Materials and Design 38 (2012) 59–63

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Materials and Design

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Short Communication

The effect of duplex plasma nitriding-oxidizing treatment on the corrosion

resistance of AISI 4130 steel
N. Yasavol a, F. Mahboubi b,⇑
a
Department of Materials Engineering, Tarbiat Modares University, P.O. Box 14115-143, Tehran, Iran
b
Department of Mining and Metallurgical Engineering, Amirkabir University of Technology, P.O. Box 1591634311, Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Plasma nitriding is a surface treatment process, which is widely used to improve wear, fatigue and cor-
Received 8 October 2011 rosion resistance of the industrial parts. Nevertheless, corrosion resistance can be enhanced by oxidizing
Accepted 30 January 2012 of the nitrided components. This paper considers the duplex treatment of plasma nitriding and post-oxi-
Available online 20 February 2012
dizing of AISI 4130 low alloy steel. After plasma nitriding, the post-oxidizing treatment was done in the
various gas mixtures of O2/H2 and temperatures. The treated samples were characterized using metallo-
graphic techniques, XRD, SEM, micro-hardness and potentiodynamic test. The X-ray diffraction con-
firmed the development of gamma prime and epsilon iron nitride phases during the nitriding, and
hematite (Fe2O3) and magnetite (Fe3O4) phases under the oxidizing process. The sample oxidized under
O2/H2 volume ratio of 1/3 showed the best corrosion resistance, which is attributed to the formation of an
almost single phase magnetite oxide layer on the top of the compound layer.
Crown Copyright Ó 2012 Published by Elsevier Ltd. All rights reserved.

1. Introduction The corrosion resistance of the nitrided steels compared with

Low-alloy steel automobile components such as AISI 4130 and
AISI 4140 are often exposed to a corrosive environment due to road
conditions. In the last few years promotion of the corrosion resis-
tant of industrial parts with high stability coatings has attracted
attention from many investigators’ [1]. Plasma nitriding is exten-
sively used to improve the wear, fatigue and corrosion resistance
of ferrous metals such as low [2–5] and high alloyed steels [6],
the tool steels [7,8], and stainless steels [9–11], as well as non-fer-
rous metals such as titanium [12–14] and chromium [15].
The process produces modified surface layers, including both
the outer compound layer and the inner diffusion zone [16]. The
outer compound layer includes iron nitrides like c0 -Fe4N and
e-Fe23N. The diffused layer has various iron nitrides with alloy
element nitrides, distributing in the enriched iron matrix [16,17].
The nitrided layer properties such as phase composition, thick-
ness, microhardness and microhardness profile easily vary with
the treatment parameters. The toughness of the nitrided layer,
including c0 single phase is higher than that of the one containing
e single phases. In addition, the c0 single phase increases the
wear resistance and fatigue strength of the parts more than that
of the e single phase does. It is found that the e single phase raises
the scuffing wear resistance of the parts and is used in highly slid-
ing loading conditions as well as intensively localized stresses [18].
⇑ Corresponding author. Tel.: +98 21 64542967; fax: +98 21 66405846.
E-mail address: mahboubi@aut.ac.ir (F. Mahboubi).
un-nitrided parts, increases due to the formation of the white layer
or compound layer. Moreover, the corrosion resistance may in-
crease even further by post-oxidizing treatment of the compound
layer. Post-oxidizing promoting the corrosion resistance of the
parts further than nitriding is caring out by various thermochemi-
cal techniques such as salt bath [19], steam and gaseous [20] and
plasma oxidizing [21]. Plasma post-oxidizing, done immediately
after plasma nitriding, has been proposed as a newly well-defined
technique. It is a more quickly operation and has more controllabil-
ity over gas mixture than those techniques mentioned before.
In plasma oxidizing, the high-energy oxidizing ions bombard
the surface simultaneously and a dense oxide layer without any
stress forms and grows. Comparing with other techniques, this
process includes more favorable interface properties, and more
compatibility of the oxide layer – sub-layer. During the plasma oxi-
dizing process, the formation of both rhombohedral hematite
(Fe2O3) phase and cubic magnetite (Fe3O4) phase is possible by
varying the gas chemical compositions or the oxygen and hydrogen
partial pressures [22]. Moreover, in corrosion and wear resistance
applications, the magnetite oxide layer is used owing to its low
frictional coefficient and high chemical stability [23].
The gas mixture of plasma post-oxidizing process has been
found to play a significant role on the final phases formed on the
surface of workpieces [18]. The purpose of this work is to recognize
the effect of oxidizing gas mixture and different plasma oxidizing
temperatures of 400 and 500 °C on the corrosion resistance of du-
plex-treated AISI 4130 steel automotive counterparts.

0261-3069/$ - see front matter Crown Copyright Ó 2012 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.matdes.2012.01.047
60 N. Yasavol, F. Mahboubi / Materials and Design 38 (2012) 59–63

2. Experiment details

The specimens in the form of 20 mm diameter and 6 mm thick

discs were made from AISI 4130 steel rod. The chemical composi-
tions are shown in Table 1. Then disks were ground and polished
with standard metallographic techniques. Plasma nitriding was
performed in a 5 kW conventional DC power with 4-mbar pressure
using a constant volume fraction of N2/H2:3/1 at the invariable
temperature of 550 °C. After the nitriding process, the post-oxidiz-
ing treatments were carried out through evacuating the nitriding
atmosphere and substituting the treatment chamber with the oxi-
dizing gas mixtures with volume fractions of O2/H2:1/3 and 1/9
and O2:100% under a pressure of 4 mbar at the temperatures of
400 and 500 °C.
The samples were studied using scanning metallographic tech- Fig. 1. X-ray diffraction patterns of the duplex treated samples of AISI 4130 steel
nique, optical microscopy (OM: Olympus-BX60) and scanning elec- under various gas mixtures of O2/H2 of: (a) 1/9, (b) 1/3, and (c) 100% O2.
tron microscopy (SEM: Philips-XL30). The phases detected in the
surface layers identified using X-ray diffraction analysis (Cu Ka
radiation, k = .7889 Å). Microhardness measurements were per-
formed (Vickers’s indenter 50 gf) at least three times on the surface
of the samples. Corrosion resistance of the samples was evaluated
in 5% NaCl, the ASTM standard B117 Salt Spray (Fog) test, [23,24]
aerated solution using the potentiodynamic method at room tem-
perature, and the results were compared with that of the untreated
sample. The corrosion resistance of the treated samples was stud-
ied by the anodic and cathodic electrochemical polarization tech-
nique, using three electrodes potentiodynamic (a saturated
calomel reference electrode, an auxiliary platinum electrode and
the sample) and the Tafel curves.

3. Results and discussion

Fig. 2. X-ray diffraction patterns of the duplex treated samples of AISI 4130 steel in
3.1. XRD analysis various plasma oxidizing temperatures: (a) 400 °C and (b) 500 °C.

The X-ray diffraction patterns of the surface layers after different

treatments are shown in Figs. 1 and 2. These patterns show that the
compound layer formed under different conditions consists of Fe3N,
Fe4N, Fe2O3, Fe3O4 and Fe phases. As seen in Fig. 1, in post-oxidizing
process of the nitrided samples, in addition to the nitrided phases of
c0 -Fe4N and e-Fe23N, new phases, including Fe3O4, Fe2O3 and Fe are
detectable. According to Xi et al. [25], during the oxidizing treat-
ment, as the oxide layer grows, the c0 -Fe4N phase degrades and then
the nitrogen atoms are released. Thus, some released nitrogen
atoms diffuse upward and escape to the plasma atmosphere, while
others diffuse into the matrix, accumulate close to the nitride–oxide
interface, and cause transformation of c0 -Fe4N to e-Fe23N in the
white layer. Alternatively, as Borgioli et al, reported the Fe appear-
ance in phase analysis results can be elucidated by two reasons.
First, decomposition of c0 ?c0 + (a-Fe, N), due to exposure to treat-
ment temperature during plasma oxidizing, which produces a iron.
Second reason refers to more penetration of the X-ray beam into
deeper depth of the substrate, owing to the lower absorption coef-
ficient of iron oxides than that of iron nitrides [23].
The X-ray patterns in Fig. 1c illustrate the presence of Fe2O3 and
Fe3O4 phases in the post-oxidized sample at 100% O2. By changing
the gas composition to a mixture of hydrogen plus oxygen gases,
the intensity of Fe2O3 and Fe3O4 peaks decreased. At the gas mix-
ture of O2/H2:1/3, shown in Fig. 1b, the oxide layer contains
Fe3O4, attributed to the reduction of oxygen ionization and
suppression of iron and oxygen ions interactions. Increasing the
volume fraction of hydrogen gas at O2/H2 ratio of 1/9, in Fig. 1a,
due to the reduction of oxygen ions, fewer oxide phases formed.
Meanwhile, the amount of hematite (less oxygen containing phase)
is more than magnetite phase, which is in good agreement with re-
sults obtained by Hong et al. On the other hand, according to the
Fe–O binary phase diagram, the oxygen amount of hematite phase
is more than that of the magnetite phase. In conclusion, decreasing
oxygen partial pressure, more magnetite phase is formed [21]. The
other way of nucleation and growth of the oxide layer is mainly by
diffusion of the oxygen atoms into the nitride layer according to
the parabolic law [18] and thus their combination with the iron
cations’ nitrides.
According to the XRD patterns, shown in Fig. 2, the oxide layer
formed in the plasma oxidizing temperature at 400 °C produced
Fe2O3 and few amounts of Fe3O4 phases. By increasing of the plas-
ma oxidizing temperature, due to diffusion of more oxygen atoms,
the oxide layer gets thicker and the probability of magnetite phase
formation increases.
3.2. Microstructures study
The morphology and the thickness of the nitrided and oxidized
layers, studied using scanning electron microscopic images is illus-
trated in Fig. 3. According to this figure, the plasma treatment, pro-
ducing modified surface layers consist of an outer gray oxide layer

Table 1
Chemical composition of AISI 4130 steel (wt.%).

C Cr Mn Mo Ni Si Cu P S
0.27–0.34 0.8–1.15 0.35–0.60 0.15–0.25 0–0.25 0.15–0.35 0–0.35 0–0.035 0–0.04
 N. Yasavol, F. Mahboubi / Materials and Design 38 (2012) 59–63
and an inner white layer. In addition, SEM analysis of the cross-sec-
tion of the samples indicates that the oxide layers formed in all gas
oxide compositions, including O2/H2:1/3, 1/9, and 100% O2 is ob-
served clearly on the surface of white layer. The thickness of the
white layer formed during the plasma nitriding, is about 12 lm,
while the oxide layers’ thickness obtained from the plasma post-
oxidizing in the gas compositions of O2/H2:1/3 and 1/9 and 100%
O2 is 1, 1.3 and 1.6 lm, respectively.
3.3. Corrosion resistance testes
Corrosion rate and corrosion voltage and current data of the un-
treated, plasma nitrided and post-oxidized samples are displayed
Fig. 3. SEM micrograph using SE detector of the cross section of duplex treated
samples of AISI 4130 steel under various gas mixtures of O2/H2 of: (a) 1/3, (b) 1/9
and (c) 100% O2.
61
in Table 2. The oxidized layer produced in the plasma oxidizing
treatment under the 100% O2 gas mixture, in spite of having the
thickest layer comparing with the other oxidizing conditions, did
not show the highest corrosion resistance. Indeed, the lower corro-
sion resistance attributed to the simultaneous attendance of hema-
tite and magnetite oxide phases in the oxide layer. The oxide layer
grown on the O2/H2:1/3 oxidizing gas mixture showed more corro-
sion resistance, because of containing the dense magnetic oxide
phase despite having a lower thickness than that of 100% O2. The
lower O2/H2 ratio of plasma oxidizing treatment gas mixture fol-
lowed by fewer magnetite phase values than other gas mixtures
decreased the corrosion rate of the plasma-modified surfaces.
Insufficient oxide film thickness and lack of magnetite phase in-
creased the corrosion rate of the nitrided and post-oxidized sample
at 500 °C [18].
Fig. 4 shows that, the potentiodynamic polarization curves of
the untreated, nitrided and nitrided-post-oxidized samples under
the O2/H2 volume ratio of O2/H2:1/3 and 1/9 and 100% O2 is com-
parable with each other. The untreated sample shows an active
behavior confirming a low corrosion potential and very high anodic
current limited only by concentration polarization. There is a gen-
eral and uniform corrosion observed on the corroded samples.
Nitriding treatment improved the corrosion resistance of AISI
4130 in the test solution [21,26]. In addition, all the nitriding-
post-oxidizing treatments indicated more corrosion resistance
than the nitriding treatment alone, attributing to the denser oxide
film [24] with higher corrosion resistance, formed on the surface of
the white layer and filling the surface pits of that layer [18]. The
sample, post-oxidized in the gas mixture of O2/H2:1/3 demon-
strated the highest corrosion potential and the lowest corrosion
currents than the other oxidized samples and showed the more
passive behavior than the others did. This behavior is, firstly, re-
lated to the presence of only magnetite oxide phase, which has a
high corrosion resistance. The oxide layer, formed in the other
plasma-oxidized conditions, having the hematite oxide phase and
show lower corrosion resistance. Secondly, in this plasma oxidized
condition, the probability of having less vacancy in the magnetite
layer has promoted the passive behavior [24]. Thirdly, comparing
to hematite oxide layer, the magnetite oxide layer formed on the
top of the nitrided layer is denser and more adherent to it, leading
to higher corrosion resistance. Additionally, magnetite phase with
cubic structure shows more coincidence in lattice parameter and
phase with the FCC white layer phase than hematite phase with
rhombohedral structure [23].
Increasing of plasma oxidizing temperature (500 °C) causes the
formation of magnetite phase, resulting to higher corrosion resis-
tance, while at 400 °C; it leads to the hematite phase constitution
rather than the magnetite phase (Fig. 5) [23,26]. In conclusion,
the maximum corrosion potential, the minimum corrosion rate
and the highest passive corrosion behavior refers to the sample
treatment of nitriding plus post-oxidizing condition of O2/H2:1/3
at the oxidizing temperature of 500 °C. This result is not in good
agreement with those acquired by the Jeong et al., found that by
increasing the treatment temperature, higher corrosion resistant
achieved.
3.4. Microhardness measurements
The microhardness results of the plasma nitrided, plasma ni-
trided-post-oxidized and untreated samples are shown in Fig. 6.
These results represent the increase in the microhardness of the
surface layer achieved by the plasma nitriding and little decrease
in the microhardness of the surface layer gained after plasma
oxidizing. Plasma nitriding treatment increases as received
microhardness (230 HV0.05) to 870 HV0.05 value, concerning to
the gamma prime of the white layer formation. In contrast, duplex
62 N. Yasavol, F. Mahboubi / Materials and Design 38 (2012) 59–63
Table 2
The corrosion test results of duplex treated samples.
Plasma oxidizing treatment condition parameters
T = 500 °C, O2/H2:1/3
T = 500 °C, O2/H2:1/9
T = 500 °C, O2:%100
T = 400 °C, O2/H2:1/3
Fig. 4. Potentiodynamic polarization curves of the untreated, plasma nitrided and
plasma nitrided-post-oxidized under various gas mixtures of plasma oxidizing of
AISI 4130 steel samples at 500 °C.
Fig. 5. Potentiodynamic polarization curves of plasma nitrided-post-oxidized of
AISI 4130 steel samples under various plasma temperatures in the gas mixture of
O2/H2:1/3.
plasma oxidizing treatment reduces the microhardness of the ni-
trided layer, because of the lower hardness of the oxide phase than
the nitride one [23]. In addition, as shown in Fig. 6, in the gas com-
position of O2/H2:1/3, comparing to the other conditions of plasma
oxidizing, since the magnetite phase hardness is more than that of
the hematite phase did [18], includes the highest Fe3O4 value indi-
cated higher microhardness.
Another effective agent in the microhardness increase of the
oxide layer produced in O2/H2:1/3 relates to the interface of this
oxide film feature, which is denser than that of hematite phase.
Additionally, there is more coincidence in the white layer and mag-
netite interface than in the white layer and hematite interface [23].
Comparing to temperature of 400 °C, the post-oxidized sample at
the temperature of 500 °C with O2/H2:1/3 constant, showed more
surface microhardness, owed to have thicker layer oxide and for-
mation of the magnetite phase (with higher hardness than hema-
tite) [21,23,26].
ICorr (A/cm2) ECorr (V) CR (mm/year)
9
6.92  10 0.09 0.0057
3.39  108 0.20 0.0121
8.87  108 0.30 0.0089
9.09  107 0.39 0.0077
Fig. 6. Surface microhardness of the untreated, plasma nitrided and plasma
nitrided-post-oxidized samples of AISI 4130 steel under various plasma tempera-
tures and gas mixtures.
4. Conclusions
In this research, the possibility of the plasma oxidizing treat-
ment on the surface of the AISI 4130 plasma nitrided samples
was investigated. The plasma nitriding treatment was done under
the gas mixture of N2/H2:3/1 at the constant temperature of 550 °C
in the 5 h. The oxidizing treatments accomplished in the atmo-
sphere of O2/H2:1/3 and 1/9 and 100% O2 at 400 and 500 °C. The
X-ray analysis revealed the formation of iron nitride phases of c0 -
Fe4N and e-Fe3N during the plasma nitriding and iron oxide phases
of hematite (Fe2O3) and magnetite (Fe3O4) through the post-oxi-
dizing treatment. In fact, the possibility of Fe2O3 and Fe3O4 phases’
deposition were increased by increasing of the oxygen ionization.
Plasma oxidizing under the O2/H2 volume ratio of 1/3 led to the
formation of almost a single-phase magnetite layer on the top of
the compound layer, while more intensive oxidation, caused to
the formation of hematite phase in addition.
With respect to the results obtained for the post-oxidising
treatments, the corrosion resistance of the all nitrided samples in-
creased strongly. Additionally, the highest rate relates to the sam-
ple post-oxidized in the gas composition of O2/H2 1/3, suggested
that these results can be ascribed to the formation of Fe3O4. Fur-
thermore, oxidizing treatments at 500 °C in the same gas mixture
shows more corrosion resistance than that of 400 °C. This behav-
iour is attributed to the higher corrosion resistance of the single
magnetite phase than the hematite phase. Moreover, being denser
and more adherents of magnetite to the nitrided layer than hema-
tite made the better corrosion properties effectiveness. In conclu-
sion, the plasma oxidizing treatments reduced the corrosion rate
of the nitrided sample from 0.3124 to 0.0057 mm/year.
In addition, the surface microhardness of post-oxidized samples
decreased a little compared to the plasma nitrided sample which
can be ascribed to the relatively low hardness of iron oxides.
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