D EUTSCHE NORM January 1998

Heat treatment of ferrous materials {

Part 4: Nitriding and nitrocarburizing
17022-4

ICS 25.200

Wärmebehandlung von Eisenwerkstoffen – Verfahren der Wärmebehandlung – Teil 4: Nitrieren und

Nitrocarburieren

In keeping with current practice in standards published by the International Organization for Standardization
(ISO), a comma has been used throughout as the decimal marker.

Contents
Page
Foreword . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2 Normative references . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3 Concepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
4 Principle of methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
4.1 Nitriding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
4.2 Nitrocarburizing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
5 Purpose of nitriding and nitrocarburizing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
6 Identification of heat treatment condition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
7 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
7.1 Pretreatment and preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
7.2 Heating to treatment temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
7.3 Nitriding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
7.4 Nitrocarburizing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
7.5 Cooling/quenching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
7.6 Secondary treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
8 Heat treatment media . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
8.1 Nitriding media . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
8.2 Nitrocarburizing media . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
8.3 Cooling and quenching media . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
9 Effects of nitriding and nitrocarburizing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
9.1 Effects on case structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
9.2 Effects on hardness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
9.3 Effects on shape and dimensions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
10 Heat treatment equipment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
10.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
10.2 Equipment for nitriding and nitrocarburizing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
10.3 Equipment for cooling and quenching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
11 Testing nitrided and nitrocarburized products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
12 Straightening . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
13 Designing for heat treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
14 Defects in heat treated products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

Continued on pages 2 to 16.

Translation by DIN-Sprachendienst.
In case of doubt, the German-language original should be consulted as the authoritative text.

© No part of this translation may be reproduced without the prior permission of

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Foreword
This standard has been prepared by Technical Committee Wärmebehandlungstechnik of the Normenausschuss
Werkstofftechnologie (Materials Technology Standards Committee).

1 Scope
This standard describes the heat treatment methods ‘nitriding’ and ‘nitrocarburizing’, especially of products
made of rolled steel, cast steel, or cast iron, or steel powder compacts.

2 Normative references
This standard incorporates, by dated or undated reference, provisions from other publications. These normative
references are cited at the appropriate places in the text, and the titles of the publications are listed below. For
dated references, subsequent amendments to or revisions of any of these publications apply to this standard
only when incorporated in it by amendment or revision. For undated references, the latest edition of the
publication referred to applies.
DIN 6773 Heat treatment of ferrous materials – Heat treated parts, representation and indications
on drawings*)
DIN 17014-3 Heat treatment of ferrous materials – Symbols for heat treatment processes
DIN 17022-1 Heat treatment of ferrous products – Hardening and tempering
DIN 17022-2 Heat treatment of ferrous materials – Heat treatment methods – Hardening and
tempering of tools
DIN 17023 Heat treatment of ferrous metals – Forms – Orders for heat treatment (WBA)
DIN 17052 Heat treatment furnaces – Requirements relating to uniformity of temperature
DIN 17211 Nitriding steels – Technical delivery specifications
DIN 50133 Vickers hardness testing of metallic materials – HV 0,2 to HV 100
DIN 50190-3 Determination of the effective case depth of heat treated parts after nitriding
DIN EN 10052 Vocabulary of heat treatment terms for ferrous products
ISO 4516 : 1980 Metallic and related coatings – Vickers and Knoop microhardness tests
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ISO/DIS 4516 : 1999 Metallic and related coatings – Vickers and Knoop microhardness tests*)

3 Concepts
For the purposes of this standard, the heat treatment terminology given in DIN EN 10052 shall apply.

4 Principle of methods
4.1 Nitriding
Nitrogen is introduced into the surface layer of a ferrous product, the nitrogen source usually being ammonia
under normal atmospheric pressure, although in the case of plasma nitriding the source is nitrogen. The
treatment is carried out at a temperature below the eutectoid temperature of the iron-nitrogen system, preferably
at a temperature between 480 °C and 550 °C, and lasts for several hours to several days. Upon completion of
the treatment, the product is usually cooled in a gaseous medium to room temperature.
If the nitriding medium contains oxygen, the process is called ‘oxynitriding’, while if sulfur is present, it may be
referred to as ‘sulfonitriding’.
Nitriding is primarily used to treat alloyed ferrous products.
4.2 Nitrocarburizing
Here both nitrogen and carbon are introduced into the surface layer of a ferrous product. The treatment medium
is either a salt bath, gas or powder, although plasma can also be used. The treatment is carried out preferably
at a temperature between 570 °C and 580 °C, and lasts for a few minutes to several hours.
Upon completion of the treatment, the product is either cooled in a gaseous medium or quenched in a liquid;
this may be followed by ageing.
If the nitrocarburizing medium contains oxygen, the process is called ‘oxynitrocarburizing’, while if sulfur is
present, it is called ‘sulfidizing’.
Nitrocarburizing is used to treat both alloyed and unalloyed ferrous products.

5 Purpose of nitriding and nitrocarburizing

Nitriding and nitrocarburizing are used to enhance the fatigue strength and corrosion resistance of ferrous
products.**)

*) Currently at draft stage.

**) Translator's note. In English, both nitriding and nitrocarburizing are considered case hardening processes.

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Nitriding is primarily used on alloyed steel – in particular the so-called nitriding steel specified in DIN 17211 –
to create a hard case which will enhance the fatigue strength of the product, as well as its resistance to wear
due to adhesion, abrasion and rolling strain.
With nitrocarburizing, a compound layer rich in both nitrogen and carbon is produced to lower the coefficient
of friction, wear and corrosion resistance.

6 Identification of heat treatment condition

The heat treatment condition shall be indicated on drawings as specified in DIN 6773.
Instructions for performing nitriding or nitrocarburizing shall be formulated using either the ‘WBA’ form specified
in DIN 17023 or in a ‘heat treatment plan (WBP)’. Symbols used to designate the heat treatment method shall
be as specified in DIN 17014-3.

7 Procedure
7.1 Pretreatment and preparation
Products shall be pretreated and prepared to ensure a suitable surface condition, to ensure that residual stresses
do not interfere with the heat treatment process, and to localize the effects of the treatment, if so desired.
7.1.1 Pretreatment
7.1.1.1 Stress relieving
If residual stresses (e.g. resulting from machining) might cause distortion of the product during treatment, it is
recommended that stress relieving be carried out at a temperature that is 30 °C above treatment temperature.

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Any resulting distortion can then be corrected by subsequent machining, although there shall be an allowance
great enough to allow full removal of any unwanted changes to the surface layer (e.g. decarburization).
The stress relief temperature shall be close to, but shall not exceed, the transformation temperature Ac1 of the
material being treated. In the case of quenched and tempered products, this temperature shall be lower than the
tempering temperature in order to maintain strength, and soaking for more than thirty minutes during the heating
phase will not be necessary. Heating and cooling shall be carried out slowly to prevent new residual stresses
from building up.
Cold-worked products should not be stress relieved, but rather normalized, if there is a risk that recrystallization
would result in grain coarsening.
7.1.1.2 Normalizing
Residual stresses in untreated products may be relieved by normalizing, which at the same time alters the
microstructure, thus preventing grain coarsening in critical areas.
Normalizing parameters (temperature and duration, cooling) shall be taken from the steel manufacturer’s
specifications or other documents.
7.1.1.3 Quenching and tempering
It may be necessary to subject the product to quenching and tempering prior to nitriding or nitrocarburizing to
obtain the desired strength. See DIN 17022-1 and DIN 17022-2 regarding the procedure.
The tempering temperature should be about 30 °C above the nitriding/nitrocarburizing temperature. Note that
the tempering temperature and time have an influence on the hardness profile.
To ensure that any changes to the surface layer (e.g. decarburization or oxidation) which occur during quenching
and tempering do not adversely affect subsequent treatment, the product surface should be machined before
further treatment.
It can be expected that nitriding or nitrocarburizing over several hours will result in reduced hardness and
strength in the product’s core, depending on the tempering resistance of the material.
7.1.2 Preparation
Machining or cutting residues (e.g. oxide layers, residues of cooling lubricants, cleaning agents or preservatives)
can greatly impede nitrogen absorption, especially in the case of gas nitriding or nitrocarburizing. Furthermore,
chips, burrs, rust, scale and nonferrous metals can alter the chemical composition of salt baths and thus inhibit
their effect. It is therefore necessary to thoroughly clean or otherwise treat the products prior to nitriding/
nitrocarburizing, depending on the degree of surface impurity and the required quality. The products and their
holders are to be dried after cleaning.
Bolts or screws used to plug bores or threaded holes shall be removed before cleaning. For safety reasons, parts
with sealed hollow spaces are not to be nitrided or nitrocarburized.
7.1.2.1 Cleaning
Products shall be cleaned to remove any surface residues (e.g. cooling lubricants, preservatives, scale, rust,
coloring or fluxing agents), as well as adherent chips, rolling or forging skin. Cleaning methods include washing,
deburring, blasting, pickling and oxidizing.

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7.1.2.1.1 Washing
Normally, products are washed in hot water with suitable cleaning agents. To ensure that the surface is fully
cleaned, it may be necessary to subject the surface to water-blast cleaning or ultrasound cleaning prior to
washing.
After washing, the products shall be thoroughly dried, for when they are placed in the furnace, any moisture on
them can lead to a rise in pressure during the heating phase. In addition, insufficiently dried products can cause
dangerous eruptions in the salt baths when nitrocarburizing.
7.1.2.1.2 Deburring
Burrs caused by machining can be removed by blasting, or chemical or thermal deburring. It should be noted
that thermal deburring processes oxidize the product’s surface, while in chemical processes the material reacts
with the electrolyte, so that in both cases the absorption of nitrogen can be impaired.
When removing adherent chips, the product should be demagnetized.
7.1.2.1.3 Blasting
Dry or wet blasting with suitable cleaning agents can be used to remove burrs, scale, rolling, forging or casting
skin, colorants or flux residues. After blasting, the blasting medium should be completely removed to avoid a
reduction in nitrogen absorption.
7.1.2.1.4 Pickling
It may be necessary to activate the surface of alloyed steel products before nitrogen can be absorbed. Pickling,
particularly before gas nitriding, has proven to be useful; sputtering before plasma nitriding or plasma
nitrocarburizing has a similar effect. Pickling is suitable for removing rust, scale, or rolling, forging or casting
skin.
Care should be taken to fully remove all pickling residue, since this can begin to rust. Furthermore, too intensive
pickling can leave pits in the surface layer.
7.1.2.1.5 Pre-oxidizing
In some cases it has proven useful to locally oxidize the surface before gas nitriding/nitrocarburizing. This cleans
the surface thermally and activates it at the same time, which enhances nitrogen absorption. An oxidizing
temperature of about 300 °C is recommended for unalloyed or low-alloy steel, while for high-alloy steel the
temperature should be 400 °C to 500 °C.
7.1.2.2 Preparation for localized nitriding/nitrocarburizing
If certain areas of the product are not to be nitrided or nitrocarburized, either
– include an allowance which can be removed by machining afterwards;
– cover the area with a protective coating (e.g. paste, or an electroplated copper, nickel or tin coating); in
the case of nitrocarburizing in salt baths, only a nickel coating may be used;
– fit the area with a protective covering (e.g. sleeve on shaft ends); this is only effective with plasma nitriding
or plasma nitrocarburizing.
The unexposed areas will thus only undergo thermal changes during treatment.
The width of the transition zone between exposed and unexposed areas will depend on the surface protection
method and the nitriding/nitrocarburizing method used. Since nitrided screws and bolts can crack even when
they are only tightened, threads should be protected from nitriding/nitrocarburizing.
7.1.2.3 Arrangement of products
Products shall be arranged in such a manner that
– all areas to be treated are fully exposed to the treatment medium,
– (for plasma nitriding/nitrocarburizing) the density of the arrangement is suitable for the treatment
parameters, and
– (for quenching) all areas to be treated are uniformly exposed to the quenching medium and an appropriate
flow rate of the medium is ensured.
Bulk material should not be piled too high or packed too densely. If necessary, either intermediate grids are to
be used, the products are to be treated separately or are to be kept moving in the medium, or the medium is to
be circulated to ensure movement.
Full-surface contact between products is to be avoided, as should linear contact be. The effects of point contact
are normally negligible, except in the case of plasma treatment.
Products shall be packed so that they are not deformed by their own mass nor by that of the products lying on
them.

7.2 Heating to treatment temperature

Figure 1 shows a schematic illustration of the temperature changes over time taking place in the core and at the
surface of a product of simple design having a more or less uniform cross section. When the cross section varies
greatly, the time-temperature curves are different for each cross section.

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Temperature
Nitriding or nitrocarburizing temperature

Surface

Core

Preheating time Soaking Time

Equalization
Total heating time

Figure 1: Schematic representation of heating procedure during nitriding/nitrocarburization

During the first part of the heating cycle, the core and surface temperatures vary. This temperature difference
is directly proportional to the cross-sectional size of the product and the heating rate, and indirectly proportional
to the thermal conductivity of the material. Because great temperature differences produce residual stresses
which may cause distortion in large products and products with varying cross sections, especially those of
alloyed steel, such products are to be slowly heated or heated in stages.
Figure 2 gives recommended times for the total heating time for products of circular cross section.

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Heating time, in minutes

Diameter of product, in mm
Heating to 600 °C in gas
Heating to 500 °C in gas
Heating to 570 °C in a salt bath

Figure 2: Heating time as a function of diameter

7.3 Nitriding
Nitriding is to be carried out at a temperature ranging from 450 °C to 600 °C, preferably between 480 °C and
550 °C, with the products in contact with a nitrogenous medium. At temperatures above 580 °C the surface layer
can become austenitized, depending on the product material and nitrogen content of the treatment medium.

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Gas nitriding is accomplished with ammonia gas that dissociates on the surface of the product, which acts as
a catalyst. The resulting atomic nitrogen is partially absorbed at the product surface, while the remainder, being
molecular nitrogen, becomes part of the furnace atmosphere. The ammonia gas also dissociates on the inner
furnace walls and the racks supporting the products. The reaction is described by equation (1), and involves a
doubling of the ammonia gas volume.
NH 3 = N + 3/2 H 2 (1)
The temperature, gas supply rate, pressure and product surface area influence the ammonia, hydrogen and
nitrogen contents. Thus, the effects of nitriding vary with the gas composition (e.g. they can be modified by
adding nitrogen or hydrogen to the gas mixture). These effects can also be modified by adding oxygen or air,
as is done with oxynitriding.
Various quantities may be used to characterize the atmospheric composition in the furnace and for process
control purposes. The simplest method is to measure the ammonia content in the furnace atmosphere to
determine the degree of dissociation, taking the doubling of the gas volume into consideration.
The actual degree of dissociation, a, (as a percentage), is given by equation (2):

100 − NH3 measured

a= ⋅ 100 (2)
100 + NH3 measured

If additional hydrogen or nitrogen has been introduced into the furnace, this is also to be taken into consideration
when determining the degree of dissociation.
The ammonia content and degree of dissociation are not sufficient for characterizing the nitriding effect,
however. Instead, the nitriding factor K N is often used, which is derived from the ammonia dissociation and is
given by the ratio of the partial pressure of ammonia to that of hydrogen in the furnace atmosphere, as shown
in equation (3):

pNH3
KN = (3)
( pH2 )1, 5

Since the nitriding effect increases in direct proportion with KN, the latter can be used to influence the
composition and structure of the nitrided case at a given temperature and pressure. This can be done with the
help of the Lehrer phase diagram (see figure 3).
KN

Temperature

Figure 3: Iron-nitrogen phase diagram according to E. Lehrer

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Nitriding can be performed at a varying or a constant KN value. For instance, in a two-stage process, nitriding
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begins at a high KN value, then after a certain period of time, KN is reduced by adjusting the atmospheric
composition. This process can be used to control the thickness of the compound layer, for example.
In plasma nitriding, nitrogen is the treatment medium. Here, the products are attached to a cathode and the
furnace wall is attached to an anode. The furnace is evacuated to a pressure of less than 10 mbar, and then a
potential difference is created between the anode and cathode by applying a constant or intermittent direct
current of a given amperage to create a plasma in which the molecular nitrogen is ionized, giving off nitrogen
ions which are drawn to and absorbed by the product surface. The nitrogen supply is determined by the ratio
of nitrogen to hydrogen in the gas mixture. Higher nitrogen contents lead to higher KN values.

7.4 Nitrocarburizing
Nitrocarburizing should be performed at a temperature between 570 °C and 580 °C, with the products in contact
with a medium containing mostly nitrogen but also some carbon. At temperatures above 580 °C the surface layer
may become austenitized, depending on the product material and nitrogen content of the treatment medium.
With gas nitrocarburizing, the ammonia content can be measured and the K N value determined, as with nitriding,
except that the hydrogen content must also be known to obtain KN, since other constituents are present in the
gas due to the addition of a carbon source such as carbon monoxide or carbon dioxide.
Nitrocarburizing yields different K N values than does gas nitriding, and K N is normally not varied during the
nitrocarburizing process.
In practice, the carbon supply is not measured as a function of the carbon level (as with carburizing) and
controlled. Instead, different carbon-containing gas mixtures are used to influence the nitrocarburizing action.
The quantity and type of carbon source determine the composition of the compound layer. In salt baths cyanate
is used as both the nitrogen and the carbon source. With plasma nitrocarburizing, methane is usually added as
the carbon source.

7.5 Cooling/quenching
Once the desired effective case depth (cf. subclause 9.2) or compound layer thickness is obtained, the products
are cooled to room temperature. After gas and plasma nitriding, this is normally done in a gaseous atmosphere,
while after nitrocarburizing the cooling medium is either gas, oil, water or a salt bath, depending on the product
material, the treatment medium and the equipment used.
To obtain optimum fatigue strength, it is necessary to rapidly cool unalloyed steel products (i.e. by quenching),
using either water with or without additives, or oil.
Experience has shown that, after nitrocarburizing, quenching products in an oxidizing medium greatly increases
corrosion resistance.

7.6 Secondary treatment

After nitriding/nitrocarburizing, products are further treated to optimize their material or surface condition.
7.6.1 Ageing
Ageing nitrocarburized products of unalloyed ferrous materials can modify the state of dissolution of the
nitrogen, thereby improving the products’ deformability, although their fatigue strength is reduced at the same
time. Because of this, nitrocarburized products are to be quenched to room temperature, heated to a
temperature between 120 °C and 300 °C and then held at this temperature for about one hour. After the soaking
time, the pieces are to be cooled again to room temperature at any cooling rate.
7.6.2 Postoxidizing
Experience has shown that oxidizing nitrided or nitrocarburized pieces in water vapour, another suitable gas,
or salt baths at a temperature between 350 °C and 550 °C increases the corrosion resistance of the compound
layer.

8 Heat treatment media

8.1 Nitriding media
Ammonia and nitrogen are suitable sources of nitrogen.
Although the nitrogen released during the dissociation of ammonia gas can be diffused as it is, when nitrogen
is the sole source, it must be ionized below standard pressure to break down the molecules into atoms which
can be diffused.
At standard pressure, nitrogen or an inert gas (e.g. 75 % (V/V) N2 + 25 % (V/V) H2 ) can reduce the ammonia
content and thus lower the KN value and the nitrogen supply, whereas gases containing oxygen increase the KN
value.

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8.2 Nitrocarburizing media

8.2.1 Salt baths
Currently, only cyanate-based salt baths in titanium or nickel crucibles are used as nitrocarburizing media.
Cyanate is recovered from carbonate by adding a regenerator.

8.2.2 Gaseous media

The main constituent for gas nitrocarburizing is ammonia, while for plasma processes it is nitrogen. In both cases
carbon is added in the form of carbon monoxide, carbon dioxide, hydrocarbons, a CO-containing endothermic
or CO2- containing exothermic gas, or another suitable medium.

8.3 Cooling and quenching media

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Depending on the equipment used, gaseous or liquid cooling and quenching media may be used.
The medium shall be selected based on the shape of the products, the material they are made of, their
deformability and their required wear characteristics.
Products are to be uniformly exposed to the cooling medium, since the cooling action is greatly influenced by
the flow rate and temperature of the medium.

8.3.1 Liquid cooling media

Common media include water with or without additives, oil, or salt baths. Water without additives should be no
warmer than 25 °C, that with additives should have a temperature of up to 70 °C. It should be noted that polymer
additives lower the cooling rate as compared to water without additives. Oil is normally used at temperatures
up to 80 °C, while salt baths are used at temperatures between 350 °C and 400 °C.
Aqueous media and oils are used for rapid cooling (quenching).

8.3.2 Gaseous cooling media

Still or forced air, nitrogen or ammonia may be used as gaseous cooling media. However, air may only be used
if the resulting discoloration of products is acceptable.
Nitrogen or ammonia are normally used after gas nitriding, while after nitrocarburizing, oil may also be used.
The cooling action of gas is considerably lower than that of liquid, although this can be increased by raising the
pressure or flow rate.

9 Effects of nitriding and nitrocarburizing

9.1 Effects on case structure
Nitriding and nitrocarburizing have an effect on the following characteristics:
– concentration profiles of the alloying elements of the original material, the diffused elements (N or N + C),
and any other elements present;
– thickness, structure and phases of the compound layer;
– structure and depth of the diffusion zone;
– hardness and hardness profiles;
– residual stress profile.
The extent of the nitrogen enrichment of the surface layer is described by the nitrogen concentration profile (see
figures 4 and 5 for examples). After an unimpeded nitrogen absorption, the curves will be determined by the
– material composition, particularly the type and concentration of nitride-forming alloying elements;
– original condition of the material;
– K N value or the degree of ammonia dissociation;
– nitriding/nitrocarburizing temperature;
– duration of the nitriding/nitrocarburizing process;
– cooling/quenching process selected.
In current practice, nitriding/nitrocarburizing produces a nitrogen concentration on the surface that leads to
nitride formation within only a few minutes of treatment.

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10
Ck 45 steel, gas nitrided
9
570 °C, 2h, NH3, KN = 1
8

6
Nitrogen
Percentage by mass

2
Carbon
1

0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28
Distance from surface, in mm

Figure 4: Concentration profiles of compound layer of a grade C45 steel, gas nitrided at 570 °C for
2 hours (GDOES*) analysis)

10

8
--```,`,,,,,``,,```,,`,,`,`,,,,-`-`,,`,,`,`,,`---

6
Nitrogen
Percentage by mass

4
Carbon
3

0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28
Distance from surface, in mm

Figure 5: Concentration profiles of compound layer of a grade C45 steel, gas nitrocarburized at
570 °C for 2 hours (GDOES analysis)

As nitrogen is absorbed, the nitrides continue to build, forming a solid layer called the ‘compound layer’. The
outer region of this layer is porous. Figure 6 shows the typical appearance of a compound layer when viewed
under a microscope.

*) Glow Discharge Optical Emission Spectrometry.

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Figure 6: Compound layer of a nitrocarburized grade C15 steel

Immediately beneath this layer is the ‘diffusion zone’ in which the nitrogen concentration more or less continually
decreases with increasing distance from the surface. In unalloyed steel, the nitrogen is at first dissolved in the
ferrite, and nitrides are precipitated when the products are slowly cooled. If the cooling is rapid, nitride
precipitates can be formed during the ageing stage. With alloyed steel, the nitrides formed contain other
elements such as aluminium, chromium, vanadium, titanium, molybdenum, etc.
Nitrocarburizing produces a surface layer enriched with nitrogen and – in the compound layer – with carbon.
However, less carbon is diffused than with carburizing or carbonitriding, and is normally limited to the compound
layer.
The same principles apply to nitrogen concentration profiles produced by nitrocarburizing as to those produced
by nitriding.

9.2 Effects on hardness

The introduction of nitrogen into the surface increases hardness. The hardness of the compound layer –
measured as the microhardness of a microsection – can be over 1 000 HV, depending on the material
composition of the layer. The hardness of the diffusion zone is obtained by precipitation hardening; in ferrous
alloys the precipitates are nitrides combined with other alloying elements, in unalloyed steel the precipitates are
ferrous nitrides.
The nitrogen concentration profile determines the hardness profile, which can be used to determine the effective
case depth (denoted Nht in German) as specified in DIN 50190-3 (cf. figure 7).

Case hardness
HV/0,5
50 HV
Hardness

Hardness limit
Core hardness

Nht
--```,`,,,,,``,,```,,`,,`,`,,,,-`-`,,`,,`,`,,`---

Distance from surface, in mm

Figure 7: Hardness profile after nitriding or nitrocarburizing and determination of effective case
depth, Nht (schematic; cf. DIN 50190-3)

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The effective case depth should only be determined for nitrided alloyed steel after nitriding. In the case of
unalloyed steel products and after nitrocarburizing, however, this is not practical because of the lower hardness,
and therefore only the compound layer thickness is measured and used for quality purposes. The desired
hardness and hardness profile are influenced by the
– material composition;
– material condition prior to nitriding/nitrocarburizing;
– nitriding temperature;
– duration of nitriding/nitrocarburizing;
– nitrogen supply.
Greater quantities of dissolved nitride-forming alloying elements give a greater case and surface hardness,
produce a steeper gradient between the case hardness and the core hardness indicated in the hardness profile,
and give a smaller effective case depth.
Longer nitriding/nitrocarburizing times give thicker compound layers, greater case depths, and a greater case
and surface hardness. The nitrogen supply and temperature can be used to influence the nitrogen concentration
and hardness profile. In the case of steels, particularly, a greater hardness is achieved at lower temperatures than
at high ones.
The final condition of the product is also influenced by its original condition before treatment, especially in the
case of quenched and tempered products, because the nitride-forming alloying elements are already bound
during the quenching/tempering process. The tempering temperature should be selected so that a thermally
stable condition suitable for nitriding/nitrocarburizing is obtained (cf. subclause 7.1.1.3). For longer nitriding
times, a reduction in the core hardness cannot be avoided.
Subjecting the nitrided or nitrocarburized product to diffusion treatment in an inert gas or vacuum at a
temperature within or slightly above the nitriding/nitrocarburizing temperature range can be done to modify the
hardness profile and the effective case depth; for instance the surface or case hardness can be reduced, if
necessary. Depending on the nitriding temperature, the composition and structure of the compound layer can
also be greatly modified.
--```,`,,,,,``,,```,,`,,`,`,,,,-`-`,,`,,`,`,,`---

9.3 Effects on shape and dimensions

The elements diffused into the product surface during nitriding/nitrocarburizing increase the product’s volume,
thus changing its dimensions. Furthermore, the surface roughness is increased and residual stresses are
produced. Products which do not have a uniform shape can therefore become distorted. Edges of products may
warp due to the diffusion of nitrogen on both sides.
Furthermore, products which had residual stresses prior to treatment or which were not sufficiently tempered
can undergo thermal distortion during nitriding or nitrocarburizing.

10 Heat treatment equipment

10.1 General
The following information should not be regarded as being comprehensive, and the manufacturer’s instructions
should be referred to in each case.
The following are to be taken into consideration when selecting heat treatment equipment:
– the product material and material condition;
– the treatment temperature and limit deviations;
– the duration of heat treatment;
– the cooling procedure;
– the size and number of products;
– the throughput (i.e. number of pieces processed per unit of time);
– the requirements of process control;
– the steps to be carried out during heat treatment (e.g. quenching and ageing).
10.2 Equipment for nitriding and nitrocarburizing
The following factors should be taken into account when selecting nitriding or nitrocarburizing equipment:
– the steps in the heat treatment procedure;
– the required heating capacity of the furnace;
– the limits within which the temperature in the furnace can be maintained1) (see table 1 for details);
– the treatment medium used;
– the arrangement of products (e.g. hanging, lying, poured, placed in upright position) and the batch size;
– any safety requirements for the furnace.

1) These limits are determined by the accuracy of the temperature control system and the temperature
distribution within the effective volume of the furnace (cf. DIN 17052).

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10.3 Equipment for cooling and quenching

The following factors should be taken into account when selecting cooling and quenching equipment:
– the cooling schedule;
– the size and shape of products;
– the type and temperature of the cooling medium;
– the amount of medium used and whether it is to be circulated;
– the arrangement of products (e.g. hanging, lying, poured, placed in an upright positions) and the batch
size;
– the need for removing quenching residue from products.
All cooling and quenching equipment should be designed so that the medium can circulate to prevent a loss of
heat, and should be provided with a recooling system to ensure the cooling schedule is maintained2). It is
recommended that the heating temperature of the quenching medium be controlled.
Where oil or a salt bath is the quenching medium, the capacity of the equipment should be at least six times the
mass of the batch, although a considerably larger capacity is recommended for products with a large surface
area relative to their mass or when quenching in oxidized baths.
Where gas is used as the quenching medium, the system should be provided with injection valves and nozzles
to ensure uniform cooling throughout the batch.
Where an oil quenching medium is to be recooled by means of water, an external cooling system should be
provided to prevent the two solutions from coming in contact with each other. The recooling of salt baths should
be achieved by forced air circulation.

11 Testing nitrided and nitrocarburized products

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The main criteria to be considered when testing nitrided products are the effective case depth, the compound
layer thickness and the case hardness. Although surface hardness is also often measured, it is not possible to
derive the effective case depth from this parameter.
In the case of nitrocarburized products, the compound layer thickness, and sometimes the thickness of the
porous region of that layer, as well as the effective case depth, when necessary, are measured.
When the effective case depth and compound layer thickness are determined, the product is destroyed. If this
is not permitted, a reference specimen, preferably of the same material condition as the product, should be heat
treated along with the products.
Table 2 on page 15 lists methods for testing the effectiveness of the heat treatment procedure. If a batch of
several products has been treated, sampling should be carried out following statistical principles.
The product user shall decide whether test results are suitable for determining the performance characteristics
of the product.

12 Straightening
When straightening nitrided or nitrocarburized products, it should be noted that the nitrided case has practically
no deformability and can therefore break even when only slightly deformed. For this reason, straightening of
such products should be avoided.
Slight distortions can be removed by bending the product using a straightening press, although the residual
stresses induced by straightening may create renewed distortion.

13 Designing for heat treatment

The product shape and size are major factors influencing the stresses created during the nitriding or
nitrocarburizing process and the resulting distortion. Figures 8 and 9 show product shapes which will almost
certainly become distorted. By selecting a suitable design, the likelihood of distortion can be minimized, and
often the life of the product can be increased. The following design principles should therefore be taken into
account.
– A suitable mass distribution can be obtained by drilling additional holes or providing recesses, although
there should be no blind holes (cf. figures 10 and 11).
– Symmetrical designs should be used wherever possible (cf. figure 11).
– Features which will facilitate handling during treatment (e.g. holes for lifting devices, threaded holes or
lugs) should be provided.
– For localized treatment, make sure the transition zones between treated and untreated areas are not
located within structurally sensitive areas.

2) Make sure the quenching medium manufacturer’s instructions are also taken into consideration.

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Figure 8: Example of an unsuitable product Figure 9: Example of an unsuitable product

design design

A Unsuitable B Suitable

Figure 10: Examples of suitable and unsuitable designs

A Unsuitable B Suitable
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Figure 11: Examples of suitable and unsuitable designs

14 Defects in heat treated products

Defects in heat treated products are rarely due to a single cause. In addition to the heat treatment process itself,
possible causes include the material and shape of the product, the machining process and service conditions.
Table 3 lists some of the most common defects which occur in practice and which can be attributed to the
nitriding/nitrocarburizing process.
Table 1: Guide to furnace selection

Heat treatment Temperature Limit Parameters Usual

range, deviation, to be treatment Furnace type Remarks
phase
in °C in °C controlled media
Stress 500 to 700 ± 25 Time and Air or inert Shaft, pot, Furnaces
relieving temperature gas1 ) hood-type, with
box or circulating
Normalizing 820 to 950 ± 10 hearth-hood medium are
furnace to be given
preference.
Preheating Up to 350 No No Air or inert Shaft, pot,
require- requirements gas1 ) hood-type,
ments specified. box or
specified. hearth-hood
furnace

(continued)

For 1), see page 14.

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Table 1 (concluded)

Heat treatment Temperature Limit Parameters Usual

range, deviation, to be treatment Furnace type Remarks
phase
in °C in °C controlled media
Preoxidizing 300 to 600 No Time and Air, Shaft, pot,
require- temperature water vapour hood-type,
ments box or
specified. hearth-hood
furnace
Nitriding 500 to 600 ± 10 Time, Ammonia Retort, hood- Furnaces
(gas) temperature, type or box2) should have
gas flow furnace circulating
rate, medium,
ammonia retort fur-
content, naces
hydrogen should be
content capable of
being
evacuated.
450 to 600 ± 10 Time, Nitrogen and Retort or box Furnaces
(plasma) temperature, hydrogen furnace should be
furnace capable of
pressure, being
plasma evacuated.
parameters,
N2 : H2 ratio
Nitrocarburiz- 570 to 650 ± 10 Time, Ammonia Retort, hood- Furnaces
ing (gas) temperature, and carbon- type, hearth- should have
gas flow containing hood, box or circulating
rate, NH3 or gas continuous2 ) medium.
H2 content, furnace
CO2 or CO
content
(salt baths) Time, Salt bath Salt bath, Crucible of
temperature, crucible or titanium or
cyanate tank nickel, salt
content furnace3) bath should
be ventilated.
(plasma) Time, Nitrogen and Retort or box Furnaces
temperature, hydrogen furnace should be
furnace and methane capable of
pressure, being

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plasma evacuated.
parameters,
N 2 : H2 : CH4
ratio
Ageing 50 to 300 ± 10 Time, Air, salt bath Shaft, hood
temperature type, box,
salt bath,
crucible or
tank furnace
Postoxidizing 350 to 550 ±5 Time and Salt bath, Shaft, pot,
temperature air, water hood-type,
vapour, CO 2, box or
N2O continuous
furnace
1) For safety reasons, furnaces are to be purged before using inert gases that contain flammable
components such as hydrogen or carbon monoxide.
2) Box furnaces may contain a tank filled with oil for quenching or a chamber filled with gas for cooling.
When quenching in water with or without additives, cooling equipment is to be placed outside the box
furnace.
3) Tank or crucible furnaces for salt baths shall be heated electrically or externally with gas.

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Table 2: Testing nitrided or nitrocarburized products

Property / characteristic tested Test method

1 Hardness, microhardness As in DIN 50133 and ISO 4516 : 1980
2 Microstructure: Nitride precipitates in Optical microscopy
the diffusion zone
Nitride phases in the X-ray diffraction

--```,`,,,,,``,,```,,`,,`,`,,,,-`-`,,`,,`,`,,`---
compound layer
3 Layer thickness Nitriding depth a) Microanalysis
b) GDOES1 )
c) Optical microscopy2)
Effective case depth Using hardness profile, see DIN 50190-3
Thickness and porosity Optical microscopy
of compound layer
4 Concentration profiles a) Microanalysis (using microprobes, AES*))
b) GDOES1 )
5 Soft spots a) Hardness testing
b) Visual or macroscopic examination of etched
(preferably polished 3)) or blasted surface
1) Glow Discharge Optical Emission Spectroscopy.
2) In the case of unalloyed steel containing ferrite, the depth is determined by examining acicular
precipitates, while for alloyed steel, it is determined by etching the surface.
3) Polishing shall be carried out so that the soft spots in the surface layer are not removed.
*) Auger Electron Microscopy

Table 3: Defects and their possible causes

Refer to
Defect Cause Heat treatment error
subclause
1 Surface hardness too 1.1 Nitriding depth or a) Nitriding/nitrocarburizing 7.3, 7.4, 9.2
low effective case depth too time too short
small b) Too little nitrogen absorbed 7.3, 7.4
c) Nitriding temperature too 9.2
high (for alloyed steel only)
d) Insulating top layer formed 9.1
e) Surface passivation 9.1
occurred
1.2 Austenite below Treatment temperature too high 7.3, 7.4
compound layer
1.3 Nitride precipitates in a) Cooling procedure too slow 9.1
ferrite in diffusion layer, (for unalloyed steels only)
too few free nitride- b) Error in
forming agents (formed quenching/tempering
during tempering) process
2 Effective case depth a) Treatment temperature too 9.2
too small low
b) Treatment time too short 9.2
3 Compound layer too c) Insufficient nitriding action 9.2
thin d) K N value too low 7.3, 7.4
e) Insulating top layer formed 9.1
f) Surface passivation occurred 9.1
4 Surface hardness too a) Nitriding temperature too 9.1, 9.2
great low (for alloyed steel only)
b) Diffusion treatment not or 9.2
insufficiently carried out

(continued)

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Table 3 (concluded)

Refer to
Defect Cause Heat treatment error
subclause
5 Effective case depth a)Treatment temperature too 9.2
too great high
b) Treatment time too long 9.2
6 Compound layer too c) KN value too high 9.2
thick
7 Core hardness too a) Temperature too high 9.2
low (where original condition is
quenched/tempered)
b) Treatment time too long 9.2
8 Compound layer too a) Nitriding action too great 7.3, 7.4
porous b) Salt baths too 7.4
contaminated
c) Cyanate content too high 7.4
9 Too much distortion 9.1 Thermal stresses too a) Products heated too quickly 7.2
high or not uniformly or not uniformly enough
distributed b) Products unfavourably 7.2
arranged
c) Products cooled too quickly 7.5
or not uniformly enough
d) Nitriding action not uniform 9.1
9.2 Residual stresses too Stress relieving incorrectly or
high or not uniformly not carried out prior to
distributed nitriding/nitrocarburizing
10 Cracks a) Products heated too quickly 7.2
or improperly
b) Products cooled too quickly 7.5
or inappropriately (e.g.
tools, cast iron parts)

Bibliography
DIN 17022-3 Heat treatment of ferrous materials – Case hardening
DIN 17022-5 Heat treatment of ferrous materials – Surface hardening
Chatterjee-Fischer, R. et al. Nitrieren und Nitrocarburieren (Nitriding and nitrocarburizing). Expert-Verlag,
2nd ed, 1995.

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