Principles of Gas Nitriding (Part 2)

by Daniel H. Herring
May 3, 2011


Editors note: This is the third of a four-part
presentation, including an online-exclusive article in April. In an effort
to establish a logical order, we will label figures consecutively as they
appear, including the online content. Consequently, the numbering of
some figures may appear to be missing, depending on your starting
point.



Nitriding is a case-hardening process in which nitrogen is introduced
into the surface of a ferrous alloy such as steel by holding the metal
at a temperature below that at which the crystal structure begins to
transform to austenite on heating (Ac
1
) as defined by the Iron-Carbon
Phase Diagram.



Fig. 14. Dissociation of ammonia and nitrogen
pickup in steel during gas nitriding[4]

Gas Nitriding Reactions
Gas nitriding is typically done using ammonia with
or without dilution of the atmosphere with dissociated ammonia or
nitrogen (or nitrogen/hydrogen) in the temperature range of 925-
1050F (500-565C). Ammonia (NH
3
) is allowed to flow over the
parts to be hardened.



Fig. 15. Nitriding surface and subsurface reactions[5]

Due to the temperature and the catalytic effect of the steel surface,
the ammonia dissociates into atomic nitrogen and hydrogen in
accordance with equation 1:

2NH
3
2N + 6 H (1)

This is immediately followed by atomic nitrogen combining to form
molecular nitrogen per equation 2:

2N + 6 H N
2
+ 3 H
2
(2)

During the period in which this nitrogen passes through the atomic
state, it is capable of being absorbed into the steel (Fig. 14).

So, the entire reaction equation 3, Figure 15 becomes:

2NH
3
N
2
+ 3 H
2
(3)


Gas Nitriding Activity
In accordance with the laws governing diffusion, the degree of
nitrogen penetration is governed by the temperature and the amount
of nitrogen that can penetrate and diffuse into and away from the
outer layer of the steel.



Fig. 16. Schematic representation of ammonia dissociation and
nitrogen absorption[5]

In gas nitriding, the nitrogen activity is controlled by the degree of
dissociation and the flow rate of the gas (Fig. 16). The nitrogen is
supplied by the dissociation of ammonia at the steel surface in
accordance with equation 4, a modified form of equation 1.

NH
3
[N] + 3/2 H (4)

By comparison with gas carburizing, the nitriding atmosphere is not
in equilibrium since the flow rate of ammonia is too high to allow
equilibrium to be achieved.

The amount of ammonia present in the outlet gas is a measure of the
degree of dissociation. The higher the flow rates of ammonia, the
higher the ammonia percentage in the exiting gas stream and the
lower the degree of dissociation. However, a greater percentage of
ammonia is present at the surface.

Equation 5 provides an explanation of the nitrogen activity in which
the activity constant (a
N
) is directly proportional to the degree of
ammonia dissociation and the flow rate.

a
N
a v (5)

where a
N
is the activity of atomic nitrogen
a is the degree of dissociation
v is the ammonia flow rate

Consequently, the nitrogen activity is a function of the number of
ammonia molecules dissociated at the steel surface per unit of time.
At constant pressure and temperature, the degree of dissociation is
reduced as the flow rate increases, but the product (a v) increases
and so does aN.

Thus, the nitrogen potential (KN) derived from equation 4 can be
expressed as:

K
N
= pNH
3
/ (pH
2
)
3/2
(6)

The amount of white layer can be controlled by minimizing the
nitriding potential. AMS 2759/10 (Automated Gaseous Nitriding
Controlled by Nitriding Potential) indicates nitriding potential values
(Table 5) for the various classes of white layer.

Nitrogen potential is also referred to as the
nitriding parameter. At a constant temperature,
the nitrogen activity, and consequently the nitrogen content, at the
surface of the nitrided surface layer are determined by the nitriding
potential. The various phases formed are expressed in the Lehrer
Diagram (Fig. 17).





Fig. 17. Lehrer relationship between nitriding potential and the phase
formed within the compound layer[4]

It is also important to guarantee that there is an adequate amount of
nitrogen available during the process to harden the parts to
specification. If there is not enough nitrogen available, the
consequence will be low case depths and hardness, with related
reductions in physical characteristics.

On the other hand, too much nitrogen at the part surface will result in
formation of a brittle and excessively thick white layer, resulting in
embrittlement of the nitrided case.

One of the keys to successful nitriding is controlling the percentage of
ammonia available per square area of (work) surface that will supply
atomic (nascent) nitrogen at the surface. It is important to realize
that nitriding is due only to the dissociation of ammonia at the part
surface, not due to the presence of molecular nitrogen (N
2
) or
dissociated ammonia (N
2
+ 3 H
2
).

The nitriding reaction (Eq. 1, 2) will ultimately go to completion, but
this is a very slow reaction. Empirical work has resulted in a rule of
thumb that says if the furnace atmosphere is changed four times
every hour, the amount of ammonia that is dissociated is 2510%.
An approximate relationship between ammonia flow rate and
percentage dissociation exists (Fig. 18). The general shape of the
curve will vary as a function of the furnace style, workload size and
surface area.



Fig. 18. Percentage dissociation as a function of furnace volume[6]

Hence, the best control method for the process is one that measures
and controls the percentage of ammonia. When we talk about a 30%
dissociation rate, we normally refer to a concentration of 70%
ammonia and 30% dissociated ammonia in the exhaust gas. In
reality, due to the volume change involved, only 82.3% is ammonia
while 17.7% is dissociated ammonia.

To nitride successfully, an adequate supply of atomic nitrogen must
be available at the part surface. Thus, in gas nitriding, it becomes
very important to circulate the ammonia in such a way as to
constantly resupply the active nitrogen on all areas to be hardened.


Gas Nitriding Cycles and Case-Depth Determination
Two types of nitriding processes are used: the
single-stage process and two-stage or Floe (pronounced flow)
process named after its inventor, Dr. Carl Floe.

Case-depth and case-hardness properties vary not only with the
duration and type of nitriding being performed but also with steel
composition, prior structure and core hardness. Case depths are
typically 0.008-0.025 inches (0.20-0.65 mm) and take 10-80 hours
to produce.

Single-Stage Nitriding Process
In the single-stage process, a temperature range of 925-975F (500-
525C) is typical. The dissociation rate of ammonia into nitrogen and
hydrogen ranges from 15-30%. The process produces a brittle,
nitrogen-rich layer known as the white layer (compound zone) at
the surface and is comprised of various iron nitrides (FeN, Fe
4
N,
Fe
16
N
2
).

Two-Stage Floe Process (U.S. Patent No. 2,437,249)
The two-stage process (Table 7 and 8) was developed to reduce the
amount of white layer formed by single-stage nitriding. The first
stage is, except for time, the same as that of the single-stage
process. In the second stage, however, the addition of a dilutant gas
(dissociated ammonia or nitrogen) increases the percent dissociation
to around 65-85%. The temperature is typically raised to 1025-
1075F (550-575C), and the result is the reduction of the depth of
the white layer, producing a deeper case of slightly lower hardness. If
the two-stage method is used, it is frequently possible to meet
dimensional tolerances without any final grinding operation.



Dissociated ammonia is generally required for high second-stage
dissociation (otherwise erratic control may result), and it is commonly
used as a dilutant (to change the percentage per square area that
NH
3
molecules are exposed to). In some cases, nitrogen is used.
However, white-layer control and porosity can be affected. Loading
arrangement and the use of a furnace circulating fan are very
important so that a high dissociation level may be achieved. The
nitrogen potential varies with the composition of the gas mixture that
is being sent into the furnace.


Crystal (Lattice) Structure
Ferrite, or alpha () iron, which is a body-centered
cubic (bcc) in crystal structure (Fig. 19), dissolves 0.001% nitrogen
at room temperature and 0.115% nitrogen at 1095F (590C).
Gamma prime (), or Fe4N, has a face-centered cubic (fcc) crystal
structure (Fig. 20) and dissolves 5.7-6.1% nitrogen. Fe
2
N and Fe
3
N
are called epsilon (), which has a hexagonal closed packed (hcp)
crystal structure and dissolves between 8.0% and 11.0% nitrogen.


Fig. 19. Body-centered cubic (bcc) crystal structure; Fig. 20. Face-
centered cubic (fcc) crystal structure

Control of the Nitriding Process
There are several methods of controlling the
nitriding process based on analysis of the
percentage of dissociation.

One method involves the use of an ammonia analyzer (Fig. 21),
which is tied into ammonia and dissociated ammonia (or nitrogen)
flowmeters (for use during the second stage of nitriding). Based on
the output from the ammonia analyzer, the process can be accurately
controlled.


Fig. 21. Ammonia control system (courtesy of Super Systems Inc.)

Another method used to measure the degree of dissociation is an
analysis of the amount of hydrogen in the exhaust gas (Fig. 22).
From equation 4 we see:


1 volume NH
3
1/2 volume
N
4
+ 3/2 volume H
4
(7)


Fig. 22. Anatomy of a hydrogen sensor[5]


For example, if the measured volume percentage of hydrogen is
30%, the volume percentage nitrogen is 10% (30/3), and the
remaining ammonia volume is 60% (100% 30% 10%). Given the
original volume of ammonia supplied () into the furnace chamber,
equation 8 allows us to calculate the degree of dissociation () in the
exhaust gas.

1 /100 = (1 /100)
[(1 /100 + 2(/100)] (8)
Instruments for in-situ measurement of the nitriding potential via the
hydrogen content (and other methods) are commercially available
and under development. These types of continuous-measurement
devices are especially important for the short cycles up to 20 hours.

Alternately, a manual method for the control of the nitriding
atmosphere involves the use of a dissociation pipette or burette (Fig.
23).



Fig. 23. Manual measurement of percentage dissociation[8]


Ammonia is completely soluble in water. When water is introduced
into the dissociation pipette, any ammonia present dissolves,
instantly forming ammonia hydroxide (NH
4
OH). Water continues to
enter until it occupies a volume equivalent to that previously occupied
by the ammonia. The remainder of the exhaust gas, being insoluble
in water, collects at the top of the pipette. The height of the water
level is read directly from the scale of graduations, and this reading
indicates the percentage of non-water-soluble hydrogen-nitrogen gas
in the sample.

This reading, although not completely accurate, is the degree of
dissociation. It should be noted that the dissociation of ammonia
involves a twofold increase in volume as shown in equation 3. IH










References available in Aprils online exclusive

For more information: Dan Herring is president of THE HERRING GROUP
Inc., P.O. Box 884 Elmhurst, IL 60126; tel: 630-834-3017; fax: 630-
834-3117; e-mail: heattreatdoctor@industrialheating.com; web:
www.heat-treat-doctor.com. Dans Heat Treat Doctor columns appear
monthly in Industrial Heating, and he is also a research associate
professor at the Illinois Institute of Technology/Thermal Processing
Technology Center.







Daniel H. Herring