Surface Modification of Commercial

Low-Carbon Steel using Glow Discharge

Nitrogen Plasma and its Characterization

S. Srikanth, P. Saravanan, Alphonsa

Joseph & K. Ravi

Journal of Materials Engineering and

Performance

ISSN 1059-9495

J. of Materi Eng and Perform

DOI 10.1007/s11665-013-0533-z

1 23
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Surface Modification of Commercial Low-Carbon Steel

using Glow Discharge Nitrogen Plasma and its
Characterization
S. Srikanth, P. Saravanan, Alphonsa Joseph, and K. Ravi

(Submitted September 18, 2012; in revised form March 14, 2013)

Plasma nitriding under glow discharge nitrogen plasma has been undertaken on laboratory scale for
surface engineering of commercial low carbon steels. The treatment has been shown to confer exceptional
improvement in surface properties, viz., hardness and corrosion resistance. The results have been discussed
in light of microstructural changes occurring on steel surface and its interior as a result of Fickian nitrogen
diffusion and correlated with influences of nitriding-temperature and alloying elements (Mn, Nb, and Si) in
steel.

The substitution of carbon by nitrogen as an interstitial element

Keywords corrosion, low-carbon steel, microstructure, nitrogen
pearlite, plasma nitriding in steel metallurgy is of considerable interest. By redefining
steel as also a Fe-N alloy, the possibilities are immense because
high nitrogen steels offer superior mechanical properties as well
as corrosion resistance. Compared with carbon, nitrogen has
two distinct advantages: (1) higher maximum interstitial
1. Introduction solubility in ferrite (0.1 wt.%), and in austenite (2.8 wt.%)
leading to higher solid-solution strengthening effects in ferrite
(Ref 1-5) and higher austenite stability (Ref 1-4, 6); and
Interstitially alloyed high nitrogen steels and Fe-N alloys are
(2) lower eutectoid temperature (592 C), leading to substantial
novel, promising new class of materials. They form the focus of
savings in energy consumption in heat treatments (Ref 1-4).
burgeoning research owing to their exceptional combination of
Nitrogen is also a cheap and abundant alloying resource, which
corrosion and mechanical properties. As the world slowly
can go a long way in realizing the human aspirations for a
gropes for viable solutions for less carbon-intensive human
carbon-free world. For these reasons, the design of nitrogen
existence, it is logical to presume that nitrogen may acquire a
steels with low alloy contents is one of the prime concerns in
pivotal role both as an alloying element and useful substitute
development of high strength steels.
for carbon in steels, which have been traditionally classified as
The immense potential of nitrogen as useful alloying
iron-carbon alloys. This is because nitrogen is similar to carbon
element has already been exploited successfully in high-
in many ways:
strength nitro-vanadium steels, austenitic stainless steels, high-
•
temperature creep-resistant stainless alloys, case-hardened tool
Nitrogen is next only to carbon in periodic table of ele-
steels, and other specialty materials. However, it has rarely been
ments (atomic number of nitrogen is 7 and that of carbon
studied in pearlitic, dual-phase (DP), and transformation-
is 6).
•
induced plasticity (TRIP) Fe-N binary steels. One of the
Both have similar atomic radii (65 pm against 70 pm for
principal reasons for this lack of interest is the very low
carbon).
•
nitrogen solubility in molten liquid iron (0.046 wt.% at
Both exist as interstitial solute atoms in steel.
•
1600 C, 1 atm pressure) (Ref 7, 8), in which the alloying
Fe-N and Fe-C phase diagrams are strikingly similar at
elements are added during steelmaking. This low solubility of
the eutectoid transformation point. Fe-N alloy system
nitrogen in liquid iron is a barrier to the development of high-
offers stability of same phases as Fe-C system, viz., fer-
strength nitrogen steels by traditional liquid metallurgy route.
rite, pearlite, austenite, and martensite.
•
The iron-nitrogen binary system, similar to the iron-carbon
Both cause yield point phenomenon and strain ageing in
system, undergoes an eutectoid transformation which leads to
steels.
the decomposition of austenite at the eutectoid point (592 C
and 2.4 wt.% N). This eutectoid transformation product, com-
posed of a-ferrite and c¢-Fe4N nitride, is called nitrogen pearlite
or false pearlite because of its similarity to the lamellar carbon
S. Srikanth, P. Saravanan, and K. Ravi, R & D Centre for Iron and
Steel (RDCIS), Steel Authority of India Limited (SAIL), Ranchi
pearlite. This lamellar pearlitic microstructure was first
834002, India; and Alphonsa Joseph, Facilitation Centre for Industrial observed in 1905 by Braune (Ref 9). In 1923, Fry (Ref 10)
Plasma Technologies (FCIPT), Institute for Plasma Research, Gandhinagar named the structure ÔÔBraunite.ÕÕ The structure-property of this
382044, India. Contact e-mail: [email protected]. nitrogen pearlite has not been studied until very recently (Ref 9-14)

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 Author's personal copy
because of little industrial interest compared with carbon of Atomic Energy, Gandhinagar, India. The steels chosen for
pearlite. nitriding experiments were essentially low alloy steels, which
The role of nitrogen on the corrosion behavior of austenitic belong to proprietary, work-tested, cold-reducible (WTCR)
stainless steels is now well understood. It has profound grades and are eventually fabricated into formed automotive
influence on localized corrosion (pitting and crevice corrosion) components such as mufflers, exhausts, live axles, fuel tanks,
resistance and passivity of stainless steels, even when alloyed in etc. The steels were deliberately selected to be low in carbon
small amounts (0.15-0.30 wt.%). This potency of nitrogen in content (interstitial content) to maximize the uptake of soluble
conferring pitting corrosion resistance to stainless steels is nitrogen in steel with concomitant formation of ferrite + nitro-
reflected in the widely used expression for Pitting Resistance gen pearlite (a-Fe(N) + c¢-Fe4N) microstructure on steel sur-
Equivalent Number (PREN). face. The experimental temperatures for glow discharge plasma
nitriding were accordingly chosen with reference to well-
PREN ¼ %Cr þ 3:3  %Mo þ 16  %N ðEq 1Þ
known LehrerÕs diagram (Ref 20) commonly used for gaseous
Several studies in the past have shown that nitrogen has a nitriding. The nitriding treatments have been carried out in a
dominant role in controlling the local decrease of pH within a pre-evacuated (102 mbar) plasma-nitriding chamber using
corroding pit or crevice and in promoting steel repassivation hydrogen-nitrogen gas mixtures in the ratio of 4:1 at a gas
(Ref 15-18). The following mechanistic theories have been pressure of 3.9 mbar at three different treatment temperatures,
propounded to explain the beneficial role of alloyed nitrogen i.e., 500, 450, and 400 C for 5 h each. The objective of these
on corrosion of steels: (1) ammonia formation theory (2) sur- experiments was to establish a treatment temperature that
face enrichment theory, (3) anodic segregation, (4) synergy would yield maximum uptake of soluble nitrogen in steel
with alloying elements like Cr and Mo, (5) formation of cor- concomitantly with a ferrite + nitrogen pearlite microstructure
rosion-resistant surface nitrides, and (6) chloride repulsion for the study. The plasma-nitrided test specimens have been
theory (Ref 19). However, the thrust of these studies has been subsequently subjected to structure-property characterization
the replacement of expensive nickel with nitrogen as an effec- using optical and electron microscopy, surface hardness
tive austenite former and stabilizer in face-centered cubic measurements, surface/depth profile analysis, and electrochem-
(fcc) austenitic stainless steels. The corrosion behavior of fer- ical corrosion testing.
rite/nitrogen pearlite microstructure in hypoeutectoid Fe-N
binary alloys has, however, not been the subject of investiga-
tion. 2. Experimental Procedure
In the present study, the feasibility of producing steels as
iron-nitrogen alloys with conventional ferrite-pearlite micro-
structure (nitrogen or false pearlite, in this case) has been Low-carbon steel coupons of size 30 9 30 9 4-5 mm and
explored. As a preliminary step toward this goal, surface chemical composition given in Table 1 were prepared and
engineering of commercial low-carbon steels has been under- polished to 0.05 lm Ra using conventional metallographic
taken by means of controlled low-temperature plasma nitriding.
Unlike its conventional use for case hardening of steels through
formation of hard, wear-resistant alloy nitrides, the sole purpose Table 1 Chemical composition (in wt.%) of low-carbon
of nitriding here has been to evolve a steel microstructure steel used for plasma nitriding under glow discharge
composed of ferrite + nitrogen pearlite (a-Fe(N) + c¢-Fe4N) to nitrogen plasma for surface enrichment with soluble
facilitate its study. Accordingly, plasma-nitriding experiments nitrogen and formation of ferrite-nitrogen pearlite micro-
have been conducted under a glow discharge nitrogen plasma structure
using test specimens of pure iron and commercial low-carbon
C Mn Si S P Al
steels (C: 0.05-0.06 wt.%, Mn: 0.18-1.04 wt.%) for surface
enrichment with soluble nitrogen at Facilitation Centre for
0.054 0.18 0.032 0.018 0.017 0.029
Industrial Plasma Technologies (FCIPT) under the Department

Fig. 1 Photographs showing plasma-nitriding treatment in progress under purple-coloured nitrogen glow discharge plasma in a pre-evacuated
nitriding reactor (Color figure online)

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procedures. The test coupons were subsequently cleaned in ferrite-nitrogen pearlite in steel microstructure at the surface of
acetone to degrease and remove contamination from the the coupons.
surfaces. Plasma nitriding was carried out in a plasma-nitriding After plasma-nitriding treatment, the test coupons were
reactor, which was heated both externally and by means of measured for surface hardness under 100 g load using Leitz-
glow discharge nitrogen plasma. The following procedure was make Vickers microhardness tester. Three indentations were
adopted for plasma nitriding. After putting the specimens into made on each sample from which average hardness values were
the nitriding chamber, the chamber was initially evacuated to computed. Thereafter, the coupons were cut down to smaller-
1.0 9 102 mbar (1 Pa). Before nitriding treatment, the spec- sized specimens, and the transverse sections were mounted in
imens were thoroughly sputter-cleaned for 30 min using conducting copper resin, polished, and etched with 2% nital for
nitrogen plasma. Hydrogen-nitrogen gas mixture in a ratio of microstructural and nitrided layer-depth analysis using optical
4:1 was then introduced into the vacuum chamber at a pressure and scanning electron microscopy. The light optical microscopy
of 3.9 mbar and the samples were plasma nitrided variously of nitrided steel specimens was carried out using Olympus
at 500, 450, and 400 C. In each case, the nitriding treatment digital microscope, while the secondary electron imaging of
was carried on for 5 h. The temperature was constantly nitrided layer microstructure was done using JEOL JSM-840A
monitored and recorded using a J-type thermocouple with a scanning electron microscope (SEM). The identification of
tolerance of ±5 C. Before the samples were removed from the various phases present in nitrided steel layers was performed
vacuum chamber, they were cooled down to less than 180 C to using Bruker Model D8 X-ray diffractometer. Auger electron
prevent any risk of steel oxidation. Figure 1 shows the spectroscopy (AES) was also employed to characterize the level
photographs of the plasma-nitriding reactor at FCIPT, which of nitrogen enrichment on the surfaces of steel specimens
was used for the plasma-nitriding experiments. Table 2 sum- nitrided at 500 and 450 C. For this, the Auger electron spectra
marizes the specific combination of plasma-nitriding parame- of nitrided steel specimens were recorded in a JEOL JAMP-
ters employed in three different experiments, which were 7100 scanning Auger microprobe (SAM) using primary
conducted for establishing the optimized process condition electron beam accelerating voltage of 10 KeV and probe
for enhancing the uptake of soluble nitrogen and achieving current of 106 A. The spectra were concurrently analyzed
semiquantitatively to discern the surface nitrogen contents.
The electrochemical corrosion behavior of nitrided steel
Table 2 Plasma-nitriding parameters employed for coupons was investigated using potentiodynamic polarization
determining optimal conditions for enhancing uptake of and electrochemical impedance spectroscopy (EIS) techniques
soluble nitrogen and achieving ferrite-nitrogen pearlite in in 3.5% sodium chloride (NaCl) solution. The electrochemical
steel microstructure at surface corrosion experiments were carried out in a standard flat
corrosion testing cell (supplied by Princeton Applied Research
Experiment Pressure, Gas Time, (PAR), USA) in freely aerated 3.5% NaCl solution of pH 7
No. Temperature, °C mbar composition h using silver-silver chloride reference electrode (E = 197 mV
versus SHE) and platinum wire mesh as an auxiliary electrode.
1 500 3.9 1:4 (N2:H2) 5 Potentiodynamic polarization scans were performed using
2 450 3.9 1:4 (N2:H2) 5
computer-controlled EG&G PAR 273A potentiostat and Pow-
3 400 3.9 1:4 (N2:H2) 5
erCORR software (from PAR, USA). A potential scan rate of
0.5 mV/s was employed during the polarization experiments.
The polarization scans were subsequently analyzed for evalu-
ation of electrochemical parameters such as passive current
densities, breakdown potentials, and corrosion rates by Tafel
extrapolation technique.
For EIS, a PAR FRD100 frequency-response detector was
annexed to EG&G PAR 273A potentiostat to facilitate sinu-
soidal AC potential perturbations at test frequencies. EIS scans
were then performed by applying discrete, sinusoidal AC
potential perturbations of 10 mV rms with frequency sweep
ranging from 100 kHz to 50 mHz. The impedance response of
Fig. 2 Visual appearance of plasma-nitrided steel coupons (Color nitrided steel coupons was recorded at different test frequencies
figure online) in the form of EIS spectra comprising complex plane Nyquist,

Table 3 Summary of metallographic characteristics of plasma-nitrided steel coupons

Depth of Phases observed Surface nitrogen
Treatment Surface nitrogen across coupon content (wt.%
temperature, °C hardness, HV enrichment, lm cross section from AES)

500 209 600 Iron-nitride, austenite, nitrogen 6.53

pearlite + nitrogen-enriched ferrite, ferrite
450 164 500 Iron-nitride, nitrogen pearlite + nitrogen-enriched 7.15
ferrite, ferrite
400 157 200 Nitrogen pearlite + Nitrogen-enriched ferrite, ferrite …
Untreated 112 Nil Ferrite Nil

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Fig. 3 Composite light optical micrographs of cross section of plasma-nitrided steel coupons (a) 500 C, (b) 450 C, (c) 400 C showing sta-
bilities of various phases (iron-nitrides, austenite and nitrogen pearlite with progressive depth as a function of nitrogen concentration gradient
governed by Fickian diffusion kinetics (Mag: 9500)

Fig. 4 Secondary electron images of phases observed in plasma-nitrided steel coupons: (a) Iron-nitride (e-Fe3N/c¢-Fe4N) at the top of the
micrograph, (b) Austenite (c), (c) Nitrogen-enriched ferrite and granular nitrogen pearlite, (d) ferrite in base steel (Mag: 91000)

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Bode magnitude and Bode phase plots. The EIS data were 500, 450, and 400 C, juxtaposed for comparison. The micro-
subsequently regressed using equivalent electrical circuit of graphs clearly show the layered formation and growth of an array
type R(QR) using ZSimpwin software (from PAR, USA) to of phases and microstructures from surface to the interior of steel
compute the charge transfer (or polarization) resistances and specimens: iron-nitrides (e-Fe3N/c¢-Fe4N), austenite, and nitro-
double-layer capacitances. All EIS measurements were con- gen pearlite, besides ferrite microstructure of the base steel. This
ducted at open circuit potential (OCP) at room temperature. manifestation of varied microstructures with progressive depth is
In the later part of the study, the specific roles of alloying clearly attributable to the gradual gradient in nitrogen concen-
elements like Mn, Si, and Nb in commercial low-carbon steels tration from surface to the steel interior resulting from Fickian
on electrochemical corrosion behavior of nitrogen-enriched nitrogen diffusion. The test coupon nitrided at 500 C was found
surface layers were also investigated in 3.5% NaCl and 0.1 N to exhibit iron-nitride layer (e-Fe3N/c¢-Fe4N) at the surface
H2SO4 solutions, and the results are compared with plasma- followed by austenite (c), mixture of nitrogen-enriched ferrite
nitrided pure iron. For these studies, plasma nitriding of three (solid solution of nitrogen in bcc iron, denoted as a-Fe(N)) and
different compositions of commercial low-carbon steels and
pure ARMCO grade iron given in Table 6 was carried out at a
single treatment temperature of 450 C for 5 h at FCIPT,
Gandhinagar, using the same treatment conditions presented in
Table 2. The nitrided steel coupons, thus produced, were
subjected to potentiodynamic polarization and EIS in 3.5%
NaCl and 0.1 N H2SO4 solutions using test procedures
described hereinabove to investigate their electrochemical
corrosion behavior.

3. Results and Discussion

Figure 2 shows the comparative visual appearance of the steel

coupons after plasma nitriding at 500, 450, and 400 C. The
coupons were found to exhibit characteristic grayish-looking
surfaces after plasma-nitriding treatment, which is discernible
from the photographs. The coupon nitrided at higher temperature,
viz., 500 C showed slight darkening of the edges owing to the
‘‘hollow cathode effect’’ commonly associated with glow Fig. 6 Ferrite peak broadening in XRD spectra with plasma-nitrid-
discharges. Table 3 summarizes the metallographic characteris- ing treatment signifies lattice strain induced by interstitially dissolved
tics of nitrided steel coupons. Figure 3 shows the composite light nitrogen in ferrite. N atoms are accommodated in octahedral sites in
optical micrographs of crosssection of the coupons nitrided at iron lattice (Color figure online)

Fig. 5 Superimposed XRD spectra of low-carbon steel surface plasma nitrided at 400, 450 and 500 C showing a progressive increase in
formation of iron-nitrides (c¢-Fe4N/e-Fe3N) and even austenite (c-Fe at 500 C) with concomitantly gradual decrease in ferrite (a-Fe) with treat-
ment temperature (Color figure online)

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nitrogen pearlite (eutectoid product composed of a-ferrite and The superimposed XRD spectra of low-carbon steel surface
c¢-Fe4N nitride), and ferrite microstructure of base steel, in that as-untreated and after plasma nitriding at 400, 450 and 500 C
order. On the contrary, the test pieces nitrided at 450 and 400 C are depicted in Fig. 5. A progressive increase in formation of
were found to exhibit predominantly a mixture of nitrogen- iron nitrides (c¢-Fe4N/e-Fe3N) and even austenite (c-Fe) at
enriched ferrite (a-Fe(N)) and nitrogen pearlite in the nitrided 500 C with concomitant gradual decrease in ferrite (a-Fe) with
surface layer with a granular micro-morphology. The presence of treatment temperature is clearly discernible from these spectra.
these phases in the nitrided layers of steel was also confirmed Figure 6 shows the superimposition of only the ferrite peaks
through scanning electron microscopy and X-ray diffraction from X-ray diffraction spectra obtained from steel specimens
analysis. Figure 4 shows typical magnified secondary electron after plasma nitriding at 500, 450, and 400 C as well as for the
images of phases observed in plasma-nitrided steel coupons, viz., untreated steel. The ferrite peaks are found to exhibit consid-
iron-nitrides (e-Fe3N/c¢-Fe4N), austenite (c), mixture of nitro- erable broadening with nitriding treatment, presumably indic-
gen-enriched ferrite and granular nitrogen pearlite and the ferrite ative of lattice strains associated with interstitially dissolved
microstructure of base steel. nitrogen in bcc-ferrite. Incidentally, nitrogen atoms are accom-

Fig. 7 Auger electron spectra of steel specimens showing significant enrichment of surface with nitrogen due to formation of e-Fe3N/c¢-Fe4N
nitrides in steel surface after plasma nitriding at (a) 500 C, (b) 450 C

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modated in octahedral sites in iron lattice (Ref 21). The peak the active corrosion behavior exhibited by untreated low-
broadening is also found to become more prominent with an carbon steel. Pitting/passive film breakdown potentials of over
increase in plasma-nitriding temperature implying a concurrent 600 mV and corrosion rates as low as 0.1-0.2 mpy were
increase in the uptake of soluble nitrogen. recorded for the nitrided steel specimens. The untreated steel,
The overall depth of nitrogen enrichment (diffusion zone with on the other hand, was found to exhibit a steady, active
compound layer) was estimated to be about 600, 500 and 200 lm, corrosion behavior without any passivity and was found to
respectively, for treatment temperatures of 500, 450, and 400 C. exhibit an overall corrosion rate of 2.7 mpy. The passivity of
Surface hardness measurements recorded at 100-g load revealed low-carbon steel was found to improve with an increase in
average Vickers microhardness of 209, 164, and 157 HV for steel plasma-nitriding-treatment temperature. This is reflected in the
test pieces nitrided at 500, 450, and 400 C, respectively, as against passive current density values of 1.07, 9.93, and 21 lA/cm2
an average microhardness of 112 HV for the untreated low-carbon recorded at 100 mV, respectively, for test pieces treated at 500,
steel. The microhardness results clearly indicate an increase in 450, and 400 C.
surface hardness after the treatment, signifying the ingress and Figure 9 shows the overlaid EIS spectra of plasma-nitrided
enrichment of interstitial nitrogen in the experimental low-carbon and untreated low-carbon steel coupons in 3.5% NaCl solution.
steel driven by Fickian diffusion kinetics. The surface enrichment The equivalent electrical circuit model used to regress the EIS
of nitrogen in plasma-nitrided test pieces was also characterized spectra for computing impedances of plasma-nitrided steels is
and confirmed through AES and was found to be as high as 6.53- depicted in Fig. 10. Table 5 gives the corresponding charge
7.15 wt.% due to the formation of e-Fe3N/c¢-Fe4N nitrides in the transfer resistance and double-layer capacitance values for the
steel microstructure. The Auger electron spectra in Fig. 7 confirm coupons computed from their Nyquist plots. The plasma-
the copious presence of nitrogen on steel surface due to formation nitrided test pieces were found to exhibit dramatic increase in
of e-Fe3N/c¢-Fe4N nitrides in microstructure after plasma nitriding charge transfer (or polarization) resistances to the order of
at 500 and 450 C. 104 X cm2 in comparison to a polarization resistance of only
Figure 8 shows the potentiodynamic polarization plots of 102 X cm2 for the untreated steel, thus emphasizing the
plasma-nitrided as well as untreated low-carbon steel coupons extremely beneficial role of nitrogen in alleviating corrosion
in 3.5% NaCl solution. Table 4 gives the electrochemical of steel.
parameters deduced from the potentiodynamic polarization Further experiments were performed to investigate the
scans. The plasma-nitrided steel test pieces were found to specific effects of alloying elements such as Mn, Si, and Nb in
exhibit distinct passivity in 3.5% NaCl solution in contrast to steel on corrosion behavior of nitrogen-enriched surface layers.
For these studies, plasma nitriding of three different compo-
sitions of commercial low-carbon steels and one pure ARMCO
grade iron was carried out at a treatment temperature of 450 C
for 5 h. Table 6 gives the chemical composition (in wt.%) of
the commercial low-carbon steels and pure ARMCO iron,
which were nitrided under glow discharge nitrogen plasma for
the purpose. Figures 11, 12, and 13 show the potentiodynamic
polarization plots and electrochemical impedance spectra (in
form of Nyquist, Bode magnitude, and Bode phase plots) for
plasma-nitrided as well as untreated low-carbon steels and pure
iron in 3.5% NaCl solution. Tables 7 and 8 show the
corresponding electrochemical corrosion parameters deduced
from the potentiodynamic polarization scans and electrochem-
ical impedance spectra. The equivalent electrical circuit model
used to regress the EIS spectra for computing impedances of
plasma-nitrided steels has been depicted in Fig. 10. It can be
discerned from Table 7 that the nitrided steels and nitrided pure
iron exhibit relatively nobler electrochemical corrosion poten-
tials, stable passivities, and lower corrosion currents in
Fig. 8 Potentiodynamic polarization plots of plasma-nitrided and comparison with the untreated steels and pure iron, respec-
untreated low-carbon steel coupons in 3.5% NaCl solution showing tively. Corrosion rates as sluggish as 0.05-0.72 mpy, pitting
distinct passivity and high pitting potentials attained with plasma potentials as high as 600-800 mV and charge transfer resis-
nitriding treatment (Color figure online) tances of the order of 104 X cm2 were observed for the nitrided

Table 4 Potentiodynamic polarization data showing corrosion, passivation and pitting characteristics of plasma-nitrided
experimental low-carbon steel in 3.5% NaCl
Passive current Equilibrium
Treatment Open circuit density at 100 mV, Breakdown corrosion current Corrosion
temperature, °C potential, OCP, mV Ipassive, lA/cm2 potential, Ebd, mV density, Icorr, lA/cm2 rate, mpy

500 ()170 1.07 (+)693 0.22 0.10

450 ()174 9.93 (+)695 0.28 0.13
400 ()192 21.00 (+)667 0.43 0.20
Untreated ()525 … … 5.94 2.73

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Fig. 9 EIS spectra of plasma-nitrided and untreated low-carbon steel coupons in 3.5% NaCl solution showing higher impedances for nitrogen-
enriched steels indicative of their higher charge transfer (or polarization) resistance: (a) Nyquist plot, (b) Bode magnitude plot, (c) Bode phase
plot (Color figure online)

steels and nitrided iron as against active corrosion rates of

4-6 mpy and charge transfer resistances of the range of
102 X cm2 for untreated steels and pure iron in the highly
corrosive test environment of 3.5% NaCl.
Likewise, Fig. 14, 15, 16, and 17 show the potentiodynamic
polarization plots and electrochemical impedance spectra (in
form of Nyquist, Bode magnitude, and Bode phase plots) for
plasma-nitrided as well as untreated low-carbon steels and pure
Fig. 10 Equivalent electrical circuit model used to regress EIS iron in 0.1 N H2SO4 solution. Tables 9 and 10 show the
spectra for computing impedances of plasma-nitrided steels corresponding electrochemical corrosion parameters deduced
from these potentiodynamic polarization scans and electro-
chemical impedance spectra. It is evident that even in the
Table 5 Electrochemical impedance spectroscopy data strongly reducing environment of 0.1 N H2SO4, the plasma-
showing impedance of plasma-nitrided experimental low- nitrided steels and pure iron reveal a tendency to pas-
carbon steel in 3.5% NaCl sive film formation, exhibit high breakdown potentials of
1185-1444 mV, and greater charge transfer resistances of
Treatment Double layer Charge transfer 83-133 X cm2 as against active corrosion and charge transfer
temperature, °C capacitance, F/cm2 resistance, X cm2 resistances of only 22-80 X cm2 for untreated steels and iron.
The remarkable improvements in corrosion resistances of
500 8.86 9 105 5.79 9 104 plasma-nitrided and nitrogen-enriched steels are attributed to
450 6.43 9 105 7.29 9 104 the tendency of nitrogen to form ammonium ions (NH4+) upon
400 3.89 9 105 5.98 9 104
dissolution, which buffer and increase the pH at corroding steel
Untreated 2.12 9 104 6.46 9 102
surface and induce steel passivation (Ref 19, 22, 23).

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Table 6 Chemical composition (in wt.%) of commercial low-carbon steels and pure ARMCO iron nitrided under glow
discharge nitrogen plasma at 450 °C to study the specific effects of alloying elements like Mn, Si, and Nb on corrosion
behavior of nitrogen-enriched steel surfaces
Steel C Mn Si S P Nb Al

1 0.054 0.18 0.032 0.018 0.017 … 0.029

2 0.057 1.01 0.039 0.012 0.018 0.031 0.049
3 0.052 1.04 0.320 0.016 0.019 0.036 0.071
4 (pure iron) 0.0036 0.34 0.022 0.012 0.008 … 0.063

Fig. 11 Potentiodynamic polarization plots of low-carbon steels and pure iron plasma-nitrided at 450 C showing lower corrosion currents,
nobler corrosion potentials, marked passivity and high pitting potentials in 3.5% NaCl solution (Color figure online)

Fig. 12 Complex plane Nyquist plots of low-carbon steels and pure iron showing dramatic increase in diameters of capacitive loops in electro-
chemical impedance spectra after plasma-nitriding treatment at 450 C in 3.5% NaCl indicative of higher charge transfer (or polarization) resis-
tance (Color figure online)

The potentiodynamic polarization of nitrided steels and iron Nitrogen, both as interstitial element in solid solution in bcc-
in 0.1 N H2SO4 also provides two curious but valuable insights ferrite and as nitride (c¢-Fe4N) in nitrogen pearlite has a
into the specific role of alloying additions such as Mn, Nb, and dominant role in increasing the hardness and corrosion
Si in steel. On the one hand, the plots in Fig. 14 especially resistance (Ref 7, 19, 22, 23). The solubility of nitrogen in
reveal the highly beneficial influence of Mn and Nb in steel on body-centred cubic (bcc) iron (a-Fe) is at least two and five
kinetics and stability of passivation on nitrided steel surface. On times greater than that of carbon at temperatures of 20 and
the other hand, the results also depict the particularly damaging 590 C, respectively (Ref 24), resulting in a decrease in
and deleterious effect of silicon in steel through annulment of tendency for precipitation at a given level of strengthening (Ref 25).
passivity in plasma-nitrided steel. Therefore, nitrogen as an interstitial atom for strengthening of

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Table 7 Potentiodynamic polarization data showing corrosion, passivation and pitting characteristics of experimental
low-carbon steels plasma-nitrided at 450 °C in 3.5% NaCl
Open circuit Passive current Breakdown Equilibrium corrosion
Treatment potential, density at 100 mV, potential, current density, Corrosion
Steel temperature, °C OCP, mV Ipass, lA/cm2 Ebd, mV Icorr, lA/cm2 rate, mpy

1 450 125 2.07 708 0.12 0.05

Untreated 567 … … 12.26 5.63
2 450 205 18.1 794 0.78 0.36
Untreated 624 … … 13.35 6.13
3 450 286 64.9 605 1.56 0.72
Untreated 672 … … 8.20 3.76
4 (pure iron) 450 239 17.45 734 0.63 0.29
Untreated 658 … … 8.73 4.01

Table 8 Electrochemical impedance of experimental low-carbon steels plasma-nitrided at 450 °C in 3.5% NaCl
Steel Treatment temperature, °C Double layer capacitance, F/cm2 Charge transfer resistance, X cm2

1 450 8.53 9 105 7.96 9 104

Untreated 2.33 9 104 8.57 9 102
2 450 1.22 9 104 4.39 9 104
Untreated 2.81 9 104 3.92 9 102
3 450 2.87 9 105 3.23 9 104
Untreated 2.36 9 104 2.13 9 102
4 (pure iron) 450 1.99 9 105 4.97 9 104
Untreated 2.19 9 104 2.43 9 102

Fig. 13 (a) Bode magnitude and (b) Bode phase plots of low-carbon steels and pure iron in 3.5% NaCl solution showing higher electrochemi-
cal impedances after plasma-nitriding treatment at 450 C indicative of higher charge transfer (or polarization) resistance (Color figure online)

iron and its alloys is superior to carbon. The powerful have also observed that the active dissolution of nitrides from
strengthening effect of interstitial nitrogen makes high nitrogen nitrided surfaces can promote formation of ammonia (NH3)
steels a specific class of engineering materials. Meanwhile, it or ammonium ions (NH4+) through cathodic reduction of
has been understood that nitrogen can also improve corrosion nitrogen and lead to buffering of pH at corroding steel sur-
properties (in dissolved state) and creep and wear resistance (as face and its passivation.
stable-nitrides) in iron-based alloys (Ref 26). Osazawa and
Okata (Ref 27) were the first to propose that the dissolution of ½N þ 3Hþ þ 3e ! NH3 ðEq 3Þ
nitrogen from steel during corrosion process can lead to
formation of ammonium ions (NH4+), which consume H+ NH3 þ H2 O ! NH4 OH ðEq 4Þ
protons and thereby increase the pH in incipient pits and
promote steel passivation. NH4 þ þ H2 O ! NH4 OH þ Hþ ðEq 5Þ

½N þ 4Hþ þ 3e ! NH4 þ ðEq 2Þ The inhibiting effects of nitrites and nitrates are well known,
and nitrate formation during dissolution could inhibit pit
The presence of NH4+ (or NH3) has been detected in the pas- growth. Mudali and Raj (Ref 23) have proposed mechanisms
sive films on steels by many authors using X-ray photoelec- by which ammonium ions (NH4+) could form inhibiting
tron spectroscopy (XPS) (Ref 19, 23). Likewise, researchers species, such as NO2 or NO3 through following steps:

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 Author's personal copy
NH4 þ þ 2H2 O ¼ NO2  þ 8Hþ þ 6e ðEq 6Þ

NH4 þ þ 3H2 O ¼ NO3  þ 10Hþ þ 8e ðEq 7Þ

NO2  þ H2 O ¼ NO3  þ 2Hþ þ 2e ðEq 8Þ

NO3  þ 10Hþ þ 8e ¼ 3H2 O þ NH4 þ ðEq 9Þ

Grabke (Ref 22) has delineated the dual role of nitrogen and
suggested that during dissolution, it is present both as Nd on
steel surface and as NH3 or NH4+ in passive layer. It was also
pointed out that desorption of the aggressive chloride ions
(Cl) could be induced by the segregated Nd on steel sur-
face.
Several earlier studies have confirmed that nitriding of steels
(low and high carbon) inevitably improves their corrosion
Fig. 14 Potentiodynamic polarization plots of low-carbon steels resistance. The effects of the nitriding processes on localized
and pure iron plasma-nitrided at 450 C revealing tendency for pas- corrosion (Ref 28), fatigue limit (Ref 29), and corrosion fatigue
sive film formation and high breakdown potentials in strongly reduc- (Ref 30-35) have been investigated by several researchers and
ing 0.1 N H2SO4 solution (Color figure online)
are now well documented. The results presented in this study

Fig. 15 Complex plane Nyquist plots of low-carbon steels and pure iron showing increase in diameters of capacitive loops in electrochemical
impedance spectra after plasma-nitriding treatment at 450 C in strongly reducing 0.1 N H2SO4 indicative of higher charge transfer (or polariza-
tion) resistance (Color figure online)

Fig. 16 Bode magnitude plots of low-carbon steels and pure iron in 0.1 N H2SO4 solution showing higher electrochemical impedances after
plasma-nitriding treatment at 450 C indicative of higher charge transfer (or polarization) resistance (Color figure online)

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Table 9 Potentiodynamic polarization data showing passivation and pitting characteristics of experimental low-carbon
steels plasma-nitrided at 450 °C in 0.1 N H2SO4
Primary
Open circuit passivation Passive current
Treatment potential, potential, density at 1000 mV, Passive potential Breakdown
Steel temperature, °C OCP, mV Epp, mV Ipass, lA/cm2 range, mV potential, Ebd, mV

1 450 490 827 65.70 972-1185 1185

2 450 498 407 35.00 528-1194 1194
3 450 497 … … … …
4 (pure iron) 450 503 323 17.20 441-1444 1444

Table 10 Electrochemical impedance of experimental low-carbon steels plasma-nitrided at 450 °C in 0.1 N H2SO4
Steel Treatment temperature, °C Double layer capacitance, F/cm2 Charge transfer resistance, X cm2

1 450 6.54 9 105 1.26 9 102

Untreated 2.77 9 105 21.99
2 450 1.13 9 104 82.61
Untreated 2.88 9 105 21.68
3 450 1.06 9 104 86.30
Untreated 2.54 9 105 25.98
4 (pure iron) 450 8.82 9 105 1.33 9 102
Untreated 2.02 9 105 79.95

nitride (NbN) can exert a beneficial influence on steel

corrosion through ammonia formation mechanism upon its
dissolution, although in the present study the presence of
neither manganese nor niobium nitride could be explicitly
confirmed. The results of the present study corroborate these
points of discussion.

4. Conclusions
[1] Plasma nitriding of commercial low-carbon steels has
been carried out under glow discharge nitrogen plasma
at three temperatures viz. 500, 450, and 400 C for
establishing the surface-treatment conditions favorable
for improving the uptake of soluble nitrogen concomi-
Fig. 17 Bode phase plots of low-carbon steels and pure iron in tantly with the formation of ferrite-nitrogen pearlite
0.1 N H2SO4 solution showing higher electrochemical impedances microstructure in steel.
after plasma-nitriding treatment at 450 C indicative of higher charge [2] Layered formation and stabilization of a wide array of
transfer (or polarization) resistance (Color figure online) phases have been found possible through plasma nitrid-
ing of low-carbon steels. The feasible phases comprise
iron nitrides (e-Fe3N/c¢-Fe4N), austenite (c), mixtures of
are, however, confined to ferrite-nitrogen pearlite microstruc- nitrogen-enriched ferrite, and nitrogen pearlite depending
ture achieved through controlled nitriding under glow discharge on nitriding temperature and concentration gradient of
nitrogen plasma and do not call for a comparison with findings ingressed nitrogen governed by Fickian diffusion.
previously published since they reflect the properties for the [3] The most striking aspect of the plasma-nitriding process,
nitrided compound layer composed variously of e-Fe3N and which is discernible from the present study, is that the
hard alloy nitrides of Cr, Al, and Si. formation of conventional steel phases and microstruc-
The beneficial effects of Mn and Nb in steel on kinetics tures such as austenite, pearlite, and interstitially alloyed
and stability of passivation on nitrided steel surface can be ferrite is entirely possible at markedly low-treatment
correlated to the observation that both Mn and Nb increase the temperatures between 400 and 500 C in ferritic domain
solubility of nitrogen in steel (Ref 19, 36). This has been of low-carbon steel. Thus, plasma nitriding can be gain-
attributed to an increase in number of potential interstitial sites fully employed for microstructural evolution, engineer-
for the nitrogen atoms owing to a corresponding increase in ing, and control on surfaces in low-carbon steels,
lattice mismatch resulting from different sizes of Mn, Nb, and besides being used as only a case-hardening heat-treatment
Fe atoms. It is also surmised that the formation of niobium procedure.

Journal of Materials Engineering and Performance

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[4] The study has also revealed that it is possible to achieve 13. T. Bell and B.C. Farnell, Proceedings of the International Symposium
the conventional ferrite-pearlite microstructure on the on Metallurgical Chemistry—Applications in Ferrous Metallurgy,
Sheffield, 1971
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an interstitial solid solution of nitrogen in bcc-iron Behavior of Austenitic Stainless Steels, Corros. Sci., 2002, 44(10),
(a-Fe(N)), and the pearlite thus produced is labeled p 2393–2407
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