PLASMA NITRIDING PROCESS

1. Introduction

Plasma nitriding, known also as ion nitriding is a form of case hardening process. It is an
extension of conventional nitriding process, utilizing plasma discharge physic to diffuse nitrogen
into the surface of a ferrous alloy.

Plasma nitriding can be further branched out into plasma nitrocarburising. In this process, carbon
together with nitrogen was introduced into the metal surface. The harden case, which is the
nitriding layer is commonly known as ‘diffused case’ or ‘diffusion zone’.

1.1 Advantages of case hardening

Less distortion compared to through hardening steel

Fatigue properties of a part can be controlled and frequently improved
Relatively inexpensive steel can be given wear-resisting properties which would be
normally attained through the use of more highly alloyed and more expensive steels
Hardening of the surface of steels which cannot be normally capable of being hardened to
a high degree by altering the surface composition
Combination of case and core properties can be attained that are not possible with
conventional hardening treatment
Scaling and decarburisation are minimized during surface hardening, offering advantages
in producing machined parts
Can be applied to very large parts, which due to very large mass or because of danger of
cracking would be impractical to harden, by conventional heating and quenching.
Selected area can be hardened on any sized place that are difficult with conventional
heating and quenching
High surface hardness, improve resistance to wear and galling, improve fatigue life,
improve corrosion resistance (stainless steel is an exception)

1.2 Types of case hardening methods:

Carburizing
Carbonitriding
Nitriding (Gas nitriding, liquid nitriding, plasma nitriding)
Nitrocarburizing
Boriding
Sulfurizing
Sulfonitrocarburizing
Oxidation
Induction (Flame, magnetic, shell, electron-beam, laser)
Plating
Sprayed metal coating

1.3 Advantages for utilizing plasma nitriding

 Ability to automate the system which gives good reproducibility of results
Shorter cycle time
No environmental hazard
Improve control of case depth
Ability to select the compound layer type to suit the required usage
Good friction, wear, and fatigue properties
High hardness of the treated surface
Flexibility to nitride stainless steels, titanium alloys
Possibility to lower nitriding temperature and to limit distortion

1.4 Process Parameters

Temperature (400-600°C)
Pressure (0.5 – 7 mbars)
Gas composition (Ammonia, Nitrogen, Methane Hydrogen and Argon)
Time (4 - 30 hrs depending on case depth)

Additional process parameters are

Voltage
Current intensity
Pulse duration
Pulse pause frequency
Pulse pause duration

2. Diffusion

Plasma (ionized gas) is the fourth material state. It is a very reactive medium, which contains
ions, very energetic neutral particles, as a result of dissociation (separation) of gas molecules in
an electric field. The glow layer surrounding the job part is formed by these positive ions.

Plasma nitriding is achieved using a D.C glow discharge technology, whereby the nitrogen gas
inside the furnace is converted into nitrogen ions and absorbed by the metal. Molecular nitrogen
is first broken into atomic nitrogen through direct plasma dissociation.

N2 + e- → N + N + e-

Atomic nitrogen is then further converted into nitrogen ion through plasma ionization

N + e- → N+ + 2e-

The nitrogen ion, N+, will then diffuse into the metal surface as finely dispersed nitrides,
imparting high hardness to the surface. Thus, case hardening is achieved. Fig.1 shows a
schematic of the plasma nitriding process. During the plasma nitriding process, the job part and
the cathode inside the furnace will be emitting a purple glow. This is because voltages had
dropped sharply at these regions. This provided a large amount of discharged energy, which
causes the cathode and job part to glow. Fig.2 shows a job part undergoing plasma nitriding
treatment.

To put it simply, plasma nitriding utilizes a Direct Current electricity source to break up nitrogen
gas (N2) into nitrogen ion (N+). This nitrogen ion is then absorbed by the metal surface to
harden it.

3. Typical plasma nitriding process

A typical plasma nitriding process is shown in Fig.3 and the processing parameters are detailed
in Table 1.
4. Nitrided layers

There are three types of nitriding layer that could be formed during plasma nitriding treatment
are featured in Fig.4. The details are summarized in Tables 2 and 3.
 DIMENSIONAL STABILITY OF TOOLS & DIES/MOULDS
Dimensional stability of dies/moulds and tools in service is rising in importance with the technology advancement requiring high
level of precision. Attainment of adequate dimensional stability in high precision dies and tools is often a difficult problem
because such factors as material variation, design, machining, heat treatment and stamping process impose practical limitations
on controlling dimensional stability since dimensional change occurs in all tools and dies made of high alloy tool steels. The
harmful dimensional change could result in oversize of a finished workpiece or even catastrophic failure.

Why does the dimensional change occur

Dimensional change of tool steels is affected mainly by the level of retained austenite but not all. It is also influenced by
the internal stress, transformation of retained austenite and martensite decomposition in parts. Tool steels, especially
having high carbon and high chromium contents, can have high amount of retained austenite after heat treatment.

Retained austenite

Retained austenite is a specific crystalline form of iron and steel, which is soft and tough. It forms due to a combination of
variables including high carbon and alloy content, long austenitizing time or high temperature, discontinuing the quench process
too soon, or other factors in the process may cause the martensite start temperature (Ms) to become depressed to below room
temperature.

As steel is heated up and down through the different phase ranges, it’s crystalline structure shifts back and forth from one type of
crystal to another. In steel that is heated to austenite and cooled down very quickly, the crystals don’t have the time they need to
shift from austenite into ferrite. Rapid cooling results in a new crystalline form that is called martensite. In high-carbon steels,
martensite has a greater volume than both austenite and ferrite. Martensite is created in a special reaction that occurs during rapid
cooling and begins at a relatively low temperature specific to the chemistry of the steel. For AISI D2 tool steel, Ms is around 120
degree C and for typical case-carburized bearing steels this temperature will be 260 degree C. Fig.1 shows the Time-
Temperature-Transformation (TTT) diagram for a D2 equivalent steel, indicating Ms. As the steel cools below Ms, martensite
begins to form. As the temperature decreases, the amount of martensite in the steel will increase until a temperature is reached
where practically all of the available austenite is transformed into martensite. This is known as the martensitestop temperature.
Typically, the martensite stop temperature is impracticably low (usually well below 0 degrees C). Since the martensite stop
temperature is not achieved during quenching, some of the austenite in the parts remains untransformed. This austenite, which is
left over from when the steel was hot, is now mingled with the newly formed martensitic structure. Since this austenite is
"retained" from the heat treating process, it is commonly referred to as retained austenite.

Depending upon the steel chemistry and the specific heat treatment, the retained austenite level can vary from over 50% of the
structure to nearly zero. Retained austenite is metastable. This means that when given the opportunity, it has a characteristic
tendency to change from austenite into martensite. This metastability is an important characteristic of retained austenite. Its
transformation can result in a corresponding expansion in volume.

The net result on volume change of a workpiece during usage is a combined effect of the considerable expansion due to
transformation of retained austenite and the slight shrinkage arisen from decomposition of the newly formed martensite. These
two changes take place in addition to any thermal expansion or contraction that is taking place. They can sometimes lead to
unexpected growth in service, causing loss of accuracy.
 Fig.1 Time-Temperature-Transformation diagram (D2 equivalent steel)

Corrective measures
Fig.2 shows the chart of retained austenite against the tempering temperature for AISI D2 equivalent, indicating a 10% of
austenite will be retained when tempering at 475°C and around 8% of retained austenite will be expected under the
tempering temperature of 500°C, resulting in volumetric changes of 0.4% and 0.32% respectively. It is obvious that the
8% level of retained austenite is still too high for the control of dimensional stability of our parts.

With cryogenic (subzero) treatment, the amount of retained austenite can be

remarkably reduced after just heat treating depending on the material and control of
specifications. Subzero treatment is useful to improve the dimensional stability and
wear properties by eliminating retained austenite and untempered martensite, but it
increases the likelihood of cracking. Alloys with greater than 0.4% carbon require
subzero treatment to finish martensite transformation. For D2 steel, martensite finish
temperature Mf (a temperature at which the transformation of martensite is essentially
complete) lies between -80ºC and -110ºC. At the temperature down to -100ºC,
retained austenite in the as-quenched microstructure transforms to martensite,
resulting in an increase in hardness and a reduction in toughness. In meanwhile, high
stresses were arisen as a result of temperature change and phase change. It is very
important to ensure that the die plate design will tolerate immediate cold treating
rather than immediate tempering for this type of high carbon/high alloy steels. Design
features such as sharp corners and abrupt changes in section should be minimized.
 Fig.2 Retained austenite vs tempering temperature
It is advisable to employ multiple tempering in conjunction with subzero treatment for the complicated parts, but subzero
treatment requires the grade of steel and the product design to tolerate immediate cold treating after quenching without cracking.

Experimental results
An investigation into dimensional control of the parts made of various grades of D2 equivalent steels was carried out to identify
the materials response and optimize heat treating processes and parameters. The results showed that for the good dimensional
stability, the retained austenite shall be below 4%. The amount of retained austenite can be remarkably reduced to less than 4%
against 10% by using a combination of two tempers and one subzero processes. Two tempers at a temperature between 450 and
525°C for a certain material may result in a hardness level of around 58 HRc in case of gas quenching. The harness of 58 – 60
HRc can be achieved by oil quenching but the risk of distortion and cracking will be higher.