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Corrosion Science 50 (2008) 1422–1432

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Corrosion resistance of AISI 1018 carbon steel in NaCl solution

by plasma-chemical formation of a barrier layer
F. Depenyou Jr. a,b, A. Doubla a, S. Laminsi a, D. Moussa b, J.L. Brisset b,*, J.-M. Le Breton c
a
Department of Inorganic Chemistry, Laboratory of Mineral Chemistry, University of Yaoundé I, Cameroon
b
Electrochemistry Laboratory (LEICA), UFR Sciences, University of Rouen, 76821 Mont Saint-Aignan Cedex, France
c
Groupe de Physique des Matériaux UMR 6634, UFR Sciences, University of Rouen, 76801 St. Etienne du Rouvray, France

Received 23 November 2007; accepted 22 December 2007

Available online 2 February 2008

Abstract

The oxidizing OH and NO radicals generated by a gliding electric discharge in humid air induce passive film formation at the surface
of AISI 1018 steel discs, as showed by changes in corrosion electric parameters (Ecor, Jcor) in aqueous (0.5 M) NaCl solution with the
exposure time to the plasma. The protecting treatment and wettability are largely improved by rotating the sample during exposure.
X-rays analysis evidences the apparition of a-Fe phase at the surface and Mössbauer spectra enlights a slight contribution of lepidocro-
cite FeOOH phase.
Ó 2008 Elsevier Ltd. All rights reserved.

Keywords: A. Mild steel; B. Gliding electric discharge; B. Polarization; B. X-ray diffraction; C. Passive film

1. Introduction gliding discharge but changes in surface properties may

The non-thermal quenched plasma generated at atmo-
spheric pressure by a gliding electric discharge (i.e., the
‘‘gliding arc” or ‘‘glidarc”) in humid air is a technique oper-
ated close to ambient temperature which has been success-
fully applied to the degradation of liquid solutes [1–3] for
pollutant abatement, decontamination of micro-organisms
[4] and oxidation of stainless steels surfaces [5]. The anti-
corrosive properties of the stainless steel materials with a
chromium content higher than 12% are assigned to the
spontaneous formation on the surface of a passive thin film
layer, mainly composed of chromium and iron oxides/
hydroxides.
Other metallic materials such as copper alloys were con-
sidered [6] but mild steel has not yet been exposed to the
*
Corresponding author. Present address: University of Rouen, UFR
Sciences, LMDF (UPRES-2123), 55 rue St Germain, F-27000 Evreux,
France. Tel.: +33 681 945 719; fax: +33 232 291 566.
E-mail addresses: brissjl@club-internet.fr, Jean-Louis.Brisset@univ-
rouen.fr (J.L. Brisset).
reasonably be expected [7,8]. The AISI 1018 carbon steel
is widely used in industry despite its low corrosion resis-
tance in various aggressive environments. We report in this
paper on the ability of the glidarc technique to enhance the
anticorrosion properties of this material.
The plasma treatments represent nowadays an impor-
tant technique for modifying and improving the chemical
and surface properties of solid materials, such as increasing
the corrosion resistance, etching, and cleaning [7–9]. A
large part of these treatments is achieved under reduced
pressure and at ambient temperature, while high tempera-
ture treatments are usually performed at atmospheric
pressure.
The gliding discharge (or ‘‘glidarc”) is one of the few
plasma technique that allows working at atmospheric pres-
sure and quasi-ambient temperature: this makes it attrac-
tive to the industrial world. It was first proposed by
Lesueur et al. [10] for the treatment of gases and is still
under development for surface treatments, solute pollu-
tants abatement and inactivation of bacteria [4]. The glid-
arc is actually a quenched plasma which involves the

0010-938X/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2007.12.011
 F. Depenyou Jr. et al. / Corrosion Science 50 (2008) 1422–1432
interesting chemical properties of activated gaseous matter
without noticeable thermal effect. Briefly, two diverging
conductors are connected to a High Voltage source such
as a transformer. An arc forming at the electrode smallest
gap is actually a thermal plasma. A gas flow directed along
the axis of the reactor gently pushes the arc feet along the
conductors towards the electrodes tips up to the arc is
short-circuited by a new one and breaks in a plasma plume.
Then the process resumes. Therefore, the length of the elec-
tric channel increases and the gas temperature falls, so that
the resulting plasma plume is actually a quenched plasma,
the macroscopic temperature of which is close to ambient.
The solid target placed in front of the electrodes is thus
submitted to the flux of the impinging activated species
formed in the discharge. The glidarc device is an easy to
operate source of chemically reactive species the nature
of which depends on those of the gas and the electrodes.
Interesting chemical properties of gliding discharges in
humid air are mainly due to the presence of the highly reac-
tive hydroxyl OH and nitric oxide NO radicals in the
plasma plume [11,12]. The radical OH is known as a strong
oxidizing agent (Standard potential E°OH/H2O = 2.85 V/
NHE) while NO is more usually referred to as an acidic
one, since it induces the formation of transient nitrous acid
and stable nitric acid in the treated solution or at the target
surface. The aim of this study is to enhance the corrosion
resistance of AISI 1018 carbon steel by generating a passive
film on the surface using a treatment of non-thermal glid-
ing arc plasma of humid air.
The modifications of the corrosion resistance character-
istics of the steel due to the treatment are investigated by
electrochemical tests. The Tafel’s technique is performed
in this work in order to compare and analyse the corrosion
potential and the corrosion current density of treated sam-
ples in corroding 0.5 M NaCl solution. The influence of the
rotation of the steel surface during plasma treatment is
evaluated. The properties of the protective barrier layer
Humid air
Flow
meter
Bubbling
water flask
d Rupture
Air inlet
M Motor
Steel
sample
Fig. 1. Scheme of the experimental setup, transformer HV = 10 kV, electrode gap d = 2.5 cm. (a) Immobile sample holder and (b) rotating sample holder.
1423
formed during plasma-surface interaction are investigated
by contact angle measurements, electrochemical analysis
in NaOH 0.025 mol L1, X-rays diffractometry and Möss-
bauer spectroscopy.
2. Experimental setup
A scheme of the experimental setup is given in Fig. 1.
This cheap atmospheric plasma reactor uses compressed
humid air saturated by passing through a bubbling water
flask. The gas flow is directed along the axis of the reactor,
i.e., between two diverging electrodes connected to a
220 V/10 kV Aupem-Sefli high voltage transformer. The
ignited electric arc at the neck (shortest electrode
gap = 2.5 mm wide) is pushed downwards to the electrode
lower tips, and its length increases. The arc voltage
increases until it reaches the breakdown voltage of the
starting gap; then a new arc forms at the electrode gap,
short-circuiting the first one that gives rise to a plasma
plume. The gas flow rate can be adjusted from 0 to
25 L min1 by means of a Show Rate Brooks flow meter.
All the treatments were made at a distance d/ = 2.5 cm
from the tips of the electrodes to the steel surface and at
the gas flow rate 16.25 L min1.
The selected AISI 1018 carbon steel samples provided
by Goodfellow contain about 0.18% by weight of carbon
and 0.6–0.9% by weight of manganese. The carbon steel
discs (15 mm diameter and 5 mm thick) were polished
using various grinding papers (400, 800, and 1200) and fin-
ished with a Mecaprex self-adhesive polishing disc using
3 lm diamond paste. They were cleaned with acetone,
rinsed with distilled water and dried with non-abrasive fil-
ter paper. The mirror-like surface obtained was then
exposed to the incident plasma gas as shown in Fig. 1.
Contact angle to water was measured after the plasma
treatment, using a classic contact angle apparatus, when
samples are cooled to room temperature.
Generator (H.T )
starting
Thermal zone
Tempered zone
out equilibrrium
Glass wall
1424 F. Depenyou Jr. et al. / Corrosion Science 50 (2008) 1422–1432
The electrochemical analyses were performed using a
Potentiostat/Galvanostat Model 273 (Princeton Applied
Research) coupled to an IBM PC. The electrochemical cell
is fitted with a platinum auxiliary electrode, the working
electrode involving the plasma treated sample, and a SCE
reference electrode. The electrolyte solution, (i.e., 0.5 M
NaCl; pH = 6.4; T = 20 °C), is purged before each run
for nearly 30 min with nitrogen. The potential sweep rate
is fixed at 1 mV s1 for all runs. The characteristic curve
current intensity (A) vs. applied potential (V) is plotted
straightaway.
3. Results and discussion
3.1. Rotation of the sample
3.1.1. Effects of surface rotation on the profile of incident
flowing plasma gas
The interaction between a reactive incident gas and a
solid surface depends on the ability of the actives species
to reach the surface and react at it. We have modified the
previously used apparatus [5] by mounting the sample
holder on the rotation axis of an electric motor, and pro-
tecting the plasma flame from the external atmosphere with
an isolating glass cylinder. The rotation speed of the motor
is monitored by a variator. Fig. 2 illustrates the plasma
flows obtained for immobile (a) and rotating (b) sample
holder.
The rotation modifies the impinging flow of the plasma
gas at the surface. Three regions are observed on the pic-
ture for the discharge, i.e., a central reddish region consti-
tuted of arc discharge filaments, a blue region surrounding
the reddish filaments, and a black region located outside
and at the end of the blue regions. These different domains
may correspond to various compositions and properties of
the plasma.
For non rotating samples, the incident plasma gas is
deviated from the metal surface, according to the behav-
iour of a gas flow falling perpendicular to a plane solid sur-
face. The black region is placed directly above the sample
Fig. 2. Plasma gas profile for the treatment of immobile (a) and rotating (b) steel sample. The tones of pictures are treated to display the regions of the
gliding discharge.
and its area is much larger than that of the blue region.
Oppositely, the volume of the plasma is more important
above the rotating sample, and the blue region is larger
and closer to the surface. The rotation of the sample holder
creates a vortex above the surface centred on the treated
sample. More numerous active species are thus forced to
go into contact with the surface before leaving the reactor.
Finally, the contact between the plasma and the treated
surface is more effective in case of a rotating target.
3.2. Tafel’s method
The interaction of the plasma gas with the carbon steel
surface induced surface modification which was followed
by electrochemical methods: the Tafel’s curves of the trea-
ted samples were recorded from 800 mV to 0.00 mV/SCE
at a sweeping rate of 1 mV s1 in sodium chloride NaCl
(0.5 mol L1, pH: 6.4) electrolyte. The corrosion potential
Ecorr is directly determined on the figure, and the corrosion
current density Jcorr is determined by Tafel’s extrapolation
method (Fig. 3).
-1
-2
Log(J(A/cm2))
-3
y = 18.725x + 7.6297
-4 R2 = 0.9943
non treated
D1
D2
-5 Linéaire (D1)
Linéaire (D2)
-6
y = -2.4305x - 6.6832
R2 = 0.9933
-7
-1.2 -1.1 -1.0 -0.9 -0.8 -0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.0
E(V)/SCE
Fig. 3. Tafel curve of non-treated AISI 1018 carbon steel in 0.5 mol L1
NaCl solution (pH¼ J6.4), showing Tafel lines for the calculation of
corrosion current density. Scan rate: 1 mV s1.
 F. Depenyou Jr. et al. / Corrosion Science 50 (2008) 1422–1432 1425

3.2.1. Tafel curve of the AISI 1018 carbon steel in -400

0.5 mol L1 NaCl solution
Fig. 3 shows the Tafel’s curves of the non-plasma-trea- -450
ted AISI 1018 carbon steel with the anodic and cathodic
-500

Ecor (mV)/SCE
linear Tafel’s lines.
The corrosion potential calculated from the recorded
-550
data is 680 mV/SCE, with a corrosion current density 3100 rpm

evaluated close to 9.3 ± 1.0 lA cm2. The potentiodynam- -600

0 rpm
2400 rpm
ic polarization diagram shows that carbon steel has no
active/passive transition when immersed in a sodium chlo- -650
ride solution, which agrees with the literature [13]. The
anodic branch of the curves shows that the carbon steel -700
undergoes a generalized corrosion. t (min)
-750
0 5 10 15 20 25 30 35 40 45 50 55 60
3.2.2. Effects of the glidarc plasma treatment and the surface
rotation speed on the electrochemical properties of carbon Fig. 5. Corrosion potential (mV/SCE) of AISI 1018 treated samples in
steel 0.5 M NaCl, pH = 6.4 as function treatment duration. Rotation speed of
The AISI 1018 carbon steel samples were treated by sample under arc discharge: (a) 0 rpm, (b) 2400 rpm, and (c) 3100 rpm.
plasma for 30 min at different rotation speeds, i.e., 0,
2400, and 3100 rotations per minute (rpm) of the sample 12
0 rpm
holder. The relevant Tafel curves are displayed in Fig. 4. 2400 rpm
3100 rpm
This figure shows that the plasma treatment induces an 10
increasing corrosion potential and a reducing current den-
Jcor (µA/cm2)

sity of the anodic branch of mild steel. The corrosion 8

potentials Ecor of samples treated on rotating holder are
higher than those of samples treated on immobile sample 6

holder. Ecor also increases when increasing the rotation

4
speed of the samples during plasma treatment.
2
3.2.3. Influence of exposure to discharge on the corrosion
parameters Ecor, Jcor in 0.5 M NaCl 0
The influence of the exposure time to discharge on the 0 5 10 15 20 25 30 35 40 45 50 55 60

corrosion potential Ecor and corrosion current density Jcor t (min)

has been studied (Figs. 5 and 6) in 0.5 M NaCl solution Fig. 6. Corrosion current density (lA/cm2) of AISI 1018 treated samples
since this medium may account for sea water. The Jcor val- in 0.5 M NaCl, pH = 6.4 as function treatment duration. Rotation speed
ues globally decrease with treatment duration, but the cor- of sample under arc discharge: (a) 0 rpm, (b) 2400 rpm, and (c) 3100 rpm.

-2

-3

-4
Log(J(A/cm2))

-5

-6

-7

E(V/SCE)
-8
-0.8 -0.6 -0.4 -0.2

non treated N= 0 rpm N= 2400 rpm N= 3100 rpm

Fig. 4. Voltammograms of AISI 1018 steels treated under plasma for 30 min. 0.5 M NaCl solution (pH= 6.4). Rotation speeds ( rpm) of sample under
arc discharge: (b) 0 rpm, (c) 2400 rpm, (d) 3100 rpm, and (a) non-treated.
1426 F. Depenyou Jr. et al. / Corrosion Science 50 (2008) 1422–1432

rosion potential Ecor does not clearly increases for immo-
bile sample treated by plasma. However, we observe a clear
decrease of the Jcor values and an increase of the Ecor values
when rotating the sample under the gliding discharge.
Fig. 5 shows that the corrosion potential increases with
treatment duration to a first maximum after 5 or 10 min,
then slightly decrease and then increases to a maximum
after 30 min of treatment. The decrease of Ecor after the
first maximum coincides with an increase of Jcor for the
same treatment duration. This observation was already
made by different authors [11,14] and is consistent with
the behaviour of an oxide film growing on a metal surface
exposed to corroding gas.
The behaviour of Ecor and Jcor as functions of the expo-
sure time to the discharge suggests the formation of a pro-
tective film, which first causes an increase in the corrosion
potential and a decrease in the corrosion current. The film
uniformly and progressively covers the surface of the sam-
ple exposed to plasma. After 5 or 10 min of treatment, the
oxide/hydroxide begins to crack, due to differences in the
crystal lattice parameters between the metal and the
(hydr)oxide, or due to temperature increase [13]. It is
assumed that cracks on the film expose the metal to the
corroding solution, which leads to a slight decrease of cor-
rosion potential and increase of corrosion current. For
longer exposure times to the discharge, Ecor increases to a
maximum value, and Jcor falls to a minimum: this suggests
an optimisation of the covering of the surface, or a physi-
cal–chemical transformation of the oxide/hydroxide layer.
Table 1 sums up the improvement of anticorrosion
parameters, such as the corrosion current density and the
corrosion potential by plasma treatment as functions of
the exposure time to the discharge for different rotation
speed of the sample. The protection represents the differ-
ence in percentage between the corrosion current of
untreated sample and that of the plasma treated sample
 
J corrt¼0  J corrt¼x
Protectiont¼x ¼ 100 
J corrt¼0
High protection percentage is more rapidly reached on
rotating samples. A decrease in Jcor by more than 88% is
obtained for 30 min exposures. That proves the efficiency
of glidarc treatment.
The increase of protection percentage upon rotation of
the treated surface implies an improved contact between
the plasma and the surface. The rotation of the sample cre-
ates a vortex above its surface, which increases the contact
between the active species of the plasma and the sample
surface. The reactive plasma gas is not deviated before it
has reached the surface, as it is the case for an immobile
sample. Moreover, an enhanced homogenized treatment
of the sample results. A rotating sample exposes all the
regions of its surface to the incident flux of active species
composing the plasma gas, improving the quality of the
barrier film compared to that of an immobile sample under
plasma.
3.2.4. Effect of pH of the solution on the polarization curves
of treated samples
The effect of pH on the electrochemical behaviour of
steels samples treated for 30 min was evaluated at neutral
and basic pH, using sodium chloride (NaCl 0.5 mol L1)
and nitrate solutions (NaNO3 102 mol L1). Figs. 7–9
show the relevant polarization curves.
In 0.5 mol L1 NaCl solution (Fig. 7), the corrosion
potential of plasma treated mild steel does not change with
pH in the considered acidity range, but corrosion current
density decreases as the pH increase. At pH = 11.8, the vol-
tammogram presents a large passive domain of about
318 mV width (from 500 mV to 182 mV/SCE). The
apparition of this large domain is due to the presence on
the metal surface of an oxide/hydroxide layer that is more
stable at basic pH (Fig. 7).
Similar experiments were performed in another electro-
lyte and a non-complexing medium was selected, e.g.,
0.01 mol L1 NaNO3, pH = 6.5 solution (Fig. 8). The cor-
rosion potential Ecor of plasma treated sample increases
and the corrosion current density decreases as pH
increases. The curves also show a larger domain of passiv-
ity close to 880 mV (i.e., from 284 mV/SCE to +628 mV/
SCE at pH 11.9). The Ecor of the 30 min plasma treated
mild steel shifts toward anodic potentials, by 82 mV at
pH = 6.5 and 154 mV at pH = 11.8. At basic pH, the width
of the passive region increases from 300 mV (for the
untreated sample) to 500 mV for the plasma treated sam-
ple. This agrees with the occurrence of a passive layer

Table 1
Corrosion potential and current density of AISI 1018 carbon steel in 0.5 mol L1 NaCl solution, pH = 6.4 after gliding arc plasma treatment for different
exposure times and various sample rotation speeds
Sample rotation speed (rpm) Treatment duration (min) 0 2 5 10 15 20 30 40 60
0 Ecor(mV/SCE) 680 652 632 600 632 698 666
Jcor (lA cm2) 9.3 4.1 7.2 8.5 6.3 1.7 3.9
Protection (%) 0 55.5 22.9 9.1 32.2 82.1 58.4
2400 Ecor(mV/SCE) 680 552 532 554 514 526 518  508 496
Jcor (lA cm2) 9.3 2.9 2.9 2.1 1.5 3.4 1.0 1.2 0.7
Protection (%) 0 69.4 69.3 77.3 83.4 63.9 88.8 87.6 92.1
3100 Ecor(mV/SCE) 680 614 542 536 554 508 474  472 464
Jcor (lA cm2) 9.3 5.7 2.3 1.9 4.2 2.6 0.6 0.6 0.5
Protection (%) 0 38.9 75.9 80.1 55.1 71.6 93.5 93.8 94.3
 F. Depenyou Jr. et al. / Corrosion Science 50 (2008) 1422–1432 1427

-1
NaCl 0.5 mol L-1
-2

-3

Log(J(A/cm2)) b
-4
c PH6.4; t=0
-5 PH6.4; t=30
PH7.6; t=30
d
PH11.8 ; t=30
-6

-7 a
E(V)/SCE
-8
-0.8 -0.6 -0.4 -0.2 0.0

1
Fig. 7. Polarization curves in 0.5 mol L NaCl of AISI 1018 steels treated under plasma for 30 min. Rotation speed: 2400 rpm. Electrolyte: 0.5 M NaCl
(a) non-treated, pH = 6.4, (b) pH = 6.4, (c) pH = 7.6, and (d) pH = 11.8.

3E-05
(NaCl 0,5 mol.L-1 + NaOH 0,006 mol.L-1). pH = 11,8

pH 11,8 t= 0 2E-05
t = 0 min t = 30 min
pH11,8 t=30

2E-05

242 mV 1E-05

5E-06
365 mV
t
u 0E+00
-0.70 -0.65 -0.60 -0.55 -0.50 -0.45 -0.40 -0.35 -0.30 -0.25 -0.20 -0.15 -0.10

90 mV -5E-06
J (A/cm2)

E(V)/ECS -1E-05

Fig. 8. Voltammograms in 0.01 mol L1 NaNO3 of AISI 1018 steels plasma treated for 30 min. Rotation speed: 2400 rpm. Electrolyte:
NaNO30.01 mol L1. (a) untreated, pH = 6.5, (b) plasma treated for 30 min, pH = 6.5, (c) Untreated, pH = 11.9, and (d) plasma treated for 30 min,
pH = 11.9.

(NaNO3 0,01 mol.L-1 + NaOH 0,006 mol.L-1). pH = 11,9

t = 0 min 7.0E -06

pH 11,9 t=0 5.0E -06

pH 11,9 t=30
t = 30 min
300 mV 3.0E -06

500 mV
x 1.0E -06

-0.8 -0.6 y -0.4 -0.2 0.0 0.2 0.4 0.6 0.8

-1.0E-06
J(A/cm2)

-3.0E-06
154 mV
E(V)/ECS -5.0E-06

Fig. 9. Polarization curves of AISI 1810 steel exposed to the discharge for 30 min. Rotation sped:2400 rpm. Electrolyte 0.01 mol L1 NaNO3 (pH:11.9).
1428 F. Depenyou Jr. et al. / Corrosion Science 50 (2008) 1422–1432

stable ascribed to FeO and other Fe(II) compounds at the Fe þ NO 

3 þ H2 O ! FeðOHÞ2 þ NO2
surface. Hydrolysis in alkaline medium yields Fe(OH)2 or FeO þ H2 O ! FeðOHÞ2
other Fe(II) oxides or hydroxides. At basic pH, the nitrate
3FeðOHÞ2 þ NO 
3 ! Fe3 O4 þ NO2 þ 3H2 O
ions NO 3 may be reduced by iron and iron oxide/hydrox-
ide to form a stable oxide/hydroxide compound. The fol- Fe3 O4 þ 2H2 O þ NO2 ! 3FeOOH þ NO þ OH


lowing reaction scheme was proposed to explain the 2Fe3 O4 þ 2NO 2 þ H2 O ! 3Fe2 O3 þ 2NO þ 2OH


denitrification in basic nitrate solutions by iron [15]:

8FeðOHÞ2 # þNO
3 þ 6H2 O ! NH3 þ FeðOHÞ3 # þOH

3.3. Contact angle to water

Contact angles were measured on plasma treated sam-

The protective iron (II) oxide/hydroxide layer formed un-
der plasma tends to stabilize in the presence of nitrate
ions by formation of iron (III) hydroxide. Other reac-
tions were proposed to explain passivating of carbon
steel by basic NaNO3 solution in the presence of nitrite
[16–18].
80
AISI 1018
70
ples and plotted as a function of the exposure time to the
discharge. Fig. 10 shows that the contact angle decreases
and tends to a steady value for increasing exposure times:
this feature suggests that polar species form on the surface
and are responsible for the increase in wettability. For
exposure times longer than 10 min, the contact angle is
almost constant, which suggests that the surface is totally
covered by the hydrophilic passive layer. Increasing treat-
ment duration would lead to the transformation of com-
pounds on the surface [14].

60 3.4. Linear cathodic polarization

50
angle (°)

Polarization curves of plasma treated samples were

40
recorded in 0.025 mol L1 NaOH solution (pH = 12.6;
30 scan rate 1 mV min1) for various exposure times to the
discharge (Fig. 11).
20
The height of the cathodic polarization wave increases
10 with the exposure time as the reduction wall attributed to
0
water reduction progressively shifts from 1.1 V/SCE to
0 5 10 15 20 25 30 35 40 45 50 55 60 about 1.25 V/SCE. Theses features agree with an increas-
AISI 1018 t (min) ing coating of the sample surface by oxide/hydroxide moi-
eties with the exposure time to the discharge.
Fig. 10. Contact angle (°) to water of AISI 1018 treated samples as For 30 min treatments, the cathodic polarization curves
function of the exposure time to the discharge. show a large reduction band, from 0.8 V/SCE to 1.0 V/

-1.3 -1.2 -1.1 -1.0 -0.9 -0.8 -0.7 -0.6 -0.5 -.40
0.0E+00
E(V)/SCE

-5.0E-06
J(A/cm2)

-1.0E-05

t = 0 min
t = 30 min
t= 40 min
t = 60 min
-1.5E-05

Fig. 11. Cathodic polarization curves in 0.025 mol L1 NaOH solution, pH = 12.6, of AISI 1018 steels treated under plasma. Surface rotation speed under
plasma: 2400 rpm. Scan rate 1 mV min1. Exposure times to discharge: (a) t = 0 min, (b) t = 30 min, (c) t = 40 min, and (d) t = 60 min.
 F. Depenyou Jr. et al. / Corrosion Science 50 (2008) 1422–1432 1429

Table 2 SCE, centred close to 0.9 V/SCE. Many iron oxide/

Experimental and theoretical reduction Potentials of some iron oxides/ hydroxides are reduced in this potential range, e.g.,
hydroxides in NaOH solution [4]
Fe2O3/Fe(0), Fe3O4/Fe(0), Fe(OH)2/Fe(0) or FeOOH/
Couple observed Ered (V/ECS) Etheo (V/ECS) Fe(OH)2 as showed in Table 2. A less broad but more
Fe2O3/Fe(0) 0.86 0.87 intense reduction band, centred at 0.86 V/SCE, appears
Fe3O4/Fe(0) 0.95 0.95 for 40 min treatment. A broad peak centred at 1.17 V/
Fe(OH)2/Fe ECS appears for 60 min treatment, consistent with the
Fe2O3/FeO 1.01 0.97 reduction of Fe(OH)3 to Fe(II).
The intensity of the peak centred at 0.86 V/SCE
Fe(OH)2/Fe (0) 1.05 1.05
increases with treatment time and follows the relation:
Fe3O4/Fe(0) 1.08
FeOOH/Fe(OH)2 1.17 1.18
jJ j ¼ 0:1134t þ 3:1108; R2 ¼ 0:9111
Fe(OH)3/Fe(II)
The relevant electronic transition can be attributed to the
FeOOH/Fe(0) 0.75 0.78
0.97 0.95
reduction of Fe2O3 to Fe(0).
However, the height of the reduction wave linearly
FeOOH/Fe(OH)2 0.77 0.8
increases with exposure time in the range 0–60 min, but
0.90 0.90
1.18 1.18 tends to be steady for treatments at least longer than
1.21 1.2 150 min (Fig. 11). The potential of the water reduction wall
however progressively shifts toward more reductive poten-

-1.30 -1.20 -1.10 1.00 -0.90 -0.80 -0.70 -0.60 -0.50

0E+00
E(V)/SCE -1E-06
-2E-06
-3E-06
-4E-06
-5E-06
-6E-06
-7E-06
-8E-06
-9E-06
-1E-05
-1E-05
-1E-05
-1E-05
-1E-05
-2E-05
J(A.cm-2)

-2E-05
-2E-05
t = 150 t = 60 t=0 -2E-05

Fig. 12. Voltammograms of AISI 1018 steels treated under plasma. Rotation speed: 2400 rpm. Electrolyte: 0.025 mol/L NaOH solution, pH = 12.6; scan
rate 1 mV min1: t = 0 min (a), t = 60 min (b), and t = 150 min (c).

-F e
(1 1 0 )
-F e
-F e
(2 2 0 )
(2 0 0 )
Intensity (a.u.)

In cid e n ce ra sa n te (1°)

-F e
(1 1 1 )

In cid e n ce n o n
E 5
ra sa n te (15°- 60°) : -F e
co n fig u ra tio n (2 0 0 ) -F e -F e -F e
B ra g g -B re n ta n o
(2 2 0 ) (3 1 1 ) (2 2 2 )

30 40 50 60 70 80 90 100 110 120

2θ (°)

Fig. 13. X-ray diffractogram of the AISI 1018 carbon steel treated by plasma for 5 min (E5).
1430 F. Depenyou Jr. et al. / Corrosion Science 50 (2008) 1422–1432

tials (Fig. 12). It is close to 1.20 V/SCE for untreated 3.6. Mössbauer spectroscopy
mild steel, 1.25 V/SCE for 60 min treated samples and
1.30 V/SCE for 150 min exposure to the discharge. For Mössbauer spectra of plasma 150 min treated (E150)
long treatments, compounds at the surface tend to trans- and untreated (E0) samples were recorded at room temper-
form into more stable species which are hardly reduced ature. The analysed depth is close to 10 nm.
at the electrode The spectrum of the E0 sample is characteristic of
a AISI 1018 steel. It shows contributions from austenite
3.5. X-rays analysis
Velocity (mm/s)
The mild steel samples were analysed with a Bruker D8
-10 0 +10
diffractometer. Various analyses were performed with vari-
able incident angles fixed in the 15–60° range according to 1.09
a Bragg–Brentano (h–2h) setting, i.e., a configuration which
enables investigating the upper 5 lm layer of the sample.
Then, the incident angle was set to low values (1° and 3°) to
reduce the analysed depth and to increase the contribution

Absorption (%)
of the surface in the diffractogram. Figs. 13 and 14 report
the X-rays spectra of the 30 min plasma treated samples.
1.00
All the results obtained in Figs. 13 and 14 are coherent. 1.09
Diffractograms recorded in Bragg–Brentano configuration
show the peaks of austenite c-Fe. Analyses realised with
small incident angle (1°) show that the surface of the plasma
treated AISI 1018 steel is enriched in ferrite phase a-Fe.
These results suggest that austenite present at the solid sur-
face transforms into ferrite during the plasma treatment.
This observation is consistent with the following 1.00
reaction:
c  Fe þ H2 O þ O2 þ e ! a  FeOOH þ OH Untreated AISI 1018 carbon steel (E0)
At high temperature
Paramagnetic contribution from austenite γ-Fe
a  FeOOH ! a  Fe2 O3 δ = - 0,10 ± 0,01 mm/s
However, there is not a clear difference between the diffrac- Δ = 0,15 ± 0,01 mm/s
61 % of the spectrum surface area
tograms of treated steels, whatever the treatment duration
is. The accuracy of the X-rays diffractometry technique is
limited in measuring the influence of the plasma treatment Paramagnetic contribution from ferrite α-Fe
on the surface change of the steel. This implies that a pas- δ = - 0,02 ± 0,02 mm/s
sive film is first formed during the sample polishing. Expos- 2ε = - 0,04 ± 0,03 mm/s
ing to the discharge then induces the formation of a thin B = 25,5 ± 0,2 T
(few nanometers) passive layer [17,18], which is mainly 39 % of the spectrum surface area
composed of amorphous or not well crystallized oxides/ Fig. 15. Mössbauer spectra at room temperature of the untreated AISI
hydroxides. 1018 carbon steel (E0). Contributions from the two phases present at the
surface are displayed.

-F e
(1 1 0 )
-F e -F e
(2 0 0 ) (2 2 0 )
Intensity (u.a.)

I n ci d e n c e ra sa n te (1 °)

I n c i d e n c e ra sa n te (3 °)

-F e
(1 1 1 )

I n c id e n c e n o n
E 150
ra sa n te (1 5 °- 60 °) : -F e -F e -F e -F e
c o n fi g u ra tio n (2 0 0 )
B ra g g -B re n ta n o (2 2 0 ) (3 1 1 ) (2 2 2 )

30 40 50 60 70 80 90 100 110 120

2θ (°)

Fig. 14. X-ray diffractogram of the AISI 1018 carbon steel treated by plasma for 150 min (E150).
 F. Depenyou Jr. et al. / Corrosion Science 50 (2008) 1422–1432
c-Fe and ferrite a-Fe. The austenite is adjusted with a sin-
glet, corresponding to a paramagnetic contribution. The
ferrite is adjusted with a sextuplet, corresponding to a mag-
netic contribution. These contributions can be observed in
Fig. 15.
The adjustment is coherent with X-rays analyses show-
ing that the studied steel contains mostly austenite, with
an important proportion of ferrite at the surface.
The spectrum of the sample treated for 150 min (E150)
is adjusted with the contributions of austenite (c-Fe) and
ferrite (a-Fe). The spectra of samples E0 and E150 are
compared in Fig. 16. A supplementary paramagnetic con-
tribution constituted by a doublet was adjusted in order
to take into account a slight broadening at the basis of
the austenite contribution.
Hyperfine parameters of this contribution correspond to
iron oxyhydroxides such as FeOOH. However, the very
low Mössbauer intensity of this signal is close to the detec-
tion limit of the analysis. An acceptable adjustment of the
spectrum can be obtained without this contribution
As observed for the treatment of stainless steels [5] the
humid air plasma interacts with the steel surface and mod-
Velocity (mm/s)
-10 0 +10
1.09
Absorption (%)
1.00
1.08
1.00
Comparison of samples E0 and E150
Sample E0 (upper)
austenite : 61 %
ferrite : 39 %
Sample E150 (lower)
austenite : 63 %
ferrite : 35 %
FeOOH : 2%
Fig. 16. Mössbauer spectra at room temperature of the AISI 1018 carbon
steel. Untreated sample (E0) and sample treated during 150 min ( E150).
The oxyhydroxide FeOOH contribution is shown on the spectrum of the
sample E150.
1431
ifies the phase distribution, or transforms the (a-Fe) phase
into an oxide. The ratio of the (a-Fe) phase in the untreated
AISI 1018 mild steel is 39%, while for 150 min exposure
time to the discharge, it falls down to 35%. This feature
may suggest that of the (a-Fe) phase transforms into the
(c-Fe) phase, as observed lepidocrocite (c-FeOOH), or
the formation of an Iron oxide. The latter suggestion
is more likely owing to the appearance of reduction
peaks in the electrochemical investigation of the treated
surfaces.
The Mössbauer spectra of treated and untreated sam-
ples are not very different, which may be related to the lim-
ited changes in the surface composition resulting from the
plasma treatment and to the intrinsic sensitivity of the
method.
4. Conclusion
Using a gliding discharge technique for the treatment of
carbon steel provided interesting results which are directly
related to the chemical properties of the instable species
formed in the discharge. The highly oxidative properties
of the OH radicals alter the surface sample and form more
resistive barrier layers which improve the corrosion poten-
tial and dramatically decrease the corrosion current for
30 min plasma treatment.
The contact angle measurement showed that the hydro-
philic character of the mild steel surface was largely
increased, which confirmed the effects already observed
for AISI 304 stainless steel [19]. This hydrophilic character
is related to the presence of a passive film, involving polar
species at the surface.
Polarization curves showed that the presence of a pas-
sive film increased the corrosion potential and reduced
the corrosion current density in 0.5 mol L1 NaCl solution.
Better corrosion protection was obtained on sample
exposed on a rotating sample holder, which confirms the
positive effect of sample rotation on improving the
plasma-surface interaction. The large passive domain of
the treated samples showed by the polarization curves in
0.01 mol L1 NaNO3 at pH: 11.8 suggest the presence of
Fe(II) oxides or hydroxides, as Fe3O4 and Fe(OH)2. Catho-
dic polarization curves recorded in 0.025 mol L1 NaOH
pH: 12.8 showed reduction peaks that are tentatively
assigned to compounds such as Fe(OH)3, FeOOH,
Fe3O4, Fe2O3.
The presence of lepidocrocite FeOOH on treated sam-
ples was also suggested by Mössbauer spectroscopy. X rays
analysis showed the presence of a very thin surface layer
enriched in ferrite (a-Fe) phase. X rays analysis and the
decrease of the reduction wave intensity in NaOH suggest
that the difficult reducible compound observed on the
plasma treated surface for long time (150 min) could be
a-Fe2O3. Identification of the hydroxides/oxides formed,
which are likely Fe(OH)3, FeOOH, Fe3O4 or Fe2O3, needs
confirmation by more sensitive surface techniques.
1432 F. Depenyou Jr. et al. / Corrosion Science 50 (2008) 1422–1432
Acknowledgements
The authors are grateful to the French Government for
a Grant attributed to one of them (F. Depenyou Jr.). This
financial support allowed performing the experimental part
of F. Depenyou’s co-directed Thesis (University of Yaoun-
de-I, Cameroon and University of Rouen, France) and
strengthening the co-operation research program between
these universities.
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