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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.

as the reference). The two scans are comparable, with the main
EXPERIMENTAL difference being the existence of a substantial anodic pre-peak
(before the main anodic peak) in the acetate solution; there was
Iron electrodes were prepared as described previously, 10 no indication of this peak in the sulfate solution. The maximum
electropolished, and were then cathodically reduced at 20 µA anodic current is somewhat higher in the acetate solution, and the
cm -2 to remove the previous oxide film before initiating either an total anodic charge passed is correspondingly somewhat higher in
anodic scan at 5 mV s ' or a potential step into the passive re-
-
acetate [510 millicoulomb (mcoul) cm -2 compared to 340 mcoul
gion. All experiments were conducted at 25 C. 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-
RESULTS odic current and charge are higher.
In the next series of experiments, instead of scanning the
Figure 1 shows the anodic scans for Fe in both pH 8.4, 0.15 potential anodically, the potential of the oxide-free iron electrode
N Na 2 SO 4 and pH 5.0 acetic acid/sodium acetate (made by mixing was stepped to 0 V (i.e., well into the passive region) and the an-
solutions of 0.1 N CH 3 000H and 1.0 N CH 3 COONa) in the poten- odic current-time response was monitored. The results obtained in
tial range from -1.4 to 0.6 V (with respect to Hg/Hg 2 SO 4 /Na 2 SO 4 the acetate and sulfate solutions are shown in Figure 2, a very
large difference in the efficiency of passivation is immediately evi-
Submitted for publication April 1988. dent. In the sulfate solution, an anodic charge of 1150 mcoul cm -2
*Division of Chemistry, National Research Council of Canada, Ottawa, Ontario, passes during 60 s, while in acetate, the corresponding charge is
Canada, KIA 0R9. only 7.6 mcoul cm -2 , which would represent the formation of -4.0
0010-9312/88/00205/$3.00/0
CORROSION—Vol. 44, No. 11 © 1988, National Association of Corrosion Engineers 789
CORROSION SCIENCE

1
a.

10" 10` 10' 10 10' 102 -1400 -900 -400 100 600
TIME (sec) POTEN11AL (mV)
FIGURE 2. Log i-log t pro files for electropolished and cathodically FIGURE 3. Anodic potentiodynamic profiles for Fe at 5 mV s ' in -

reduced Fe upon stepping the potential to 0 V in pH 5.0 acetate acetate solutions of various pH values: (—) pH 5.7; (— — —) pH
solution (—) and pH 8.4 Na 2 SO 4 (— — —)
6.4; (— •— ) pH 7.5. Electrodes were electropolished and cathodi-
cally reduced before the anodic scan.

nm of y-Fe 2 03 . The majority of the anodic charge which passes in R


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
-1400 -900 -400 100 600
5.7, 6.4, and 7.5 respectively. Despite the change in anodic elec-
trode activity determined potantiodynamically (Figure 3), little or no POTEN11AL (mV)
difference exists between the potential step charges, with current FIGURE 4. Anodic potentiodynamic pro files for Fe at 5 mV s ' in pH
-
efficiencies for film formation being very high in all cases. The next 7.5 acetate solutions with different amounts of added pH 7. 5 borate
series of experiments illustrates that the potentiodynamically deter- buffer: (— - —) 0%; (— • —) 5%; (— — —) 25%. Also shown is the
mined anodic activity can change substantially, even at the same pro file obtained in pH 7.5 borate buffer solution (—). Electrodes
(buffered) pH, if different solution anions are present. This is were electropolished and cathodically reduced before the anodic
shown in Figure 4 with anodic scans obtained in solutions ranging scan.
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 corrosion and should be obtained from potentiostatic techniques,
anodic behavior of iron as determined by potentiodynamic scans. such as anodic potential stepping, or surface scratching to disrupt
For the solutions in Figure 4, the anodic potential step passivation an existing film. Potentiodynamic scans can lead to incorrect pre-
charges are between 6.7 mcoul cm -2 (pH 7.5 acetate) and 6.1 dictions of potentiostatic behavior in the present case (Figure 1)
mcoul cm -2 (pH 7.5 borate); i.e., the anodic current efficiency for because different processes are involved in iron passivation in the
oxide film formation is high in each case. This is another situation sulfate as compared to the acetate solutions. In sulfate, passiva-
where there can be substantially different anodic sweep character- tion is achieved by the formation of a salt-type film at or near the
istics for systems which all display highly efficient anodic potential- electrode and this involves the dissolution of very large amounts of
step passivation behavior. 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-
DISCUSSION tion can be achieved; this is true even if high anodic potentials are
applied immediately with a potential step approach (Figure 2).
These results show that great caution must be used when However, passivation in the buffered acetate solution occurs
predicting oxide repassivation behavior from anodic potentiodyna- through a surface-controlled oxidation reaction, such as M + H 2 0
mic scans. While the anodic scans do provide useful information —> MO + 2H ' + 2e, and does not rely on supersaturating the
about certain types of corrosion behavior, they can also lead to solution near the electrode with Fe e ions (as with sulfate). The
entirely incorrect predictions about such things as efficiency of ox- iron dissolution that occurs during an anodic scan in acetate in the
ide formation (or reformation) in the cases above. This laffer infor- so-called "active" region (Figure 1) is incidental to the passivation
mation is very important when dealing with the local oxide break- process and occurs simply because the potential is not sufficiently
down and reformation processes involved in (eventual) pitting anodic in the early stages of the scan for the passive oxide film to

790 CORROSION—November 1988


CORROSION SCIENCE

be established. (An oxide film may actually be on the surface in film formation). This subject will be discussed further in an upcom-
this region, but it is not an effective barrier to iron dissolution.) In ing paper.
acetate solution, when the potential is sufficiently high, a passive
oxide film is established and blocks any further iron dissolution. In REFERENCES
this case, the quicker the passive potentials are achieved, the
more rapidly (and efficiently) passivation is established. For this 1. J. M. West, Brit. Oorros. J., Vol. 5, p. 65, 1970.
reason, anodic potential step passivations facilitate a nearly 100% 2. P. E. Morris, R. C. Scarberry, Corrosion, Vol. 26, p. 169, 1970.
efficient passivation (in dramatic contrast to the situation for sul- 3. R. L. Chance, T. P. Schreiber, W. D. France, Jr., Corrosion, Vol. 31, p. 296,
1975.
fate).
4. E. A. Lizlovs, A. P. Bond, J. Electrochem. Soc., Vol. 122, p. 719, 1975.
The reason for the fundamental differences in the electro- 5. P. E. Morris, R. C. Scarberry, Corrosion, Vol. 28, p. 444, 1972.
chemical behavior of iron in sulfate and acetate solutions probably 6. F. Mansteld, M. Kendig, Corrosion, Vol. 37, p. 545, 1981.
does not result from the buffered nature of the laffer. The explana- 7. P. E. Manning, Corrosion, Vol. 36, p. 468, 1980.
8. O. W. Siebert, Electrochemical Techniques for Corrosion Engineering, R.
tion may, instead, involve the ability of the acetate anions to inter-
Baboian, Ed., NACE, Houston, Texas, p. 81, 1986.
act with the iron surface and facilitate the formation of a prepas- 9. H. P. Leckie, J. Electrochem. Soc., Vol. 117, p. 1152, 1970.
sive oxide film (see Reference 11), which can be the basis for 10. J. A. Bardwell, B. MacDougall, M. J. Graham, J. Electrochem. Soc., Vol. 135, p.
facile development of the passive oxide film. With sulfate, no such 413, 1988,
11. J. OM. Bockris, M. A. Genshaw, V. Brusic, H. Wroblowa, Electrochim. Acts, Vol.
beneficial anion surface interaction is possible and other means
16, p. 1859, 1971.
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*
W. E. Ruther, W. K. Soppet, and T. F. Kassner'

ABSTRACT

The relative effect of 13 anionic species, in conjunction with hy- tributed to a decrease in the open circuit corrosion potential of
drogen and sodium cations, on the stress corrosion cracking steel <-0 mV[standard hydrogen electrode (SHE)] at the higher
(SCC) behavior of lightly sensitized AISI" 304 stainless steel temperature. A large decrease in the crack growth rates of frac-
(SS) was investigated in constant extension rate tests (CERTs) at ture-mechanics-type specimens of the steel was also found when
289 C in water with 0.2 ppm dissolved oxygen at total conductiv- the temperature was increased from 289 to 320 C in high-purity
ity va/ues of <_ 1 p.S/cm. The resu/ts show that the sulfur species, water with 0.2 ppm dissolved oxygen.
either in acid or sodium form, produce the highest degree of in-
tergranular stress corrosion cracking (IGSCC) relative to the other
INTRODUCTION
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 The roles of dissolved oxygen, impurity species, and temperature
a dissolved oxygen concentration of 0.2 ppm. The CERT parame- on intergranular stress corrosion cracking (IGSCC) of sensitized
ters were correlated with the electrochemical potential of platinum AISI 304 stainless steel (SS) is of considerable interest in relation
and AISƒ 304 SS electrodes in the high-temperature environ- to the numerous incidents of cracking in recirculation piping of
ments. Maximum IGSCC occurred at temperatures between commercial boiling water nuclear reactors (BWRs). In a recent
-200 and 250 C in high-purity water, and the addition of sulfate paper,' the present authors reported that lightly sensitized AISI
increased the average crack growth rates at all temperatures 304 SS exhibited a particularly high degree of IGSCC susceptibil-
> 150 C and broadened the temperature range over which maxi- ity in constant extension rate tests (CERTs) at 289 C in water con-
mum susceptibility occurred. A distinct transition in the crack taining >0.05 ppm dissolved oxygen and <'-1.0 ppm sulfate as
morphology from intergranular to transgranular and ultimately to a H 2 SO 4 . At that time, it was unclear whether the phenomenon was
ductile failure mode was observed as the temperature increased peculiar to sulfate or whether other anion species would have a
from -270 to 320 C in high-purity water. This transition was at- 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
Submitted for publication April 1985; revised February 1988.
steel in the lightly sensitized condition has been evaluated at 289
Materials and Components Technology Division, Argonne National Laboratory,
C in water containing 0.2 ppm dissolved oxygen. The effect of
Argonne, Illinois 60439.
temperature on the SCC behavior of the steel was also investi-
I' 1 American Iron and Steel Institute (AISI), Washington, DC.

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CORROSION—Vol. 44, No. 11 @ 1988, National Association of Corrosion Engineers 791

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