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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. The nitriding
temperature for all steels is between 495 and 565°C (925 and 1050°F).
Jig and Fixture
Jigs and Fixture Design
Principal reasons for nitriding are:

To obtain high surface hardness

To increase wear resistance and antigalling properties
Materials treatment
To improve fatigue life
Annealing metal
To improve corrosion resistance
Case hardening
To obtain a surface that is resistant to the softening effect of heat at
Density
temperatures up to the nitriding temperature.
Electrical Conductivity
Because of the absence of a quenching requirement, with attendant volume
heat treatment process
changes, and the comparatively low temperatures employed in this process,
heat treating steel
nitriding of steels produces less distortion and deformation than either
Thermal Expansion
carburizing or conventional hardening.

Nitridable Steels
Of the alloying elements commonly used in commercial steels, aluminum,
Material chromium, vanadium, tungsten, and molybdenum are beneficial in nitriding
Aluminum because they form nitrides that are stable at nitriding temperatures.
Alu comparison table Molybdenum, in addition to its contribution as a nitride former, also reduces the
Aluminum Tempering risk of embrittlement at nitriding temperatures. Other alloying elements, such
Carbon Steel as nickel, copper, silicon, and manganese, have little, if any, effect on minding
Copper alloy characteristics.
Low alloys Although at suitable temperatures all steels are capable of forming iron nitrides
Material nations & in the presence of nascent nitrogen, the nitriding results are more favorable in
Equivalents those steels that contain one or more of the major nitride-forming alloying
Nickel alloys elements. Because aluminum is the strongest nitride former of the common
Stainless Steel alloying elements, aluminum-containing steels (0.85 to 1.50% Al) yield the best
Stainless Steel nitriding results in terms of total alloy content. Chromium-containing steels can
comparison table approximate these results if their chromium content is high enough. Unalloyed
Tool Steel equivalent carbon steels are not well suited to gas nitriding because they form an
Tungsten Carbide extremely brittle case that spalls readily, and the hardness increase in the
Wrought stainless Steel diffusion zone is small.

The following steels can be gas nitrided for specific applications:

Manufacturing Aluminum-containing low-alloy steels 7140 (Nitralloy G, 135M, N, EZ)

Conversion Charts Medium-carbon, chromium-containing low-alloy steels of the 4100, 4300, 5100,
Drill Angle 6100, 8600, 8700, and 9800 series
Drill size Hot-work die steels containing 5% chromium such as H11, H12, and H13
Energy Efficiency Low-carbon, chromium-containing low-alloy steels of the 3300, 8600 and 9300
Math Area series
Machining Cutting Time Air-hardening tool steels such as A-2, A-6, D-2, D-3 and S-7
Technical articles High-speed tool steels such as M-2 and M-4
Work Done Nitronic stainless steels such as 30, 40,50 and 60
Velocity Ferritic and martensitic stainless steels of the 400 and 500 series

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Austenitic stainless steels of the 200 and 300 series

Precipitation-hardening stainless steels such as 13-8 PH, 15-5 PH, 17-4 PH,
Geometric 17-7 PH, A-286, AM350 and AM355.
Tolerancing Aluminum-containing steels produce a nitrided case of very high hardness and
GDT excellent wear resistance. However, the nitrided case also has low ductility,
Tolerance chart ISO and this limitation should be carefully considered in the selection of aluminum-
Surface Roughness containing steels. In contrast, low-alloy chromium-containing steels provide a
Surface Texture nitrided case with considerably more ductility but with lower hardness. Tool
steels, such as H11 and D2, yield consistently high case hardness with
exceptionally high core strength.

Nitriding Process
Quality Control Prior Heat Treatment. All hardenable steels must be hardened and tempered
AQL before being nitrided. The tempering temperature must be high enough to
Process Capability CPK guarantee structural stability at the nitriding temperature: the minimum
Sampling plan tempering temperature is usually at least 30°C (50°F) higher than the
Level I, II, III maximum temperature to be used in nitriding.
In certain alloys, such as series 4100 and 4300 steels, hardness of the nitrided
case is modified appreciable by core hardness: that is, a decrease in core
Engineering Plastic hardness results in a decrease in case hardness. Consequently, in order to
Machining of plastic obtain maximum case hardness, these steels are usually provided with
Selection of plastic maximum core hardness by being tempered at the minimum allowable
tempering temperature.

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 (925 to
975°F) 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 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 (1025 to 1050°F): 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.

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 pans can be successfully nitrided immediately after vapor
degreasing. However, some machine-finishing processes such as buffing,
finish grinding, lapping, and burnishing may produce surfaces that retard
nitriding and result in uneven case depth and distortion. There are several
methods by which the surfaces of parts finished by such methods may be
successfully conditioned before nitriding.
One method consists of vapor degreasing pans and then abrasive cleaning
them with aluminum oxide grit or other abrasives such as garnet, or silicon
carbide, immediately prior to nitriding. Any residual grit must be brushed off
before pans are loaded into the furnace. Pans should be handled with clean
gloves.

A second method consists of preoxidizing the pans in an air atmosphere at

approximately 330°C (625°F). This may be done as a separate operation, or it
may be incorporated as part of the healing portion of the nitriding cycle if
suitable precautions are taken.

Furnace Purging. After loading and sealing the furnace at the start of the
nitriding cycle, it is necessary to purge the air from the retort before the furnace
is heated to a temperature above 150°C (300°F). This prevents oxidation of
parts and furnace components, and, when ammonia is used as the purging
atmosphere, avoids production of a potentially explosive mixture. Nitrogen is
preferred in place of ammonia for purging, but the same precautions should be

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taken to avoid oxidation of parts, except when preoxidation is intentionally

included as part of the cycle.

A typical purging cycle using anhydrous ammonia follows:

Close furnace and start flow of anhydrous ammonia gas at as fast a flow rate
as is practical with first step.
Set furnace temperature control at 150°C (300°F) simultaneously. Heat furnace
to this temperature but do not exceed.
When the furnace has been purged to the degree that 10% or less air and 90%
or more ammonia are present in the retort, the furnace may be heated to the
nitriding temperature.
It is not feasible to incorporate preoxidation as part of the cycle unless nitrogen
is available as a purging medium at the end of the 320°C (625°F) oxidizing
stage. Under no circumstances should ammonia be introduced into a furnace
containing air at 330°C (625°F) because of the explosion hazard.
Purging is employed also at the conclusion of the nitriding cycle when the
furnace is cooled from the nitriding temperature. It is common practice to
remove the ammonia remaining in the retort with nitrogen to reduce the amount
of ammonia that would otherwise be released into the immediate area when
the load is removed. Dilution of the ammonia lessens the discomfort to
employees working near the furnace. The introduction of nitrogen into the retort
can be delayed until the nitrided parts have cooled to below 150°C (300°F).

Nitrogen versus Ammonia for Purging. Advantages of nitrogen as a purging

gas include its safety, ease of handling, and ease of control. The use of
nitrogen, however, requires additional equipment, including piping.

Ammonia requires no additional equipment and is relatively safe when properly

handled; mixtures of 15 to 25% ammonia in air, however, are explosive if
ignited by a spark.

Dissociation Rates. The nitriding process is based on the affinity of nascent

nitrogen for iron and certain other .metallic elements. Nascent nitrogen is
produced by the dissociation of gaseous ammonia when it contacts hot steel
parts.

Although various rates of dissociation can be used successfully in nitriding, it is

important that the nitriding cycle begin with a dissociation rate of about 15 to
35% and that this rate be maintained for 4 to 10 h. Depending on the duration
of the total cycle, temperature should be maintained at about 525°C (975°F).

Typically ammonia is supplied at a flow rate to achieve a minimum of four (4)

atmosphere changes in the retort per hour. This initial cycle develops a shallow
white layer from which diffusion of nitrogen into the main case structure
proceeds.

When nitriding with dissociation rate of 15 to 35%, it is normal to control this

rate entirely by the flow rate of ammonia. At a dissociation rate of 75 to 80%,
however, it is necessary to introduce completely dissociated ammonia.

Distortion and Dimensional Changes. Distortion in nitriding may result

from:

Relief of residual stresses from prior operations such as welding, hardening,

machining, and so forth
Stress introduced during nitriding due to inadequate support in the furnace, or
too rapid or nonuniform heating or cooling.
Stress is introduced by the increase in volume that occurs in the case. This
change causes a stretching of the core, which results in tensile stresses that
are balanced by compressive stresses in the case after the parts have cooled
to room temperature. The magnitude of the permanent set in the core and case
is affected by yield strength of the material, thickness of the case, and by the
amount and nature of the nitrides formed.
Stabilizing Treatment. In nitrided pans, there is a balance between
compressive stresses in the case and tensile stresses in the core. If this
balance is upset by grinding off a part of the case, slow dimensional changes
may occur as the stresses approach equilibrium. To prevent these changes,
nitrided pans are first ground almost to the final dimensions, then heated to
565°C (1050°F) for 1 h. and finally finish ground or lapped. Parts nitrided and
not ground after nitriding have excellent dimensional stability.

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Finishing Costs. The amount of distortion resulting from nitriding is small

compared to that resulting from other case-hardening processes, which involve
quenching to form martensite. Consequently, the increase; cost of the nitriding
operation and of steel suitable for nitriding often can be offset by the savings
resulting from finishing to size prior to nitriding.

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