Case Hardening of Stainless

Steel Using Nitrogen

Using nitrogen in the formation of the hard case overcomes the
problems associated with case carburizing including depletion of
matrix chromium and carbon with accompanying lower hardness
and corrosion resistance.

The desired surface content of nitrogen is obtained at a given

alloy composition, process temperature and nitrogen pressure,
and gradually decreases toward the core.

Case hardening is a thermochemical heat treatment transferring

carbon from a carburizing atmosphere into the surface of a low-
carbon, low-alloy steel, austenitized at a temperature of, for
example, 950 C (1740 F), which upon quenching, leads to a hard
martensitic case surrounding a softer core. Without the high load-
bearing capacity and the compressive residual stresses of the
case, gears in motor vehicles would have a reduced service life,
and so would have many other machine parts without case
hardening.

There appears to be a need to extend this process to stainless

steels, not necessarily to gears, but for example, to tooling used
in the polymer and food industries and to many stainless steel
components subjected to wear. Respective efforts have, however,
shown that one ends up with the precipitation of chromium
carbides, depleting the matrix of both chromium and carbon,
which impairs the corrosion resistance as well as the hardness of
martensite.

Using nitrogen in the formation of the hard case offers a way to

overcome this problem. Like carbon, this element is interstitially
dissolved in the austenite; that is, in the intersticies of the gamma
iron face-centered cubic (FCC) lattice, and upon quenching,
increases the hardness of martensite to the same extent as
carbon [1]. Work on high-nitrogen stainless steel [2] has revealed
that compared with carbon, nitrogen widens the austenite phase
field, enhances the solubility of nitrogen and retards the
precipitation of chromium nitrides. Therefore, if case hardening of
stainless steel (for example, AISI 420, or X20Cr13) is carried out
using nitrogen instead of carbon, it is reasonable to expect a
higher interstitial solubility and better corrosion resistance. The
methodology and results are discussed below.

Fig 1 Phase diagram of stainless steel AISI 420 (X20Cr13)

calculated by Thermocalc including isobars of equilibrium N2
pressure. At a temperature of 1100¿C and P(n2) just below 1 bar,
for example, a nitrogen content of 0.35% is expected in the steel
surface which, together with 0.2% C in the bulk material, is
sufficient to produce a surface hardness of about 59 HRC.
The SolNit(r) process

Carburizing is carried out in equilibrium with a carbonaceous gas

atmosphere to reach a desired surface carbon content. The same
concept is applied to nitriding, which is called solution nitriding
(SolNit) to distinguish it from conventional nitriding carried out at
temperatures <600 C (1110 F). The nitriding atmosphere consists
of pure nitrogen (N2), which is a protective gas below 900 C
(<1650 F), but becomes active by thermal dissociation at higher
temperatures.

The solution nitriding temperature, T(n), is selected between 1050

and 1150 C (1920 and 2100 F). This increase over the
temperature level of conventional case hardening is necessary
because of the high chromium content, which retards diffusion.
AISI 420 (X20Cr13) stainless steel contains 13% Cr and 0.2% C.
After selecting T(n) and the alloy chemical composition, the third
process variable, the nitrogen pressure P(n2), controls the
process to obtain the desired surface content of nitrogen, which
gradually decreases as you proceed from surface toward the core.
The case depth increases with T(n) and the solution nitriding
duration, t(n), but so does the grain size, just as in conventional
case hardening. A nitrogen penetration or case thickness, s(n), of
2.5 mm (0.1 in.) was achieved, but s(n) often is smaller than 1
mm (0.04 in.) to keep t(n) below 4 hours.

As nitrogen is a volatile element, a pN2 on the order of 100 bar

would be required to force it into the surface of a low-alloy case-
hardening steel, which naturally, nobody wants to engage in.
Chromium, however, attracts nitrogen atoms and lowers P(n2),
which is further reduced as T(n) is lowered. Therefore, solution
nitriding of high-chromium stainless steels may be carried out at
0.2 to 2 bar, a pressure which is easy to handle and to control.

A vacuum furnace (after a few adjustments) is best suited to carry

out the process. The near-net shape parts are heated in N2 gas to
allow convection. When T(n) is reached, P(n2) is adjusted to give
the required nitrogen content in the surface. The adjustment is
made on the basis of thermodynamic calculations, an example of
which is given in Fig. 1. After t(n), the parts are quenched using
N2 gas at a pressure of 5 to 10 bar.

Fig 2 Part of a polymer extruder (a) made of stainless steel AISI

420 (X20Cr13), SolNit-M(r) treated to a surface hardness of 59
HRC (photo courtesy of Gerster AG, Egerkingen); and hardness
profile (b).

Application of SolNit-M(r)

A part of a polymer extruder treated using SolNit-M (M =

martensitic case) is shown in Fig. 2a. The hardness profile of the
tool from the surface toward the core is depicted in Fig. 2b. Due
to the strengthening effect of chromium, the hardness of the
martensitic core is higher than in a low-alloy, case-hardening
steel containing 0.2% carbon. To lower the core hardness, a
ferritic-martensitic stainless steel such as AISI 429 (X10Cr13) may
be chosen, or you can use a grade having a higher chromium
content (Fig. 3). However, an alloy content that is too high results
in retained austenite (RA) in the case, which lowers the hardness
and may require a cryogenic treatment (deep freezing).

Fig 3 Flanges (a) made of free machining stainless steel

X14CrMoS17 having a chemical composition of 0.14% C, 17% Cr,
0.5% Mo and 0.2% S, SolNit-M(r) treated to a surface hardness of
58 to 59 HRC (photo courtesy of Gerster AG, Egerkingen); and
hardness profile (b).

Other applications are stainless files, knives, chains, medical

instruments and wear parts. With a surface hardness of close to
60 HRC, SolNit-M treated parts are harder than through-hardening
stainless steels such as X46Cr13 or the AISI 440 series, for
example. In addition, the corrosion resistance is improved by
nitrogen.
Fig 4 Impeller (a) and disk (b) castings made of duplex stainless
steel G-X 3CrNiMoCuN26-6-3-3 having a chemical composition of
greater or less than 0.03% C, 26% Cr, 6% Ni, 3% Mo, 3% Cu and
0.2% N (photos courtesy of KSB, Pegnitz); and mass loss after
1,842 hours service in a recirculation loop of a sewage digestion
plant at 37 C (c). The increase of service life of SolNit-A(r) treated
parts compared with solution-annealed parts is estimated at 60%.

Extending the treatment

What can be done about austenitic and duplex stainless steels?

After solution nitriding and quenching, a high-strength, yet
ductile, austenitic case is formed. Instead of calling the process
case hardening, we refer to this SolNit-A(r) process as case
strengthening.
The austenitic stainless steel AISI 304 (X5CrNi18-10) dissolves
about 0.45% N, which more than doubles its yield strength.
Because of their higher Cr/Ni ratio, the ferritic-austenitic duplex
stainless steels AISI 329 and X2CrNiMoN22-5-3 dissolve 0.8% N,
which leads to a fully austenitic case.

SolNit-A increases the resistance of duplex stainless steels to

cavitation by about an order of magnitude. Resistance to erosion
is improved as well. Therefore, applications could be possible in
the field of fluid-flow machinery, such as pumps, turbines,
valves, elbows, etc. (Fig. 4). Again, the corrosion resistance is
distinctly enhanced by nitrogen (Fig. 5). In thin parts made of
sheet or tube, the nitrogen content may be increased throughout
the cross section to increase strength and corrosion resistance.
For example, diaphragms were cold formed in the soft solution-
annealed condition, and then strengthened using the SolNit-A
process.

Fig 5 Polarization curves of SolNit-A(r) treated and solution

annealed duplex stainless steel having a chemical composition of
0.02% C, 22% Cr, 5% Ni, 3% Mo and 0.2% N, and tested in
aqueous 0.2 M H2SO4 + 3% NaCl at 25¿C. Treating using the
SolNit-A(r) process reduces the active current density by about
one third, and increases the breakthrough potential by about 0.4
V.

Further advantages
The superior properties induced by solution nitriding are not just
accidental, but are based on fundamentals, such as for example,
the increase of free electrons in the lattice caused by the
dissolution of nitrogen, which leads to ordering, strengthens the
metallic character of interatomic bonding and stabilizes the
austenite [2]. Recent studies [3, 4] show that the concentration of
free electrons is highest if the stainless steel contains both,
carbon and nitrogen. This is used within the case of AISI 420
(X20Cr13) where 0.2% carbon in the steel is met with 0.3%
nitrogen introduced by solution nitriding. As a result, the
austenitic phase field is widened and the interstitial C+N content
is readily dissolved without promoting grain boundary
precipitates. Unfortunately, this beneficial C+N effect cannot be
extended to austenitic steels, because usually they contain little
carbon.

The thermodynamics of SolNit are given in [5] as well as some

kinetic data. This information assists in the selection of suitable
stainless steels [6]. The resistance to wear and corrosion is
discussed in [7]. The treatment is further defined in patents [8].
Based on these and other references, the user may appreciate
that the new heat treatment process is well understood.

Advantages of the process in addition to those mentioned above

include:

 In comparison to CO, CH4, NH3 gases of other

thermochemical heat treatments, N2 is neither toxic nor
explosive.
 There is no inner oxidation along grain boundaries as in
conventional case hardening and the parts stay rather
bright.
 An oxygen cell is superfluous as the nitriding equilibrium is
governed by pN2.
 The thermal dissociation of N2 allows for recombination N2
2N, which keeps the atmosphere fresh and active. Therefore,
no gas flux is required, which also helps to save energy.
  Narrow gaps and blind holes are evenly solution nitrided,
and the furnace may be loaded as densely as allowed by the
quenching requirements. Gas quenching reduces distortion.

 Because stainless steel parts have to be hardened or

solution annealed anyway, only the cost of additional
furnace time may be allotted to solution nitriding. Therefore,
thin parts having a shallow case depth s(n), after a duration
t(n) in the one-hour range, are especially cost effective.

At this stage, the SolNit process is offered by Ipsen International

(Kleve) and Gerster AG (Egerkingen).

References

 Mittemeijer, E.J., Tempering of Iron-Nitrogen Martensite, Z.

Metallkd., 74, 7, p 473-483, 1983
 Gavriljuk, V.G., Berns, H., High Nitrogen Steels, Springer
Verlag, Berlin-New York, 1999
 Gavriljuk, V.G., Berns, H., Precipitates in Tempered Stainless
Martensitic Steels Alloyed with Nitrogen, Carbon or Both, in:
High Nitrogen Steels '98, Eds. H.H¿inen, S.Hertzman, J.Romu,
Proc. of 5th Intl.Conf. on High Nitrogen Steels, Espoo,
Finland, Stockholm, Sweden, Trans. Tech. Publications Ltd.,
Switzerland-Germany-UK-USA, p. 71-80, 1999
 Shanina, Bela D., Gavriljuk, V.G., Berns, H. and Schmalt, F.,
Concept of a new high-strength austenitic stainless steel,
Steel Research, 73, 3, p 105-113, 2002
 Berns, H., Juse, R.L., Bouwman, J.W. and Edenhofer, B.,
Solution Nitriding of Stainless Steels - A New
Thermochemical Heat Treatment Process, Heat Treatment of
Metals, 2, p 39-45, 2000
 Berns, H., Stainless steels suited for solution nitriding, Mat.-
wiss. u. Werkstofftech, 33, p 5-11, 2002
 Berns, H., et al., Solution Nitriding of Stainless Steels for
Process Engineering, Mat.-wiss. u. Werkstofftech. 31, p 152-
161, 2000
 Patents DE 40 33 706 and DE 43 33 917