a r t i c l e i n f o a b s t r a c t
Article history: Stainless steels grade AISI 316 was subjected to high temperature solution nitriding and low-temperature
Received 12 January 2017 nitriding in order to dissolve various amounts of nitrogen in the bulk (up to approx. 0.45 wt%) and in a
Received in revised form 15 May 2017 surface layer (up to approx. 13 wt%), respectively. Potentiodynamic polarization tests in a 0.1 M NaCl
Accepted 7 June 2017
solution and crevice corrosion immersion tests in 3 wt% FeCl3 solution were studied before and after the
Available online 9 June 2017
bulk and surface treatments.
Nitrogen addition in the bulk proved to have a beneficial effect on the pitting resistance of the alloy.
Keywords:
The formation of a zone of expanded austenite at the material surface through low-temperature nitriding
High nitrogen steel
Low-temperature nitriding
resulted in a considerable improvement of the pitting potential and the crevice corrosion performance
Expanded austenite of the steels.
High-temperature solution nitriding © 2017 Elsevier B.V. All rights reserved.
Corrosion
Pitting
Crevice corrosion
http://dx.doi.org/10.1016/j.apsusc.2017.06.094
0169-4332/© 2017 Elsevier B.V. All rights reserved.
F. Bottoli et al. / Applied Surface Science 431 (2018) 24–31 25
Table 1
Chemical composition AISI 316 in wt% as provided by the suppliers, Lemvigh Muller.
C Si Mn Cr Ni Mo N S
AISI 316 0.07 0.4 1.6 17.0 10.55 2.0 0.05 ≤0.030
Fig. 1. Isopleth in the phase diagram for AISI 316 showing the phase stability of
The crevice corrosion performance of the materials was eval-
austenite in the temperature range 1223–1623 K (950–1350 ◦ C) vs. nitrogen content
uated by immersion tests inspired by, and close to, the ASTM in the solid state. Superimposed on the isopleth, N2 isobars are given that would
standard G48-11 [46]. A hole of 6 mm was drilled in the centre provide the corresponding equilibrium nitrogen contents.
of 0.7 mm thick samples with dimensions 5 × 2 cm2 . For the HTSN
samples the hole was drilled after HTSN treatment; for the LTN
samples the hole was drilled before the LTN treatment. Two Teflon
crevice washers were applied on the two parallel flat surfaces of the
sample and hand-tightened (by the same person for all samples)
with bolts; the torque for fastening was not measured. Immer-
sion tests were carried out at room temperature for 168 h (1 week)
in a 3 wt% FeCl3 solution of pH 1; the exposure time was chosen
96 h longer than the time recommended in standard testing. The
mass reduction after immersion was measured with a precision
balance (0.0001 g). The crevice corrosion immersion experiments
were carried out twice.
Fig. 2. Reflected light micrograph on low-temperature nitrided AISI 316, after etch-
ing with Kallingı́s reagent no. 1 for 8 s.
2.4. Microstructure and materials characterization
The microstructures of the samples after HTSN and LTN were fact the same. The only parameter that was changed was the par-
investigated in cross-section with reflected light microscopy. The tial pressure of nitrogen gas (nitrogen activity) which determines
samples were ground, polished and etched for 8 s with Kalling’s the equilibrium content of nitrogen that can be dissolved in the
reagent no. 1. stainless steel.
Microhardness indentation measurements were performed on Fig. 1 shows an isopleth of the phase diagram for AISI 316 with
a Future-Tech FM700 instrument using a load of 0.05 N for the eval- increasing nitrogen content as calculated with Thermocalc. Isobars
uation of the microhardness of the “case”. The surface morphology of total N2 pressures are superimposed onto the isopleth to demon-
of the samples after the potentiodynamic polarization measure- strate the range of compositions and phase stabilities that can be
ments was investigated with scanning electron microscopy, using obtained under equilibrium between steel and gas (see Ref. [24] for
a Jeol JSM-5900 microscope at an acceleration voltage of 10 kV. details of the calculations). An excellent agreement between the
Glow discharge emission spectroscopy (GD-OES) was applied for experimental values and the calculated equilibrium nitrogen con-
the determination of the surface composition profiles after LTN tents was concluded for a range of austenitic stainless steels with
treatments. The controlled sputtering of the surface was performed different compositions [24], among these the type under investi-
with a plasma at 1000 Pa and 40 W using a Horiba Jobin Yvon GD gation in this work. XRD investigation (not shown) revealed that
profiler 2. Quantification of the concentration depth-profiles was austenite is the only phase present in the as received condition and
achieved using a selection of stainless steel reference materials sup- after the HTSN treatments.
plemented with a custom-made ␥’-Fe4 N layer on pure iron as the
nitrogen reference. 3.2. Characterization of the low-temperature nitrided samples
Fig. 3. GD-OES Compositional depth profiles for nitrogen and carbon after low-
temperature nitriding.
Fig. 5. SEM micrograph showing the pits formed in the annealed AISI 316 after the
potentiodynamic measurements.
Fig. 7. SEM micrograph of the AISI 316 LTN after the potentiodynamic measure-
ments.
Fig. 8. Weight loss after crevice corrosion immersion tests of AISI 316 after various
treatments. The tests were performed in a 3 wt-% FeCl3 pH ≈ 1 solution for 168 h.
The micrographs show the attack at the location of the Teflon washer. The error bars
represent the highest and lowest value (of 2) measured for the mass loss.
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