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Localized Corrosion: Passive Film Breakdown vs. Pit Growth Stability:

Part III. A Unifying Set of Principal Parameters and Criteria for Pit
Stabilization and Salt Film Formation
To cite this article: Tianshu Li et al 2018 J. Electrochem. Soc. 165 C762

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C762 Journal of The Electrochemical Society, 165 (11) C762-C770 (2018)

Localized Corrosion: Passive Film Breakdown vs. Pit Growth

Stability: Part III. A Unifying Set of Principal Parameters and
Criteria for Pit Stabilization and Salt Film Formation
1,z 2,∗ 1,∗
Tianshu Li, J. R. Scully, and G. S. Frankel
1 Fontana Corrosion Center, The Ohio State University, Columbus, Ohio 43210, USA
2 Center for Electrochemical Science and Engineering, University of Virginia, Charlottesville, Virginia 22904, USA

The framework for pit stability established in Part II of this series is elaborated upon and expanded. The maximum pit dissolution
current density, idiff,max , which depends on temperature and maximum potential at the pit surface in a given pit environment, is
proposed and compared with the diffusion current density to determine the conditions for pit stability and salt film formation. For an
open pit, the criterion for pit stability is that idiss,max must be greater than or equal to the critical diffusion current density required for
maintaining a critical local environment for active dissolution, idiff,crit . The critical condition of idiss,max = idiff,crit is associated with
three parameters that must be exceeded for stabilization of an open pit: critical temperature Tcrit , critical potential Ecrit and critical pit
depth rcrit . Analogously, the criterion for salt film formation is idiss,max must further exceed the diffusion-limited current density ilim ,
and three parameters associated with salt film formation are: saturation temperature Tsat , saturation potential Esat and saturation pit
depth rsat . Unifying criteria for control of pit growth by charge transfer or diffusion are proposed, which provide interrelationships
for all principle parameters. The pit stability criteria for covered pits, such as metastable pits, are also described.
© The Author(s) 2018. Published by ECS. This is an open access article distributed under the terms of the Creative Commons
Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any
medium, provided the original work is properly cited. [DOI: 10.1149/2.0251811jes]

Manuscript submitted May 25, 2018; revised manuscript received July 29, 2018. Published August 16, 2018.

Background pit depth, x, and current density, i. Galvele proposed that the critical
localized acidification for sustained pit growth can only be reached at
The relative importance of passive film breakdown and pit growth
a critical value of ix.10 The model did not consider the depassivating
stability in pitting corrosion has been debated over the last few
effect of aggressive anions such as chloride on stabilizing pit growth.
decades. Recently, the authors of this paper proposed a new per-
However, as low pH and high [Cl− ] must accompany each other in
spective on the critical step of pitting by suggesting that pit growth
pit solutions, the critical value of ix can still be used to describe
stability controls pitting corrosion under aggressive conditions, i.e.
the aggressive local environment required for pit stability. In 1992,
harsh electrolytes and extreme environments and/or susceptible mi-
Pistorius and Burstein proposed a pit stabilization theory based on the
crostructures, while passive film breakdown is more likely the critical
consideration of steady-state diffusion control of metal cations out of
factor in less extreme environments and/or for less susceptible alloys.1
the pit.4 According to their theory, the local aggressive environment
Based on this perspective, a conceptual model for the critical pitting
inside the pit can only be maintained if the pit growth is controlled
temperature (CPT), which considers both pit growth stability and pas-
by diffusion of metal cations out from the pit interior into the bulk
sive film breakdown, was proposed.2 The model was able to explain
solution. Similar to the critical value of ix in Galvele’s model, they
various aspects of CPT, including those that could not be explained
proposed a critical pit stability product of ir, where r is the depth
by previous models, such as why CPT measurements can exhibit a
of a hemispherical pit and i is the pit current density. According to
distribution of values and why the CPT of an alloy can depend on a
Pistorius and Burstein, both metastable and stable growth of a pit
variety of factors such as surface treatments and the chloride concen-
are under diffusion control.4 In 1994, Salinas-Bravo and Newman
tration of bulk solution. To establish the model, a new framework for
proposed an hypothesis for pit stabilization in their CPT model by
pit growth stability was presented by considering both dissolution and
suggesting that a salt film must be present on the pit surface to sustain
diffusion processes inside the pit to maintain a sufficiently aggressive
the stable growth.13 According to their model, a pit can only transition
local environment required for active dissolution. The purpose of this
to stability above the CPT, since only then can the pit form a salt film on
paper is to elaborate upon and expand the framework to describe the
its surface. However, the crystallographic pit morphologies observed
principal parameters and criteria for pit stabilization, as well as for
in many cases14–16 cannot be explained by the perspective of diffusion
salt film formation.
control, and such observations indicate that a salt film might not be
Passive metals exhibit a low corrosion rate in aqueous environ-
required for pit stability.
ments due to the formation of a thin passivating oxide film on their
Although many details of pit stabilization remain unclear, it is
surface.3–5 Pitting corrosion arises when passivity is lost at localized
agreed that a sufficiently aggressive pit environment is required for pit
points on the metal surface, resulting in accelerated dissolution of the
stability, and such an environment must be continuously maintained
underlying metal.3–8 Irrespective of the nucleation event, for a pit to
during the sustained pit growth. The greatest challenge to extend this
undergo sustained growth, the pit surface must be kept in the active
idea lies in how to consider the competition between the dissolution
state and prevented from repassivating. Nowadays, the most prevalent
and diffusion processes inside the pit. However, at steady state, for both
viewpoint is that active pit growth requires the maintenance of a local
metastable or stable pit growth, the actual dissolution rate of metal at
aggressive environment, and several criteria have been proposed to
the pit surface always equals the actual diffusion rate of metal cations
describe pit stability based on this notion.4,9–12
out from the pit interior into the bulk solution. Because they must be
In 1976, Galvele proposed a pit stabilization theory by considering
equal, it is not beneficial to use the actual dissolution and diffusion
the influence of pit chemistry changes.9 He hypothesized that the
rates to consider the competition between the dissolution and diffusion
hydrogen ion concentration, [H+ ], is the only critical parameter in
processes. As a result, in most previous theories, only one process,
determining pit stability. Using a one-dimensional (1D) pit model and
either diffusion or dissolution, was considered. In Part II of this series
considering metal cation hydrolysis and diffusion, he calculated the
of papers, the concept of maximum dissolution current density of a pit
concentration of various ionic species as a function of the product of
was proposed to address this issue, and a new framework for pit growth
stability was established by comparing this maximum pit dissolution
∗ Electrochemical Society Fellow. current density with the critical diffusion current density required
z
E-mail: li.7911@osu.edu for maintaining a sufficiently aggressive pit environment for active
 Journal of The Electrochemical Society, 165 (11) C762-C770 (2018)
dissolution. In this paper, the framework is further expanded. Principal
parameters and criteria for pit growth stability of both metastable
and stable pits and salt film formation are proposed based on new
ideas, presenting a unified description of various aspects of pit growth.
Criteria for control of pit growth by charge transfer or diffusion are
also described. Details of the salt film formation and its role in pit
growth process will be addressed in a subsequent paper as part of this
series.
Basic Considerations for Stable Pit Growth
Pit stability requires the maintenance of a continuous active dis-
solution state at the pit surface, which depends on an aggressive pit
environment. The most aggressive species inside a pit are considered
to be H+ and Cl− . It is well known that local acidification occurs
through the hydrolysis of the metal cations, and chloride anions mi-
grate into the pit to balance the charge of the dissolved metal cations
and maintain electroneutrality.3 Therefore, the aggressive pit environ-
ment is actually derived from the accumulation of metal cations, and
thus the concentration of metal cations at the pit surface (Csurf ) can be
used to evaluate the aggressiveness of the pit environment. In addition
to Csurf , the potential drop across the pit surface/pit solution interface
(Esurf ) and the temperature (T) are two other critical parameters that
determine the active dissolution of metal at the pit surface. It can be
considered that, within a certain range of (Csurf , Esurf , T), if any two
of these three parameters are fixed, the remaining one should have
a critical value, above which the active dissolution state can be sus-
tained. In this paper, Csurf was selected as the parameter to determine
the condition for active dissolution, because maintaining Csurf above
a critical value, Ccrit , is associated with both dissolution and diffusion
processes, and this facilitates the consideration of the competition be-
tween these two processes. Even though Ccrit might be a function of
Esurf and T, these dependencies have not been well defined so Ccrit is
assumed to be independent of temperature and potential for simplicity
in this paper. Additionally, there exists a saturation concentration of
metal cations, Csat , associated with the solubility limit of the metal
chloride salt. Supersaturation of metal cations is not a stable state,17
and it is not considered here for simplicity.
The accumulation of metal cations inside the pit depends on the
dissolution of the metal at the pit surface and the transport of metal
cations out from the pit interior into the bulk solution. The pit solution
is highly concentrated and often well supported so that metal cations
carry only a small fraction of the ionic charge, thus electromigration is
typically negligible in this transport process. Furthermore, convection
is limited in a pit, so only diffusion needs to be considered as a
transport process. The focus of this work will be on Fe- or Ni-based
alloy systems in which hydrogen evolution at the bottom of pits is not
a major factor. Modifications of this framework would be required
to account for the convection associated with the copious hydrogen
evolution in pits in Al alloys.
Assuming that the pit grows as an open hemisphere, the processes
of dissolution and diffusion are schematically shown in Fig. 1. For a
given pit depth r and temperature T, the diffusion rate of metal cations
out of the pit into bulk solution is determined by the concentration of
metal cations at the pit surface, Csurf . When Csurf < Ccrit , pit growth
cannot be sustained and the pit will repassivate, whereas active disso-
lution will continue when Csurf ≥ Ccrit . Therefore, there should exist
a critical diffusion current density, idiss,crit , associated with the critical
condition of Csurf = Ccrit . Moreover, when Csurf = Csat , the diffusion
current density will reach its maximum value, which is defined as the
diffusion-limited current density, ilim . On the other hand, for a given
temperature and Csurf , the metal dissolution rate depends on the actual
potential at the pit surface, Esurf , the maximum value of which should
be:
E max = E app − sol
where Eapp is the applied potential, and sol is the solution ohmic
potential drop between the pit surface and the reference electrode,
i.e. the total ohmic potential drop of bulk solution and pit solution.
C763
Figure 1. Schematic view of an open hemispherical pit with radius r. idiss,max
represents the maximum dissolution current density at the pit surface. idiff,crit
represents the critical diffusion current density. ilim represents the diffusion-
limited current density.
Note that ohmic potential drop associated with the salt film is not
included in sol , thus Emax represents the maximum potential that can
exist at the pit surface for a given applied potential. Emax can also
be used to define a maximum pit dissolution current density, idiss,max ,
which describes the maximum value of dissolution rate at the pit
surface. In simple terms, idiss,max can be considered to be the active
dissolution current density of the bare metal when its surface potential
is anodically polarized to Emax (thus Eapp if sol is negligible) in pit-
like solution. The role of sol will be discussed in more detail in On
the Stabilization of Pits at Ccrit ≤ Csurf < Csat section.
For stabilization of an open pit to occur, the maximum rate of
metal dissolution at the pit surface must be sufficiently high to prevent
dilution of Csurf to a value lower than Ccrit by diffusion out of the pit.
In other words, to maintain Csurf ≥ Ccrit , the maximum dissolution
current density of the metal at pit surface must be equal to or larger
than the critical current density for diffusion of metal cations out of
the pit, otherwise, the pit will repassivate. Therefore, a basic criterion
for the stability of an open pit should be:
i diss,max ≥ i diff,crit [2]
Two further situations must be considered here. When idiff,crit ≤
idiss,max < ilim , metal dissolution is the slow step and Csurf will thus
adjust to a value below Csat to balance the diffusion current density
with idiss,max . The pit growth is therefore under charge transfer (or
activation) control with a pit surface that is crystallographic if the
pit growth can be maintained under this condition for an extended
period. When idiss,max ≥ ilim , diffusion is slow and the pit growth will
be under diffusion control. Under this condition, idiss,max will not be
reached since the actual dissolution current density will be limited
by ilim . A natural consequence of idiss,max > ilim is that the metal
cations at pit surface will eventually accumulate to reach the saturation
concentration and a salt film will form, resulting in an electropolished
pit surface. Note that, in practice, the supersaturation of metal cations
might be required for salt film formation, thus idiss,max must be higher
than the corresponding diffusion current density associated with the
supersaturation concentration to precipitate the salt film.
Critical Values of Temperature, Potential and Pit Depth
Considering an open hemispherical pit, as shown in Fig. 1, and
assuming the concentration of metal cations in the bulk solution is
negligible, the current density associated with diffusive transport of
metal cations out of the pit, idiff , can be approximated by:4
3n F DCsurf
i diff = [3]
2πr
where n is the average oxidation state of the metal cations, F is the
[1]
Faraday constant, D is the effective diffusion coefficient of metal
cations that takes into account the effect of concentration-dependent
diffusivity in the pit and the possible influence of electromigration,17,18
r is the pit depth or the radius of the hemispherical pit, and 2πr/3 is the
C764 Journal of The Electrochemical Society, 165 (11) C762-C770 (2018)

effective diffusion length4 . Using Ccrit and Csat to replace Csurf results
in expressions for idiss,crit and ilim , respectively:
3n F DCcrit
i diss,crit = [4]
2πr

3n F DCsat
i lim = [5]
2πr
On the other hand, idiss,max describes charge transfer controlled
dissolution, thus for a given Csurf , idiss,max should be a function of
T and Emax , i.e. idiss,max (T, Emax ). If Emax is set at a constant value
of Econst , the maximum dissolution current density can be expressed
as idiss,max (T, Econst ). Similarly, if the temperature is set at a constant
value of Tconst , the maximum dissolution current density can be ex-
pressed as idiss,max (Tconst , Emax ). For simplification, idiss,max (T, Econst )
and idiss,max (Tconst , Emax ) are written as idiss,max (T) and idiss,max (Emax ), re-
spectively. Obviously, both idiss,max (T) and idiss,max (Emax ) are increasing
functions.
As mentioned above, Ccrit is assumed to be independent of potential
and temperature for simplicity. D is a weak function of temperature and
thus assumed to be independent of temperature, which is supported
by the analysis given in Appendix A. Additionally, D should also be
independent of potential. Therefore, according to Eq. 4, idiff,crit (T) and
idiff,crit (Emax ) can be considered to be constant for a given pit depth
r. On the other hand, ilim (T) is an increasing function, but should be
a weaker function of T than imax (T), as shown in Appendix A. In
addition, ilim (Emax ) should be constant, independent of the potential.
For fixed values of Emax and pit depth r, the relationships between
idiff,crit (T), ilim (T) and idiss,max (T) are shown in Fig. 2a, and the rela-
tionships between idiff,crit (Emax ), ilim (Emax ) and idiss,max (Emax ) for fixed
values of T and r are shown in Fig. 2b.
According to Fig. 2a, if Emax and r are fixed, there should be a criti-
cal temperature that must be exceeded for stabilization of an open pit,
Tcrit . At temperatures below Tcrit , the critical concentration of metal
cation (Ccrit ) required for active dissolution cannot be maintained be-
cause idiss,max < idiff,crit , and open pits will passivate. The measurement
of CPT during a potentiostatic temperature-scanning experiment in
which a pit initiates and grows so that both r and T increase with
time was addressed previously.2 In that situation, idiff,crit for a given
pit decreases with T, but only because the pit depth, which deter-
mines the idiff,crit , increases with time (and thus with T). Only potential
is controlled and the pit stabilization therefore depends on a critical
combination of r and T. Fig. 2a describes a situation for fixed r and
Emax , so it is an instant in time for a growing pit. It should also be
noted that the form of Fig. 2a is similar to the concepts put forth by
Newman and coworkers, which describe the CPT as the point where
two currents cross.13,19 However, the currents described in Fig. 2a
are different than those considered by Newman et al., as has been
discussed in our previous paper.2
There also exists a critical temperature for salt film formation, Tsat .
At temperatures above Tsat , the metal cations at pit surface will even-
tually accumulate to reach the saturation concentration (Csat ) because
idiss,max > ilim , a salt film will form on the pit surface, and pit growth
will transition to diffusion control. Therefore, Tsat is also a critical Figure 2. Schematic representations of idiff,crit , ilim and idiss,max dependencies
temperature for diffusion control. If r is fixed at a larger depth, ac- on temperature, maximum potential at pit surface and pit depth, showing that
there are two critical values for both of the (a) temperature (Tcrit and Tsat ), (b)
cording to Eqs. 4 and 5, both idiss,crit and ilim will be decreased, then maximum potential at pit surface (Ecrit and Esat ) and (c) pit depth (rcrit and rsat ).
both Tcrit and Tsat will decrease accordingly. This indicates that both For simplification, the increasing functions in (a) and (b) are just represented
Tcrit and Tsat will decrease with increasing r. by straight lines.
Analogous to the previous discussion, if T and r are given, there
should exist a critical Emax for pit stabilization, Ecrit , and a critical
Emax for salt film formation and diffusion control, Esat , as shown in
Fig. 2b. When Emax ≥ Ecrit , an open pit can be stabilized, and when If T and Emax are both fixed for an open pit, there should exist
Emax > Esat , a salt film will form on the pit surface. Both Ecrit and Esat a critical pit depth for pit stabilization, rcrit , and a critical pit depth
will also decrease with increasing r . Eapp = Ecrit + sol is thus the for salt film formation and diffusion control, rsat . For the given T and
repassivation potential for a growing pit. It is worth noting that the Emax , and considering that idiff,crit and ilim are given by Eqs. 4 and 5,
concept of repassivation potential for a growing pit is different from respectively, values of rcrit and rsat are obtained as shown in Fig. 2c.
that of repassivation potential that might be measured for an alloy. Additionally, when T or Emax is fixed at a larger value, idiss,max will
Details on this will be discussed in a subsequent paper. increase, then both rcrit and rsat will decrease accordingly.
 Journal of The Electrochemical Society, 165 (11) C762-C770 (2018) C765

Based on the above analysis, the basic criterion for the stability
of an open pit, idiss,max ≥ idiff,crit , can be developed into three specific
criteria:
T ≥ Tcrit [6]

E max ≥ E crit [7]

r ≥ rcrit [8]
Similarly, the basic criterion for salt film formation and diffusion
control of an open pit, idiss,max ≥ ilim , can also be developed into three
other specific criteria:
T ≥ Tsat [9]

E max ≥ E sat [10] Figure 3. Assumed configuration of a covered metastable pit. The pit, with
radius r, is covered by a film that contains a centrally located perforation of
radius a.
r ≥ rsat [11]
Note that Tcrit , Ecrit and rcrit are equivalent representations of the
It should be noted that DCcrit in Eq. 14 and DCsat in Eq. 16 are
same critical condition where idiss,max = idiff,crit , so Eqs. 6, 7 and 8 are
assumed to be independent of temperature to simply the equation. For
just different forms of the same criterion, which means if any one
DCsat , this approximation should be valid within a small temperature
criterion is satisfied, the other two criteria will be satisfied at the same
range, probably ∼10◦ C as indicated in Appendix A.
time. Similarly, Eqs. 9, 10 and 11 are also identical criteria for salt film
Analogously, if T is given, Ecrit and rcrit can be obtained by equating
formation and diffusion control. Using the set of parameters (T, Emax ,
Eq. 4 and Eq. 13:
r) to define the state of an open pit, stability will be achieved if (Tcrit ,
Ecrit , rcrit ) are exceeded, and if (Tsat , Esat , rsat ) are further exceeded, pit 3n F DCcrit
E crit (r ) = E corr + βa ln [18]
growth will transition to diffusion control with the presence of a salt 2πi corr r
film on the pit surface. When Tcrit ≤ T < Tsat , Ecrit ≤ Emax < Esat or
rcrit ≤ r < rsat , pit growth is controlled by charge transfer, and salt film 3n F DCcrit
rcrit (E max ) =   [19]
will not precipitate on the pit surface. Under this condition, the actual 2πi corr exp Emaxβ−Ea
corr

pit current density, ipit , equals idiss,max and is a function of Emax and T.
It is therefore necessary to obtain the values of (Tcrit , Ecrit , rcrit ) and Similarly, Esat and rsat can be obtained by equating Eq. 5 and Eq. 13:
(Tsat , Esat , rsat ).
3n F DCsat
As idiss,max represents the charge transfer controlled dissolution rate E sat (r ) = E corr + βa ln [20]
of active metal in pit-like solution, idiss,max (T) should obey the Arrhe- 2πi corr r
nius equation, while idiss,max (Emax ) should obey the Tafel equation. 3n F DCsat
Therefore, if Emax is given, the dependency of idiss,max on T should be: rsat (E max ) =   [21]
  2πi corr exp Emaxβ−E corr
−G ∗a a
i diss,max (T ) = Aexp [12]
RT The pit stability criteria given by Eqs. 6, 7 and 8 and the principal
parameters (Tcrit , Ecrit , rcrit ) are valid for open pits that are stabilized
where A is the pre-exponential factor, G ∗a is the activation energy of
by their own depth. Any pits growing under conditions that do not
active metal dissolution under a polarized surface potential of Emax in
meet these criteria are metastable. Therefore, the criteria of Eqs. 6, 7
pit-like solution, and R is the gas constant.
and 8 are also the criteria for the transition of a pit from metastable
On the other hand, if T is given, the dependency of idiss,max on Emax
to stable growth. The factors stabilizing metastable pit growth must
should be:
  then be understood.
E max − E corr
i diss,max (E max ) = i corr exp [13]
βa
Stability of Metastable Pits
where Ecorr , icorr and βa are the corrosion potential, corrosion current
density and anodic Tafel slope in pit-like solution, respectively. Eq. 4 shows that idiff,crit varies inversely with pit radius so the value
Therefore, when Emax is given, Tcrit and rcrit can be obtained by of idiff,crit for very small pits is very large and the situation where idiss,max
applying the critical condition of idiss,max = idiff,crit . Combining Eq. 4 < idiff,crit may easily arise. Therefore, an additional diffusion barrier
and Eq. 12: is required for maintaining the critical pit environment for very small
pits, which is the situation for metastable pits. According to previous
G ∗a researchers,4,12,20,21 the pit cover is the additional diffusion barrier for
Tcrit (r ) = [14]
Rln 3n 2πAr
F DCcrit
metastable pits. It was previously reported that the undermined passive
film is the pit cover that creates a diffusion barrier on metastable pits
3n F DCcrit in stainless steel.12 Larger pits may be covered by a so-called lacy pit
rcrit (T ) =  ∗
 [15]
−G a cover that includes undermined passive film and unreacted metal.22–25
2πAexp RT
According to Pistorius and Burstein,4 the simplest configuration of a
Similarly, applying the critical condition of idiss,max = ilim and using metastable pit with an undermined cover is shown in Fig. 3, where
Eq. 5 gives Tsat and rsat : a is the radius of a centrally located perforation in the pit cover. The
G ∗a diffusion current for such a covered hemispherical pit, Idiff,cov , can be
Tsat (r ) = [16] approximated by:4
Rln 3n2πAr
F DCsat
Idiff,cov = can F DCsurf [22]
3n F DCsat
rsat (T ) =  ∗
 [17] where c is a dimensionless constant with a value between 2 and 3.
2πAexp −G
RT
a
Therefore, the critical diffusion current density for a covered pit,
C766 Journal of The Electrochemical Society, 165 (11) C762-C770 (2018)

Table I. Principal parameters and criteria for pit stability, charge transfer control, diffusion control and salt film formation.

idiss,max = idiff,crit or idiff,crit,cov idiss,max = ilim or ilim,cov Pit Stability Charge Transfer Control Diffusion Control and Salt Film Formation
Tcrit Tsat T ≥ Tcrit Tcrit ≤ T < Tsat T ≥ Tsat
Ecrit Esat Emax ≥ Ecrit Ecrit ≤ Emax < Esat Emax ≥ Esat
rcrit rsat r ≥ rcrit rcrit ≤ r < rsat r ≥ rsat
acrit asat a ≤ acrit asat < a ≤ acrit a ≤ asat

idiff,crit,cov , can be expressed as: Under the condition of a ≤ asat , the increase in pit current is derived
can F DCcrit from the rupture events of the pit cover, and discrete rupture events
i diff,crit,cov = [23] of the pit cover might result in a discontinuous increase in pit current.
2πr 2 A current jump might also be observed at the end of the metastable
Similarly, the diffusion-limited current density for a covered pit, growth because of a large rupture of the pit cover to an extent above
ilim,cov , should be: acrit . When asat < a ≤ acrit , a salt film will not precipitate on the pit
can F DCsat surface and the growth of a covered pit is controlled by charge transfer.
i lim,cov = [24] Therefore, the actual pit current density ipit equals idiss,max , and thus
2πr 2 it should be a function of Emax and T. Under this condition (asat <
Because of the presence of the pit cover, the maximum potential a ≤ acrit ), the current transient of a metastable pit should increase
that can be applied at the pit surface should be Eapp − sol − pc , continuously and smoothly, and a current jump will not be observed
where pc is the ohmic potential drop across the pit cover. As detailed at the end of the metastable growth.
in Appendix B, if the thickness of pit cover is small but a is not an The principal parameters and criteria for pit stability, charge trans-
extremely small value, then pc can be neglected. Therefore, Emax of fer control, diffusion control and salt film formation are summarized
a covered pit is still equal to that of an open pit. in Table I, which shows that a salt film is not required for pit stabiliza-
Similar to the basic pit stability criterion for an open pit proposed tion, it is just a consequence of a pit achieving diffusion-controlled
in Eq. 2, the basic stability criterion for a covered pit should be: growth. It also indicates that both metastable and stable pit growth can
i diss,max ≥ i diff,crit,cov [25] be controlled either by charge transfer or by diffusion. This perspec-
tive is different than the viewpoint held by Pistorius and Burstein,4
and the basic criterion for salt film formation and diffusion control for who considered that the growth of both metastable and stable pits is
a covered pit then should be: under diffusion control. According to the proposed framework, when
i diss,max ≥ i lim,cov [26] pit growth is controlled by charge transfer, the pit current density
equals idiss,max , while if pit growth is controlled by diffusion, the pit
There should exist a critical perforation radius for stabilization of a current density equals ilim (for open pits) or ilim,cov (for covered pits).
covered pit, acrit , above which repassivation occurs because of the loss However, although a pit can grow under charge transfer control, such
of the critical pit environment (Ccrit ) required for active dissolution. a pit will tend to concentrate the pit solution and transition to diffusion
There should also exist a smaller critical perforation radius for salt control. This will be discussed in detail below.
film formation and diffusion control, asat . For a perforation radius Interestingly, the principal parameters for stability of open pits,
smaller than asat , the growth of a covered pit is under diffusion control Tcrit , Ecrit and rcrit , can also be deduced from the perspective of
and a salt film will form on the pit surface. metastable growth. In fact, they represent a critical state where acrit =
The values of acrit and asat can be obtained by applying the critical r. Similarly, the principal parameters for salt film formation and dif-
conditions of idiss,max = idiff,crit,cov and idiss,max = ilim,cov , respectively. If fusion control of open pits, Tsat , Esat and rsat , represent a critical state
Emax is given, acrit can therefore be obtained by equating Eq. 12 and where asat = r. This is derived in Appendix C. Although the expres-
Eq. 23: sions of these principal parameters are derived for hemispherical pits,
  the concept of these parameters is applicable to any pit geometry.
−G ∗
2πAr 2 exp RT a The derivation of the set of parameters (Tcrit , Ecrit , xcrit ) and (Tsat , Esat ,
acrit (r, T ) = [27] xsat ) for a one-dimensional (1D) artificial pit geometry is presented in
cn F DCcrit
Appendix D. However, as the 1D pit does not have a pit cover, the
Similarly, asat can be obtained by equating Eq. 12 and Eq. 24: concept of metastable pitting is not applicable, so the concepts of acrit
  and asat are also not applicable to 1D pits.
−G ∗
2πAr 2 exp RT a
asat (r, T ) = [28]
cn F DCsat
On the Stabilization of Pits at Ccrit ≤ Csurf < Csat
Analogously, if T is given, acrit can be obtained by equating Eq. 13
and Eq. 23: The dissolution of metal at the pit surface and the diffusion of metal
  cations out of the pit occur in sequence. Therefore, when a pit grows
2πi corr r 2 exp Emaxβ−E
a
corr at steady state, the actual dissolution current density (idiss,act ) should
acrit (r, E max ) = [29] always equal the actual diffusion current density (idiff,act ). According
cn F DCcrit to the proposed framework, when idiff,crit ≤ idiss,max < ilim (for open
and asat can be obtained by equating Eq. 13 and Eq. 24: pits) or idiff,crit,cov ≤ idiss,max < ilim,cov (for covered pits), pit growth is
  under charge transfer control with Ccrit ≤ Csurf < Csat . For any given
2πi corr r 2 exp Emaxβ−E
a
corr
pit, the actual diffusion current density (idiff,act ) can be expressed by:
asat (r, E max ) = [30]
cn F DCsat n F DCsurf
i diff,act = [33]
Therefore, the stability criterion for metastable pit growth is: deff
a ≤ acrit [31] where deff is the effective diffusion length, which is determined by the
pit geometry.
and the criterion for salt film formation and diffusion control of
On the other hand, for a given temperature and Csurf , idiss,act is
metastable pit is:
determined by the potential drop across the pit surface/pit solution
a ≤ asat [32] interface Esurf , i.e. the actual potential applied on the pit surface.
 Journal of The Electrochemical Society, 165 (11) C762-C770 (2018)
Because Csurf is smaller than Csat , a salt film will not form on the
pit surface, so there is no ohmic potential drop associated with a salt
film and the actual potential at the pit surface is Emax , thus idiss,act
equals idiss,max . Two further situations must now be considered. In the
first situation, the total ohmic potential drop of bulk and pit solutions
(sol ) is assumed to be negligible, hence Emax = Eapp . Therefore, idiss,act
can be expressed by:
 
E app − E corr
i diss,act = i corr exp [34]
βa
This equation shows that idiss,act is constant during pit growth for a
given Eapp . As idiff,act = idiss,act , and according to Eq. 33, the concen-
tration of metal cations at the pit surface can be expressed as:
i diss,act deff
Csurf = [35]
nFD
Because idiss,act is constant and deff increases during pit growth, Csurf
will keep increasing to a supersaturated level and then a salt film will
eventually precipitate with Csurf equal to Csat . It can be concluded that,
when the solution resistance is negligible, Csurf cannot be maintained
at a constant value below Csat during sustained pit growth. However,
according to Eq. 35 the time required to reach Csat will depend on pit
growth rate, i.e. ddeff /dt, which is actually determined by idiss,act . Note
that the effect of Csurf change between Ccrit and Csat on idiss,act is ignored
here for simplicity. When Eapp is large, idiss,act will be large and Csurf will
reach Csat very quickly so that pit growth will consequently transition
to diffusion control with the presence of a salt film. In contrast, if
Eapp is small, then it will take a relatively long time for Csurf to reach
Csat , during which time the pit will grow under charge transfer control
without the presence of a salt film. Therefore, the pit morphology
will be crystallographic for a pit growing without a salt film for an
extended period, which might occur during immersion at the open
circuit potential16 or polarization at a relatively low potential.15
It is also of interest to understand conditions in which Csurf can be
maintained at a constant value less than Csat and not changed during the
whole pit growth process. To address this issue, the second situation
must be considered, in which sol is not negligible. Thus, idiss,act can
be expressed by:
 
E app − sol − E corr
i diss,act = i corr exp [36]
βa
When the pit grows in a steady state, idiff,act = idiss,act . Thus, combining
Eq. 36 with Eq. 33,
n F DCsurf
sol = E app − E corr − βa ln [37]
deff i corr
On the other hand,
sol = I R [38]
where I is the pit current, R is the total resistance of the solution
between the pit surface and reference electrode, which should be a
function of pit depth x, i.e. R(x), and also a function of time, i.e. R(t).
Combining Eqs. 33, 37 and 38 along with the definition of current
density as I/Apit , where Apit is the area of pit surface, and considering
Apit and deff as functions of time, i.e. Apit (t) and deff (t), then R(t) can
be expressed by:
E app − E corr − βa ln dneff
F DCsurf
(t)i corr
R (t) = [39]
n F DCsurf
· Apit (t)
deff (t)
To maintain Csurf at a constant value between Ccrit and Csat , the
variation of idiss,act with pit depth must change in a synchronized
manner with that of idiff,act , thus the actual solution resistance, Ract (t),
needs to strictly obey Eq. 39. In other words, the variation of Ract (or the
variation of actual ohmic potential drop of the solution) must balance
idiss,act with idiff,act without the presence of the salt film, otherwise Csurf
will change to offset their difference. This offset effect will increase
as Ract deviates from that described by Eq. 39 during the pit growth.
C767
Generally, Ract is unlikely to follow Eq. 39 exactly. For a 1D pit,
the ideal resistance in Eq. 39 can be expressed as a function of pit
depth (x):
E app − E corr − βa ln n FxiDC surf
R (x) = corr
[40]
n F DCsurf
.A1D
x
where A1D is the cross-sectional area of the 1D pit. However, the
actual solution resistance (Ract ) of a 1D pit increases linearly with the
pit depth.17 Therefore, the situation described by Ccrit ≤ Csurf < Csat
for a 1D pit is not a steady state condition during sustained pit growth.
In fact, for most pits, Ccrit ≤ Csurf < Csat is just a transient state
during the sustained pit growth, and Csurf will keep increasing until a
salt film is eventually formed on the pit surface. In other words, the
pit growth under charge transfer control will tend to spontaneously
shift to diffusion control. This perspective is in agreement with the
observations by Frankenthal and Pickering,14 who found that the pits
on iron are initially crystallographic, but then become electropolished.
According to the proposed framework, a high potential or temperature
will accelerate the transition from charge transfer control to diffusion
control by decreasing rsat (for open pits) or by increasing asat (for
covered pits), and also by increasing the pit growth rate. However,
in some specific cases, if sol increases rapidly during growth under
charge transfer control, i.e.
   
 dsol (r )   d E crit (r ) 
  >   [41]
 dr   dr 
rcrit ≤r <rsat rcrit ≤r <rsat
so that it might lower Emax below Ecrit , then the pit growth can also be
naturally terminated during the charge transfer control stage, leaving
a crystallographic pit morphology. Based on the above analysis, the
perspective held by Pistorius and Burstein that both metastable and
stable growth of a pit are under diffusion control4 is a special case for
large open pits or covered pits with small asat , or for high potential
and temperature.
Whereas Csat should be the steady state during sustained pit growth,
under conditions in which Ract (t) happens to obey Eq. 39 or share the
same variation tendency, it is possible for Csurf to be maintained at a
constant value between Ccrit and Csat during the sustained pit growth.
As revealed above, a salt film is not required for pit stability,
and it is just a consequence of a pit achieving diffusion-controlled
pit growth. However, the possible role of salt film in the pit growth
process should still be considered, and details will be discussed in
a subsequent paper. Verification of the proposed framework for pit
growth will also be reported in future works.
Summary
The new framework for pit stability established in Part II of this
series based on maintaining a sufficiently aggressive pit environment
required for active dissolution, i.e. Csurf ≥ Ccrit , has been elaborated
upon and expanded. The concept of maximum pit dissolution cur-
rent density, idiff,max , which depends on temperature and maximum
potential at the pit surface for a given pit environment, is proposed to
establish a unifying framework for pit growth. By comparing idiff,max
with the diffusion current density, a set of principal parameters and
criteria for pit growth stability and salt film formation are proposed to
unify and clarify various aspects of pit growth. The main points are
summarized as follows:
(1) Considering both the dissolution process of the metal at pit sur-
face and the diffusion process of the metal cations out of the
pit interior into the bulk solution, basic criteria for pit stabiliza-
tion are proposed: idiss,max ≥ idiff,crit (for open pits) or idiss,max ≥
idiff,crit,cov (for covered pits). Basic criteria for salt film formation
and diffusion control are also proposed: idiss,max ≥ ilim (for open
pits) or idiss,max ≥ ilim,cov (for covered pits). Additionally, when
idiff,crit ≤ idiss,max < ilim (for open pits) or idiff,crit,cov ≤ idiss,max <
ilim,cov (for covered pits), pit growth will be under charge transfer
control.
C768 Journal of The Electrochemical Society, 165 (11) C762-C770 (2018)

(2) The set of parameters (T, Emax , r) can be used to define the state Table AI. The calculated saturation concentration (Csat ), average
of a pit, and if any two of these three parameters are given, the viscosity of pit solution (ηpit ), effective diffusivity (D) in pit solution
remaining one has a critical value that must be exceeded for pit and DCsat product at different temperatures.
stability. Accordingly, three critical values for pit stability of an
open pit exist: Tcrit , Ecrit and rcrit , which represent the critical Csat , D, × 10−5 DCsat , × 10−8
condition where idiss,max = idiff,crit , and three criteria describe T, K (◦ C) mol/L ηpit , cP cm2 s−1 mol cm−1 s−1
pit stability: T ≥ Tcrit ; Emax ≥ Ecrit ; r ≥ rcrit . There are also
three critical values for salt film formation and diffusion control 288 (15) 4.33 2.187 0.660 2.86
of an open pit: Tsat , Esat and rsat , which represent the critical 293 (20) 4.39 1.948 0.753 3.31
condition where idiss,max = ilim , and three criteria describe salt 298 (25) 4.46 1.756 0.850 3.79
303 (30) 4.55 1.590 0.954 4.34
film formation and diffusion control: T ≥ Tsat ; Emax ≥ Esat ; r ≥
308 (35) 4.66 1.451 1.063 4.95
rsat . Additionally, when Tcrit ≤ T < Tsat or Ecrit ≤ Emax < Esat or
313 (40) 4.73 1.342 1.168 5.53
rcrit ≤ r < rsat , the growth of an open pit will be under charge 333 (60) 5.32 1.014 1.645 8.75
transfer control without the presence of a salt film. 353 (80) 6.05 0.819 2.159 13.06
(3) Before the critical values (Tcrit , Ecrit , rcrit ) are reached, the pits are 358 (85) 6.09 0.769 2.332 14.20
metastable and their sustained growth needs a pit cover acting as
an additional diffusion barrier. There exists a critical perforation
radius of the pit cover, acrit , which represents the critical condi-
tion where idiss,max = idiff,crit,cov and below which a metastable pit
can be sustained. Otherwise, it will repassivate because of loss of
the critical pit environment (Ccrit ). In fact, Tcrit , Ecrit or rcrit also
represent the critical state where acrit = r. Additionally, there
also exists another critical perforation radius of the pit cover for
salt film formation and diffusion control, asat , which represents
the critical condition where idiss,max = ilim,cov and when a ≤ asat
the metastable growth will be under diffusion control. Similarly,
Tsat , Esat or rsat represent the critical state where asat = r. More-
over, when asat < a ≤ acrit , the metastable growth will be under
charge transfer control without the presence of a salt film.
(4) A salt film is not required for pit stability, it is just a consequence
of a pit achieving diffusion-controlled pit growth. In most cases,
Ccrit ≤ Csurf < Csat is a transient state during sustained pit growth.
A pit in this condition is under charge transfer control, and it will
tend to spontaneously transition to diffusion control through pit
growth with a salt film eventually precipitated on the pit surface
and Csurf = Csat .
Figure A1. The viscosity profile along the pit depth at different temperatures
(15 ∼ 40◦ C) obtained from the OLI Systems software Stream Generator.
Acknowledgments
This work was supported as part of the Center for Performance and
Design of Nuclear Waste Forms and Containers, an Energy Frontier the viscosity profile along the pit depth at different temperatures can be obtained by OLI
Systems, as shown in Fig. A1. The viscosity at pit bottom corresponds to that of saturated
Research Center funded by the U.S. Department of Energy, Office
FeCl2 solution, while the viscosity at the pit mouth should equal the viscosity of pure
of Science, Basic Energy Sciences under Award # DE-SC0016584. water. The average viscosity of the pit solution from the pit bottom to pit mouth, ηpit , can
Discussions with Dr. N. Sridhar are greatly appreciated. then be calculated by:

Appendix A: Evaluation of Temperature Dependency of DCsat
A diffusion model of the artificial pit (1D pit) of pure iron is used here to determine
the DCsat value. According to the proposed framework for pit stability, the metal cations
at the pit bottom will be saturated (Csurf = Csat ) if the critical pit depth for salt film
formation is reached. It should be noted that a 1D pit is uncovered by its nature. Three
simplifications are also made to obtain a tractable physical model. The first simplification
for the model is that, for an iron-based corrosion resistant alloy such as stainless steel,
Fe2+ is the only metal cation species and Cl− is the only aggressive anion inside the pit.
The second simplification is that the concentration of metal cation decreases linearly along
the pit depth and is zero at the pit mouth. The third simplification is that the formation of
metal ion complexes is ignored.
Csat of Fe2+ at the pit bottom equals the solubility of FeCl2 , which can be obtained
through the Stream Analyzer software from OLI Systems. The calculation results show
that the saturation concentration of FeCl2 only weakly depends on the temperature within
a range of ∼10◦ C, as summarized in the second column of Table AI.
The diffusivity of metal cations in a pit will also be affected by the concentration
of the pit solution. The Stokes-Einstein equation shows that diffusivity decreases with
increasing solution viscosity:26
kT
D= [A1]
6πηrMe
where k is the Boltzmann constant, T is absolute temperature, rMe is the radius of a
diffusing metal cation, and η is the dynamic viscosity of the solution at the temperature T.
A decrease in FeCl2 concentration along the pit depth will cause a decrease in viscosity of
pit solution and thus an increase in diffusivity. For a linear FeCl2 concentration gradient,
∫d0 ηd x
ηpit = [A2]
d
where d is the depth of the 1D pit. The calculated values of ηpit at different temperatures
are listed in the third column of Table AI.
At 25◦ C in liquid solution, the diffusion coefficients of metal cation species,
such as Fe2+ , Cr3+ and Ni2+ , have been commonly assumed to be 0.7 × 10−5 ∼
1 × 10−5 cm2 s−1 .4,9,27–31 An effective diffusivity of metal cations was suggested to
take into account the effect of concentration-dependent diffusivity and the possible in-
fluence of electromigration.17,18 Kuo and Landolt suggested the effective diffusivity for
Fe2+ in concentrated chloride solution to be 0.85 × 10−5 cm2 s−1 .18 Gaudet et al. also
obtained a similar result, and the effective diffusivity of metal cations in pit solution fitted
to their data is 0.824 × 10−5 cm2 s−1 (for SS304).17 In this work, the effective diffusivity
of Fe2+ in pit solution at 298 K is assumed to be 0.85 × 10−5 cm2 s−1 . It is also assumed
that the effective diffusivity obeys the Stokes-Einstein equation. The effective diffusivity
at other temperatures can then be determined using Eq. A1 from:
T /298
DT = D298 [A3]
ηpit T /ηpit 298
where T is the pit solution temperature in Kelvin, ηpit_298 is the average dynamic viscosity
of pit solution at 298 K, 1.756 cP as shown in Table AI, and D298 is 0.85 × 10−5 cm2 s−1 .
The calculated diffusivity of Fe2+ in pit solution at different temperatures, as summarized
in the fourth column of Table AI, indicates that D also weakly depends on the temperature
within a range of ∼10◦ C. The calculated DCsat product at different temperatures, as
summarized in the fifth column of Table AI, is compared to previously reported values
over a range of temperature for different stainless steels27,32–35 in Fig. A2. The calculated
DCsat plot fits the experimental results very well. Fig. A3 shows the Arrhenius plot of
 Journal of The Electrochemical Society, 165 (11) C762-C770 (2018) C769

Eqs. 22 and B2 into Eq. B1:

cnl F DCsurf
pc = [B3]
κp πa
If the pit cover just consists of passive film, whose thickness is extremely thin, i.e.
l → 0, and the perforation radius (a) is not an extremely small value, then pc can be
neglected.

Appendix C: Derivation that (Tcrit , Ecrit , rcrit ) Represents a

Critical State Where acrit = r and (Tsat , Esat , rsat ) Represents a
Critical State Where asat = r
When Emax is given, substituting Eq. 27 into acrit = r leads to:
G ∗a
T (r ) = [C1]
Rln cn F2πAr
DC crit

cn F DCcrit
r (T ) =  ∗ [C2]
−G a
2πAexp RT

Similarly, when T is given, substituting Eq. 29 into acrit = r leads to:

cn F DCcrit
Figure A2. The calculated DCsat values and experimental results at different E max (r ) = E corr + βa ln [C3]
2πi corr r
temperatures. Newman32 - 17Cr11Ni3Mo, Laycock33 and Ernst34 - SS 316,
Moayed27 - SS 302, Jun35 - SS Super 13Cr. r (E max ) =
cn F DCcrit
  [C4]
2πi corr exp Emaxβ−E a
corr

On the other hand, if acrit = r, the pit cover is no longer necessary for the stability of
a metastable pit, and the dimensionless constant, c, for an open hemispherical pit should
equal 3.4 Then Eqs. C1, C2, C3 and C4 equate to Eqs. 14, 15, 18 and 19, respectively.
Thus, it is verified that (Tcrit , Ecrit , rcrit ) represents a critical state where acrit = r. Using
Csat to replace Ccrit in Eqs. C1 ∼ C4, it can be verified that (Tsat , Esat , rsat ) represents a
critical state where asat = r.

Appendix D: Derivation of (Tcrit , Ecrit , xcrit ) and (Tsat , Esat , xsat )

for a 1D Pit
According to Fick’s first law and Faraday’s Law, the critical diffusion current density
(idiff,crit,1D ) and diffusion-limited current density (ilim,1D ) for a 1D pit can be expressed as:
n F DCcrit
i diff,crit,1D = [D1]
x
n F DCsat
i lim,1D = [D2]
x
where x is the pit depth.
If Emax is set at E const , the Tcrit and xcrit for 1D pit can be obtained by applying
idiss,max = idiff,crit,1D . Combining Eq. D1 and Eq. 12:
Figure A3. Arrhenius plot of ln(DCsat ) versus 1/T.
G ∗a
Tcrit (x) = Ax
[D3]
Rln n F DC
crit
ln(DCsat ) versus 1/T, which can be perfectly fitted by the equation: n F DCcrit
  xcrit (T ) =  ∗ [D4]
−G a
−19720.6 Aexp
DCsat (T ) = 1.082 × 10−2 exp [A4] RT
RT
and Tsat and xsat can be obtained by applying idiss,max = ilim,1D . Combining Eq. D2 and
where R is the gas constant and the unit of DCsat is mol m−1 s−1 . Therefore, the activation Eq. 12:
energy of DCsat (G ∗DCsat ) is 19.7 kJ mol−1 . G ∗a
On the other hand, the activation energy of dissolution for iron-based alloy in concen- Tsat (x) = Ax
[D5]
Rln n F DC
trated acid solution commonly ranges from 40 ∼ 85 kJ mol−1 ,36–38 which indicates that sat

the ilim (T) is a weaker function of T than idiss,max (T). Additionally, the variation of DCsat n F DCsat
xsat (T ) =  ∗ [D6]
within a small temperature range ∼10◦ C is not significant, and it can be considered to be Aexp
−G a
RT
a constant to simply the expression of Tsat .
Similarly, if T is fixed, Ecrit and xcrit can be obtained by combining Eq. D1 and Eq. 13:
n F DCcrit
Appendix B: Evaluation of Ohmic Potential Drop Across the Pit E crit (x) = E corr + βa ln [D7]
i corr x
Cover, pc
n F DCcrit
It can be considered that, xcrit (E max ) =   [D8]
E max −E corr
i corr exp βa
pc = Idiff,cov Rperf [B1]
and Tsat and xsat can be obtained by combining Eq. D2 and Eq. 13:
where Rperf is the resistance of the perforation. Assuming the perforation is an ionic
conductor with cylinder shape, its resistance should be: n F DCsat
E sat (x) = E corr + βa ln [D9]
l i corr x
Rperf = [B2]
κp πa 2 n F DCsat
xsat (E max ) =   [D10]
E max −E corr
where κp is the conductivity of the perforation electrolyte, a is the radius of the perforation, i corr exp βa
and the l is the thickness of the perforation, i.e. the thickness of pit cover. Substituting
C770 Journal of The Electrochemical Society, 165 (11) C762-C770 (2018)
ORCID
Tianshu Li https://orcid.org/0000-0001-8664-092X
J. R. Scully https://orcid.org/0000-0001-5353-766X
G. S. Frankel https://orcid.org/0000-0003-0573-3548
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