Corrosion Science 45 (2003) 9951010

www.elsevier.com/locate/corsci

Pit formation and growth of alloy 600 in

Cl
ion-containing thiosulphate solution at
temperatures 298573 K using fractal geometry
Jin-Ju Park, Su-Il Pyun

Department of Materials Science and Engineering, Korea Advanced Institute of Science

and Technology, 373-1 Guseong-Dong, Yuseong-Gu, Daejeon 305-701, South Korea
Received 25 February 2002; accepted 15 October 2002

Abstract
Pit formation and growth of alloy 600 has been investigated in aqueous 0.1 M
Na2 S2 O3 0:1 M NaCl solution at elevated solution temperatures 298573 K and at pressures
0.18 MPa in terms of fractal geometry using potentiodynamic polarisation experiment, potentiostatic current transient technique, scanning electron microscopy (SEM), image analysis
method and ac-impedance spectroscopy. From SEM observation, it was realised that pit
morphology changed from cylindrical shape developed at 60 C to highly branched shape
formed at 150 C. Furthermore, corrosion pits formed and further grew without any morphological change during the whole pitting process below 200 C. On the other hand, above
200 C, the morphology of the pits changed from highly branched shape in the early stage of
the pitting process to widely grooved shape in the later stage. After SEM observation of the
pits, the fractal dimension of pits was determined as a function of solution temperature 60150
C using perimeterarea method. The value of the fractal dimension of the pits increased with
increasing solution temperature. This is caused by the increase in the ratio of perimeter to area
at higher solution temperature, indicating the formation of pits with highly branched shape.
The appearance of specic shape and fractal dimension value of the pits at each solution
temperature implies that the formation and growth of pits proceed with the typical fractal
geometry throughout the whole pitting process irrespective of pit size. In addition, constant
phase element (CPE) behaviour observed from the impedance spectra is discussed in terms of
the fractal dimension of pits.
2002 Elsevier Science Ltd. All rights reserved.
Keywords: Alloy 600; Pit growth; Perimeterarea method; Fractal dimension; Solution temperature

Corresponding author. Tel.: +82-42-869-3319; fax: +82-42-869-3310.

E-mail address: sipyun@mail.kaist.ac.kr (S.-I. Pyun).

0010-938X/03/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 0 - 9 3 8 X ( 0 2 ) 0 0 2 1 2 - 3

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1. Introduction
Inconel alloy 600 has been widely used as the steam generator tube material in
pressurized water reactors nuclear power plants. Since the discovery of pitting in
alloy 600 steam generator tube [1,2], there has arisen a need to understand the pitting
process in the steam generator tube.
Fractal geometry has been used to characterise disorderly structures in a wide
range of dierent elds, and the use of fractal geometry to obtain a quantitative
characterization of the morphology of corroded surfaces has been described in
several recent works [36]. Especially, pitting corrosion can lead to rough surfaces
because of the formation and decay of a protective layer. Considerable interest is
shown in the formation and growth of rough surfaces [7,8]. In this respect, pitting
corrosion attracted signicant attention because of the challenging problem in the
development of irregular corrosion pits observed in bulk metals. Recently, many
investigators characterised the pitting corrosion to determine fractal roughness of
aluminium electrode using electrochemical impedance spectroscopy [9], light scattering [10] and image analysis [5,11].
In general, corrosion morphologies are rarely uniform. Pits observed on corroded
surfaces may be small or large in diameter, drawing a variety of sizes and shapes.
Therefore, it is of great importance to characterise the morphology of pits quantitatively in relation to fractal geometry. In addition, the role of solution temperature in morphology of pits in Cl
ion-containing solution has not been clearly
examined.
The present work was undertaken to correlate the morphology of the pits of alloy
600 with their fractal dimension in aqueous 0.1 M Na2 S2 O3 0:1 M NaCl solution
as a function of solution temperature. For this purpose, rst, potentiodynamic polarisation experiments and potentiostatic current transient technique were employed
to characterise passivity of oxide lm and the formation and growth of pits by means
of anodic current ow across the specimen as a function of solution temperature.
Finally, the relationship between morphology of the pits formed at various solution
temperatures and their fractal dimension has been established using scanning electron microscopy (SEM), image analysis method and ac-impedance spectroscopy.
Changes in morphology, the fractal dimension and constant phase element (CPE)
behaviour of pits during the whole pitting process have been discussed with respect
to solution temperature in terms of passivity of oxide lm.

2. Experimental
In this work, the specimen was made from Inconel alloy 600 with a composition
(wt.%) of 15.4% Cr, 8.0% Fe, 0.3% Mn, 0.1% Si, 0.01% C and Ni bal. For electrochemical experiments, the squared rod specimen was set in a block of polyimid.
The upper surface of the block was ground with emery paper successively up to 2000
grit. Two kinds of electrolyte were employed in the present work: 0.5 M Na2 SO4
solution of 25 C for ac-impedance measurements at open-circuit potential and a

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997

mixed aqueous solution of 0.1 M Na2 S2 O3 and 0.1 M NaCl solution of 25, 60, 100,
150, 200, 250 and 300 C for all electrochemical experiments. All electrochemical
experiments at elevated solution temperatures and pressures were carried out using
autoclave. An external Ag/AgCl electrode and a platinum wire were used as the
reference electrode and counter electrode, respectively. Three electrodes were introduced into the autoclave through a high-pressure tting.
The potentiodynamic polarisation experiments were made on the square rod
specimen with an exposed area of 2:9  10
1 cm2 in the applied potential range of

0.5 to 1.5 V (Ag/AgCl) with a scan rate of 0.5 mV s
1 by using a Potentiostat/
Galvanostat (EG&G Model 263A) interfaced with an IBM compatible computer.
The current density was recorded potentiostatically with time at an applied anodic
potential of 0.8 V (Ag/AgCl) in aqueous 0.1 M Na2 S2 O3 0:1 M NaCl solution at
various solution temperatures to characterise passivity of oxide lm and the
pitting process of the specimen by using a Potentiostat/Galvanostat (EG&G Model
263A).
The morphology of corrosion pits formed on the specimen was examined as
functions of solution temperature and pit depth using SEM. For the SEM observation, pits were made on the specimens by applying constant anodic potential of 0.8
V (Ag/AgCl) for 300 s at dierent solution temperatures. The pitted specimen was
rinsed with distilled water and then was cleaned with acetone immediately before
SEM observation. Thereafter, pit morphology observed by SEM was digitized and
then transferred to a computer for further image analysis. The digitized image of pit
morphology was analysed quantitatively by image analysis method. The fractal dimension of pits was determined as functions of solution temperature and pit depth
using perimeterarea method [8,12]. A computer program was programmed to
measure the perimeter and area of each of pits. The yardstick, which was pixel edge,
was calibrated to be 0.01 lm. The plot of perimeter against area on a logarithmic
scale was linearly tted, and twice the slope was the fractal dimension of contour
lines of pits.
AC impedance measurements were carried out with a Solartron 1255 frequency
response analyzer connected with the Solartron 1287 electrochemical interface. The
impedance spectra were recorded from 105 Hz down to 0.1 Hz frequency using 5 mV
amplitude perturbation. Two types of measurements were done: (A) For the determination of the oxide lm resistance Rox the impedance spectra were measured as
functions of applied potential and solution temperature in aqueous 0.1 M Na2 S2 O3
0:1 M NaCl solution at various solution temperatures; Rox was determined using a
complex non-linear least squares (CNLS) tting method [13]. (B) To correlate pit
morphology with impedance behaviour, rst the corroded surfaces were prepared
electrochemically at 0.8 V (Ag/AgCl) for 300 s in aqueous 0.1 M Na2 S2 O3 0:1 M
NaCl solution at various solution temperatures; thereafter the impedance spectra
were recorded under open-circuit conditions at room temperature in 0.5 M Na2 SO4
solution.
For the sake of reproducible data, potentiodynamic polarisation experiment,
potentiostatic current transient experiment and ac-impedance measurement were
carried out three to ve times.

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3. Results
Fig. 1 presents potentiodynamic polarisation curves for alloy 600 with a scan rate
of 0.5 mV s
1 in aqueous 0.1 M Na2 S2 O3 0:1 M NaCl solution at various solution
temperatures. As solution temperature increased, corrosion rate rose and at the same
time the value of current density increased at any given anodic potential. Here,
corrosion rate is dened as the open-circuit current density. The increase in the value
of current density in chloride solution is known to arise from the increase in the
passive current density below the pitting potential, whilst it is indeed due mainly to
the formation and growth of a stable pit on the surface above the pitting potential.
This implies that the increasing solution temperature is destructive to passivity of
oxide lm formed on the specimen, leading to an occurrence of pitting corrosion [14
16].
Fig. 2(a) and (b) depicts typical impedance spectra in Nyquist presentation obtained from alloy 600 at various applied anodic potentials in aqueous 0.1 M
Na2 S2 O3 0:1 M NaCl solution at various solution temperatures of 25 and 100 C.
It can be seen that the value of total impedance at 100 C is much lower than that at
25 C. This means that oxide lm formed at higher solution temperature has lower
degree of passivity compared with that formed at room temperature. In order to
compare the degree of passivity of oxide lm quantitatively as a function of solution
temperature, real and imaginary components of measured impedance were analysed
by using CNLS tting method suggested by Macdonald [17] and modied in this
laboratory [13] on the basis of the equivalent circuit which is given in Fig. 2(c) below
the pitting potential. The equivalent circuit consists of charge transfer resistance Rct
in parallel to the double layer capacitance Cdl and the oxide lm resistance Rox and

Fig. 1. Potentiodynamic polarization curves of alloy 600 with a scan rate of 0.5 mV s
1 in aqueous 0.1 M
Na2 S2 O3 0:1 M NaCl solution at various solution temperatures 25300 C.

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999

(a)

(b)

(c)

Fig. 2. Impedance spectra in Nyquist presentation obtained from alloy 600 at various applied anodic
potentials in aqueous 0.1 M Na2 S2 O3 0:1 M NaCl solution at various solution temperatures of (a) 25 C
and (b) 100 C. (c) Equivalent circuit used for the analysis of impedance spectra. Rs solution resistance, Rct
charge transfer resistance, Cdl , double layer capacitance, Rox oxide lm resistance, CPEox CPE of oxide
lm.

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Fig. 3. Changes in the oxide lm resistance Rox with applied anodic potential on a semi-logarithmic scale
obtained from alloy 600 in aqueous 0.1 M Na2 S2 O3 0:1 M NaCl solution at various temperatures 25
300 C.

the CPE of oxide lm CPEox in parallel to Rox . Charge transfer resistance Rct is
neglected because it is so small. Thus Rox is considered to correspond to the measured
total resistance.
Fig. 3 gives changes in the value of Rox with applied anodic potential on a semilogarithmic scale obtained from alloy 600 in aqueous 0.1 M Na2 S2 O3 0:1 M NaCl
solution at various solution temperatures. The value of Rox decreased with applied
anodic potential, irrespective of solution temperature. It is generally agreed [18,19]
that the presence of chloride ion on the metal surface hinders the oxide lm formation. In this work, it is conceivable that the concentration of adsorbed chloride
ions on the metal surface increased with increasing applied potential due to their
higher electronegativity. Consequently, the increase in the adsorbed chloride ion
concentration on the metal surface hindered the oxide lm formation by competitive
adsorption between oxygen containing species and chloride ions [20], resulting in the
decrease of the oxide lm resistance Rox . In addition, the value of Rox decreased with
increasing solution temperature over the whole applied anodic potential, suggesting
the formation of a more non-protective oxide lm at higher solution temperature.
Fig. 4 exhibits potentiostatic current transients of alloy 600 subjected to a constant anodic potential of 0.8 V (Ag/AgCl) in aqueous 0.1 M Na2 S2 O3 0:1 M NaCl
solution at various solution temperatures. In this gure, it can be seen that the
pitting process is categorized into the three stages, i.e. the rst passivation stage, the
second pit formation and growth stage and the nal steady-state stage. The anodic
current density of the rst stage descended abruptly with time and then reached
current minimum at time t1 . The fall of current density indicates the thickening of

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Fig. 4. Potentiostatic current transients of alloy 600 subjected to a constant anodic potential of 0.8 V (Ag/
AgCl) in aqueous 0.1 M Na2 S2 O3 0:1 M NaCl solution from 60 to 150 C.

oxide lm on the surface. In the second stage, the value of current density ascended
from the moment just after t1 to t2 , which is attributed to lm breakdown caused by
the formation and growth of pits. In the presence of thiosulphate ions in chloride
containing solution, after pit initiation, pitting corrosion product such as black
sulphide would be precipitated inside the pits. The corrosion product blocks up the
pits and hence hinders the current ow through the pits. Thus, a steady-state was
attained between the metal dissolution and oxide lm formation including a
blockade by pitting corrosion product in the third stage of current transient after t2 .
In the third stage, the increment in current density caused due to the metal dissolution just equals the sum of the decrement in current density due to oxide lm
formation and the decrement of current density due to the blockade by pitting
corrosion product, leading to nearly constant current density.
The current transient revealed that there is a growing tendency that the rate of
passivation dominates over the rate of oxide dissolution as solution temperature
decreased, resulting in the increase in t1 . From the experimental ndings that the
slope of current transient in the range from t1 to t2 is drastically increased with increasing solution temperature, it is deduced that the rate of growth of pits increased
with solution temperature [2022]. Moreover, since the amount of charge consumed

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during the whole pitting process at higher solution temperature is much larger than
that at lower solution temperature, it can be said that the pit area density increased
with solution temperature. Increasing tendency of the pit area density with solution
temperature was validated by SEM micrographs of Fig. 5. Fig. 5(a) and (b) illustrates SEM micrographs of pit morphology of the surface of alloy 600 subjected to
a constant anodic potential of 0.8 V (Ag/AgCl) for 300 s in aqueous 0.1 M
Na2 S2 O3 0:1 M NaCl solution at 60 and 150 C, respectively. In this gure, it was
easily found that the ratio of pitted area to total surface area increased with increasing solution temperature.
Fig. 6(a)(g) shows typical SEM micrographs of pit morphology of the surface of
alloy 600 subjected to a constant anodic potential of 0.8 V (Ag/AgCl) for 300 s in
aqueous 0.1 M Na2 S2 O3 0:1 M NaCl solution at 25, 60, 100, 150, 200, 250 and 300
C, respectively. It was observed that no stable pitting phenomena occurred on the
specimen exposed to room temperature solution. On the contrary, there was an

Fig. 5. SEM micrographs of pit morphology on the surface of alloy 600 subjected to a constant anodic
potential of 0.8 V (Ag/AgCl) for 300 s in aqueous 0.1 M Na2 S2 O3 0:1 M NaCl solution at (a) 60 C and
(b) 150 C.

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Fig. 6. Typical SEM micrographs of pit morphology on the surface of alloy 600 subjected to a constant
anodic potential of 0.8 V (Ag/AgCl) for 300 s in aqueous 0.1 M Na2 S2 O3 0:1 M NaCl solution at (a) 25,
(b) 60, (c) 100, (d) 150, (e) 200, (f) 250 and (g) 300 C.

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occurrence of intense pitting corrosion on the specimen exposed to elevated temperature solutions 60300 C. Moreover, it was also found that pit morphology
changed from cylindrical shape made at 60 C to highly branched shape formed at
150 C [23,24] and nally it changed from highly branched shape in the early stage of
the pitting process to widely grooved shape in the later stage above 200 C.
Fig. 7 illustrates logarithmic plots of pit perimeter vs. area for pit morphology of
alloy 600 subjected to a constant anodic potential of 0.8 V (Ag/AgCl) for 300 s in

(a)

(b)
Fig. 7. (a) Logarithmic plots of pit perimeter vs. area for the pit morphology of alloy 600 subjected to a
constant anodic potential of 0.8 V (Ag/AgCl) for 300 s in aqueous 0.1 M Na2 S2 O3 0:1 M NaCl solution
from 60 to 150 C. (b) Logarithmic plots of pit perimeter vs. area for the pit morphology of alloy formed at
150 C by sectioning the plane with pit depth of 5 and 10 lm.

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1005

aqueous 0.1 M Na2 S2 O3 0:1 M NaCl solution as functions of solution temperature

and pit depth. In particular, in the case of 150 C, image analysed data obtained
from the pits by sectioning the plane with pit depth of 5 and 10 lm in the downward
direction are plotted in Fig. 7(b). In this gure, it was found that the linear relationship between pit area and pit perimeter given in Fig. 7(b) is the nearly same as
that linear relationship shown in Fig. 7(a). It is generally known [8,12] that twice the
slope of the plot of perimeter against area on a logarithmic scale is the fractal dimension Df of contour lines of pits. In this gure, solution temperature raised the
fractal dimension as follows: Df 60 C 1:04  0:04, Df 100 C 1:24  0:06
and Df 150 C 1:40  0:1. Higher value of the fractal dimension at 150 C is due
to the increase in ratio of perimeter to area, indicating the formation of pits with
highly branched shape as shown by SEM observation.
Fig. 8(a) envisages impedance spectra in Nyquist presentation obtained from alloy
600 at open-circuit potential in aqueous 0.5 M Na2 SO4 solution at room temperature
after anodic polarisation of 0.8 V (Ag/AgCl) for 300 s in aqueous 0.1 M Na2 S2 O3
0:1 M NaCl solution from 60 to 150 C. Constant phase element (CPE) was observed
in the frequency range of 103 1 Hz. For the better understanding of CPE behaviour,
the total impedance was reduced to the values of tan
1 d
Z 00 =dZ 0
and CPE exponent as a function of frequency. Fig. 8(b) plots the changes in the values of
tan
1 d
Z 00 =dZ 0
and CPE exponent with frequency obtained from alloy 600 at
open-circuit potential in aqueous 0.5 M Na2 SO4 solution at room temperature after
anodic polarisation of 0.8 V (Ag/AgCl) for 300 s in aqueous 0.1 M Na2 S2 O3 0:1 M
NaCl solution from 60 to 150 C. The values of tan
1 [d
Z 00 =dZ 0 ] and CPE exponent showed nearly constant in the frequency ranges from 102 to 10 Hz and from 10
to 1 Hz, irrespective of solution temperature as indicated as dashed arrow in Fig.
8(b).

4. Discussion
4.1. Eect of passivity of oxide lm on change in pit morphology with solution
temperature during the whole pitting process
In Fig. 6(b) and (d), it was found that pit morphology changed from cylindrical
shape at 60 C to highly branched shape at 150 C. This morphological change is
under the control of degree of passivity of oxide lm formed on the specimen as a
function of solution temperature. From the experimental results of Figs. 1, 3 and 4, it
is recognised that degree of passivity of oxide lm was diminished with increasing
solution temperature.
Since no obvious inclusion was revealed on the surface of the specimen by using
high resolution SEM, it is assumed that pit formation and growth sites covered with
less protective oxide lm are uniformly distributed over the specimen surface. It is
therefore expected that once corrosion pit embryos are generated at 60 C at such
sites covered with less protective oxide lm, the pit embryos would be then surrounded on all sides immediately with the region covered mainly with more

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J.-J. Park, S.-I. Pyun / Corrosion Science 45 (2003) 9951010

(a)

(b)
Fig. 8. (a) Impedance spectra in Nyquist presentation and (b) plots of tan
1 [d
Z 00 =dZ 0 ] and CPE exponent vs. frequency obtained from alloy 600 at open-circuit potential in aqueous 0.5 M Na2 SO4 solution
at room temperature after anodic polarization of 0.8 V (Ag/AgCl) for 300 s in aqueous 0.1 M
Na2 S2 O3 0:1 M NaCl solution from 60 to 150 C.

protective oxide layer owing to higher degree of passivity of oxide lm at 60 C.

Thus, the viable pit embryos have the same tendency to grow further in all radial
direction and hence the grown pits nally form cylindrical shape. In contrast, corrosion pit embryos generated at 150 C would be plausibly surrounded on all sides

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1007

directly with the region covered predominantly with less protective oxide lm due to
lower degree of passivity of oxide lm at 150 C. The coverage by less protective
oxide layer of the region immediately adjacent to pit embryos may limit pit growth in
all radial direction. Thus, the viable pit embryos have a preferred tendency to grow
further in specic direction and hence the grown pits nally form highly branched
shape. With higher solution temperature the eect would be much greater.
Above 200 C, the morphology of the pits changed from highly branched shape in
the early stage of the pitting process to widely grooved shape in the later stage. This
is due to the fact that since the passivity of oxide lm was lowered above 200 C, all
the pit embryos would be surrounded on all sides with the region covered with nonprotective oxide layer. Thus, they grow further in all directions, resulting in the
transition in pit morphology from highly branched shape to widely grooved shape.
As solution temperature increased, the transition in pit morphology appeared more
markedly.
4.2. Relationship between morphology and the fractal dimension of the pits as a
function of solution temperature during the whole pitting process
Now, let us establish the relationship between morphology and the fractal dimension of pits. SEM micrographs of Fig. 5 revealed that specic one pit among
many small pits with cylindrical shape at 60 C grew with merging the neighbouring
small pits and then nally grew into a large one without any morphological change
during the whole pitting process. In the case of highly branched pits formed at
150 C solution, it is noted that each of small pits with many branches grew individually and then nally coalesced into a large branched one. Similarly, pit morphology is unchangeable during the whole pitting process at 150 C.
From the fractal dimension theoretically derived from fractal surface, it is accepted [7,8] that adherence to the same pit morphology is a sucient condition for
keeping constant fractal dimension of pits during the whole pitting process. From
the fractal dimension determined (Fig. 7), based upon pit morphology in Fig. 6 using
perimeterarea method, it is noted that the fractal dimension of the pits maintains
nearly constant in value during the whole pitting process, irrespective of pit size.
Consequently, it has been experimentally born out that keeping constant fractal
dimension is a necessary condition for the development of the same pit morphology
during the whole pitting process of alloy 600 specimen.
The unchanged fractal dimension of the pits in value during the whole pitting
process can be explained in terms of the relation between the diusivity of defects
and solution temperature. In general, defects in oxide lm play an essential role as
active sites in pit formation and growth [25,26]. Moreover, the distribution of defects
across oxide lm is determined by the value of their diusivity, and at the same time
the value of the diusivity of defects is also determined by solution temperature.
Therefore, when a solution temperature remained unchanged, the distribution of
defects in oxide lm was then also remained constant, which leads to the xed pit
morphology during the whole pitting process. Thus, the fractal dimension of the pits
maintains nearly constant in value during the whole pitting process.

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It is widely known [12,27] when pit morphologies are derived from initial surfaces
with the fractal dimension Df , the value of the fractal dimension of their perimeters is
xed for Df
1. This relation involves implicitly that the unity 1 indicates that the
value of the fractal dimension in the downward direction is constant irrespective of
pit depth. From the result of Fig. 7, it was recognised that the image data analysed
from pit morphology under various pit depths at 150 C gave the nearly same linear
relationship between pit area and pit perimeter, regardless of pit depth. This implies
that the pits form and grow with the same fractal dimension in the downward
direction.
At this point, in order to justify the fractal dimension determined from pit morphology, it should be mentioned about cuto range, i.e. inner cuto and outer cuto.
In the present work, it is very dicult to determine the cuto range by means of
perimeterarea method. However, one would determine roughly the cuto range by
considering the length of yardstick and the diameter of the largest pit. Firstly, when
the length of yardstick is smaller than that of inner cuto, the fractal dimension of
Df 1 was observed by perimeterarea relation. Because the region of fractal dimension Df 1 was not observed from Fig. 7, it can be deduced that the value of
inner cuto is at least smaller than the length of yardstick of 0.01 lm. Furthermore, it
is reported [7,28] that outer cuto might be the diameter of the largest circle encompassing an island for slit-island method. It is therefore reasonable to consider that
the diameter of the largest circle encompassing a pit is just the value of outer cuto.
Consequently, the value of outer cuto may be considered to be atleast 170 lm.
4.3. Eect of the fractal dimension on impedance behaviour of the pits formed on the
electrode surface at various solution temperatures during the whole pitting process
In Fig. 8, constant value of tan
1 d
Z 00 =dZ 0
was observed in the frequency
ranges from 102 to 10 Hz and from 10 to 1 Hz. One of the most possible causes of the
constant value of tan
1 d
Z 00 =dZ 0
is known to be of geometric origin: an irregular
and porous electrode geometry causes current density inhomogeneities and thus
yields deviations from ideal behaviour. The impedance of a real electrode is frequently represented by an equivalent circuit containing CPE showing power law
frequency dependence as follows [17]:
Zx 1=rjx

a

where r and a mean the CPE coecient and the CPE exponent, respectively, and x
represents the angular frequency. In recent years, it has been demonstrated by many
researchers [2932] that the deviation from ideal capacitive behaviour observed on a
real electrode, i.e. CPE exponent a is intimately related to surface roughness. Such
CPE behaviour has often been found in the porous, rough and irregular electrode.
In a similar way, in this work, the CPE exponent becomes the measure of surface
irregularity, i.e., the fractal dimension. For example, for a perfectly smooth surface
at all scales, the value of CPE exponent is unity. In other words, if there is such
surface inhomogeneity as pore and roughness, the value of CPE exponent is lower
than unity. In Fig. 8(b), it was found that the value of CPE exponent at 60150 C is

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1009

lower than unity. Therefore, it can be deduced that lowered value of CPE exponent
at 60150 C is due to the increase in the surface roughness of the specimen by the
formation and growth of pits with a certain value of fractal dimension.
In addition, from the result of Fig. 8(b), it was noted that the values of CPE
exponent in the frequency range from 102 to 10 Hz and that frequency range from 10
to 1 Hz were found to be about the same irrespective of solution temperature, respectively. At the same time, it was found that impedance spectra in the Nyquist plot
of Fig. 8(a) measured from the pitted specimen exposed to elevated temperature
solutions of 60150 C were similar to one another in value and shape. At this point,
it should be stressed that impedance spectra experimentally measured at dierent
solution temperatures were similar to one another even though the value of fractal
dimension of the pits increased with increasing solution temperature. This is probably because the impedance of the large sized pits mostly contributed to the total
impedance of the pits as compared with the impedance of the small and medium
sized pits [33]. As a result, impedance spectra experimentally measured from the
pitted specimens as a function of solution temperature were similar to one another in
value and shape, resulting in the nearly same value of CPE exponent irrespective of
solution temperature.

5. Conclusions
1. From SEM observation, it was found that pit morphology changed from cylindrical shape at 60 C to highly branched shape at 150 C. In as much as their
region immediately surrounding pit embryos generated at 60 C is likely covered
mainly with more protective oxide lm, the viable pit embryos have the same tendency to grow further in all radial direction and hence the grown pits nally form
cylindrical shape. By contrast, since their region immediately neighbouring pit embryos generated at 150 C is plausibly covered predominantly with less protective
oxide lm, the viable pit embryos have a preferred tendency to grow further in
specic direction and hence the grown pits nally form highly branched shape.
2. Below 200 C, SEM micrographs showed that pits formed and further grew
throughout without any morphological change. From the fractal dimension determined based upon pit morphology observed by SEM using perimeterarea method,
it is concluded that the fractal dimension of the pits maintains nearly constant in
value during the whole pitting process at each solution temperature.
3. Above 200 C, SEM micrographs showed that the morphology of the pits
changed from highly branched shape in the early stage of the pitting process to
widely grooved shape in the later stage. Because the passivity of oxide lm was
lowered above 200 C, all the pit embryos would be surrounded on all sides with the
region covered with non-protective oxide layer. It follows therefore they grow further in all directions, leading to the transition in pit morphology from highly
branched shape to widely grooved shape.
4. From the measured impedance spectra, the occurrence of CPE was observed in
a certain frequency range 102 1 Hz at the pitted specimen exposed to the corrosive

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J.-J. Park, S.-I. Pyun / Corrosion Science 45 (2003) 9951010

electrolytic solution at 60150 C. This CPE behaviour is caused by the roughening

of the electrode surface resulting due to the formation and growth of the pits
characterised with a certain value of fractal dimension at each solution temperature.

Acknowledgements
The authors are gratefully indebted to Dr. H.-C. Shin working as a postdoctoral
research fellow at Corrosion and Interfacial Electrochemistry Research Laboratory
in Korea Advanced Institute of Science and Technology for his help with the image
analysis procedure. This work was partly supported by the Brain Korea 21 project
and the nano programme 2002/2003 of MOST, Korea.

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