CORROSION SCIENCE

Technical Note: The Need for Caution in

the Use of Cyclic Voltammetry for Predicting
Iron Corrosion Behavior*
B. MacDougall and J. A. Bardwell*

INTRODUCTION
a0
0
The potentiodynamic scan technique has been extensively used
as an accelerated electrochemical test to establish the active and
passive characteristics of numerous metals and alloys in various
environments.' -5 The maximum anodic current in the active-poten-
tial region, called the critical current density, indicates the ease of
passivation for the particular specimen-environment combination.
In this way, a series of alloys (or environments) can be ranked
according to their tendency to passivate and long-term perfor-
mance characteristics can be predicted. There has been consider-
able discussion in the literature about the most appropriate scan
rate to use for reliable ranking and predicting (slow vs intermediate
vs fast) 6-8 and the fact that certain material corrosion properties,
such as pitting potentials, are strongly influenced by the scanning
rate used. 9 Nevertheless, the potentiodynamic approach has been
1
—1400 —900 —400 100 600
reasonably successful as a rapid, accelerated test of long-term
corrosion susceptibility. In this note, results pertaining to iron pas- POTMAL (mV)
sivation in different solutions will be presented. It will be shown
FIGURE 1. Anodic potentiodynamic pro files for Fe at 5 mV s ' in pH
-

that the anodic current and/or charge associated with the active
5.0 acetate solution (—) and pH 8.4 Na 2 SO 4 (- - Elec
-).

dissolution peak is not a good indication of the ease of passivation

trodes were electropolished and cathodically reduced before the
in certain cases, and indeed may lead to completely incorrect pre-
anodic scan.
dictions about specimen repassivation kinetics.

EXPERIMENTAL
Iron electrodes were prepared as described previously, 10
electropolished, and were then cathodically reduced at 20 µA
cm -2 to remove the previous oxide film before initiating either an
anodic scan at 5 mV s ' or a potential step into the passive re-
-
gion. All experiments were conducted at 25 C.
RESULTS
Figure 1 shows the anodic scans for Fe in both pH 8.4, 0.15
N Na 2 SO 4 and pH 5.0 acetic acid/sodium acetate (made by mixing
solutions of 0.1 N CH 3 000H and 1.0 N CH 3 COONa) in the poten-
tial range from -1.4 to 0.6 V (with respect to Hg/Hg 2 SO 4 /Na 2 SO 4
Submitted for publication April 1988.
*Division of Chemistry, National Research Council of Canada, Ottawa, Ontario,
Canada, KIA 0R9.
0010-9312/88/00205/$3.00/0
CORROSION—Vol. 44, No. 11 © 1988, National Association of Corrosion Engineers 789
as the reference). The two scans are comparable, with the main
difference being the existence of a substantial anodic pre-peak
(before the main anodic peak) in the acetate solution; there was
no indication of this peak in the sulfate solution. The maximum
anodic current is somewhat higher in the acetate solution, and the
total anodic charge passed is correspondingly somewhat higher in
acetate [510 millicoulomb (mcoul) cm -2 compared to 340 mcoul
cm -2 ]. In both solutions, an extensive passive potential region is
observed from ---0.4 to 0.6 V. The potentiodynamic results sug-
gest that, if anything, iron passivation is more difficult in the ace-
tate solution than in the sulfate solution, since both the critical an-
odic current and charge are higher.
In the next series of experiments, instead of scanning the
potential anodically, the potential of the oxide-free iron electrode
was stepped to 0 V (i.e., well into the passive region) and the an-
odic current-time response was monitored. The results obtained in
the acetate and sulfate solutions are shown in Figure 2, a very
large difference in the efficiency of passivation is immediately evi-
dent. In the sulfate solution, an anodic charge of 1150 mcoul cm -2
passes during 60 s, while in acetate, the corresponding charge is
only 7.6 mcoul cm -2 , which would represent the formation of -4.0
CORROSION SCIENCE
1
a.
10" 10` 10' 10 10' 102
TIME (sec)
FIGURE 2. Log i-log t pro files for electropolished and cathodically
reduced Fe upon stepping the potential to 0 V in pH 5.0 acetate
solution (—) and pH 8.4 Na 2 SO 4 (— — —)
nm of y-Fe 2 03 . The majority of the anodic charge which passes in
the acetate solution contributes directly to the growth of the passive
oxide film. In the sulfate solution, most of the charge is consumed
by metal dissolution, with <l% being consumed during film forma-
tion. The potential step results are important for oxide repassiva-
tion, e.g., if passivity were established potentiostatically and the
oxide film failed locally. In such a situation, the results from anodic
potentiodynamic scan experiments would incorrectly predict the
tendency of the electrode to repassivate in the two different solu-
tions.
The anodic scans obtained in acetate solutions of various
pHs are shown in Figure 3. Solution pH significantly influences the
maximum anodic currents and peak potentials of both the pre-
peak and the main peak. The anodic potential step charges for a
60 s polarization at 0 V were 6.7, 6.9, and 6.7 mcoul cm -2 at pH
5.7, 6.4, and 7.5 respectively. Despite the change in anodic elec-
trode activity determined potantiodynamically (Figure 3), little or no
difference exists between the potential step charges, with current
efficiencies for film formation being very high in all cases. The next
series of experiments illustrates that the potentiodynamically deter-
mined anodic activity can change substantially, even at the same
(buffered) pH, if different solution anions are present. This is
shown in Figure 4 with anodic scans obtained in solutions ranging
from pH 7.5 acetate to pH 7.5 borate buffer. Borate substantially
decreases the anodic electrode activity, and in pure borate, the
anodic peak currents are very low indeed. Evidently, the anions
present in the borate buffer have a very beneficial effect on the
anodic behavior of iron as determined by potentiodynamic scans.
For the solutions in Figure 4, the anodic potential step passivation
charges are between 6.7 mcoul cm -2 (pH 7.5 acetate) and 6.1
mcoul cm -2 (pH 7.5 borate); i.e., the anodic current efficiency for
oxide film formation is high in each case. This is another situation
where there can be substantially different anodic sweep character-
istics for systems which all display highly efficient anodic potential-
step passivation behavior.
DISCUSSION
These results show that great caution must be used when
predicting oxide repassivation behavior from anodic potentiodyna-
mic scans. While the anodic scans do provide useful information
about certain types of corrosion behavior, they can also lead to
entirely incorrect predictions about such things as efficiency of ox-
ide formation (or reformation) in the cases above. This laffer infor-
mation is very important when dealing with the local oxide break-
down and reformation processes involved in (eventual) pitting
790 CORROSION—November 1988
-1400 -900 -400 100 600
POTEN11AL (mV)
FIGURE 3. Anodic potentiodynamic profiles for Fe at 5 mV s ' in -
acetate solutions of various pH values: (—) pH 5.7; (— — —) pH
6.4; (— •— ) pH 7.5. Electrodes were electropolished and cathodi-
cally reduced before the anodic scan.
R
-1400 -900 -400 100 600
POTEN11AL (mV)
FIGURE 4. Anodic potentiodynamic pro files for Fe at 5 mV s ' in pH
-
7.5 acetate solutions with different amounts of added pH 7. 5 borate
buffer: (— - —) 0%; (— • —) 5%; (— — —) 25%. Also shown is the
pro file obtained in pH 7.5 borate buffer solution (—). Electrodes
were electropolished and cathodically reduced before the anodic
scan.
corrosion and should be obtained from potentiostatic techniques,
such as anodic potential stepping, or surface scratching to disrupt
an existing film. Potentiodynamic scans can lead to incorrect pre-
dictions of potentiostatic behavior in the present case (Figure 1)
because different processes are involved in iron passivation in the
sulfate as compared to the acetate solutions. In sulfate, passiva-
tion is achieved by the formation of a salt-type film at or near the
electrode and this involves the dissolution of very large amounts of
iron, with whatever experimental approach (potentiodynamic or
potentiostatic) is used. In other words, substantial changes in the
solution chemistry near the electrode are required before passiva-
tion can be achieved; this is true even if high anodic potentials are
applied immediately with a potential step approach (Figure 2).
However, passivation in the buffered acetate solution occurs
through a surface-controlled oxidation reaction, such as M + H 2 0
—> MO + 2H ' + 2e, and does not rely on supersaturating the
solution near the electrode with Fe e ions (as with sulfate). The
iron dissolution that occurs during an anodic scan in acetate in the
so-called "active" region (Figure 1) is incidental to the passivation
process and occurs simply because the potential is not sufficiently
anodic in the early stages of the scan for the passive oxide film to

be established. (An oxide film may actually be on the surface in
this region, but it is not an effective barrier to iron dissolution.) In
acetate solution, when the potential is sufficiently high, a passive
oxide film is established and blocks any further iron dissolution. In
this case, the quicker the passive potentials are achieved, the
more rapidly (and efficiently) passivation is established. For this
reason, anodic potential step passivations facilitate a nearly 100%
efficient passivation (in dramatic contrast to the situation for sul-
fate).
The reason for the fundamental differences in the electro-
chemical behavior of iron in sulfate and acetate solutions probably
does not result from the buffered nature of the laffer. The explana-
tion may, instead, involve the ability of the acetate anions to inter-
act with the iron surface and facilitate the formation of a prepas-
sive oxide film (see Reference 11), which can be the basis for
facile development of the passive oxide film. With sulfate, no such
beneficial anion surface interaction is possible and other means
are required to assist passive oxide film development (e.g., salt
Effect of Temperature and lonic Impurities at
Very Low Concentrations on Stress Corrosion
Cracking of AISI 304 Stainless Steel*
ABSTRACT
The relative effect of 13 anionic species, in conjunction with hy-
drogen and sodium cations, on the stress corrosion cracking
(SCC) behavior of lightly sensitized AISI" 304 stainless steel
(SS) was investigated in constant extension rate tests (CERTs) at
289 C in water with 0.2 ppm dissolved oxygen at total conductiv-
ity va/ues of <_ 1 p.S/cm. The resu/ts show that the sulfur species,
either in acid or sodium form, produce the highest degree of in-
tergranular stress corrosion cracking (IGSCC) relative to the other
anions. The effect of temperature on SCC behavior was investi-
gated in CERTs over the range of 110 to 320 C in high-purity wa-
ter and in water containing 0.1 and 1.0 ppm sulfate as H2 SO 4 at
a dissolved oxygen concentration of 0.2 ppm. The CERT parame-
ters were correlated with the electrochemical potential of platinum
and AISƒ 304 SS electrodes in the high-temperature environ-
ments. Maximum IGSCC occurred at temperatures between
-200 and 250 C in high-purity water, and the addition of sulfate
increased the average crack growth rates at all temperatures
> 150 C and broadened the temperature range over which maxi-
mum susceptibility occurred. A distinct transition in the crack
morphology from intergranular to transgranular and ultimately to a
ductile failure mode was observed as the temperature increased
from -270 to 320 C in high-purity water. This transition was at-
Submitted for publication April 1985; revised February 1988.
Materials and Components Technology Division, Argonne National Laboratory,
Argonne, Illinois 60439.
I' 1 American Iron and Steel Institute (AISI), Washington, DC.
0010-9312!88/00207/$3.00/0
CORROSION—Vol. 44, No. 11 @ 1988, National Association of Corrosion Engineers 791
CORROSION SCIENCE
film formation). This subject will be discussed further in an upcom-
ing paper.
REFERENCES
1. J. M. West, Brit. Oorros. J., Vol. 5, p. 65, 1970.
2. P. E. Morris, R. C. Scarberry, Corrosion, Vol. 26, p. 169, 1970.
3. R. L. Chance, T. P. Schreiber, W. D. France, Jr., Corrosion, Vol. 31, p. 296,
1975.
4. E. A. Lizlovs, A. P. Bond, J. Electrochem. Soc., Vol. 122, p. 719, 1975.
5. P. E. Morris, R. C. Scarberry, Corrosion, Vol. 28, p. 444, 1972.
6. F. Mansteld, M. Kendig, Corrosion, Vol. 37, p. 545, 1981.
7. P. E. Manning, Corrosion, Vol. 36, p. 468, 1980.
8. O. W. Siebert, Electrochemical Techniques for Corrosion Engineering, R.
Baboian, Ed., NACE, Houston, Texas, p. 81, 1986.
9. H. P. Leckie, J. Electrochem. Soc., Vol. 117, p. 1152, 1970.
10. J. A. Bardwell, B. MacDougall, M. J. Graham, J. Electrochem. Soc., Vol. 135, p.
413, 1988,
11. J. OM. Bockris, M. A. Genshaw, V. Brusic, H. Wroblowa, Electrochim. Acts, Vol.
16, p. 1859, 1971.
W. E. Ruther, W. K. Soppet, and T. F. Kassner'
tributed to a decrease in the open circuit corrosion potential of
steel <-0 mV[standard hydrogen electrode (SHE)] at the higher
temperature. A large decrease in the crack growth rates of frac-
ture-mechanics-type specimens of the steel was also found when
the temperature was increased from 289 to 320 C in high-purity
water with 0.2 ppm dissolved oxygen.
INTRODUCTION
The roles of dissolved oxygen, impurity species, and temperature
on intergranular stress corrosion cracking (IGSCC) of sensitized
AISI 304 stainless steel (SS) is of considerable interest in relation
to the numerous incidents of cracking in recirculation piping of
commercial boiling water nuclear reactors (BWRs). In a recent
paper,' the present authors reported that lightly sensitized AISI
304 SS exhibited a particularly high degree of IGSCC susceptibil-
ity in constant extension rate tests (CERTs) at 289 C in water con-
taining >0.05 ppm dissolved oxygen and <'-1.0 ppm sulfate as
H 2 SO 4 . At that time, it was unclear whether the phenomenon was
peculiar to sulfate or whether other anion species would have a
similar effect on the intergranular cracking behavior. Consequently,
the relative effect of various anionic species at a concentration of
0.1 ppm, in conjunction with hydrogen and sodium cations, on the
stress corrosion cracking (SCC) susceptibility of the same heat of
steel in the lightly sensitized condition has been evaluated at 289
C in water containing 0.2 ppm dissolved oxygen. The effect of
temperature on the SCC behavior of the steel was also investi-