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High nitrogen steels (HNS) are a new class of high alloy martensitic, austenitic or duplex grades

with up to 0.9 mass% of N in solid solution.


The solubility of nitrogen in alloyed austenite is higher than in liquid metal and for this reason
austenitic steels are smelted under normal pressure with the nitrogen content ranging from 0.4 to
0.5%.
Nitrogen as an alloying element, has been known and used in technical applications since the
1940s, initially under the premise for nickel substitution in stainless grades. Nitrogen in low
alloy steels is undesirable due to the formation of brittle nitrides; however, the use of nitrogen in
high alloy steels has an array of advantages that makes it appear interesting as an alloying
element:
Significant increase of strength without restricting ductility
Improvement of corrosion resistance
Increasing the high temperature tensile strength
Extended / stabilized austenite form
No formation of tension induced martensite with high cold working rates
Inhibits the discharge of inter-metallic phases
High nitrogen steels (HNS) are a new class of high alloy martensitic, austenitic or duplex grades
with up to 0.9 mass% of N in solid solution. They are applied e.g. to stainless tools and bearings,
in chemical engineering and for high strength non-magnetic components.
The use of nitrogen as an alloying element in steel has its specific peculiarities, due to the fact
that it is in gaseous state under normal conditions. Nitrogen can be introduced into steel by the
addition of ferroalloys containing nitrogen in the steelmaking process, by treating the steel with
fused salts containing nitrogen, or by blowing the steel with ammonia or with pure nitrogen.
Alloying of steel with ferro-alloys containing nitrogen has been used industrially. Nitrogen
ferrochrome and ferromanganese are most frequently used for this purpose, usually added to
thoroughly deoxidized steel at the end of the heat, either in the furnace or in the ladle.
Considerable progress has been made in recent years in the understanding of alloying steels with
nitrogen under normal and high pressures and in studying the nature of the processes of forming
the structure and properties of HNS, and in doing so, new areas of the application of these steels
have been set out. The commercial-scale production of high-nitrogen steel products for the
power industry, transport, chemical pharmaceutical, and food industries, has grown.
It should be emphasized however, that the use of HNS still does not meet the potentials for
improving the properties of the steels, which result from their nature. Nitrogen, as an austenite-
forming element, is a substitute for nickel and nickel prices are growing at an accelerated rate.
At least two causes of this phenomenon can be mentioned, namely: the increased demand for
nickel for production of nickel-based special alloys, and the systematic growth in the production
of the classical 18-8 stainless steel, though in many instances this steel could be substituted with
a high nitrogen steel with a low nickel content, or even with a grade of steel without nickel.
In addition, nickel has proved to be an allergen, which also favors the spreading use of nickel-
less steels. In this situation, the basic trend will be an unavoidable spread of the production and
use of economically advantageous nitrogen-alloyed steels with low nickel content or steels not
containing this expensive metal, of various structural types (austenitic, martensitic, and
multiphase).
With any method of introducing nitrogen to the liquid steel the nitrogen content will be
determined by the pressure of the nitrogen gaseous phase. Hence, the nitrogen pressure may be
the basis for the most generalized classification of nitrogen alloyed steels. According to the
classification, the alloying of steels with nitrogen can be divided into three groups, depending on
the nitrogen pressure during their smelting: micro-alloy steels with nitrogen, nitrogen steels and
high nitrogen steels.
At a pressure equalized with ambient pressure, nitrogen steels and micro-nitrogen steels can be
smelted. The difference between them is determined by the chemical composition of the steels.
Micro-nitrogen steels have a ferritic matrix. The solubility of nitrogen in ferrite is much lower
than in liquid metal. Therefore, in order to avoid blistering, the nitrogen content in micro-
nitrogen steels prior to their casting must be lower than the equilibrium content for P
N2
=0.1 MPa.
For example, in low alloy steels this is normally not more than 0.02-0.03%.
Nitrogen steels contain Cr, Ni, Mn and crystallize following the austenite mechanism. The
solubility of nitrogen in alloyed austenite is higher than in liquid metal and for this reason
austenitic steels are smelted under normal pressure with the nitrogen content ranging from 0.4 to
0.5%. High nitrogen steels, in international terminology called HNS, have nitrogen contents
higher than the equilibrium content for P
N2
=0.1MPa and therefore, specialized hyperbaric
reactors are required for the production of these steels. The nitrogen content in austenitic high-
nitrogen steels may even be higher than 1.0%.


Figure 1: High-nitrogen steel for super precision angular, contact ball bearings
itrogen alloyed stainless steels, both austenitic and martensitic, exhibit attractive properties such
as high strength and ductility, good corrosion resistance and reduced tendency to grain boundary
sensitization.
The melting of high nitrogen steels (HNSS) poses two problems: how to get high nitrogen
contents into the melt and how to keep it in solution during the process of solidification. Gas
porosity formation takes place in the solidification stage because of the low solubility limit of
nitrogen into the ferrite phase: as a consequence, the liquid is strongly enriched in nitrogen.
There are two possible ways to overcome the low solubility of nitrogen in molten iron and to
achieve a high nitrogen content in the steel: alloying with elements which lower the nitrogen
activity or melting under pressure.
For this reason the development of pressure electroslag remelting (PESR) is becoming a
predominant interest for the production of steels having nitrogen content largely above the
solubility limit under atmospheric pressure.
Energietechnik Essen GmbH has been making special forged products and pressure-nitrided
alloys for many years. In order to meet the ever increasing customer demands with regard to the
physical and chemical properties, such as strength, toughness and corrosion resistance, there
have been further enhancements to the pressure electro slag remelting (PESR) process at the
company's works in Essen so that they are now able to produce pressure-nitrided steels with
outstanding property profiles on an industrial scale with the aid of this technology.
The PESR process makes it possible to increase the nitrogen content beyond the solubility limit.
The advantages of an increased nitrogen content are higher hardness and better corrosion
resistance. Where austenitic steels are concerned, the austenitic structure is stabilized and the
tensile strength increased without reducing the toughness.
The following material qualities are produced at Energietechnik Essen GmbH at the present
time:
Name Mat. No. Designation Structure
Cronidur 30 1.4108 X 30 CrMoN 15 1 Martensite
P 900 N 1.3815 X8CrMnN19-19 Austenite
P 900 N Mo 1.4456 X8CrMnMoN18-18-2 Austenite
P 2000 1.4452 X13CrMnMoN18-14-3 Austenite
The common advantages of the Pressure/Protective Gas Electroslag Remelting (PESR) process
are:
No hydrogen pick up
Nitrogen alloying up to approx. 0.8%
Absence of ingot segregation
Only minor crystal segregations
Minimum sulphur contents
Minimum levels of nonmetallic inclusions
Excellent material properties
Low melting loss of elements with high oxygen afinity
As illustration Figure 1 shows the sketch of the Pressure/Protective Gas Electroslag Remelting
(PESR) process.

igure 1: Pressure/Protective Gas Electroslag Remelting (PESR) 1-Pressure sealing 2-Furnace Head 3-
Extension Chamber 4-Stinger 5-Stub 6-Electrode 7-Static Mold 8-Slag 9-Liquid Metal 10-Ingot 11-Alloy
Feeder; DC-Power Supply

Since the beginning of their invention, the melting practices for High Nitrogen Steels, has two
recognizable problems:
1. How to introduce high nitrogen contents into the melt;
2. How to keep nitrogen in solid solution during the process of solidification thus avoiding
porosities in cast ingots.
To overcome these problems, nitrogen solubility evaluation models in the liquid state and solid
state as well as different manufacturing routes were developed at the ETH Zurich.
Nitrogen can be added in many ways. It may come from molecular or ionised gas in the
atmosphere at normal or elevated pressure or it may be offered by nitride ferro-alloys (FeCrN,
FeMnN, FeVN, CrN, MnN) or highly concentrated ceramic nitrides (Si
3
N
4
).
Introduction may be made directly into the melt or indirectly through the slag [Feich99].
Figure 1 summarizes schematically, the alloy design for high nitrogen austenitic stainless steel
produced without overpressure; an austenite free of porosities is achieved when the CrMnNi and
eventually Mo contents are correctly balanced.
For these reasons ultrahigh strength austenitic stainless steel with high nitrogen amounts belong
to the multicomponent system Fe-Cr-Mn-Ni-C-N, and they can be made with the following
facilities:
Electroslag Remelting Furnace (ESR);
Induction or Electric Arc Furnaces, blowing N
2
instead of Ar during the refining
Process in the Argon Oxygen Decarburisation (AOD) converter.

Figure 1: Schematic effect of main alloying elements used for high nitrogen austenitic stainless
steels on austenite stability, pore formations and nitrogen solubility
Production of high nitrogen austenitic stainless steels by means of traditional steel making
facilities, without overpressure, requires a balanced chemical composition of nitrogen solubility
enhancer elements to prevent pore formation during the solidification.
Although many models for nitrogen solubility calculations exist in the literature of HNS,
software like ThermoCalc are widely used among alloy developers, and they allow for empirical
models for nitrogen solubility evaluation, based on analysis of a large number of experimental
data. This may be very useful for a first estimation of the nitrogen content that might be expected
on the base of the only chemical composition.
From a large number of high nitrogen austenitic steel grades developed at the ETH Zurich, the
following model for nitrogen solubility was developed (alloying elements in weight percent):
N = 0.05 - Cr + 0.03 - Mn - 0.75 ...[ 1 ]
During this work many other high nitrogen austenitic stainless steels were melted, enriching the
experimental databank for nitrogen solubility, and a new correlation was proposed fitting better
the experimental data, as shown in Figure 2:
N = 0.066Cr + 0.02Mn + 0.19C - 0.025Ni + 0.05Mo - 1.05 ...[2]
17-78wt% Cr
0-30wt% Mn
0-49wt% Ni
0-7.3wt% Mo
0-0.3wt% C
0.3-1.5wt% N

Figure 2: Nitrogen solubility measured and calculated by equations [1] and [2] in austenitic
stainless steels with chemical composition in the range
Equation [2] should be considered only as a rough estimation for nitrogen solubility as other
important factors, like the temperature, are not included. Even with exclusion of these key
variables a good fit within an error of about 15% was found.