Understanding localized

corrosion
The breakdown of a protective passive film leading to accelerated
dissolution at localized sites is an important practical issue and a vexing
scientific problem. The small dimensions, short timescale, and dynamic
interplay between a heterogeneous surface and changing potential
and solution concentration gradients complicate the development of a
complete understanding of the phenomena. This review touches on some
of the recent developments in the field, including scanning tunneling
microscopy imaging of the earliest stages of pitting which supports a
new model explaining the localization of attack, pitting in thin aqueous
layers relevant to atmospheric corrosion, the factors controlling crevice
corrosion, and predictive modeling of localized corrosion.
G. S. Frankela* and N. Sridharb
aFontana Corrosion Center, The Ohio State University, Columbus, OH 43210, USA
bDNV Research and Innovation, Dublin, OH 43017, USA
*E-mail: frankel.10@osu.edu
Localized corrosion is the accelerated attack of a passive metal

that many pits cease to grow at this stage); stable growth of localized

in a corrosive environment at discrete sites where the otherwise

corrosion sites that can grow quite large; and finally if conditions

protective passive film has broken down1. Common forms of

permit repassivation or cessation of attack. Localized corrosion is

localized corrosion include pitting on a boldly exposed surface,

known to initiate above a critical potential and repassivate below

corrosion in a creviced region shielded from the bulk environment,

another, lower potential1. Once initiated, the attack is stabilized by

intergranular corrosion of an alloy with a susceptible grain

the localized development of aggressive conditions as the result of

boundary region, and exfoliation corrosion, which is a form of

metal cation hydrolysis and Cl migration. A conservative criterion

intergranular corrosion involving the prying apart of elongated

for localized corrosion is the prediction that it can occur at potentials

grains by a voluminous grain boundary corrosion product.

above the repassivation potential and should not occur if the corrosion

The various localized corrosion phenomena have been studied

for decades and considerable understanding has been achieved. The
process of localized corrosion can be divided into a sequence of

38

steps1:

potential remains below the repassivation potential by a margin of

safety that should be at least 100 mV.
Despite the advances that have been made, fundamental

initiation by the breakdown of the passive film; metastable growth of

understanding and prediction of localized corrosion is a difficult

small pits on the verge of stability (metastable in this context indicates

problem for a number of reasons. First of all, the events take place on

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ISSN:1369 7021 Elsevier Ltd 2008

Understanding localized corrosion

REVIEW

that of the passive film outside of the pits, suggesting that the pits
were never depassivated but rather that there was accelerated attack
through the passive film at these sites. Such a view is consistent with
the adsorption mechanism of passivity breakdown4.
A recent publication has shown that the nanometer-sized pits,
which can form on Ni single crystals even in Cl-free solutions such as
H2SO4, are found primarily at the boundaries between grains in the
passive oxide film5. A model for pit initiation based on the reactivity of
the oxide grain boundaries was also presented5. This model considers
that these oxide grain boundary regions have a lower resistance to
ionic transport and are thus the sites of oxide breakdown. Cl competes
with OH adsorption and accelerates ion transport at the local defect
sites. The experimental evidence cannot distinguish between local
thinning and suboxide void formation as the initiation mechanism.
However, this model presents the first explanation for the localization
of attack on the surface of a homogeneous metal sample.
Localized corrosion has been studied almost exclusively in bulk
solutions relevant to complete immersion conditions. However, there
Fig. 1 STM image of pits formed in single-crystal Ni(111). The surface was
passivated first at 0.96 V SHE in 0.05 M H2SO4 + 0.095 M NaOH and then NaCl
was added to 0.05 M. z range = 12.3 nm 3.

are a number of important applications where localized corrosion of

passive metals under atmospheric corrosion conditions might play a
role. The proposed site for disposal of high-level radioactive waste

a very small scale, with a passive film nanometers in thickness and

in the United States is Yucca Mountain in Nevada. This location

initiation sites of a similar size. Immediately after initiation, the rate

is well above the water table but the metal waste canisters in the

of pit growth can be extremely high, even tens of A/cm2 2. Therefore,

emplacement tunnels will be exposed to atmospheric corrosion

the situation is extremely dynamic with rapidly moving boundaries and

conditions associated either with dripping water or deliquescence of

rapidly changing chemistries. Moreover, initiation events are relatively

surface salts or dust in a humid environment6,7. Atmospheric localized

scarce, with maybe a few sites per

cm2,

and stochastic in nature. As a

corrosion can also occur in the vapor space above a closed storage

result, it is not possible to predict exactly when and where breakdown

tank8. No standard electrochemical methods exist for the study

will occur, which makes high-resolution observation of initiation

of atmospheric corrosion9, but Stratmann and coworkers1013 and

events extremely difficult. Finally, the exact susceptibility of sites for

Nishikata and coworkers1419 have developed different approaches

breakdown and the ability of other sites to sustain cathodic reactions

for electrochemical measurements under thin electrolyte layers.

depend on details of the surface film properties, such as catalytic

Stratmann and coworkers1113 developed Kelvin probe methods, but

activity, that are not well understood, difficult to measure on the scale

did not focus on localized corrosion until a recent study that showed

of the sites, and change with time as the process evolves.

no effect of solution layer thickness down to tens of micrometers

on the breakdown potential of 304 stainless steel10. Nishikata and

The following will describe some recent advances in the

understanding of localized corrosion. The topics discussed include

coworkers1719 also studied pitting corrosion of stainless steel under

scanning tunneling microscopy (STM) imaging of the earliest stages of

thin electrolyte layers. They used samples composed of a working

pitting, pitting in thin aqueous layers (which is relevant to atmospheric

electrode (WE), a counter electrode (CE), and a chloridized Ag wire

corrosion), controlling factors in crevice corrosion, and modeling of

reference electrode (RE) embedded in epoxy under thin electrolyte

localized corrosion.

layers and exposed them to cyclic wetdry conditions. The corrosion

As mentioned above, the earliest stages of localized corrosion

breakdown are the least understood. The smallest of pits have in
recent years been imaged with

STM3.

Fig. 1 shows a single-crystal

Ni surface passivated at a controlled potential in a

Cl-free

solution

rate associated with pitting was assessed by electrochemical

impedance spectroscopy measurements during cyclic wetdry cycling
on different stainless steels18. Corrosion potential measurements were
made on an embedded WE using a different design in which an agar-

followed by addition of NaCl to the solution. The resulting pits are

filled hole in the epoxy allowed ionic connection to a remote saturated

extremely small, with an average depth of only 3 nm. Such features are

calomel RE19. A decrease in the corrosion potential by hundreds of

Cl

millivolts coincided with a sharp decrease in polarization resistance

not present before the addition of

and the charge associated with

the dissolution is much too small to discern via a current transient.

and the onset of pitting corrosion as a critical Cl concentration was

The bottom of the pits has a passive film with a structure identical to

reached during drying.

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Understanding localized corrosion

(b)

(a)

Fig. 2 Schematic diagram of (a) a crevice with the cathode covered by a thinfilm of electrolyte containing particulates, and (b) a decoupled cathode simulating the
effect of area blockage by particles 22.

Tada and Frankel20,21 took an approach similar to that of Nishikata

available to sustain dissolution at the anode (Fig. 3). The cathode

et al. to investigate the effects of a particulate layer on the breakdown

capacity increases with increasing electrode kinetics as reflected by the

of 304L stainless steel in thin layers of electrolyte. They used layers

exchange current density, increasing bulk solution conductivity, and

of silica particles deposited by electrophoretic deposition to simulate

decreasing repassivation potential. The particle loading strongly affects

particles that might deposit on a surface under atmospheric conditions.

the cathode capacity for high solution resistance and fast kinetics.

Using open circuit potential and galvanic current transients, they

A variety of models have been developed to describe localized

found that the silica layer had a greater effect on propagation than on

corrosion. The most atomistically based model available for the

initiation of pitting corrosion21. The propagation of pitting corrosion for

prediction of localized corrosion susceptibility is the point defect

silica-coated samples was slower than for uncoated 304 stainless steel.

model (PDM) developed by Macdonald et al.23,24. The PDM considers

The effects of inert particulate in a thin electrolyte film on the

the transport of cation vacancies in the passive film towards the film

ability of cathodic sites to provide the necessary current for spatially

metal interface, where they can condense to form voids or nascent pits

separated localized corrosion sites to continue growing was reported

at the metalpassive film interface if the flux of vacancies arriving at

recently by Agarwal et al.22. Particles decrease the electrolyte

the interface is greater than what can be consumed by annihilation via

conductivity by volume blockage and also alter the available area.

a metal oxidation reaction. The effect of an aggressive species, such

Numerical methods were used to solve the Laplace equation and

as Cl, is hypothesized to alter the generation and transport of cation

generate three-dimensional simulations of the current and potential

vacancies. The model correctly predicts the logarithmic dependency

distributions. The anode was considered to be in a shielded crevice

of pit initiation potential on Cl concentration, the effects of some

and the particles were located in a thin electrolyte region outside of

alloying elements, and the effect of parameters such as scan rate on

the crevice (Fig. 2a). The particles blocked the cathode area, which

pit initiation. In a recent development of the PDM, Macdonald and

was modeled by a segmented decoupled cathode as shown in Fig.

Yang25 modeled the inhibitive effect of oxyanions, such as NO3 and

2b. Calculations were performed to predict the effects of a number

BO3, on pit breakdown potential of 316L stainless steel by considering

of different parameters on the cathode capacity, which is the current

the competitive adsorption of aggressive and inhibitive species at

(a)

(b)

(c)

Fig. 3 The effects of various properties on the cathode capacity assuming 25 m3 particles at an area and volume fraction of 0.306: (a) exchange current density for
the cathodic reaction; (b) bulk solution conductivity; (c) repassivation potential22.

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O vacancies at the filmsolution interface. The model predicts that the

a pit or crevice associated with hydrolysis and electrolytic migration

breakdown potential should vary with

of Cl, which combine to form an aggressive local environment that

stabilizes attack2729.

[X ]
,
log
[Y z ]

Recent work has utilized coupled multielectrode arrays to

investigate the spatial and temporal crevice corrosion of various

where [X-] is the concentration of aggressive species such as Cl- and

corrosion-resistant alloys30. Using scaling laws, these experiments have

[Yz-]

interpreted data from multiple-crevice assembly electrodes, which are

is the concentration of inhibiting

oxyanions25.

Experimental

results found this relationship to be true for 316L stainless steel in

commonly used for studying the susceptibility of an alloy to crevice

Cl + NO3 solutions (Fig. 4)25. It should be noted that criticisms of

corrosion. This scaling model predicted a variation of the critical

the PDM have focused on the linearization of the transport equations

crevice depth with the square root of crevice gap distance30. The

and how the potential drop at the oxide/electrolyte interface is

multielectrode arrays consisted of 100 close-packed circular wire cross-

handled4. Furthermore, the PDM predicts the pitting potential, whereas

sections covered by a polymer crevice former. The less resistant 316

the breakdown occurs at much lower potentials as evidenced by

stainless steel dissolved in the crevice at the mass-transport-limited

metastable pitting transients in the data25. A bilogarithmic dependence

condition, resulting in crevice corrosion that started near the mouth of

of pitting potential on

Cl

concentration is often observed, but is not

the crevice and then spread inward and outward over time. In contrast,

predicted by the PDM at present. Finally, the PDM does not explain

the more resistant alloy 625, a Ni-base alloy with 2023% Cr and 8

why breakdown is localized at discrete sites.

10% Mo, exhibited an activepassive transition in the crevice solution

Most models for describing the stability of growing localized

so that the attack started at a location deeper in the crevice where the

corrosion have focused on crevice corrosion. A growing pit is essentially

ohmic drop was sufficiently high. The location could be predicted using

identical to a growing crevice, though the transport distance varies

a model based on polarization data in simulated crevice solutions and

much less with time for a crevice as it is set primarily by the crevice

the potential distribution down the crevice30.

geometry. There are two primary models for crevice stability, which
focus on local potential or local chemistry, respectively. The critical
potential drop theory promoted by Cho and

Pickering26

describes

In recent years, Anderko et al.3134 have developed a different

approach to modeling localized corrosion by adapting Okadas35,36
irreversible thermodynamic model and combining it with a model

the ohmic potential drop associated with ionic current flow that

of thermodynamic speciation37,38. This approach focuses on the

must exist if the anodic current in the crevice is connected to an

repassivation potential, which is lower than the breakdown potential

external cathode. According to the potential drop theory, the potential

and therefore a more conservative value to use as a design parameter.

decreases from the passive region at the outside of the crevice to the

As mentioned above, localized corrosion might be possible when

active region within the crevice. These models depend on the presence

the corrosion potential is higher than the repassivation potential,

of an activepassive transition and therefore do not fully describe

and is very unlikely if the corrosion potential remains lower than

the situation for alloys that do not exhibit such a transition except

the repassivation potential by a margin of 100 mV or more. The

under low pH conditions. In fact, for alloys that do not exhibit an

repassivation potential is predicted as described below and compared

activepassive transition, the decrease in potential associated with the

to a value of the corrosion potential calculated using mixed potential

ohmic potential drop consumes overpotential in the pit or crevice and

theory37. Fig. 5 shows schematically how these quantities might

destabilizes attack. Other models focus on the change in chemistry in

vary with various experimental parameters and where the regions of

corrosion susceptibility might lie34.
The repassivation potential is the threshold condition at which
pitting or crevice corrosion is stable and the effects of alloy
composition and solution chemistry on this potential must be
understood to predict the likelihood of localized corrosion. According to
the model33, the metal (M) undergoes dissolution underneath a layer of
concentrated metal halide solution MX as shown schematically in Fig.
6. This conceptualization of repassivation of a stable pit is consistent
with Raman spectroscopic studies of artificial pits on Ni39. In the
process of repassivation, a thin layer of oxide is assumed to form at the
interface between the metal and the hydrous metal halide. The model
assumes that, at any given instant, the oxide layer covers a certain

Fig. 4 Breakdown potential of 316L stainless steel measured as a function of

Cl and NO3 concentration25.

fraction of the metal surface. This fraction increases as repassivation is

approached. The dissolution rate of the metal under the oxide is lower

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Understanding localized corrosion

than at the metalhalide interface and corresponds to the passive

(a)

dissolution rate. Thus, as the repassivation potential is approached,

the dissolution rate tends toward the passive dissolution rate. The
effects of multiple aggressive and nonaggressive or inhibitory species
are taken into account through a competitive adsorption scheme.
The aggressive species form metal complexes, which dissolve in the
active state. In contrast, the inhibitory species and water contribute
to the formation of oxides, which induce passivity. In general, the
equations that describe these processes are complex and can only
be solved numerically. However, a closed-form equation (Eq. (1)) has
been found in the limit of repassivation, i.e. when the current density
reaches a predetermined low value irp (assumed to be irp = 102 A/m2)

(b)

and the fluxes of metal ions become small and comparable to those
for passive dissolution. For a system containing NA aggressive ions
and NI inhibitory ions, this equation is given in its most general form
by33:
NI i
l ''
k FErp NA k j '' n j
j FErp
rp
=

1 + 1 k knk exp
j exp

i
i
RT
i

rp
p
rp
j
k

RT

(1)

where ip is the passive current density, irp is the experimental current

density that defines repassivation (irp = 102 A/m2), j is the partial
surface coverage fraction by solution species j, T is the temperature,
R is the gas constant, F is the Faraday constant, and kj, lk, nj, nk, j,
and k are electrochemical kinetic parameters. The summation on

(c)

the right-hand side of Eq. (1) is performed over all aggressive species
(j = 1, ..., NA) and the summation on the left-hand side pertains to
inhibitory species (k = 1, ..., NI). It should be noted that H2O molecules
are treated as inhibitory species because they contribute to the
formation of the oxide layer.
Eq. (1) has a number of adjustable parameters that need to be
determined from experimental data. These parameters are derived from
systems that contain only one or two electrochemically active anions
(e.g. Cl and NO3) and they are used to predict the behavior for more

(d)

Fig. 5 Schematic diagram of the effect of Cl (a), temperature (b), inhibitors

(c), and oxidizing redox species (d) on the relative values of the repassivation
potential (Erp) and corrosion potential (Ecorr). The shaded areas denote the
ranges in which localized corrosion can be expected34.

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OCTOBER 2008 | VOLUME 11 | NUMBER 10

Fig. 6 Schematic summary of the phases and interfaces considered in the

derivation of the model (M, metal; MX, metal halide; MO, metal oxide; the
numbers indicate the interfaces between the phases)34.

Understanding localized corrosion

REVIEW

Fig. 7 Calculated and experimental repassivation potentials for type 316L stainless steel in solutions containing Cl, NO3 and CH3COO as a function of NO3
activity for systems with Cl concentrations fixed at 0.42 M and CH3COO concentrations equal to either 0 or 1.344 M33.

complex solutions, such as the Cl + NO3 + CH3COO mixture. This

without inhibitory species. For example, simulation results for solutions

is illustrated in Fig. 7, where it is shown that a presence of CH3COO

containing only Cl are compared to experimental data for a number

results in a decrease in the concentration of NO3 required to inhibit

of commercial alloys in Fig. 832,40. The model was then used to predict

localized corrosion in a

Cl

solution33.

The effect of CH3

COO

on

the localized corrosion behavior of several alloys in a chemical plant

the inhibition efficiency of NO3 was predicted purely by the model

that operated with a proprietary brine chemistry41. In this case, the

without utilizing experimental data from the Cl + NO3 + CH3COO

corrosion and repassivation potentials were modeled for three alloys in

mixture. Similarly, the effects of alloying elements Cr, Mo, W, and N,

the process chemistry. The predicted values agreed with measurements

on the parameters are derived from experimental data of different

performed in the laboratory using solutions obtained from the chemical

alloys in Cl only solutions.

plant41. The model was further used to predict maximum pit growth

This approach has been successfully used in modeling commercial

alloys in different solutions containing aggressive species with or

rate. The current density predicted by the model as a function of

potential is given by:

Fig. 8 Comparison of Erp values obtained from the generalized correlation with alloy composition with experimental data for various alloys at 368.15 K32.

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Understanding localized corrosion

k ''
j

i=

j FE
FE
+ l i '' ini exp i
exp
RT
RT i

FE
1

1 + l i '' ini exp i

ip i
RT

nj
j

(2)

Eq. (2) reduces to Eq. (1) for E = Erp and i = irp. Since Eq. (2) is a limiting
law, its accuracy gradually deteriorates as the potential increasingly
deviates from Erp. Eq. (2) cannot be regarded as a complete description
of the propagation rate of an actively growing pit because it does not
take into account factors such as the ohmic potential drop, diffusion
limitations, pit shape, etc. However, the current density predicted
using Eq. (2) for E > Erp is useful because it provides an estimate of the
maximum propagation rate of an isolated pit as a function of potential.
Such an upper estimate is particularly convenient because it relies only
on parameters that have been calibrated using repassivation potential
data. The predicted propagation rate using Eq. (2) was then compared
to electrochemical measurements conducted in the process piping41.

Fig. 9 Comparison of experimental apparent pitting rates with calculated

maximum rates of pit propagation for corrosion potentials obtained from
short-term experiments. The vertical bars show the range of predicted pitting
rates when the corrosion potential varies from 0.20 V to 0.14 V (vs. SCE) and
the temperature varies from 95 to 105 C 41.

The results are depicted in Fig. 9. There is general agreement between

strides toward advancing the understanding of localized corrosion.

the range of predicted and measured growth rates.

However, there are many remaining challenges associated with the

understanding and prediction of the various phenomena. The ultimate

Concluding comments

goal of such studies is to be able to predict the time, location, and

The complexities of localized corrosion require sophisticated

extent of localized corrosion, and to understand fully the effects of

experimental and computational tools. Recent work has made

microstructure and environment.

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