Inuence of Cu and Sn content in the corrosion

of AISI 304 and 316 stainless steels in H

2
SO
4
A. Pardo
*
, M.C. Merino, M. Carboneras, F. Viejo,
R. Arrabal, J. Mun oz
Departamento de Ciencia de Materiales, Facultad de Qumica, Universidad Complutense,
28040 Madrid, Spain
Received 22 March 2004; accepted 13 May 2005
Available online 20 July 2005
Abstract
This paper addresses the inuence of Cu and Sn addition on the corrosion resistance of
AISI 304 and 316 stainless steels in 30 wt% H
2
SO
4
at 25 and 50 C. The corrosion process
was evaluated by gravimetric tests, DC measurements and electrochemical impedance spec-
troscopy (EIS). The corrosion products were analysed by SEM, X-ray mapping and XPS
before and after accelerated tests. The behaviour of both AISI 304 and 316 stainless steels
in sulphuric acid solution was greatly improved by increasing Cu concentration and the syn-
ergic eect of Cu and Sn. Addition of Sn increased corrosion resistance, but less than addition
of copper.
2005 Elsevier Ltd. All rights reserved.
Keywords: Stainless steel; Acid corrosion; General corrosion
1. Introduction
Austenitic stainless steel manufacturers have started to replace iron oxide ores
with iron scrap as raw material. Usually, iron scraps are contaminated with Cu
0010-938X/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2005.05.002
*
Corresponding author. Tel.: +34 1 3944348; fax: +34 1 3944357.
E-mail address: anpardo@quim.ucm.es (A. Pardo).
Corrosion Science 48 (2006) 10751092
www.elsevier.com/locate/corsci
and Sn, which can signicantly alter the corrosion behaviour of stainless steels.
Moreover, Cu and Sn contents above 3 wt% and 0.12 wt% respectively can nega-
tively aect hot workability during manufacturing.
With this in mind, if Cu and Sn additions were not too much detrimental in
behaviour of stainless steels, these alloys could be fabricated from recycled iron scrap
without the need to reduce copper and tin to below the limits established by stan-
dards in the steelmaking process.
The use of copper as an alloying element in austenitic stainless steels can be jus-
tied as follows: (a) copper stabilizes austenite [1], making it possible to reduce the
nickel content in the alloy. This entails a signicant economic saving since nickel
content is high, and nickel is expensive; (b) copper is a good stabilizer against mar-
tensitic transformation [2,3], giving rise to more stable austenite; (c) Copper increases
general corrosion resistance and helps to improve steel corrosion resistance in sul-
phuric acid [47].
The behaviour of stainless steels in sulphuric acid is complex, since these are nei-
ther strong oxidizing nor strong reducing solutions. In this sense, small amounts of
metal salts or organic substances in solution are enough to transform stainless steels
from the passive to the active state [8]. Easily reducible cations such as Fe
3+
, Cu
2+
,
Sn
4+
and Ce
4+
are oxidizing agents, capable of inhibiting attack on stainless steels in
H
2
SO
4
[9]. Therefore, in addressing stainless steel resistance in sulphuric acid solu-
tions, we need to specify the exact composition of the corrosive medium.
Vernau et al. [10] have reported that copper always increases stainless steel corro-
sion resistance in acid media, although its inuence depends on the oxidizing
strength of the solution. Many other researchers have studied the benecial eect
of copper addition on stainless steels corrosion in acid mediums [1114].
Regarding the mechanism of the benecial eect of copper, several authors [15,16]
have pointed out that this is based on the suppression of anodic dissolution by ele-
mental copper deposition on the steel surface immersed in the corrosive medium.
The role of copper in stainless steel passivation is complex and leads to apparently
incongruent results, which could be related to the synergetic eect between dierent
elements in the alloy. For instance, Wilde and Greene [1719] noted that copper, due
to its low hydrogen overpotential, has a benecial eect on stainless steel passivation
in non-oxidizing acid mediums. Similarly, Ramchandran et al. [20] showed the posi-
tive eect of copper on steel passivation in sulphuric acid. However, Seo et al. [5]
established that copper reduces the stability of the passive layer. Again, Lizlovs [4]
found that copper reduces the stability of the passive layer in stainless steels with less
than 1% Mo, but such stability increases for higher levels of Mo up to 3%.
There are only a limited number of references in the literature to the eect of Sn
addition and the synergy of Sn and Cu. Osozawa [21] and Takizawa et al. [22] ob-
served positive synergy of Cu and Sn in austenitic stainless steel corrosion resistance
in both diluted sulphuric and organic-chlorinated acid mediums. One possible mech-
anism suggested by these authors is preferential dissolution of Cu and Sn, favouring
the formation of a stable lm of metallic copper and tin oxides on the steel surface.
This paper attempts to evaluate the eect of Cu and Sn on the corrosion resistance
of two austenitic stainless steels (AISI 304 and 316) in 30 wt% H
2
SO
4
.
1076 A. Pardo et al. / Corrosion Science 48 (2006) 10751092
2. Experimental procedure
The test materials were AISI 304 and 316 austenitic stainless steels with dierent
concentrations of Cu and Sn. Chemical compositions of these materials are given in
Tables 1 and 2. The alloys chosen were fabricated in ingots of 40 kg in a Pfeier
VSG030 vacuum induction furnace. Vacuum was applied during the rst part of
the melting process in order to remove oxygen. No vacuum was applied in ne-tun-
ing additions and casting operations at the end of the process, which were carried out
in a 1 bar argon atmosphere. The ingots were hot forged into 4 mm plates and cold
rolled into 2.5 mm sheets.
Rectangular samples (50 25 2.5 mm) were used for the corrosion tests. Before
the general corrosion test, specimens were prepared by pickling in HNO
3
15 wt%
HF 2 wt% at 60 C for 2 min and water cleaning, followed by passivation in
HNO
3
65 wt% at 60 C for 1 min.
Gravimetric tests were carried out in 30 wt% H
2
SO
4
at 25 and 50 C open to air.
The acid solutions were renewed every three days. Before the experiment, the sample
area was measured and weighed to a precision of 0.01 mg. Upon completion of the
experiment, the sample was extracted, cleaned with water, dried at 105 C for 30 min
in a furnace and then weighed again at room temperature. The subsequent loss of
mass per unit of surface area was then calculated for the dierent test times. The tests
were performed in duplicate to guarantee the reliability of the results.
DC electrochemical measurements were performed using rectangular samples
with a surface area of approximately 14 cm
2
exposed to the test medium. A three-
electrode cell was used for electrochemical measurements. The working electrode
was the test material. The counter and reference electrodes were graphite and Ag/
AgCl respectively. Polarization measurements were carried out at a scan rate of
0.1 mV/s, from 100 mV to +100 mV with respect to the corrosion potential (E
corr
).
Table 1
Chemical composition of AISI 304 stainless steels
Material Elements (wt%)
Cu Sn C Si Mn Ni Cr P S Mo N
290 0.500 0.009 0.060 0.410 1.070 8.130 18.210 0.028 0.002 0.100 0.0288
291 1.010 0.008 0.052 0.390 1.730 8.020 18.070 0.027 0.001 0.100 0.0400
292 1.980 0.009 0.053 0.410 1.420 8.020 17.980 0.027 0.001 0.100 0.0337
293 3.100 0.008 0.050 0.420 1.670 7.980 17.630 0.029 0.001 0.100 0.0423
294 0.560 0.023 0.053 0.430 1.520 8.050 18.110 0.028 0.001 0.100 0.0404
295 0.991 0.073 0.062 0.411 1.750 8.012 17.932 0.028 0.001 0.102 0.0421
296 1.997 0.113 0.043 0.335 1.560 7.800 17.648 0.030 0.001 0.311 0.0360
297 0.280 0.012 0.046 0.344 1.599 8.056 18.101 0.030 0.001 0.320 0.0393
298 0.267 0.049 0.042 0.308 1.668 8.035 18.022 0.030 0.001 0.323 0.0424
299 0.268 0.100 0.048 0.330 1.719 8.075 17.986 0.030 0.001 0.323 0.0482
300 0.267 0.142 0.045 0.355 1.64 8.071 18.091 0.029 0.002 0.328 0.0402
301 0.262 0.188 0.044 0.354 1.487 8.094 17.978 0.030 0.002 0.329 0.0381
A. Pardo et al. / Corrosion Science 48 (2006) 10751092 1077
Table 2
Chemical composition of AISI 316 stainless steels
Material Elements (wt%)
Cu Sn C Si Mn Ni Cr P S Mo Ti Nb Co N
302 0.500 0.012 0.022 0.380 1.562 10.326 17.345 0.033 0.001 2.151 0.010 0.009 0.119 0.0365
303 0.980 0.012 0.034 0.402 1.438 10.228 17.325 0.032 0.001 2.128 0.007 0.009 0.120 0.0345
304 1.474 0.011 0.041 0.343 1.463 10.036 17.105 0.032 0.001 2.117 0.006 0.007 0.123 0.0352
305 1.988 0.011 0.037 0.366 1.381 10.170 17.148 0.034 0.001 2.107 0.005 0.009 0.119 0.0367
306 2.479 0.011 0.041 0.369 1.505 10.091 17.017 0.034 0.001 2.083 0.006 0.009 0.116 0.0392
307 0.404 0.041 0.042 0.375 1.593 10.317 17.348 0.032 0.001 2.149 0.004 0.009 0.117 0.0382
308 0.401 0.091 0.038 0.384 1.538 10.207 17.187 0.033 0.003 2.157 0.004 0.008 0.123 0.0362
309 0.401 0.132 0.033 0.368 1.555 10.214 17.152 0.033 0.001 2.140 0.004 0.008 0.125 0.0366
310 0.402 0.185 0.039 0.378 1.555 10.164 17.154 0.031 0.001 2.147 0.004 0.007 0.123 0.0370
311 0.734 0.057 0.048 0.378 1.632 10.103 17.194 0.033 0.001 2.137 0.004 0.007 0.123 0.0538
312 0.988 0.078 0.034 0.376 1.482 10.075 17.171 0.034 0.001 2.140 0.004 0.007 0.125 0.0330
313 1.483 0.090 0.045 0.376 1.531 9.987 16.958 0.032 0.001 2.120 0.003 0.007 0.123 0.0420
314 1.990 0.114 0.028 0.376 1.532 9.905 16.956 0.032 0.001 2.111 0.003 0.007 0.125 0.0327
1
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a
r
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o
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.
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C
o
r
r
o
s
i
o
n
S
c
i
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n
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(
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1
0
9
2
Electrochemical impedance measurements were performed using an AUTOLAB
model PGSTAT12 potentiostat with frequency response analyzer (FRA) software.
The frequency ranged from 100 kHz to 1 mHz with ve points/decade. In each case,
the target material was immersed in 30 wt% H
2
SO
4
at 25 C. The immersed area was
2 cm
2
.
The morphology of the corrosion products was analysed by SEM. Stainless steels
were examined by X-ray mapping and X-ray photoelectron spectroscopy (XPS) be-
fore and after gravimetric tests. XPS spectra were taken in an ultra high vacuum
chamber (UHV) equipped with an energy electron analyser (VG 100 AX) (pressure
around 10
9
Torr, Mg K
a
radiation, 15 kV and 20 mA). Before analysis, the samples
were degassed overnight (10
7
Torr) in the pre-treatment chamber and then placed
in the analysis chamber. After subtraction of a Shirley-type non-linear baseline,
the spectra were decomposed using a commercial tting program (VGX 900) with
a Gaussian/Lorentzian ratio of 85/15. Binding energies are referenced to the
C(C, H) component of the C(1s) adventitious carbon xed at 284.6 eV. Atomic
ratios were calculated from relative intensities corrected by the elemental sensitivity
factor of each atom [23].
3. Results and discussion
3.1. Gravimetric tests
Fig. 1a shows the variation of the corrosion rate with increasing Cu, Sn and
Cu + Sn contents in 30 wt% H
2
SO
4
at 25 and 50 C for AISI 304 stainless steels.
Addition of Cu drastically reduced the corrosion rate of AISI 304 material in diluted
H
2
SO
4
. This eect was more signicant when the test temperature was reduced from
50 to 25 C. Addition of Sn reduced the corrosion rate of AISI 304 stainless steels in
sulphuric acid. Nevertheless, the corrosion rate was high at all Sn concentrations
tested, indicating that Sn provided less protection than Cu. Additionally, the corro-
sion rate drastically decreased with temperature. The synergic eect of Cu and Sn
Fig. 1. Variation of the corrosion rate with Cu and Sn concentration: (a) AISI 304 and (b) AISI 316.
A. Pardo et al. / Corrosion Science 48 (2006) 10751092 1079
signicantly increased the corrosion resistance of AISI 304. The corrosion resistance
due to the synergic eect of Cu and Sn was similar to that of materials with only Cu
addition.
Fig. 1b shows the variation of the corrosion rate of AISI 316 stainless steels with
increasing Cu, Sn and Cu + Sn contents in 30 wt% H
2
SO
4
at 25 and 50 C. The cor-
rosion rates were lower in AISI 316 than in AISI 304 stainless steels. The eect of Cu,
and Cu + Sn addition on corrosion behaviour in AISI 316 stainless steels was similar
to the eect in AISI 304 stainless steels, but less intense. Addition of Sn did not aect
general corrosion of AISI 316 in sulphuric acid, but the corrosion rate was high at all
Sn concentrations tested. Sn provided less protection than Cu. The corrosion rate
increased drastically with temperature.
Tables 3 and 4 show the kinetic laws calculated for all tests from the experimental
data. In each case the kinetics were calculated adjusting to a linear equation y = a +
bt, where y coordinate represents the mass loss in units of mg/cm
2
, t is the
immersion time in days, and a and b are the parameters of the linear regression,
being b the corrosion rate in mg/cm
2
d. In all cases, the t regression parameters
(r
2
) were close to unity. For AISI 304, copper addition up to 3 wt% reduced the cor-
rosion rate from 54.89 to 2.51 mg/cm
2
d at 25 C and from 350.73 to 23.94 mg/cm
2
d
at 50 C. The synergic eect of Cu and Sn presented a similar pattern. The inuence
of tin addition was slighter, and the corrosion rate decreased from 58.43 to 50.06 mg/
cm
2
d at 25 C and from 600.13 to 210.21 mg/cm
2
d at 50 C. Corrosion rates in
AISI 316 were lower. Addition of 2.479 wt%Cu reduced the corrosion rate from
0.26 to 0.05 mg/cm
2
d at 25 C and from 59.60 to 9.00 mg/cm
2
d at 50 C. Addition
of 0.185 wt%Sn reduced the corrosion rate from 6.30 to 4.96 mg/cm
2
d at 25 C and
from 56.80 to 47.96 mg/cm
2
d at 50 C. In the AISI 316 stainless steel, copper addi-
tion practically inhibited corrosion in stainless steel immersed in 30 wt% H
2
SO
4
at
room temperature and open to air.
Table 3
Kinetic laws of gravimetric tests of AISI 304 stainless steels in 30 wt% H
2
SO
4
at 25 and 50 C for 6 days
Material Kinetic law [y (mg/cm
2
), t (d)]
H
2
SO
4
30 wt%, 25 C H
2
SO
4
30 wt%, 50 C
290 y = 54.89t 67.96 2 6 t 6 6 (r
2
= 0.995) y = 350.73t + 22.41 0 6 t 6 2 (r
2
= 0.988)
291 y = 30.05t 53.10 2 6 t 6 6 (r
2
= 0.994) y = 214.24t 5.27 0 6 t 6 3 (r
2
= 0.999)
292 y = 6.27t 9.78 2 6 t 6 6 (r
2
= 0.986) y = 67.31t 2.03 0 6 t 6 6 (r
2
= 1)
293 y = 2.51t 2.99 2 6 t 6 6 (r
2
= 0.985) y = 23.94t 0.43 0 6 t 6 6 (r
2
= 0.997)
294 y = 49.25t 56.90 1 6 t 6 6 (r
2
= 0.994) y = 304.33t 7.71 0 6 t 6 2 (r
2
= 0.998)
295 y = 19.91t 22.80 1 6 t 6 6 (r
2
= 0.993) y = 135.81t 4.53 0 6 t 6 4 (r
2
= 0.999)
296 y = 3.44t 4.10 1 6 t 6 6 (r
2
= 0.993) y = 23.91t 1.89 0 6 t 6 6 (r
2
= 0.999)
297 y = 58.43t 57.70 1 6 t 6 6 (r
2
= 0.999) y = 600.13t 1778.8 3 6 t 6 4 (r
2
= 1)
298 y = 55.22t 60.03 1 6 t 6 6 (r
2
= 0.999) y = 478.76t 751.30 2 6 t 6 3 (r
2
= 1)
299 y = 56.70t 77.83 2 6 t 6 6 (r
2
= 0.988) y = 281.96t + 21.56 0 6 t 6 2 (r
2
= 0.983)
300 y = 49.25t 81.76 2 6 t 6 6 (r
2
= 0.972) y = 226.31t 0.24 0 6 t 6 2 (r
2
= 1)
301 y = 50.06t 82.15 2 6 t 6 6 (r
2
= 0.988) y = 210.21t 229.31 2 6 t 6 4 (r
2
= 0.996)
1080 A. Pardo et al. / Corrosion Science 48 (2006) 10751092
3.2. DC electrochemical results
The repassivation eect of Cu and the synergic eect of Cu and Sn were checked
by carrying out consecutive polarization tests on the same sample at dierent immer-
sion times in 30 wt% H
2
SO
4
. Between measurements the system evolved freely, so
that each polarization measurement indicates the degree of repassivation due to
the presence of Cu on surface material. Fig. 2a shows the polarization curves
of the AISI 304 stainless steel without Cu (material 290). After 6 days of immersion
the material showed a marked tendency to dissolve. With the addition of 3.1 wt%Cu
(material 293) the corrosion rate decreased sharply. After the rst day of immersion
this material tended to revert to its original behaviour, which suggests that the cop-
per dissolved was deposited on the surface, causing repassivation of the material
(Fig. 2b). However, AISI 316 presented high corrosion resistance when immersed
in 30 wt% H
2
SO
4
at 25 C in all cases (Fig. 2c and d), probably due to the synergic
eect of Mo and Cu. The synergic eect of Cu and Sn was comparable to the eect of
adding 3 wt%Cu in AISI 304 (Fig. 2e and f). The synergic eect of Cu and Sn was
less positive in AISI 316, probably due to synergism between Mo, Cu and Sn
(Fig. 2g and h). The reduction in the corrosion rate produced by Sn addition was
smaller in both AISI 304 and AISI 316 stainless steels in 30 wt% H
2
SO
4
.
3.3. AC Electrochemical results
The eect of Cu addition on the corrosion resistance of AISI 304 and AISI 316
stainless steels in 30 wt% H
2
SO
4
at 25 C was evaluated by electrochemical imped-
ance spectroscopy (EIS). Fig. 3a and b shows the Nyquist diagrams as a function
of the immersion time for materials 290 and 293. A rst arc was observed at high
and intermediate frequencies followed by a second arc or ill-dened tail. The rst
Table 4
Kinetic laws of gravimetric tests of AISI 316 stainless steels in 30 wt% H
2
SO
4
at 25 and 50 C for 6 days
Material Kinetic law [y (mg/cm
2
), t (d)]
H
2
SO
4
30 wt%, 25 C H
2
SO
4
30 wt%, 50 C
302 y = 0.26t 0.54 2 6 t 6 6 (r
2
= 0.974) y = 59.60t + 0.82 0 6 t 6 6 (r
2
= 0.998)
303 y = 0.18t 0.41 2 6 t 6 6 (r
2
= 0.978) y = 20.47t 3.05 0 6 t 6 6 (r
2
= 0.996)
304 y = 0.18t 0.34 2 6 t 6 6 (r
2
= 0.999) y = 15.79t 0.06 0 6 t 6 6 (r
2
= 0.999)
305 y = 0.10t 0.18 2 6 t 6 6 (r
2
= 0.998) y = 11.11t 1.17 0 6 t 6 6 (r
2
= 0.997)
306 y = 0.05t 0.04 3 6 t 6 6 (r
2
= 0.987) y = 9.00t 0.99 0 6 t 6 6 (r
2
= 0.999)
307 y = 6.30t 13.08 2 6 t 6 6 (r
2
= 0.990) y = 56.80t + 6.17 0 6 t 6 6 (r
2
= 0.999)
308 y = 5.06t 10.75 2 6 t 6 6 (r
2
= 0.985) y = 56.78t + 6.39 0 6 t 6 6 (r
2
= 0.999)
309 y = 5.83t 12.74 2 6 t 6 6 (r
2
= 0.982) y = 47.26t + 1.42 0 6 t 6 6 (r
2
= 1)
310 y = 4.96t 9.36 2 6 t 6 6 (r
2
= 0.996) y = 47.96t 0.08 0 6 t 6 6 (r
2
= 1)
311 y = 3.48t 7.17 2 6 t 6 6 (r
2
= 0.994) y = 28.33t + 3.81 0 6 t 6 6 (r
2
= 0.997)
312 y = 2.53t 5.52 2 6 t 6 6 (r
2
= 0.988) y = 17.33t 1.11 0 6 t 6 6 (r
2
= 0.998)
313 y = 1.89t 2.46 2 6 t 6 6 (r
2
= 0.986) y = 11.41t 3.48 0 6 t 6 6 (r
2
= 0.992)
314 y = 0.86t 2.45 3 6 t 6 6 (r
2
= 0.992) y = 8.94t 0.26 0 6 t 6 6 (r
2
= 1)
A. Pardo et al. / Corrosion Science 48 (2006) 10751092 1081
Fig. 2. Polarization curves for stainless steels in 30 wt% H
2
SO
4
at 25 C. Materials: (a) 290; (b) 293;
(c) 302; (d) 306; (e) 294; (f) 296; (g) 311 and (h) 314.
1082 A. Pardo et al. / Corrosion Science 48 (2006) 10751092
arc is attributed to charge transfer, associated with the eect of ionic double layer
capacity. Fig. 3c and d shows the Nyquist diagrams as a function of the immersion
time for materials 294 and 296. The Nyquist diagram was similar for both 294 and
290 stainless steels. However, the synergic eect of Cu and Sn produced changes in
the diagrams of stainless steels with higher percentages of these elements, generating
arcs that did not intersect with the x-axis at any point in the frequency interval.
Fig. 4a and b shows the Nyquist diagrams as a function of immersion time for
materials 302 and 306 (AISI 316). At a low Cu concentration the behaviour was sim-
ilar to material 290. When Cu concentration increased to 2.479 wt% the arc widened
to low frequencies after 3 days of immersion, without intersecting with the x-axis.
After 3 days of immersion the corrosion behaviour was similar to material 302
but lower in intensity. Fig. 4c and d shows the Nyquist diagrams as a function of
the immersion time for materials 311 and 314. The synergic eect of Cu and Sn pro-
duced changes in the diagrams. Both 311 and 314 stainless steels presented arcs that
did not intersect with the x-axis and which widened into low frequencies. These arcs
became smaller as immersion time increased.
Tables 5 and 6 show the values of R
ct
(charge transfer resistance) and C
dl
(double
ionic layer capacity), deduced from the arcs at high and intermediate frequencies.
Fig. 3. Nyquist diagrams of AISI 304 stainless steels in 30 wt% H
2
SO
4
at 25 C for 14 days. Materials:
(a) 290; (b) 293; (c) 294 and (d) 296.
A. Pardo et al. / Corrosion Science 48 (2006) 10751092 1083
Fig. 4. Nyquist diagrams of AISI 316 stainless steels in 30 wt% H
2
SO
4
at 25 C for 14 days. Materials:
(a) 302; (b) 306; (c) 311 and (d) 314.
Table 5
Charge transfer resistance (R
ct
) values for tested stainless steels in 30 wt% H
2
SO
4
at 25 C
Time (d) R
ct
(X cm
2
)
290 293 302 306 294 296 311 314
1 9 4.5 10
3
23 6.9 10
5
8 1.2 10
6
2.3 10
6
2.1 10
6
3 6 1.7 10
3
8 5.2 10
5
4 1.3 10
6
1 10
6
1.6 10
6
6 5 6.7 10
2
6 5.9 10
3
6 1.5 10
6
6.5 10
5
6 10
5
14 3 3.9 10
2
5 3.7 10
3
3 5 10
5
2.2 10
5
2.1 10
5
Table 6
Capacitance (C
dl
) values for tested stainless steels in 30 wt% H
2
SO
4
at 25 C
Time (d) C
dl
(lF/cm
2
)
290 293 302 306 294 296 311 314
1 1.3 10
4
1.9 10
2
1.6 10
4
3 1.1 10
4
31 22 13
3 4.7 10
4
2.7 10
2
4.9 10
4
4 8.6 10
4
28 49 17
6 1.3 10
5
1.3 10
3
7.8 10
4
3.6 10
2
2.5 10
5
24 77 47
14 1.1 10
5
3.8 10
3
9.3 10
4
5.7 10
2
1.4 10
5
71 2.3 10
2
1.3 10
2
1084 A. Pardo et al. / Corrosion Science 48 (2006) 10751092
Stainless steels with low Cu and Sn contents showed small values of R
ct
that did not
change signicantly with immersion time. However, addition of higher percentages
of Cu and Sn produced a sharp increase of the R
ct
value. The enormous capacitance
values measured in stainless steels with low Cu content stand out from all the other
values measured for higher Cu additions. This is logical if the electrode is porous, in
which case the active surface could be 100 to 1000 times greater than the apparent
surface. The porous morphology was probably due to an irregular corrosion attack
or to a spongy copper deposit with a dendritic morphology; this would have formed
on the corroded stainless steel surface (Fig. 5), giving rise to the formation of a por-
ous electrode. Nevertheless, the R
ct
values were substantially increased by both Cu
addition and the synergic eect of Cu and Sn.
Stern-Gearys B constant was calculated from the Tafel slopes of the polarization
curves. The i
corr
was obtained from R
ct
values for dierent immersion times from the
expression i
corr
= B/R
ct
. Current density was converted to mass loss (W), expressed
in mg/cm
2
d, by applying Faradays law and integrating the graphic of i
corr
versus
time
W KEW
Z
i
corr
dt;
where K = 8.95 10
4
mg cm
2
/lA cm
2
d, EW = alloy equivalent weight (considered
dimensionless in these calculations) and i
corr
= corrosion current density in lA/cm
2
.
Mass loss data after 1, 3, 6 and 14 days, evaluated by electrochemical impedance
spectroscopy, reveal a clear tendency for corrosion rates to increase with immersion
time after an initial induction period (Table 7).
The equivalent circuit changed as a function of Cu and Sn concentration in the
materials tested. Therefore, stainless steels with a high corrosion rate (materials
290, 294, 302) presented R
ct
values in the region of 525 X cm
2
. Besides the charac-
teristic elements of the circuit -charge transfer resistance (R
ct
), double ionic layer
Fig. 5. Dendritic morphology of Cu deposit on the surface of AISI 304 (material 293) after 6 days
immersed in 30 wt% H
2
SO
4
at 50 C.
A. Pardo et al. / Corrosion Science 48 (2006) 10751092 1085
capacity (C
dl
), ohmic resistance of electrolyte (R
s
), the inductive contribution must
be incorporated by including the L element (inductance) and the resistance R
2
con-
nected in series (Fig. 6a). Addition of higher percentages of Cu and Sn signicantly
reduced the corrosion rate because of the synergic eect CuSn and CuSnMo. In
fact, R
ct
was very high and modied the equivalent circuit represented in Fig. 6b. In
all cases, R
s
was very small (0.51 X).
3.4. Morphology of corrosion products
Fig. 7 shows an SEM analysis of AISI 316 stainless steel (material 306) surface
morphology when immersed in 30 wt% H
2
SO
4
at 50 C for 6 days. The material sur-
face showed that the corrosion rate was related to a major general corrosion attack.
X-ray mapping revealed the presence of Cu on the material surface.
Fig. 8 shows XPS spectra of Cu 2p
3/2
before and after the sulphuric immersion
test for both AISI 304 and 316 stainless steels. The Cu signal in both 293 and 306
passivated spectra was weak, since copper concentration on the surface was less than
1 at%. Both 293 and 306 spectra presented two superimposed peaks, one at 932.2 eV
corresponding to Cu
0
and another at 934.1 eV corresponding to Cu
2+
; however,
there was little Cu
2+
on the surface of the material before the test, and its surface
Table 7
Mass loss versus immersion time for tested stainless steels in 30 wt% H
2
SO
4
at 25 C
Material Mass loss (mg/cm
2
)
1 day 3 days 6 days 14 days
290 3.21 144.85 625.43 2083.97
293 0.02 0.37 1.31 6.27
302 4.15 64.11 161.34 400.93
306 0.0002 0.001 0.135 0.461
294 17.27 140.61 264.02 645.40
296 0.0001 0.0002 0.0008 0.0082
311 0.0001 0.0003 0.0008 0.0037
314 0.0001 0.0005 0.0028 0.0054
Fig. 6. Equivalent circuit models for tested materials: (a) in active state and (b) in less active state.
1086 A. Pardo et al. / Corrosion Science 48 (2006) 10751092
concentration after the test was in the range 2028 at%. Fig. 9 shows the Fe 2p
3/2
spectra for materials 293 and 306 before and after aggressive immersion, with
two overlapping peaks corresponding to Fe
3+
, one at 710.2 eV and another at
Fig. 7. Material 306 (AISI 316) after 6 days in 30 wt% H
2
SO
4
at 50 C: (a) SEM morphology of corrosion
attack and (b) Cu X-ray mapping.
Fig. 8. XPS spectra of Cu 2p
3/2
for 293 and 306 materials before and after exposure to 30 wt% H
2
SO
4
at
50 C.
A. Pardo et al. / Corrosion Science 48 (2006) 10751092 1087
712.5 eV. These peaks reect oxides and sulphates of Fe
3+
. Fe
0
was not detected on
the surface of the material after immersion in sulphuric acid. This indicates that the
corrosion layer was thicker than the initial passivated layer. Table 8 shows the XPS
results of Cu and Fe elements for materials 290, 293, 302 and 306 after immersion
tests. Table 9 shows the surface chemical composition of the same materials before
and after exposure to sulphuric medium expressed as atomic percentages calculated
from the XPS results without taking carbon and oxygen into account. Note the high
Cu concentration on the material surface exposed to sulphuric acid.
SEM, X-ray mapping and XPS studies conrmed the presence of copper metal
and ferric oxide and sulphate on the material surfaces after the immersion tests.
Both AISI 304 and AISI 316 stainless steels in contact with H
2
SO
4
can present
any of three kinds of electrochemical behaviour: active, passive or activepassive.
Without Cu, these steels presented active behaviour and a high corrosion rate when
immersed in 30 wt% H
2
SO
4
at 50 C. Since copper reduced the hydrogen overpoten-
tial, addition of up to 3.1 wt%Cu in AISI 304 and up to 2.479 wt%Cu in AISI 316
favoured activepassive behaviour and a signicant reduction of the corrosion rate.
Corrosion behaviour in this zone was not stable and produced erratic corrosion
rates. Slight changes in the environment can cause a shift towards active behaviour.
Fig. 9. XPS spectra of Fe 2p
3/2
for 293 and 306 materials before and after exposure to 30 wt% H
2
SO
4
at
50 C.
1088 A. Pardo et al. / Corrosion Science 48 (2006) 10751092
In fact, there was a regular oscillation between active and passive behaviour. Behav-
iour at 25 C was preferentially passive [24].
Tin increased the hydrogen overpotential. Addition of Sn shifted the cathodic
polarization curve to lower current densities, thus reducing the corrosion rate. The
reduction in the corrosion rate was lower than with addition of Cu.
Additions of Cu and Sn at higher concentrations than considered in this paper
seem likely to increase corrosion resistance. That increase will depend on the whether
Cu and Sn aect the process of material manufacturing negatively or positively (such
levels of Cu and Sn can aect the hot ductility of stainless steels during fabrication).
The authors propose a new mechanism: the material in contact with 30 wt% H
2
SO
4
loses its passive layer, producing mainly Cr
3+
ions (Fig. 10a). Once the passive layer
Table 8
Cu and Fe XPS adjusted results for tested stainless steels
Material Species Concentration
(at.%)
Area
(a.u.)
Position
(eV)
Height
(a.u.)
Width
(eV)
290 Cu
0
+ Cu
+
82.4 8001.1 932.2 3661.5 2.0
Cu
2+
17.6 1708.3 934.2 769.8 2.0
Fe
3
joxide
77.9 1489.0 710.2 409.6 3.3
Fe
3
jsulphate
22.1 421.4 712.5 115.9 3.3
293 Cu
0
+ Cu
+
54.5 3451.9 932.3 1573.5 2.0
Cu
2+
47.5 3125.7 934.0 1035.1 2.8
Fe
3
joxide
58.6 973.8 710.2 268.1 3.3
Fe
3
jsulphate
41.4 689.0 712.5 189.1 3.3
302 Cu
0
+ Cu
+
100 3668.7 932.3 1639.2 2.1
Fe
3
joxide
82.7 5071.9 710.2 1484.7 3.1
Fe
3
jsulphate
17.3 1058.5 712.5 291.8 3.3
306 Cu
0
+ Cu
+
51.6 3092.5 932.1 1366.8 2.1
Cu
2+
48.4 2899.7 934.2 988.7 2.7
Fe
3
joxide
85.3 2678.7 710.4 789.4 3.1
Fe
3
jsulphate
14.7 463.2 712.5 131.0 3.3
Table 9
Surface chemical composition of tested stainless steels before and after immersion in 30 wt% H
2
SO
4
at
50 C
Material Cu Si Ni Cr S Mo Fe
Before immersion tests 290 0.56 10.61 1.14 66.44 0 0 21.25
293 1.43 15.11 1.33 56.64 0 0 25.49
302 0.41 11.85 1.71 62.01 0 4.80 19.22
306 0.84 10.25 0.80 58.56 0 7.10 22.45
After immersion tests 290 23.64 53.89 0.41 5.62 12.69 0 3.75
293 13.73 48.97 0.29 2.15 30.51 0 4.35
302 15.61 15.77 6.78 3.61 20.2 16.61 21.42
306 28.8 9.81 3 2.9 23.41 19.54 12.54
A. Pardo et al. / Corrosion Science 48 (2006) 10751092 1089
has been dissolved, other elements of the metallic matrix can be incorporated into the
solution in the form of cations, such as Cu
2+
and Fe
3+
(Fig. 10b). These cations have
high reduction potentials (Fe
3+
+ 1 e

!Fe
2+
, E = 0.771 V, and Cu
2+
+ 2 e

!
Cu
0
, E = 0.34 V) and are strong oxidizing agents. In this way, Cu and Fe are reduced,
plating the surface as Cu
0
, CuSO
4
, Fe
2
O
3
and FeSO
4
. Copper plating considerably
reduces hydrogen overpotential and favours partial regeneration of the passive layer.
The layer of oxidized products is composed mainly of Cr
2
O
3
, Cu
0
, CuSO
4
, Fe
2
O
3
and
FeSO
4
(Fig. 10c). The deposition of these elements and compounds drastically re-
duces the corrosion rate of these materials when immersed in 30 wt% H
2
SO
4
at
50 C and tends to inhibit the process at room temperature.
4. Conclusions
1. The corrosion resistance of AISI 304 stainless steels in 30 wt% H
2
SO
4
at 50 C
increased sharply with the addition of Cu as an alloy element. This eect was
more signicant in AISI 316 stainless steels. However, the corrosion rate was still
Fig. 10. Corrosion mechanism proposed: (a) passive layer dissolution; (b) metal cation dissolution and
(c) Cu reduction and formation of an oxide semi-protective layer.
1090 A. Pardo et al. / Corrosion Science 48 (2006) 10751092
high. When the test temperature was reduced to 25 C, corrosion resistance was
very high and the corrosion rate was not a signicant damage factor.
2. Sn addition reduced the corrosion rate of AISI 304 stainless steels, but less than
Cu. The eect of Sn was insignicant in AISI 316 stainless steels.
3. The synergic eect of Cu and Sn was similar to the eect of Cu added solely in
AISI 304 stainless steels, and also, but to a lesser extent, in AISI 316 stainless
steels.
4. Both AISI 304 and AISI 316 stainless steels in contact with H
2
SO
4
can present
any of three kinds of electrochemical behaviour: active, passive or activepassive.
Additions of Cu to AISI 304 and AISI 316 favoured activepassive behaviour and
a signicant reduction of the corrosion rate. Additions of Sn reduced the corro-
sion rate in lower magnitude than Cu addition. The synergic eect of Cu and
Sn seems likely to increase corrosion resistance as Cu does.
Acknowledgements
The authors wish to thank both ACERINOX S:A for the supply of stainless steels
and the MCYT for the nancial support given to this work (Project MAT2003-
04931-C02-01).
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