Corrosion Science 53 (2011) 64–70

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Corrosion behaviour of AISI type 304L stainless steel in nitric acid media
containing oxidizing species
S. Ningshen, U. Kamachi Mudali ⇑, S. Ramya, Baldev Raj
Corrosion Science and Technology Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102, India

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

Article history: The corrosion behaviour of AISI type 304L stainless steel (SS) in different concentration of 0.01 M, 1 M
Received 11 March 2010 and 5 M HNO3 in presence of oxidizing ions at different temperatures has been evaluated. The main
Accepted 2 September 2010 objective of this study is to assess the corrosion resistance of type 304L SS in non-radioactive conditions
Available online 17 September 2010
encountered during storage of liquid nuclear waste. Electrochemical impedance spectroscopy (EIS) and
laser Raman spectroscopy (LRS) has clearly brought out the deleterious effect of oxidizing species on
Keywords: the passive film leading to increased corrosion along with increase in HNO3 concentration and higher
A. Stainless steel
temperature.
B. Polarization
B. EIS
Ó 2010 Elsevier Ltd. All rights reserved.
B. Raman spectroscopy
C. Acid corrosion

1. Introduction reaction is the reduction reaction of HNO3; (b) nitric acid media
containing oxidizing species, in which the cathodic reaction the
Austenitic SS are widely used as structural and storage materi- reaction of reduction of the oxidizing species and; (c) nitric media
als for handling nitric acid media in nuclear fuel reprocessing containing metallic elements electrochemically more noble than
plants owing to their excellent corrosion resistance with the for- the SS, causing galvanic coupling [2,4]. In addition, nitric acid med-
mation of a chromium rich Cr2O3 passive film on the substrate ia used in storage of spent nuclear fuel can undergo autocatalytic
[1–3]. However, during storage and operating conditions of nuclear reduction [2,4]. Hence, corrosion characteristics in such environ-
conditions of nuclear fuel reprocessing in highly oxidizing nitric ments is needed to be experimentally studied and understood
acid media, a number of corrosion problems are brought into focus properly to understand the degradation processes involved in
recently [1–5]. For example, transpassive corrosion is a phenome- non-radioactive conditions during storage of liquid nuclear waste
non observed in nitric acid, if the concentration and temperature environments.Towards the corrosion of SS in nitric acid, solute seg-
increases or highly oxidizing chemical species co-exists. Corrosion regation, thermal history, chemical homogeneity and non-metallic
potential is shifted into more noble direction over passive region inclusion of the material affect its corrosion resistance [1–3,5].
and SS suffered severe intergranular corrosion (IGC) even if the However, limited results on the effects of oxidizing ions on the cor-
steel is not sensitized [1,2,4]. The preferentially enhanced suscep- rosion behavior of SS in nitric acid media have been reported [6–
tibility of IGC attack at grain boundaries is attributed largely to 10]. Studies have confirmed that in boiling nitric acid solution,
impurities, silicon and phosphorus segregation and local chro- the presence of Np(VI) [6] and Pu(VI) [7] ions lead to aggressive
mium depletion (sensitization) brought about by the precipitation IGC attack in type 304L SS [6,7]. In such oxidizing media, metallic
of chromium carbides (Cr23C6) [1–3]. In such condition, protective ions produced from redox couples shift the redox potential higher
2
Cr2O3 film is oxidized to Cr(VI) forming HCrO 4 or HCr2 O7 and than that of nitric acid and accelerate corrosion. Similar studies
looses the corrosion resistant property, as Cr6+ ions are highly sol- carried out in presence of oxidizing ions also revealed that, for type
uble [1–5]. In nitric acid, the corrosion potential of the SS depends 310Nb SS [8] and type 304L SS [1,2], the corrosion rate is depen-
greatly on the cathodic reaction involved in the redox process be- dent both on corrosion potential and concentration of ions present
tween the elements Fe, Cr, Ni of the steel and the oxidizing ions or [1,2,6,10]. Accelerated IGC attack has also been reported; in con-
species present in the medium [2,3]. Three reasons can be attrib- fined and non-renewed nitric acid [9,10]; in HNO3 solutions con-
uted to ennoblement of SS corrosion potential in reprocessing taining ions of Mn(VII) ðMnO 
4 Þ; CrðVIÞðCr2 O7 Þ, Ce(IV), RuO(IV),
media; (a) pure nitric acid–water solution, in which the cathodic Rh(III), Fe(III) etc. [11–15]. Similarly, various workers have shown
that the rate of IGC attack increase with increases in HNO3 concen-
⇑ Corresponding author. Tel./fax: +91 44 27480121. tration, solution temperature, and specimen stress leve1
E-mail address: [email protected] (U. Kamachi Mudali). [3,4,10,12,14,15]. In nitric acid, corrosion acceleration associated

0010-938X/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2010.09.023
 S. Ningshen et al. / Corrosion Science 53 (2011) 64–70 65

with reduction of higher valence ion to lower valence ion in pres-

ence of oxidizing ions has also been reported [10,14,16]. Moreover, CPE
little information is available towards understanding the effects of
nitric acid concentration and temperature in presence of oxidizing RS
ions on the corrosion and passive film property of type 304L SS.
Thus, effects of such redox ions in different nitric acid concentra-
tion and temperature on the corrosion characteristics of SS thereby RP
simulating waste storage in non-radioactive conditions have been
attempted in this study. Fig. 1. The equivalent circuit of RS (CPE||RP) used for fitting the experimental
Nyquist plots.

2. Material and experimental methods Electrochemical interface in the frequency range of 0.01 Hz to
100 kHz by superimposing an AC voltage of 10 mV amplitude.
2.1. Materials and sample preparation The EIS results were interpreted using simple ‘‘equivalent circuit”
shown in Fig. 1. The circuit description consists of Rs (CPE||RP) ele-
The chemical composition of AISI type 304L SS used in the pres- ments, where Rs is the solution resistance; CPE is the constant
ent investigation is shown in Table 1. All the as-received SS sam- phase in parallel connection with RP which is the polarization
ples were solution annealed at 1050 °C for 30 min to homogenize resistance. The characteristic parameters of these elements values
the microstructure. Specimens of 10 mm  10 mm  2 mm were are then obtained directly by fitting the experimental impedance
cut and then polished mechanically by abrading with SiC emery curves using Zview Version 2.6 (Scribner Inc.) software.
paper up to 1000 grit size on all sides. The surface of the specimen In the present investigation, constant phase element (CPE) has
was then polished to mirror finish (1 lm finish) with diamond been used to obtain better fit for experimental data and this will
paste. After this, the specimens were ultrasonically cleaned in ace- represent the generalized form of passive film double layer capac-
tone and washed with double distilled water before using them for itance. The impedance expression of CPE is given by [5,18,19];
electrochemical experiments. A specially devised Teflon holder
was used for exposing only the polished surface to the electrolyte Z CPE ¼ 1=½TðjxÞn  ð1Þ
during the experiment. where x is the angular frequency, T and n are frequency-indepen-
dent fit parameters, j = (1)1/2 and x = 2pf, where f is the frequency
2.2. Electrochemical investigation for corrosion assessment in Hz. n is defined as being [19]:

All the electrochemical corrosion test measurements were n ¼ 1  2a=180 ð2Þ

carried out in different nitric acid (Analytical Grade) concentration where n is the depression angle (in degrees) that evaluates the
of 0.01 M, 1 M and 5 M HNO3 containing oxidizing ions in part per semi-circle deformation/depression. The factor n, defined as a CPE
million (ppm) in weight percent of Cr(VI) (5 ppm  0.000005 wt.%), power, is an adjustable fit parameter that lies between 0.5 and 1.
Ru(III) (3 ppm  0.000003 wt.%), Fe(III) (32 ppm  0.000032 wt.%) When n = 1, the CPE describes an ideal capacitor. For 0.5 < n < 1,
and Ce(IV) (2 ppm  0.000002 wt.%). The required amount of each the CPE describes a distribution of dielectric relaxation times in fre-
ions were taken from respective salts and after weighing were added quency space, and when n = 0.5 the CPE represents a Warburg
together in the volumetric flask and were dissolved in 0.01 M, 1 M impedance [18,19]. The correction factor introduced by Hsu and
and 5 M HNO3. The salts used as a source of oxidizing ions were Mansfeld [19] was used to measure capacitance of the passive oxide
CrO3, RuCl3, FeCl3.6H2O and Ce(NO3).6H2O. The corrosion measure- film.
ments were carried out at room temperature (RT), 50 °C and 70 °C. The electrochemical measurement including potentiodynamic
and EIS experiments were carried out in open to atmosphere and
2.2.1. Potentiodynamic polarization experiments non-stirred condition.
All the potentiodynamic anodic polarization experiments were
carried out using the five necks ASTM electrochemical cell consisting 2.3. Laser Raman spectroscopy measurement
of three electrodes; reference electrode (Ag/AgCl in saturated KCl),
counter electrode (Pt) and working electrode. Solartron 1287 Elec- In order to study the passive film composition, ex-situ LRS
trochemical Interface was used for conducting the polarization experiments were performed on samples developed with passive
experiments. The potentiodynamic anodic polarization experiments film formed by potential sweep in the anodic direction to passive
were carried out at the scan rate of 10 mV/min and polarization region and by holding potentiostatically at passive region for 1 h.
experiment was continued till the breakdown of transpassive poten- Prior to LRS experiments, the sample surfaces were ultrasonically
tial occurred. All the electrode potentials were measured against Ag/ cleaned with double distilled water followed by ultrasonic cleaning
AgCl (saturated KCl) reference electrode. Polarization tests were in acetone to remove the surface electrolyte contaminants, and air
conducted for triplicate specimens in each experimental condition dried for 15–20 min. The samples were properly preserved in a
and all the polarization plots were almost reproducible. The experi- vacuum desiccator and then transferred immediately for the LRS
mental details are described elsewhere [5,17]. measurement. Similarly, reference measurements were also taken
to be compare and eliminate any signal arising due to inadequate
2.2.2. Electrochemical impedance spectroscopy measurements washing or electrolyte left on the surface when dried. HR 800
The EIS measurements were carried out using Solartron (Jobin Yvon) Raman spectrometer equipped with 1800 grooves/
1255 Frequency Response Analyzer (FRA) and Solartron 1287 mm holographic grating was used. The samples were placed under
an Olympus BXFM-ILHS optical microscope mounted at the en-
trance of the Raman spectrograph. He–Ne laser of 633 nm was
Table 1
Chemical composition of alloy of type 304L SS in wt %. used as an excitation source. The laser spot size of 3 lm diameter
was focused on the sample surface using a diffraction limited 10
Alloy Cr Ni C Si Mn P S N Fe
(NA = 0.25) long distance objective. The laser power at the sample
304L 19.0 9.35 0.018 0.54 1.60 0.04 0.02 0.02 Balance
was 8.6 mW. The slit width of the monochromator was 300 lm
66 S. Ningshen et al. / Corrosion Science 53 (2011) 64–70

which corresponds to a resolution of 4 cm1. The back scattered

Raman spectra were recorded using super cooled (<110 °C)
1024  256 pixels charge-coupled device (CCD) detector, in static
mode over the range of 80–2000 cm1 with 5s exposure time
and 20 CCD accumulations. Super cooled of very low CCD temper-
ature was maintained to avoid thermal fluctuations. Raman spectra
were collected at various points of each sample, and were observed
to be reproducible.

3. Results and discussion

3.1. Passive film analysis by laser Raman spectroscopy

Laser Raman spectroscopy (LRS) measurement was carried out to

investigate the composition of passive films formed on type 304L SS.
The influence of nitric acid concentration at different temperatures
in presence of different oxidizing ions was studied. All the Raman Fig. 3. LRS shift of passive film formed on type 304L SS in different HNO3
spectra shown in Figs. 2 and 3 represent the oxides identified by concentration in presence of oxidizing ions measured at 70 °C.
comparison with standard Raman spectral references. The Raman
findings including the Raman shift (cm1), relative peak intensity 715 cm1, 610 cm1 and at 560 cm1 can be seen in addition to
of normalised to height of maximum peak in spectra and assigned broad features in between, centered at 247 cm1 and 350 cm1.
species are summarized and given in Table 2. In Fig. 2, the LRS mea- Even at higher temperature (70 °C), these spectra do not change
surement of type 304L SS at different nitric concentration at room significantly and the Raman spectra remain essentially the same
temperature is represented and all the generated LRS peaks are la- as observed in room temperature (Fig. 3) with the 800 cm1 and
beled by the location of their maximum peak intensity. The Raman 846 cm1 peaks dominating the spectra. It appears that no correla-
peaks at 525 cm1 is assigned to Cr(OH)3 and 560 cm1 for Cr2O3. tion of Raman peak intensity with nitric acid concentration and
Cr2O3 and Cr(OH)3 are the thermodynamically stable species and temperatures could be observed which may be the result of
frequently postulated as constituents of passive film. The source of involvement of other oxides formation. Moreover, it has been re-
the 500–650 cm1 peak is either due to clusters of chromium cations ported that the peak intensity of the Raman bands is proportional
and OH, or hydrated, trivalent chromium cations [20–22]. How- and related to the thickness of the passive film [24]. In addition,
ever, Melendres et al. attributed weak peaks in this range to Cr(OH)3 since the passive films are relatively thin, it is difficult for LRS to
[23]. Further, the Raman bands observed suggests that the peaks at produce distinguishing signal as passive oxides are known to pro-
around 520 cm1, 640 cm1, 670 cm1, and 715 cm1 correspond duce unique signal that are related to hydration, structure, and
mostly to c-Fe2O3 or Fe3O4. The 1050 cm1 band, which is ascribed composition [24,25]. Further, the presence of oxidizing ions could
to vibrations of NO3 is clearly visible. The broad peaks observed at not be detected probably due to low concentration of the ions
858 cm1, corresponds to mixed Cr(III)/Cr(VI) oxide and the peak and limitation in the measurement. In both room temperature
at 933 cm1 is assigned to Cr(VI) of CrO2 4 species [22]. The broad- and 70 °C measurement, the most intense Raman peaks were ob-
ness of the peaks observed stretching from 120 to 400 cm1 and in served at around 846 cm1. According to Maslar et al. this feature
between 650 and 1050 cm1 is most likely associated with an amor- is attributed to Cr–oxygen stretching modes or mixed chromium
phous or microcrystalline character to the film [20]. These results re- oxide vibrational modes [25]. To date, only few LRS studies have
veal that a heterogeneous mixture of oxides and hydroxide are been conducted on the passive films formed on type 304L SS in
present in type 304L SS. Hence, further studies will be required to HNO3. Kiuchi et al. [26] using LRS revealed that the chemical state
understand the above oxide formation using complimentary surface of the passive film constitute complex anions like CrO2 4 and NO3


analytical techniques. with cations like Mn+. Similarly in the present study, Raman active
Raman spectra of passivated samples in different nitric acid at modes for CrO24 (898 cm
1
and 348 cm1) and Cr2 O27 (946 cm
1
,
higher temperature (70 °C) are shown in Fig. 3. Raman peak at 902 cm1, 554 cm1, 251 cm1 etc.) are detected in both condi-
tions. Thus, the presence of such species can affect the passive film
0.5
304L SS at RT property and thereby influence the corrosion behaviour. The corre-
(a) 0.01 M HNO3 lations between the passive film composition measured by LRS
0.4
(b) 1 M HNO3 measurement and the corrosion behavior characterized by electro-
Normalised intensity (a.u)

(c) 5 M HNO3 chemical techniques are discussed in the later part.

0.3 - 3.2. Potentiodynamic polarization studies – effects of nitric acid

Cr(III) -(VI) mixed oxides/CrO4
concentration and temperature
Fe2O3 (c)
0.2
(a) The results of potentiodynamic polarization are shown in
-
2-
Cr2O7 CrO4
2-
(b) 2-
NO3 Figs. 4–6, respectively. All the measured parameters of the poten-
Cr2O7
0.1
Cr2O3 tiodynamic polarization measurement are given in Table 3. Tafel-
Cr(OH)3
like region could not be clearly seen in these polarization curves.
Hence, the Tafel extrapolation method [27,28] based on non-linear
0.0 least square algorithm of Levenberg-Marqurdt (LEV) method using
200 300 400 500 600 700 800 900 1000 1100 1200
-1 CorrView 2 software (Scribner Associates, Inc.) was used to extrap-
Raman shift (cm )
olate the corrosion current density (icorr) value. As shown in Fig. 4,
Fig. 2. LRS shift of passive film formed on type 304L SS in different HNO3 lower corrosion current (icorr), lower anodic passive current density
concentration in presence of oxidizing ions measured at room temperature. (Ipass) and higher transpassive breakdown (ETP vs Ag/AgCl) was
 S. Ningshen et al. / Corrosion Science 53 (2011) 64–70 67

Table 2
Raman frequencies, normalized peak intensity and assignments of various components of passive films formed on type 304L SS.

Raman shift (cm1) Normalized peak intensity (a.u.) Assign species

Room temperature 70 °C
0.01 M HNO3 1 M HNO3 5 M HNO3 0.01 M HNO3 1 M HNO3 5 M HNO3
250300 0.06 0.05 0.12 0.09 0.03 0.06 Fe–O stretching vibrations
330350 0.06 0.06 0.09 0.08 0.04 0.07 Bending vibrations from CrO2 4
525 0.04 0.05 0.06 0.08 0.03 0.06 Cr(OH)3
560 0.04 0.04 0.1 0.07 0.03 0.09 Cr2O3
640670 0.08 0.08 0.1 0.17 0.04 0.09 Fe3O4
700800 0.16 0.11 0.16 0.25 0.07 0.14 Fe–Cr spinel oxides
800850 0.17 0.16 0.2 0.37 0.09 0.18 Cr (III)–Cr (VI) mixed oxides
900950 0.06 0.07 0.09 0.15 0.03 0.06 Cr (VI) oxides
1050 0.06 0.06 0.1 0.16 0.02 0.035 NO3

2.0 2.0
304LN SS in 0.01 M HNO 3 304L SS in 5 M HNO 3
RT RT
o o
50 C 50 C
1.5 o
70 C 1.5 o
70 C
Potential, V vs Ag/AgCl

Potential, V vs Ag/AgCl
1.0 1.0

0.5 0.5

0.0 0.0

-9 -8 -7 -6 -5 -4 -3 -2 -1 0
10 10 10 10 10 10 10 10 10 10 10
-9
10
-7
10
-5
10
-3
10
-1
10
1
2
C urrent density, (A/cm ) C urrent density, (A/cm )
2

Fig. 4. Potentiodynamic polarization plots of type 304L SS measured in 0.01 M Fig. 6. Potentiodynamic polarization plots of type 304L SS measured in 5 M HNO3
HNO3 at different temperature with oxidizing ions. at different temperatures with oxidizing ions.

(vs Ag/AgCl), except in 5 M HNO3 (Fig. 6). Insignificant effect of oxi-

dizing ions on Ecorr (vs Ag/AgCl) observed may be attributed to gen-
eration of large oxidizing nitrate ions during the reduction process
of nitric acid that any effects are swamped by the nitrate ions.
Armstrong et al. [29] have reported a similar observation which re-
vealed little change in Ecorr (vs Ag/AgCl) in type 304L SS in presence
of dissolved chromium species in nitric acid which was attributed
to complexity of dissolve ions involved in reduction processes.
Moreover, since the Ecorr (vs Ag/AgCl) is the result of the combined
effect of both oxidizing and reducing ions, the relative amounts of
each will dictate its effect on the corrosion of the alloy, and conse-
quently, the passive film properties [2,5,30]. Thus, the presence of
oxidizing ions in nitric acid solutions can either increase or de-
crease Ecorr (vs Ag/AgCl) by promoting anodic reactions or retard-
ing the cathodic reduction of nitric acid by competitive surface
adsorption and thereby affect the corrosion resistance. However,
with increase in temperature and nitric acid concentrations, in-
crease in icorr and IPass is accompanied by a decrease in ETP (vs
Ag/AgCl) (Table 3) which confirms the decrease in the corrosion
Fig. 5. Potentiodynamic polarization plots of type 304L SS measured in 1 M HNO3
at different temperatures with oxidizing ions. resistance in all the cases. In higher temperature and concentra-
tion, increased redox potential of the HNO3/HNO2 system with rel-
observed at lower concentration of 0.01 M HNO3 and at RT (Ta- atively high rate of the autocatalytic reaction is expected [31,32].
ble 3). No shift in the corrosion potential (Ecorr vs Ag/AgCl) could Further, most electrochemical and chemical reactions proceed rap-
be observed even with increase in temperature. However, with in- idly at higher temperature and increasing the temperature aid to
crease in temperature, increase in Ipass and decrease in ETP (vs Ag/ faster transition to transpassive state. As a consequence, it would
AgCl) was observed (Table 3). Almost a similar trend could also be be reasonable to expect an enhanced corrosion processes occurring
observed in the polarization plots obtained in 1 M HNO3 (Fig. 5) particularly in such aggressive and corrosive condition. In the pres-
and at higher concentration of 5 M HNO3 (Fig. 6). It was observed ent case, the presence of oxidizing species has further aggravated
in all the measured conditions that oxidizing ions, temperature the corrosion of type 304L SS along with increased temperature
and nitric acid concentrations have only a marginal effect on Ecorr and nitric acid concentration. Though, the exact reason of the
68 S. Ningshen et al. / Corrosion Science 53 (2011) 64–70

Table 3
Polarization parameters obtained for type 304L SS in different nitric acid concentrations (0.01 M, 1 M and 5 M HNO3) and measured at different
temperatures.

Alloy ECorr (V vs Ag/AgCl) iCorr (A/cm2) IPass (A/cm2) ETP (V vs Ag/AgCl)

0.01 M HNO3 (IPass measured at 1 V vs Ag/AgCl)
304L (RT) 0.25 1.17  107 2.97  106 1.72
304L (50 °C) 0.22 2.18  106 8.78  106 1.58
304L (70 °C) 0.21 1.24  105 2.64  105 1.14
1 M HNO3 (IPass measured at 0.9 V vs Ag/AgCl)
304L (RT) 0.21 2.15  106 6.06  106 1.10
304L (50 °C) 0.18 1.18  105 2.95  105 1.09
304L (70 °C) 0.35 2.23  103 2.14  103 0.92
5 M HNO3 (IPass measured at 0.8 V vs Ag/AgCl)
304L (RT) 0.61 2.37  106 2.97  106 1.13
304L (50 °C) 0.28 2.38  104 1.57  104 1.1
304L (70 °C) 0.35 1.12  103 1.71  103 1.01

combined effect of such oxidizing ions is not clear, the possible role of oxidizing ions is expected to be more dominant at higher
synergistic role of oxidizing ions and temperature with nitric acid concentration and temperature. Further, the electrochemical
can be considered. mechanisms by which oxidizing ions activate IGC attack in non-
The effect of oxidizing ions observed in the present case can be sensitized SS have been described by Streicher [11] and Coriou
understood and explained in the following way. Evans [33] de- et al. [12]. Streicher [11] proposed that crystallographic factors
scribed a mechanism that explains the autocatalytic corrosion of are responsible for IGC susceptibility although it was not stated
metals in nitric acid medium. In most cases, the corrosion of SS explicitly what these factors may be. Coriou et al. [12] established
in HNO3 is attributed to generation of the HNO2 ‘‘electroactive” the close relationship between the IGC and the redox potential be-
species by the global cathodic reaction of nitrate reduction tween regions with different lattice orientations; the cells formed
[9,10,31]. The overall reduction reaction can be represented by locally may be strongly depolarized by certain, sufficiently active
the following electrochemical reactions [10,31,34]: oxidizing ions. The latter proposal attributes the susceptibility of
a material to the geometrical properties by its grain boundaries.
HNO3 þ 2Hþ þ 2e ! HNO2 þ H2 OðEo25 o
C ¼ 934 mV=SHEÞ ð3Þ
Moreover, higher accelerated corrosion observed in type 304L SS
in higher temperature and concentration can also be attributed
4HNO3 ! 2H2 O þ 4NO2 þ O2 ð4Þ
to excessive dissolution of the metal surface due to IGC attack
Reaction (3) is favoured when temperature and nitric acid con- (Fig. 7a and b). Particularly, in higher temperature (50 °C and
centration is low and Reaction (4) is favoured when temperature 70 °C) the corrosion attacked along the grain boundaries was more
and nitric concentration is higher [2,4,5,9]. Subsequently, the gen- prominent (Fig. 7a and b). Finally, the presence of decomposed
2
eration of nitrous acid by autocatalytic reduction of HNO3 arises NO 
3 along with CrO4 and Cr2 O7 species observed in LRS result
due to the production of the oxidant like NO2 [9,10,35]. Hence, (Figs. 2 and 3) are known to enhance passive film solubility
the redox potential and reduced species of nitric acid in Reactions [2,3,4–6] and hence these species can affect and further accelerate
(3) and (4) increases with increase in concentration and tempera- the corrosion reactions.
ture [10,31]. Furthermore, it has been reported that the reduction
of NO3 to NOx is accelerated when the SS corrodes [31]. Thereby, 3.3. Passive film investigation by electrochemical impedance
increasing temperature and presence of oxidizing ions in nitric acid spectroscopy
increases the oxidizing power of the solution and favors the trans-
formation of protecting chromium(III) (as insoluble Cr2O3) oxides The results of the EIS measurement of Nyquist plots behavior of
to soluble chromium(VI) (as soluble Cr2 O2 7 ) [2,4,6,14,26]. In addi- the impedance spectra, recorded under open-circuit conditions
tion, Ru(III) and Fe(III) ions which were added as additive metal (OCP) in 0.01 M, 1 M and 5 M HNO3 at different temperatures in
ions for simulating the dissolver solution are known to accelerate presence of oxidizing ions are shown in Figs. 8–10, respectively.
the corrosion in the presence of reductant such as NOx [36,37]. It The EIS measurements were carried out to elucidate the electro-
has also been reported that low valency Ru species such as the chemical and passive film properties. It is clearly observed that
nitrosyl complex influence the corrosion of SS in nitric acid and all the measured electrochemical impedance plots were character-
that the presence of Fe (III) is known to accelerate the cathodic ized by the presence of single unfinished semi-circle arc indicating
reaction of NO3/HNO2 by catalyzing the nitric acid reduction reac- similar corrosion mechanisms. This is also attributed to charge
tion with high redox potential [31,36–38]. This could clearly reveal transfer process occurring at the metal/electrolyte interface or re-
that in the presence of other oxidizing ions, the generation of ni- lated to the surface passive film property [5,17]. In Fig. 8, EIS mea-
trate is very oxidizing. Furthermore, the presence of more oxidiz- surement in 0.01 M HNO3 shows distinct difference in the
ing species, for example HCrO 4 or Ce(IV), which have high impedance spectra with increase in temperature revealing that
standard redox potentials (CrðIIIÞ=HCrO o
4 : E = 1.35 V vs SHE, the passive film stability behavior is different. The increase in the
Ce(III)/Ce(IV): Eo = 1.61 V vs SHE), [2,9,34,38] are then rapidly re- semi-circle arc indicated an increase in the film stability and
duced again by NOx [2,9]. On the other hand in type 304L SS, the decreasing in semi-circle radius indicates a decrease in the passive
effect of nitric acid concentration (1–10 M) and temperature (25– film resistance. Similar trend are observed in the impedance spec-
75 °C) has indicated the decrease in corrosion resistance for acid tra of type 304L SS measured in 1 M HNO3 (Fig. 9) and 5 M HNO3
concentrations greater than 4 M HNO3 [39]. However, the domi- (Fig. 10), respectively. However, the semi-circle arc radius (Rp) is
nant factors that control the corrosion of nitric acid is the (i) oxidiz- lowest in higher concentration of 5 M HNO3 (Fig. 10). These results
ing power that increases with concentration, (ii) boiling conditions indicate that the passive film properties are markedly different
and (iii) oxidizing species (Fe(IV), Cr(VI), Pu(VI) etc.), that ennoble depending on the acid concentration and temperature in presence
transpassive transpassive corrosion potential [2,6–8]. Hence, the of oxidizing ions. Similarly, these EIS results agree with the
 S. Ningshen et al. / Corrosion Science 53 (2011) 64–70 69

Fig. 7. Optical microstructure of 304L SS after polarization in 5 M HNO3 (a): at 50 °C and (b): 70 °C.

-90
304L SS in 0.01 M HNO 3
-80 RT
0
50 c
0
-70 70 c
-Z'', (kΩ cm )

-60
2

-50

-40

-30

-20

-10

0 10 20 30 40 50 60 70 80 90
2
Z', (k Ω cm )
Fig. 10. Nyquist plots of 304L SS measured in 5 M HNO3 at different nitric acid
Fig. 8. Nyquist plots of type 304L SS at different temperature measured in 0.01 M
concentration in presence of oxidizing ions.
HNO3 with oxidizing ions.

-90 Table 4
304L SS in1 M HNO 3 EIS fitted value of type 304L SS measured under OCP (vs Ag/AgCl) condition at
-80 RT different nitric acid concentration and temperatures.
0
50 C
-70 0 Alloy Rs (X cm2) CPE-T (F/cm2 sn) CPE-n Rp (X cm2)
70 C
-Z'', (kΩ cm )

0.01 M HNO3
2

-60
304L (RT) 1.18 8.74  105 0.828 85,521
-50 304L(50 °C) 3.21 5.35  105 0.780 23,111
304L(70 °C) 3.7 4.62  105 0.804 10,942
-40 1 M HNO3
304L (RT) 2.3 7.57  105 0.828 78,357
-30
304L(50 °C) 2.21 5.01  105 0.790 21,778
304L(70 °C) 1.7 3.82  105 0.784 6755
-20
5 M HNO3
-10 304L (RT) 3.83 3.09  105 0.802 35,821
304L(50 °C) 3.41 1.35  105 0.798 21,111
304L(70 °C) 2.58 4.48  104 0.874 5210
0 10 20 30 40 50 60 70 80 90
2
Z', (k Ω cm )

Fig. 9. Nyquist plots of type 304L SS at different temperature measured in 1 M values are observed. Similar trend is observed in measurement car-
HNO3 with oxidizing ions. ried out in 1 M HNO3 and 5 M HNO3 (Table 4).
As shown in Table 4, the values of Rp decreases with increase in
temperature and concentration. The Rp values are strongly depen-
variation of the respective corrosion current densities (Table 3) ob- dent on the passive film characteristic and corrosion resistance of
served in polarization plots (Figs. 8–10). The fitting parameters of the materials. The higher Rp value implies good corrosion resis-
all the impedance plots are given in Table 4, both as double layer tance. The decrease in the Rp value reflects the protective efficiency
capacitance (CPE-T) and polarization resistance Rp. The fitted decreases of the passive layer. The decrease in Rp is more promi-
impedance parameters shown in Table 4 revealed that in 0.01 M nent at higher 5 M HNO3 and at higher temperature (Table 4). This
HNO3 lower CPE-T values and higher Rp was observed. At higher facet revealed that if the nitric acid medium becomes excessively
temperature of 50 °C and 70 °C higher CPE-T value and lower Rp oxidizing by increase of concentration, temperatures or in presence
70 S. Ningshen et al. / Corrosion Science 53 (2011) 64–70

of oxidizing ions, decreases in protective efficiency and faster pas- observed in polarization plots. In summary the presence of oxidiz-
sive film dissolution can occurs. Lower Rp values may also be re- ing species has further aggravated the corrosion of 304L SS along
lated to increased ionic conductivity resulting in non-protective with increased temperature and nitric acid concentration.
passive film [5,17]. The increase in temperature or higher concen-
tration would markedly accelerate the dissolution processes as the
References
generated HNO2 are known to enhance localized attacks [2,9,31].
Further, the observed electrochemical impedance characteristics [1] Baldev Raj, U. Kamachi Mudali, Prog. Nucl. Energ. 48 (2006) 283–313.
in the HNO3 solutions differed significantly from those in other [2] P. Fauvet, F. Balbaud, R. Robin, Q.-T. Tran, A. Mugnier, D. Espinoux, J. Nucl.
Mater. 375 (2008) 52–64.
acidic solution [5,17,40] as lower Rp values are observed in highly
[3] V. Kain, S.S. Shinde, H.S. Gadiyar, Mater. Eng. Perf. 3 (1994) 699–705.
oxidizing nitric acid environment [5,17,41]. This is partially attrib- [4] K. Kiuchi M. Hayashi, H. Hayakawa, M. Sakairi, M. Kikuchi, Proceedings of Third
uted to complexity of metal dissolution process involved during International Conference on Nuclear fuel Reprocessing and Waste
corrosion in nitric acid; as different metals are known to exhibit Management (RECOD-91), vol. 2, Sendai, Japan, 1991, pp. 549–554.
[5] S. Ningshen, U. Kamachi Mudali, G. Amarendra, Baldev Raj, Corros. Sci. 51
different rates of dissolution under comparable experimental con- (2009) 322–329.
ditions [30,41]. Thus this will subsequently affect the passive film [6] G. Andreoletti, P. Chambrette, A. Mercier, J.-P. Moulin, F. Thurin, C. Vittoz,
stability in presence of aggressive nitric acid medium. EUROCORR-2006, Maastricht, Netherlands, 25–28th September, 2006.
[7] M. Ozawa, J. Nucl. Sci. Technol. 22 (1985) 68–69.
The measured capacitive response are generally not ideal (i.e., [8] M. Okubo, M. Shintani, H. Ishimaru, K. Tokunaga, M. Nagayama, A. Itoh.,
pure capacitance) in real electrochemical processes and thus the Proceedings of International Conference on Nuclear Fuel Reprocessing and
CPE is often used to take account of the non-ideal capacitance of Waste Management (RECOD-87) Conference, vol. 3, Paris, France, 23rd–27th
August, 1987, pp. 1181–1188.
the passive film formed. As shown in Table 4, the CPE-T values [9] F. Balbaud, G. Sanchez, G. Santarini, G. Picard, Eur. J. Inorg. Chem. 4 (2000) 665–
are relatively lower for measurement at lower temperature and 674.
concentration (Table 4). The decrease in capacitance or CPE-T re- [10] F. Balbaud, G. Sanchez, P. Fauvet, G. Santarini, G. Picard, Corros. Sci. 42 (2000)
1685–1707.
flects the amount of charge associated with the degree of oxidation [11] M.A. Streicher, J. Electrochem. Soc. 106 (1959) 161–180.
of the sample, and smaller the charge, higher is the resistance of [12] H. Coriou, J. Huruz, G. Plante, Electrochim. Acta 5 (1961) 105–111.
the sample for oxidation or corrosion [42]. However, increased [13] V. Bague, S. Chachoua, Q.T. Tran, P. Fauvet, J. Nucl. Mat. 392 (2009) 396–404.
[14] J.S. Armijo, Corrosion 21 (1965) 235–244.
CPE-T values with temperature and concentration could be attrib-
[15] J.S. Armijo, Corros. Sci. 7 (1967) 143–150.
uted to the non-homogenous nature or local defects of the protec- [16] C.R. Bishop, Corrosion 19 (1963) 308t–314t.
tive surface, which weaken the chemical bonds and the passive [17] S. Ningshen, U. Kamachi Mudali, P. Mukherjee, A. Sarkar, P. Barat, N. Padhy,
film property [5,14,39]. The nature of passive film formed in nitric Baldev Raj, Corros. Sci. 50 (2008) 2124–2134.
[18] M. Drogowska, H. Ménard, A. Lasia, L. Brossard, J. Appl. Electrochem. 26 (1996)
acid will also depend on the metal surface, defect, pores and oxi- 1169–1177.
dizing ions/species [1,2,43]. In the presence of oxidizing ions in [19] C.H. Hsu, F. Mansfeld, Corrosion 57 (2001) 747–748.
HNO3, higher solubility of the complex formed would enhance [20] L.J. Oblonsky, T.M. Devine, Corros. Sci. 37 (1995) 17–41.
[21] T.L. Sudesh, L. Wijesinghe, D.J. Blackwood, Appl. Surf. Sci. 253 (2006) 1006–
the dissolution of the passive film [5,31]. Addition of oxidizing ions 1009.
will further lead to passive film instability and acceleration of cor- [22] J.D. Ramsey, L. Xia, M.W. Kendig, R.L. McCreery, Corros. Sci. 43 (2001) 1557–
rosion. Similarly, the power index value of CPE-n (Table 4), which 1572.
[23] C.A. Melendrcs, M. Pankuch, Y.S. Li, R.L. Knight, Electrochim. Acta 37 (1992)
reflected the deviation of capacitance of the passive film from 2747–2754.
the ideal capacitive behavior, was in the range 0.8 and no charac- [24] T. Ohtsuka, J. Guo, N. Sato, J. Electrochem. Soc. 133 (1986) 2473–2476.
teristic trend in CPE-n value can be observed. These values indi- [25] J.E. Maslar, W.S. Hurst, W.J. Bowers Jr, J.H. Hendricks, M.i. Aquino, J.
Electrochem. Soc. 147 (2000) 2532–2542.
cated that the deviation from purely capacitive behavior was [26] K. Kiuchi, H. Hayakawa, Y. Takagi, M. Kikuchi, Proceedings of the Fourth
relatively small. International Conference on Nuclear Fuel Reprocessing and Waste
Management (RECOD-94), vol. 3, London, UK, 1994.
[27] W.J. Lorenz, F. Mansfeld, Corros. Sci. 21 (1981) 647–672.
4. Conclusions [28] J.R. Galvele, Corros Sci. 47 (2005) 3053–3067.
[29] R.D. Armstrong, G.E. Cleland, G.O.H. Whillock, J. Appl. Electrochem. 28 (1998)
The corrosion behaviour of type 304L SS at different nitric acid 1205–1211.
[30] V.P. Razygraev, R.S. Balovneva, E.Y. Pnomareva, M.V. Lebedeva, Prot. Met. 26
concentration (0.01 M, 1 M and 5 M HNO3) and temperatures (RT, (1990) 43–48.
50 °C and 70 °C) in presence of oxidizing ions has been evaluated. [31] K. Kiuchi, J. Atom. Ener. Soc. Jpn. 48 (2006) 871–876.
2
The presence of NO 
3 ; CrO4 and Cr2 O7 in passive film in addition
[32] J.J. Gray, C.A. Orme, Electrochim. Acta 52 (2007) 2370–2375.
[33] U.R. Evans, The Corrosion and Oxidation of Metals, Edward Arnold, London,
to Cr2O3 and Fe2O3 was observed in LRS measurement and the 1960.
presence of these oxidized species accelerated the corrosion pro- [34] M. Pourbaix (Ed.), Atlas of electrochemical Equilibria in Aqueous Solutions,
cesses. The potentiodynamic anodic polarization results revealed NACE, Houston, TX, USA, 1974.
[35] G.O.H. Whillock, S.E. Worthington, Corrosion in nitric acid, in: T.J.A.
no significant change in corrosion potential even with increase in
Richardson, B.R.A. Cottis, R. Lindsay, S. Lyon, D.J.D. Scantlebury, H. Stott, M.
temperature and nitric acid concentration in presence of oxidizing Graham (Eds.), Shreir’s Corrosion, vol. 2, Elsevier Ltd, Amsterdam, 2010, pp.
ions. This could be attributed to the generation of large amount of 1250–1269.
[36] M. Takeuchi, G.O.H. Whillock, Br. Corros. J. 37 (2002) 199–205.
oxidizing nitrate ions and any effects on the corrosion potential is
[37] M. Takeuchi, G.O.H. Whillock, J. Nucl. Sci. Tech. 41 (2004) 702–704.
swamped by these ions. However, excessive metal surface dissolu- [38] M. Mayuzumi, J. Ohta, T. Arai, Corrosion 54 (1998) 271–280.
tion with accelerated IGC processes was observed with increase in [39] G. Suresh, V.R. Raju, U. Kamachi Mudali, R.K. Dayal, Corros. Eng. Sci. Tech. 38
temperature and at higher concentrations. The passive film stabil- (2003) 309–312.
[40] X. Guo, Y. Tomoe, H. Imaizumi, K. Katoh, J. Electroanal. Chem. 445 (1998) 95–
ity measured by EIS revealed faster passive film dissolution as indi- 103.
cated by low film polarization resistance, with increase in nitric [41] A.K. Vijh, Mater. Chem. 2 (1977) 23–33.
acid concentration and temperature. The EIS results correlated well [42] J.W. Schultze, M.M. Lohrengel, Electrochim. Acta 45 (2000) 2499–2513.
[43] J.S. Armijo, B.E. Wilde, Corros. Sci. 8 (1968) 649–664.
with the variation of the respective corrosion current densities