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Manufacturing and Applications of High Nitrogen

Steels
a a
G. Stein & I. Hucklenbroich
a
VSG Energie- und Schmiedetechnik GmbH, Essen, Germany
Published online: 16 Aug 2006.

To cite this article: G. Stein & I. Hucklenbroich (2004): Manufacturing and Applications of High Nitrogen Steels, Materials
and Manufacturing Processes, 19:1, 7-17

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 MATERIALS AND MANUFACTURING PROCESSES
Vol. 19, No. 1, pp. 7–17, 2004

REVIEW

Manufacturing and Applications

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of High Nitrogen Steels

G. Stein* and I. Hucklenbroich

VSG Energie- und Schmiedetechnik GmbH, Essen, Germany

Key Words: High nitrogen steels; Pressure electro slag remelting; Nitrogen
solubility; Resistance to stress corrosion cracking and pitting corrosion; High
strength; Low magnetic permeability; Ni-free alloy.

1. INTRODUCTION

Almost more than 60 years ago attempts were made to replace nickel as an
expensive alloying element in austenitic steels by nitrogen. Beside a strong stabilizing
effect on the austenitic structure other benefits of nitrogen appeared. Interstitially
dissolved nitrogen distinctly improves the strengthening of austenites as well as
the corrosion resistance. Hence austenitic stainless steels with reduced C- and
Ni-contents and enhanced amounts of Mo and N in particular were developed, like
1.4406 (X2CrNiMoN17-12-2) or 1.4439 (X2CrNiMoN17-13-5), which are widely
used, i.e., in chemical devices due to their high yield strength and their good
corrosion resistance especially in chloridic acid solution.
However, normally the beneficial potential of nitrogen as an alloying element is
limited due to the rather low solubility of nitrogen in liquid steel. Using the
knowledge that the nitrogen solubility depends on temperature, nitrogen partial
pressure, and alloy composition this limitation can be conquered by producing high
nitrogen steels (HNS).

*Correspondence: G. Stein, VSG Energie- und Schmiedetechnik GmbH, Essen, Germany;

E-mail: g.stein@vsgeus.de.

DOI: 10.1081/AMP-120027494 1042-6914 (Print); 1532-2475 (Online)

Copyright & 2004 by Marcel Dekker, Inc. www.dekker.com
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8 Stein and Hucklenbroich

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Figure 1. Methods for nitrogen addition to a steel melt.

The melting of high nitrogen steels (HNS) poses two problems: First how to get
high nitrogen contents into the melt and second how to keep them in solution during
solidification. Figure 1 shows most of the current methods for the introduction of
nitrogen into steel melts. This may be done from the gas as well as a slag phase,
nitrogen may come from metalloid or ceramic nitrides, its gaseous transfer may be
helped by an electric arc or plasma gas and the situation may be considerably
improved by the application of higher pressures during melting and solidification.
According to the Sievert’s equation a high nitrogen content can be attained by a
suitable choice of alloying elements, using elements with a beneficial influence on
nitrogen solubility. For a given alloy, whose composition is determined by other
important considerations, the obvious remaining parameter for a stable solution is
an increase of the nitrogen partial pressure.

2. FUNDAMENTALS

2.1. Solubility of Nitrogen in Steel Melts

The thermodynamic is the basic key for the selection of a process technology and
therefore indirectly determines the usage of nitrogen steels.
Due to the fact that the definition of quality in nitrogen steels was directly
connected to nitrogen content as low as possible, the solubility of nitrogen has been
the subject of numerous authors over more than 60 years, such as Chipman and
Murphy,[1] Pehlke and Elliot,[2] or Kunze et al.[3] Therefore, most of these studies
were dedicated to low pressures and, therefore, the solubility of nitrogen closely
followed Sievert’s law. Whereas at lower concentrations of the elements Wagner’s
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Manufacturing and Applications of High Nitrogen Steels 9

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Figure 2. Influence of pressure and chromium on the nitrogen content of iron at 1600
C.

concept of the infinitely diluted solution allows ignoring the higher terms of the
Taylor series expansion for the activity coefficient, they have to be included at the
higher nitrogen concentrations of high nitrogen steels.
For alloys with high nitrogen contents the activity coefficient must include an
interaction parameter caused by the dense packaging of nitrogen atoms in the melt
structure. As a consequence, Sievert’s law is not followed in these melts.
Figure 2 shows the influence of the chromium content and nitrogen pressure on
the nitrogen content of FeCr-melts according to a study of Kolorz et al.,[4] who used
a high pressure induction furnace for the measurement of the nitrogen solubility at
pressures up to 200 bar in binary and multinary iron alloy melts of chromium,
manganese, nickel, and molybdenum. As shown in Fig. 2 and in accordance with
other authors, the influence of the interaction parameters, i.e., regarding Sievert’s
law, becomes remarkable at nitrogen contents above 0.8 wt.-%. An extensive study
of nitrogen solubility at pressures up to 10 bar and temperatures in the range
between 1800 and 2000
C was done by Grigorenko and Pomarin.[5] As a result they
give a solubility equation for practically all relevant alloying elements for a wide
range of concentrations, pressures, and temperatures.
Pure iron has a rather low solubility for nitrogen, in particular regarding the
liquid state: At a temperature of 1600
C at atmospheric pressure only 0.04 wt.-% N
is soluble. The influence of additional elements on the solubility of nitrogen in iron
base alloys is mainly governed by the interaction of the outer shell electrons of these
elements compared with the electron configuration of iron. Elements like Cr, Mn,
and V with an electron deficit strongly increase the nitrogen solubility, whereas Ni,
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Figure 3. Suitable elements for HNS-metallurgy as arranged in the periodic table.

Co, Si, and C have a surplus of electrons as compared to iron and, therefore, these
elements decrease the solubility of nitrogen.
The situation is clearly pointed out in the representation of the periodic system
as illustrated in Fig. 3. But a basic problem in thermodynamics is the fact that any
element increasing nitrogen solubility will normally also strongly heighten the
tendency towards nitride formation, e.g., Ti, Nb, and V.
For the melting practice of HNS the temperature dependency of nitrogen
solubility is another very important topic. Figure 4 shows the nitrogen solubility at
standard nitrogen pressures for iron and some binary FeCr-alloys. As the chromium
content is increased, there is a strong increase of nitrogen solubility as well as a
dramatic increase of the negative slope of its temperature dependency. While gas
solubilities in metals generally decrease with temperature, this effect is the opposite
in FeCr-alloys. This effect exists in iron-based alloys with all solubility increasing
elements like manganese and molybdenum. But as their effect on solubility is weaker
so is the influence regarding the slope. For elements that decrease the solubility this
temperature effect is consequently reversed. This means, for the production of HNS
alloys with a minimum pressure, ladle metallurgy should be done at the lowest
temperature, as close as possible to the liquidus.

2.2. Solidification of High Nitrogen Steels

Figure 4 also depicts an important fact about the solidification of HNS: If there
is ferritic solidification, there is a marked decrease of solubility, which may cause
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Manufacturing and Applications of High Nitrogen Steels 11

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Figure 4. Nitrogen solubility in FeCr-alloys at 1 bar pressure.

either the occurrence of pores, segregations, and/or nitrides due to the strong
increase of nitrogen activity in the delta-ferrite matrix.
The events during solidification are schematically presented in Fig. 5. On the left
side the advance of a ferritic solidification front is depicted together with a schematic
profile of the nitrogen concentration. As there is almost no convection between the
dendrite arms, due to the low solubility of the delta phase there is a nitrogen
concentration build-up in front of the solid phase, represented by a nitrogen
diffusion wave according to the coefficient k0 ¼ Nsol,/Nliq for its highest point. The
convection only enters a small way beyond the liquidus isotherm, which is identical
with the dendrite tips. Due to the diffusion buildup there is a considerable increase of
nitrogen activity between the dendrite arms. Besides the phenomenon of constitu-
tional supercooling, which will shift the solidification parameters, there is the danger
of nitrogen pore formation under the high local potential nitrogen pressures. In this
mixed convective-diffusive model part of the nitrogen is delivered to the rest melt
outside the diffusion boundary layer, which means that Nliq, is constantly increased,
especially in the late stages of solidification. This makes the situation still worse due
to the effect of macro-segregation. If contrary to that there is an austenitic
solidification (Fig. 5, right side), k0 will be either unity or even assume a positive
value, which leads to no buildup or even a negative buildup. In this way there can
be no sudden buildup of pressure between the dendrite arms and so, consequently,
no danger of porosity.
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Figure 5. Microsegregation of nitrogen depending on nature of solidifying phase.

Due to the above described events during solidification of high nitrogen steels,
alloys must be melted and solidificated under high pressure in order to obtain
nitrogen contents beyond the solubility limit.

3. PRESSURE ELECTRO SLAG REMELTING (PESR)

A pressure melting is possible by using induction or plasma furnaces;

these techniques are used to produce laboratory-scaled melts with high nitrogen
contents. For the production of HNS steels on an industrial scale the Pressurized
Electro Slag Remelting (PESR) is the most favorable one. The modern version of the
PESR furnace allows a remelting of ingots up to 20 t weight and 1000 mm diameter
(Figs. 6 and 7).
The unit is operating with a pressure up to 42 bar. Similar to the well known
electro-slag remelting (ESR) process electrodes having the desired chemical
composition are remelted in a closed vessel under pressure. During the remelting
process, nitrogen is added as granular silicon nitride from a container and its
quantity is determined by the melt rate as well as the composition of the steel.[6]

4. PROPERTIES AND APPLICATION

OF HIGH NITROGEN STEELS

VSG Energie- and Schmiedetechnik GmbH developed several types of high

nitrogen austenitic and martensitic steels for various applications.
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Manufacturing and Applications of High Nitrogen Steels 13

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Figure 6. Scheme of the Pressure-Electro-Slag-Remelting furnace.

Figure 7. PESR-Unit.

4.1. Austenitic Steels

In the solution annealed condition the 0.2% yield strength of conventional

austenitic steels is about 200 MPa. Advanced austenitic steels, highly alloyed with
nitrogen containing up to 0.5% N show 0.2% yield strength values of about
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Figure 8. Effect of nitrogen in solid solution.

Figure 9. Pitting potentials of different austenitic steels.

500 MPa (Fig. 8[7]). Massively alloyed austenitic steels with nitrogen contents up to
0.9%, which means beyond the equilibrium, possess yield strength up to 800 MPa in
case of solution annealing without a loss in toughness.[7] The broken lines in Fig. 8
represent calculated data for two different grain sizes using the given formula.
A further important property of HNS-austenites is their excellent resistance
against corrosion, especially stress corrosion cracking and pitting corrosion (Fig. 9).
The HNS-austenites show an unequal high pitting potential compared to the
conventional austenitic steels, which is independent of the type of electrolyte.
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Manufacturing and Applications of High Nitrogen Steels 15

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Figure 10. Rotor body with a shrink-fitted retaining ring made out of P900.

Figure 11. Osteosynthese plates.

A typical example for a sucessful alloy development of an HNS steel are the
austenitic retaining ring materials (Fig. 10), P900 (X5CrMnN18-18) and P2000
(X5CrMnN16-14-3). These austenitic steels containing Cr, Mn, and nitrogen
contents up to 0.9% were produced by PESR-melting.
Retaining ring material must meet the following requirements:

. High yield strength;

. Favourable corrosion properties;
. Adequate ductility;
. High strain hardening potential; and
. Low magnetic permeability.

The replacement of nickel by nitrogen in the 18/18 austenites led to a growing

interest in this group of alloys in the last years. That fact is not due to source saving
of expensive nickel but regarding the widely spread nickel allergy of the human skin.
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16 Stein and Hucklenbroich

The economic importance of this material becomes clear when considering the
broad area of applications that involve the human body coming into contact with
metallic materials in which nickel is undesirable (Fig. 11). The field extends from the
world of fashion to surgical and dental applications.[7]

4.2. Martensitic Steels

In martensitic steel nitrogen has a benefical influence on its properties, both in

solid solution, i.e., low tempered martensite, and in the precipitated state, i.e., in the
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solidificated ledeburitic microstructure as well as in the martensite tempered at

temperatures beyond the secondary hardness peak.
The benefit of nitrogen in solid state is not to attain strength or hardness but a
distinct improvement of corrosion resistance in stainless martensitic steels containing
more than 12% Cr. The clear superiority of nitrogen alloyed martensitic steels

Figure 12. Bearing rings after salt spry test.

Figure 13. Ball screw gearings made out of CRONIDUR 30.

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Manufacturing and Applications of High Nitrogen Steels 17

compared to carbon steels in corrosion resistance led to the applications of HNS-

martensites in present time.
Presently the most applicated HNS-martensite is the corrosion resistant cold
work tool steel CRONIDUR 30 containing 15% Cr, 1% Mo and a nitrogen content
of appr. 0.4%. Hardness values above 58HRC, an excellent resistance against wear
as well as pitting corrosion, promote this steel for application in aviation.
The results of salt spray tests, carried out on bearing rings made out of
CRONIDUR 30, pointed out the superior corrosion resistance of this steel. After
1300 h overrolling combined with a 4 h salt spray test the HNS-martensite did not
show any corrosion pits, whereas the conventional steel X102CrMo17 showed
corrosion pits after a 4 h salt spray test (Fig. 12).
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Typical applications are bearings in aviation turbines and ball screw gearing
shafts, which move airplane’s flap tracs (Fig. 13).
Moreover due to the excellent combination of properties the CRONIDUR 30 is
also used for rams in water cooled turbodrills and srews, fasteners for the chemical,
car, and construction industry, and many other applications.[8]

REFERENCES

1. Chipman, J.; Murphy, D.W. Trans. Metall. Soc. AIME 1935, 116, 179.
2. Pehlke, R.D.; Elliot, J.F. Transactions AIME 1968, 242.
3. Kunze, H.D.; Schürmann, E.; Parlee, N.A.D. Metall. Trans. 1970, 1, 281.
4. Satir-Kolorz, A.; Feichtinger, H.K.; Speidel, M.O. Giessereiforschung 1989, 41,
149.
5. Grigorenko, G.M.; Pomarin, Yu. M. Welding and surfacing rev. Soviet Techn.
Reviews; Harwood Academ. Publishers: London, 1990.
6. Menzel, J.; Stein, G. The PESR-process—A way of producing HNS-steels on an
industrial scale.
7. Speidel, M.O. Properties of High Nitrogen Steels. Proceed. of the HNS-Conf,
Aachen, Germany, 1990; 128–131.
8. Stein, G.; Hucklenbroich, I.; Feichtinger, H.K. Current and Future Applications
of High Nitrogen Steels. Proceed. of the HNS-Conf., Espoo/Stockholm,
Finnland/Sweden, 1998; 151–160.
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