well as the fatigue endurance of steel parts. [16]
Gas nitriding is a thermochemical surface treatment in which nitrogen is transferred from an
ammonia atmosphere into the surface of steels at temperatures within the ferrite and carbide
phase region. [16]

The successful gas nitriding process control depends on: 1) process parameters selection to meet
the specification, 2) accurate process parameters control during the process. [16]

The gas nitriding process parameters include temperature, time, and the nitriding atmosphere.
[16]

Salt Bath Nitriding

Shortly after the development of gas nitriding, alternative methods of nitriding were sought. One
such method was the use of molten salt as a nitrogen source. The salt bath process uses the
principle of the decomposition of cyanide to cyanate and the liberation of nitrogen within the salt
for diffusion into the steel surface. [15]

A cyanide-based salt, it was discovered, fulfilled the requirements of the process, and salt bath
nitriding began. Salt bath nitriding is in essence the same process as gas nitriding; only the
medium is different. Salt bath nitriding offers extremely good case depth uniformity. Salt Bath
nitriding utilizes the melting of a salt containing a rich nitrogen source. When heat is applied
from either an internal or external source, the salt melts and liberates nitrogen to the steel for
diffusion. When a steel workpiece is introduced into the salt and heated up to a temperature in
the molten salt, similar reactions begin to occur as in gas nitriding; that is, controlled amounts of
nitrogen are released to diffuse into the steel surface. [15]

It required a lower capital investment than gas nitriding. Operating costs also were considerably
lower, making it a cost effective method of nitriding steel. faster processing time. [15]
The advantages of using salt bath nitriding equipment were: relatively low operating cost, low
maintenance, easy operation, requiring a lower skill level, small batch-type furnace generally
used, occupying less floor space, easy startup, easy shutdown, and slightly faster diffusion cycle
times. [15]

The salt, known by ICI as N.S.450, relied on the decomposition of cyanide to cyanate. [15]

In Germany, Degussa developed the two-component process of forming both nitrides and some
carbides in the steel surface (i.e., nitrocarburizing). [15]

Salt bath nitriding can be conducted in either a batch system or a continuous

system. Either equipment system can be electrically or gas heated. [15]

The metallurgical results are the same as with the conventional gas nitriding process: A
compound layer is formed at the steel surface with a diffusion zone area immediately below the
compound layer. The surface compound layer thickness will be determined by the steel
composition. [15]

As with gas nitriding, workpieces must be cleaned prior to salt bath nitriding to prevent any oil,
grease, paint, and so forth from contaminating the bath. In addition, the steel surfaces must be
free of oxides or other contaminants [15].

Salt bath nitriding process is carried out in a molten salt bath.[16]

It can be applied to carbon steels, low-alloy steels, tool steels, stainless steels and cast iron. [16]

The case hardening medium is a nitrogen-bearing salt bath containing cyanides or cyanates. [16]

the dimensional stability of the workpiece can be preserved, thus processing of finished parts is
possible. This implies that it can be used to complement engineering properties developed during
carburizing and carbonitriding. [16]
Plasma Nitriding

GAS IONIZATION is a method of causing a gas to develop an electrical Imbalance [15]

The ion, or plasma, nitriding process, which is based on the familiar chemistry of gas nitriding,
uses a plasma discharge of reaction gases both to heat the steel surface and to supply nitrogen
ions for nitriding. [15]

The plasma technique was first put to use as a metallurgical processing tool by Dr. Wehnheldt, a
German physicist, but he was unable to control it as a nitriding process due to the instability of
the glow discharge. [15]

Today ion nitriding is carried out on virtually all steels and cast irons as well as refractory
metals, aluminum (not yet on a commercial basis), and sintered ferrous materials. [15]

plasma nitriding is considered as a low nitriding potential method, unable to produce a thick
compound zone and plasma nitriding does not penetrate small holes, cavities, etc., and, therefore,
the process can be used for hardening sintered low-density iron parts [13]
By comparison, plasma processing resulted in a significantly lower surface roughness with very
few open microgrooves and cavities in the surface. Data on surface roughness after processing
are shown in Table 2. Rmax for the plasma-nitrided surfaces, although much lower than after gas
nitriding, are still comparatively high for stamping tool applications. [13]

In the as-plasma-treated sample, the compound zone was very uniform and compact without any
significant defects. [13]

During plasma nitriding of materials having a porous surface, such as cast iron, the hardened
layers produced are superior to layers produced by gas nitriding. Plasma-produced layers are
very compact, which promotes a much smoother surface. [13]

In processing products made of gray cast irons, plasma nitriding does not penetrate deep into the
material and, therefore, formation of the nitrided layer is limited to only the surface of the
product. Therefore, plasma nitriding has no nitriding mechanism-limited application
characteristics in processing of any cast or porous materials. [13]

Plasma is formed by high-voltage electrical energy in vacuum. Nitrogen ions are then accelerated
to impinge on the workpiece which is connected as a cathode. The ion bombardment heats the
work piece, cleans the surface and provides the nascent nitrogen for diffusion into the steel
material [16].
Reference:

[13] Influence of nitriding mechanicsms on surface roughness of plasma and gas on surface
roughness of plasma and gas nitrided/ nitrocarburized gray cast iron.

[14] Study of the Effect of Gas Nitriding Time on Microstructure and Wear Resistance of
42CrMo4 Steel

[15] Practical Nitriding and Ferritic Nitrocarburizing

[16] Nitriding – Fundamentals, modeling and process optimization, Mei Yang, 2012

[17] Surface Modification of Magnesium Base Alloys by Gas/ Plasma Nitridation