Nace 2013 2633

Paper No.
2633
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Mechanisms of Inhibition of the Chloride-Induced Crevice Corrosion of Alloy 22
Martín A. Rodríguez Ricardo M. Carranza

Comisión Nacional de Energía Atómica Comisión Nacional de Energía Atómica
Instituto Sabato - UNSAM / CNEA Instituto Sabato - UNSAM / CNEA
CONICET Av. Gral. Paz 1499, San Martín, B1650KNA
Av. Gral. Paz 1499, San Martín, B1650KNA Buenos Aires, Argentina
Buenos Aires, Argentina carranza@cnea.gov.ar
maalrodr@cnea.gov.ar
Raul B. Rebak
GE Global Research
1 Research Circle, CEB2551
Schenectady, NY 12309, USA
rebak@ge.com
ABSTRACT
Chloride-induced crevice corrosion occurs due to the formation of hydrochloric acid solution in
the creviced region. Inhibitors avoid the development of this solution or hamper its deleterious
action. Anodic inhibitors are able to produce an increase of ER,CREV and / or avoid the occur-
rence of crevice corrosion at R ≥ RCRIT. This review focuses on the mechanisms of crevice
corrosion inhibition of Alloy 22. The localized acidification model is used to explain the differ-
ent effects of anodic inhibitors on ER,CREV. Papers on this topic published over the last decade
are reviewed. Hydroxyl, nitrate and phosphate are strong inhibitors; carbonate, chromate, mo-
lybdate and sulfate are moderate good inhibitors; while fluoride and organic acids are weak
inhibitors of the chloride-induced crevice corrosion of Alloy 22. ER,CREV is the sum of three con-
tributions (ECORR* + η + ΔΦ). Inhibitors produce an increase of one or more of these contribu-
tions by different mechanisms (proton consumption, pH buffering, blocking of preferential dis-
solution sites, supporting electrolyte effect, ohmic blocking action, etc.). There is a need of a
quantitative assessment of the considered mechanisms to account for the observed effective-
ness of the inhibitors.
Keywords: Alloy 22, chloride, inhibitors, crevice corrosion, repassivation potential
©2013 by NACE International.

Requests for permission to publish this manuscript in any form, in part or in whole, must be in writing to
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1
INTRODUCTION
Crevice corrosion is a form of localized corrosion that may occur in occluded metallic surfaces
where a stagnant solution is developed.1 Pitting corrosion and crevice corrosion are essen-
tially the same phenomena from an electrochemical viewpoint, although there are geometrical
differences between them.2,3 Ni-Cr-Mo alloys such as Alloy 22 may suffer crevice corrosion
when in contact with chloride containing solutions. Chloride is the main aggressive species
causing crevice corrosion of Ni-Cr-Mo alloys in industrial applications. The crevice corrosion
susceptibility of the alloys is increased as temperature and chloride concentration increase.4

Crevice corrosion inhibitors are able to mitigate or avoid the occurrence of localized attack.
They may be present in service environments or added on purpose to the environment. Crev-
ice corrosion may occur only if the corrosion potential of the alloy (ECORR) is higher than its re-
passivation potential (ER,CREV) in the field conditions. Cathodic inhibitors cause a shift of ECORR
to more active potentials, while anodic inhibitors cause a shift of ER,CREV to more noble poten-
tials. There is practically no published research on cathodic inhibitors of the chloride-induced
crevice corrosion of Alloy 22. On the other hand, there is considerable research dealing with
anodic inhibitors of the chloride-induced crevice corrosion of Alloy 22. Nitrate, sulfate, carbon-
ate, fluoride, hydroxyl, organic acids and phosphate mitigate or inhibit crevice corrosion when
added in sufficient amounts. The inhibitor to chloride concentration ratio (R) is an important
parameter. There is a critical concentration ratio (RCRIT) above which inhibition is complete. R
is defined in Equation 1 as the quotient of the inhibitor and chloride molar concentrations.
There is a critical concentration ratio (RCRIT) above which inhibition is complete. RCRIT is the
lowest R value at which crevice corrosion is not observed.5,6
R=
[Inhibitor ] (1)
[Cl ]
−
Crevice corrosion occurs due to the formation of hydrochloric acid solution in the creviced re-
gion. Anodic inhibitors act by avoiding the development of hydrochloric acid or by hampering
its deleterious action.2 Rebak proposed four different modes in which an anodic inhibitor of the
chloride-induced crevice corrosion of Alloy 22 may act: (1) stabilization of the Cr2O3-rich pas-
sive film by maintaining an oxidizing environment within the crevice; (2) reduction of the inhibi-
tor to a lower oxidation state along with protons consumption; (3) reduction of the general cor-
rosion rate in the creviced area; (4) sequestration of protons released by the hydrochloric acid
due to a lower dissociation constant of the corresponding acid.7 Effective inhibitors should act
by many of these proposed modes at the same time, while the less effective inhibitors act by
one or two of these modes. However, these four modes of inhibition are not independent from
each other. For instance, a reduction of the general corrosion rate of the alloy (mode 3) may
result from an inhibitor consuming or sequestrating protons (mode 4); an oxidizing environment
(mode 1) is generated by an inhibitor which may reduce to a lower oxidation state (mode 2).
The objective of this review is to gain further insight regarding the mechanisms of crevice cor-
rosion inhibition of Alloy 22. The localized acidification model is used to explain the different
effects of anodic inhibitors on ER,CREV. Papers on this topic published over the last decade are
reviewed.

2
THEORETICAL BACKGROUND
The localized acidification model successfully describes pitting and crevice corrosion of pure
metals and stainless steels.2,3 This model states that localized corrosion occurs as a result of
a local development of an acidic solution. This solution is build up due to cation hydrolysis.
Localized corrosion is stabilized by a high metal dissolution rate and a long diffusion path. Eq-
uation 2 states the conditions for the stable propagation of localized corrosion. A critical value
of the product x·i must be exceeded (x·i)CRIT, where x is the diffusion path and i is the anodic

current density.
x·i > (x·i)CRIT (2)
According to this model the critical potential associated with the stabilization of the localized
corrosion is the sum of three contributions, as stated in Equation 3. The contributions are the
corrosion potential of the metal in the locally acidic solution (ECORR*), a polarization necessary
to fulfill the conditions of Equation 3 (η) and the ohmic potential drop (ΔΦ).
ER,CREV = ECORR* + η + ΔΦ (3)
An anodic crevice corrosion inhibitor must produce an increase of ER,CREV by increasing one or
more of the three contributions (ECORR*, η and ΔΦ).
RESEARCH ON CREVICE CORROSION INHIBITORS
In the last decade, considerable efforts have been devoted to study the localized corrosion of
Alloy 22 regarding its use as a corrosion resistant barrier of nuclear waste containers.8 Inhibi-
tors and chloride ions are present in the groundwater potentially in contact with the nuclear
waste containers. Assessing the effect of different species in solution on the repassivation po-
tential of Alloy 22 is of main importance. The effects of anions typically found in groundwater,
such as nitrate, sulfate, fluoride, carbonate, bicarbonate ions and other less common species
have been extensively studied, covering different metallurgical conditions of the alloy, tempera-
tures, pH values, etc. Table 1 shows a summary of data reviewed from recent literature on
crevice corrosion inhibition of Alloy 22.9–19
Dunn et al. investigated the inhibiting effect of nitrate on the crevice corrosion of as welded
(ASW) Alloy 22 at 95ºC.9,12 The authors report RCRIT = 0.5 for ASW Alloy 22 in a 0.5 M Cl- so-
lution. The addition of 0.05 M NO3- to a 0.5 M Cl- solution produces an increase of 0.25 V in
ER,CREV. Nitrate ion not only is able to inhibit the localized corrosion initiation but also promotes
the repassivation of the already developed localized corrosion. Evans et al. report a significant
ER,CREV increase of Alloy 22 in 0.5 M Ca(NO3)2 + 5 M CaCl2 solution at temperatures from 45ºC
to 120ºC, when compared with the ER,CREV in a 5 M CaCl2 solution.20 Evans et al. tested mill
annealed (MA) material. Dunn et al. studied the effect of nitrate on MA and thermally aged (5
min. at 870ºC) Alloy 22 in 4 M MgCl2 at 80ºC and 110ºC.10,11 This thermal aging may cause
the precipitation of second phases at the grain boundaries which is thought to simulate a weld-
ing process. RCRIT of 0.1 and 0.15 is reported for MA Alloy 22 at 80ºC and 110ºC, respectively;
while RCRIT of 0.1 and 0.3 is reported for the thermally aged specimens at the same tempera-
tures. RCRIT = 0.12 is reported for MA Alloy 22 in 4 M NaCl at 95ºC. RCRIT for nitrate is not
strongly dependent on temperature or chloride concentration, but slightly increases for the
aged material at high temperature. Mishra and Frankel and Rincón Ortíz et al. reported RCRIT
= 0.2 for MA Alloy 22 in nitrates at 90ºC.16,18 For R < RCRIT, ER,CREV increases linearly with

3
log([NO3-]). Mishra and Frankel also investigated the effect of nitrate and sulfate mixtures.16
RCRIT = 0.15 is observed for nitrate in 1 M NaCl at 90ºC when sulfate is present at R = 0.2 and
0.5; in the absence of sulfate, RCRIT is slightly lower than 0.2 . Kehler et al. studied the crevice
corrosion susceptibility of MA alloys 625 and 22 in chloride solutions plus a mixture of nitrate
and sulfate, at temperatures from 60ºC to 95ºC.21 The alloys were tested in 5 M LiCl + 0.24 M
NaNO3 + 0.26 M NaSO4 (R = 0.1) and 5 M LiCl + 0.024 M NaNO3 + 0.026 M NaSO4 (R = 0.01)
solutions. Results show that ER,CREV increases significantly for R = 0.01 and R = 0.1 as the
temperature decreases. They inform that ER,CREV is a stronger function of R and temperature

for Alloy 22 than for Alloy 625. The inhibiting effect of nitrate on the localized corrosion of Alloy
22 has been also reported in hot concentrated brines. Rodríguez et al. inform the absence of
localized corrosion of creviced specimens of Alloy 22 after 720 days of immersion in 5 m CaCl2
+ 5 m Ca(NO3)2 brines (R = 1) at 100ºC and 120ºC.22 Creviced Alloy 22 does not suffer local-
ized corrosion after 20 months of immersion in 18 m CaCl2 + 9 m Ca(NO3)2 brine (R = 0.5) at
155ºC. However, Alloy 22 suffer pitting corrosion after immersion in 18 m CaCl2 + 0.9 m
Ca(NO3)2 (R = 0.05) brine at 155°C. When Alloy 22 is polarized at potentials above ER,CREV
three characteristic stages are observed: (1) nucleation, (2) growth and (3) stifling and arrest of
crevice corrosion. As long as R increases in chloride plus nitrate solutions, smaller crevice
corrosion sites are developed, the stage 2 is shorter and the crevice corrosion current density
is lower.23
Dunn et al. report an increase of ER,CREV at R = 0.5 for thermally aged (5 min. at 870ºC) Alloy
22 in 0.5 M NaCl plus sulfate, at 95ºC.10,11 Ilevbare studied the crevice corrosion of MA Alloy
22 in 4 M NaCl plus sulfate at temperatures between 45ºC and 105ºC.24 R = 0.01 and 0.1
were used. The alloy is immune to crevice corrosion in all the tested solutions at 45ºC. The
inhibiting effect of sulfate is noticeable at 60°C leading to a 0.6-V increase of ER,CREV for R =
0.1, and a 0.3 V increase for R = 0.01. At 75°C and higher temperatures, ER,CREV is not af-
fected by sulfate. However, a less severe localized attack is observed in sulfate containing
solutions. Dunn et al. and Ilevbare do not inform a value for RCRIT.10,11,24 Mishra and Frankel
investigated the crevice corrosion of MA Alloy 22 in chloride plus sulfate solutions at 90ºC.16
They report RCRIT = 1.5 for 1 M NaCl and RCRIT = 0.8 for 0.1 M NaCl. In similar experimental
conditions, Rincón Ortíz et al. inform RCRIT = 2 for 1 M NaCl and RCRIT = 1 for 0.1 M NaCl.18
Dunn et al. studied the inhibiting effects of carbonate and bicarbonate in 0.5 M NaCl at 95ºC,
using thermally aged (5 min. at 870ºC) Alloy 22 specimens.10 They inform RCRIT = 0.05 for
carbonate and RCRIT = 0.2 for bicarbonate. However, Rincón Ortíz et al. inform that only car-
bonate is able to inhibit the chloride-induced crevice corrosion of MA Alloy 22 at 90ºC, while
bicarbonate and carbonic acid produce no increase of ER,CREV. Rincón Ortíz et al. performed
tests at fixed pH values of 3, 7 and 11.5 which correspond to the predominance of carbonic
acid, bicarbonate and carbonate, respectively.18 Dunn et al. do not inform the tested pH val-
ues. Dunn et al. and Rincón Ortíz et al. used different crevice formers materials and aging
treatments. The differences among their results might be related with these testing conditions.
Carranza et al. studied the effect of silicate on the crevice corrosion of Alloy 22 in 0.01 M, 0.1
M and 1 M NaCl solutions, at 90ºC.15 A complete inhibition of crevice corrosion is observed in
all the testing solutions with pH ≥ 12.5, regardless of the presence of silicate. Consequently,
this effect is attributed only to the high solution pH obtained by the silicate hydrolysis. In these
solutions, Inhibition is dependent on the concentration of the hydroxyl rather than R. Fluoride
is able to mitigate and inhibit crevice corrosion for sufficiently high R values. Carranza et al.
report RCRIT from 5 to 10 for MA Alloy 22 in 0.001 M, 0.01 M and 0.1 M NaCl solutions of pH 6,

4
at 90ºC.13 Organic acids are also weak inhibitors of the crevice corrosion of Alloy 22. RCRIT =
5 is reported for citric and oxalic acids, while RCRIT = 20 is reported for acetic acid in 0.01 M,
0.1 M and 1 M chloride solutions, at 90ºC.14 Rincón Ortíz et al. tested chromate, molybdate
and tungstate as crevice corrosion inhibitors of MA Alloy 22 in 0.1 M and 1 M NaCl, at
90ºC.17,18 They report RCRIT = 1 for 1 M NaCl and RCRIT = 0.5 for 0.1 M NaCl for chromate.
Molybdate is able to inhibit crevice corrosion at RCRIT = 0.5 in 0.1 M NaCl. However, the com-
plete inhibition is not attained in 1 M NaCl at R ≤ 1 for molybdate. Tungstate was unable to
inhibit completely crevice corrosion of Alloy 22 in the tested conditions. However, it led to an

increase of ER,CREV for the highest tested R values. Miyagusuku et al. studied the effect of
phosphate on the crevice corrosion of Alloy 22 in 1 M NaCl solutions, at 90ºC.19 They inform
RCRIT = 0.3.
Table 1
Review of literature results on crevice corrosion inhibition of Alloy 22.
Metallurgical Temperature,
Authors Inhibitor [Cl-], M RCRIT
condition ºC
Dunn et al.9,12 As Welded 95 nitrate 0.1 0.5
80 nitrate 8 0.1
Mill Annealed
110 nitrate 8 0.15
80 nitrate 8 0.1
Dunn et al.10,11
110 nitrate 8 0.3
5 min. at 870ºC
95 carbonate 0.5 0.05
95 bicarbonate 0.5 0.2
0.001 7
13
Carranza et al. Mill Annealed 90 fluoride 0.01 5
0.1 10
citric acid + citrate 0.01-0.1 5
Carranza et al.14 Mill Annealed 90 oxalic acid + oxalate 0.01-0.1 5
acetic acid + acetate 0.01-0.1 20
0.01 3.16
15
Carranza et al. Mill Annealed 90 hydroxyl 0.1 0.316
1 0.0316
nitrate 1-4 0.2
16
Mishra and Frankel Mill Annealed 90 sulfate 0.1 0.8
sulfate 1 1.5
nitrate 0.1-1 0.2
0.1 1
sulfate
1 2
18
Rincón Ortíz et al. Mill Annealed 90 carbonate 0.1-1 1
0.1 0.5
chromate
1 1
molybdate 0.1 0.5
19
Miyagusuku et al. Mill Annealed 90 phosphate 1 0.3

5
Figure 1 shows RCRIT as a function of the chloride concentration for the data reviewed in Table
1 obtained in MA Alloy 22, at 90ºC by Carranza et al.13–15,18,19 For most of the inhibitors, RCRIT
remains constant or slightly increases as the chloride concentration increases. The only ex-
ception is hydroxyl. In this case, the complete crevice corrosion inhibition only depends on the
concentration of hydroxyl, regardless the chloride concentration. Hydroxyl, nitrate and phos-
phate are strong inhibitors; carbonate, chromate, molybdate and sulfate are moderate good
inhibitors; while fluoride and organic acids are weak inhibitors of the chloride-induced crevice
corrosion of Alloy 22.

Figure 1: RCRIT as a function of chloride concentration for MA Alloy 22 tested in chloride
plus inhibitor solutions, at 90ºC. 13–15,18,19
The effects of mixtures of inhibitors have been less studied. Anderko et al. report the following
empirical observations for the crevice corrosion of stainless alloys in chloride plus inhibitors
solutions: (1) in solutions containing a weak inhibitor, ER,CREV increases slowly as R increases
up to the point where the inhibitor predominates in the solution, (2) in solutions containing a
strong inhibitor, ER,CREV rises to high values at relatively low concentrations of the inhibitor, (3)
in ternary solutions, where a weak inhibitor is added to a binary mixture of chloride plus a
strong inhibitor, the concentration of the strong inhibitor required to raise ER,CREV to high values
is less than in the binary mixture.25
MECHANISM OF CREVICE CORROSION INHIBITION
In the context of the localized acidification model, anodic inhibitors should increase ER,CREV at
R < RCRIT, and avoid localized corrosion at R ≥ RCRIT. This model accounts for the increase of
ER,CREV due to the increase of any of the contributions stated in Equation 3 (ECORR*, η and ΔΦ)
and it also accounts for the complete inhibition of crevice corrosion when the condition stated
in Equation 2 is not satisfied. The addition of an inhibitor may modify the polarization curve of
Alloy 22 in the crevice solution. Oxidizing inhibitors may increase ECORR*. Figure 2 shows the
effect of an inhibitor increasing ECORR* on the ER,CREV value. Inhibitors able to produce either

6
an increase of iCRIT or an increase of the anodic Tafel slope may increase η. Figure 3 shows
the effect of an inhibitor increasing iCRIT, while Figure 4 shows the effect of an inhibitor increas-
ing the Tafel slope on the ER,CREV value. Inhibitors which produce a resistive salt film on the
alloy surface may increase ∆Φ. Figure 5 shows the effect of an inhibitor increasing ΔΦ on the
ER,CREV value. For inhibitors acting by a ΔΦ increase, the increase of ER,CREV is significant only
for large iCRIT values, while it is for small iCRIT values. Figure 6 shows the effect of an inhibitor
increasing ECORR*, η and ΔΦ. Note that if the maximum current of the polarization curve is be-
low iCRIT, crevice corrosion is inhibited at any potential. This situation is stated in Equation 2

and it holds when R ≥ RCRIT.
Figure 2: Schematic polarization curves of Figure 3: Schematic polarization curves of

Alloy 22 in the crevice solution with and Alloy 22 in the crevice solution with and
without inhibitor addition. Effect of an in- without inhibitor addition. Effect of an in-
hibitor increasing ECORR*. hibitor increasing iCRIT.
Figure 4: Schematic polarization curves of Figure 5: Schematic polarization curves of

Alloy 22 in the crevice solution with and Alloy 22 in the crevice solution with and
without inhibitor addition. Effect of an in- without inhibitor addition. Effect of an in-
hibitor increasing η. hibitor increasing Δ .

7
Figure 6: Schematic polarization curves of Alloy 22 in the crevice solution with and
without inhibitor addition. Effect of an inhibitor increasing ECORR*, η and Δ .
Several mechanisms have been proposed for the inhibition of localized corrosion by different
species. They include proton consumption, pH buffering, blocking of preferential dissolution
sites, supporting electrolyte effect, ohmic blocking action, etc. The purpose of the present
work is to distinguish among likely mechanisms by which each inhibitor act and their effects on
the different terms of Equation 3.
Nitrate has been thoroughly studied as an inhibitor of the chloride-induced pitting corrosion of
stainless steels.26–33 It retards pitting nucleation, reduces the propagation rates of metastable
pitting and reduces the current density of stable pitting propagation.32 Nitrate addition causes
an increase of the pitting potential (EPIT) and the appearance of an inhibition potential (EINH)
above which the stainless steels passivate. Nitrate acts both at low and at high potentials, re-
ducing the potential range of pitting corrosion occurrence. Inhibition at potentials above EINH is
not relevant for crevice corrosion as the potential drop (IR) within the crevice causes the poten-
tial to be below EINH and above EPIT in a region within the crevice. Figure 7 shows a scheme of
this situation. Consequently, the proposed mechanisms for the passivation of growing pits
above EINH cannot be considered for crevice corrosion inhibition.28,30
The inhibiting effects of nitrate at low potentials have been attributed to its reduction to elemen-
tal nitrogen, consuming protons and producing water according to Equation 4. Elemental ni-
trogen may block preferential dissolution sites on the surface.29,31 Repassivation of stainless
steel after scratching occurs more rapidly in the presence of nitrate as compared to chloride.33
Nitrate is an oxidizing species which may cause an increase of ECORR*. The proton consump-
tion brought about by nitrate reduction (Eq. 4) may cause an increase of η. A higher polariza-
tion is needed to reach the same iCRIT value in the presence of nitrate.
NO 3− + 6H+ + 5e − → N + 3H2O (4)

8
Figure 7: Schematic anodic polarization curve of a stainless steel in a chloride plus ni-
trate solution showing the presence of EINH and EPIT.
Sulfate has been also studied as a pitting corrosion inhibitor of stainless steels.30,31,34–36 Sul-
fate is not oxidizing in acidic solutions and it is stable as SO42- or HSO4-.37 The efficiency of
sulfate as an inhibitor decreases with temperature.34 Sulfate is thought to act by a supporting
electrolyte effect. This mechanism involves the competitive migration and adsorption of sulfate
and chloride on the alloy surface.30,31,34,35 Sulfate may accumulate at the alloy / solution inter-
face by migration preferentially over chloride.2 This is due to its higher electric charge with re-
spect to chloride. It prevents the increase of chloride concentration above the critical value
needed for depassivation. Sulfate reduces the solubility of the dissolved metal cations within
pits.36 Alloy passivation may occur below precipitated sulfate films by inward diffusion of wa-
ter.29 pH buffering by HSO4- may occur since the second dissociation constant of sulfuric acid
is low.7,30 Considering the proposed inhibition mechanisms sulfate may cause an increase of η
either by increasing iCRIT (Fig. 3) or the Tafel slope (Fig. 4).
Hydroxyl is a strong inhibitor of the localized corrosion as it is the precursor of the passive
film.38 EPIT of stainless steels increases with the hydroxyl concentration in the alkaline range of
pH.26,27 The value of (x·i)CRIT increases as the bulk solution pH increases leading to an in-
crease of η. This is depicted in Figure 3.
Anions of weak acids are localized corrosion inhibitors.2,3 They avoid or make more difficult
the acidification within the crevice due to pH buffering. They act by increasing the value of
(x·i)CRIT which leads to an increase of η (Figure 3). Carbonate, bicarbonate, phosphate and
fluoride are among these inhibitors. Weak acids such as carbonic and organic acids are un-
able to migrate since they are not charged species and they cannot take protons. Conse-
quently, their efficiency as crevice corrosion inhibitors increases in diluted solutions where they
are more dissociated.14,18 Organic acids may inhibit crevice corrosion at high RCRIT and in 0.1
M and 0.01 M chloride solutions in most of the cases. They act in the same way as the anions
of weak acids.
Chromate, molybdate and tungstate may change the ionic selectivity of the passive film from
anion selective to cation selective, preventing the ingress of chloride.39 Chromate and molyb-
date may reduce to oxides or hydroxides consuming protons according to Equations 5 and 6,

9
respectively.37 These reactions cause a decrease of the local acidity affecting the transition
from nucleation to metastable pitting.30,40 The reduced cations may be built into the film.32,41,42
The reduction products of Equations 5 and 6 may form dense precipitates with an ohmic block-
ing action. These reduction products may not be necessarily the oxides stated in Equations 5
and 6, but hydroxides or oxyhydroxides. Molybdate forms polymeric species, such as Mo7O246-
and Mo8O264-, at pH < 6.30,34 The polymerization involves proton consumption. Molybdic acid
(H2MoO4) may also form and precipitate during localized corrosion propagation, leading to re-
passivation by blocking of active sites.34 Chromate and molybdate may cause an increase of

ECORR*, η and ΔΦ (Figure 6).
CrO 24− + 5H + + 3e − → 1
2 Cr2 O 3 + 5 2 H2 O (5)
MoO 24− + 4H + + 2e − → MoO 2 + 2H2 O (6)
Tungstate is less oxidizing than chromate and molybdate. Its reduction within an active crevice
is unlikely. Tungstate may precipitate as an oxide (WO3) consuming protons at low pH.37 This
oxide may have a passivating or an ohmic blocking action. In fact, tungsten is passive at low
pH. Tungstate may act by an ohmic blocking action leading to an increase of ∆Φ (Figure 5).
Inhibitors mainly based on ohmic effects are more efficient in dilute chloride solutions.
Table 2
Terms of the Equation 3 affected by the reviewed inhibitors.
Inhibitor Affected terms of Equation 3

Nitrate ECORR* + η
Sulfate η
Carbonate η
Phosphate η
Hydroxyl η
Chromate ECORR* + η + Δ
Molybdate ECORR* + η + Δ
Tungstate Δ
Fluoride η
Organic Acids η
Table 2 summarizes the terms of Equation 3 that may be affected by each inhibitor. The pre-
sent review of crevice corrosion inhibitors of Alloy 22, the likely mechanisms and their effect on
Equation 3 from the localized acidification model is qualitative. Previously, it was proposed
that the more modes / mechanisms involved in the inhibition were indicative of a higher effi-
ciency of the considered inhibitor.7 However, nitrate is a more efficient inhibitor than chromate
and molybdate in spite of increasing two contributions of Equation 3, while chromate and mo-
lybdate increase the three contributions. An inhibitor may act stronger by a single mechanism
than others acting by many mechanisms at the same time. There is a need of a quantitative
assessment of the considered mechanisms to account for the observed effectiveness of the
inhibitors.

10
SUMMARY AND CONCLUSIONS
Alloy 22 may suffer crevice corrosion when in contact with chloride containing solutions. Crev-
ice corrosion inhibitors are able to mitigate or avoid the occurrence of the localized attack.
Crevice corrosion may occur only when ECORR > ER,CREV in the field conditions. Anodic inhibi-
tors produce an increase of ER,CREV and / or avoid the occurrence of crevice corrosion at R ≥
RCRIT. These inhibitors may act by different mechanisms such as proton consumption, pH buf-
fering, blocking of preferential dissolution sites, supporting electrolyte effect, ohmic blocking

action, etc. Based on the reported RCRIT values it is stated that hydroxyl, nitrate and phosphate
are strong inhibitors; carbonate, chromate, molybdate and sulfate are moderate good inhibi-
tors; while fluoride and organic acids are weak inhibitors of the chloride-induced crevice corro-
sion of Alloy 22.
The localized acidification model states that ER,CREV is the sum of three contributions (ECORR* +
η + ΔΦ). The addition of an inhibitor may modify the polarization curve of Alloy 22 in the crev-
ice solution and consequently increase one or more of the contributions to ER,CREV. Oxidizing
inhibitors such as nitrate, chromate and molybdate may increase ECORR*. Inhibitors able to
produce either an increase of iCRIT or an increase of the anodic Tafel slope may increase η.
This effect may be produced by proton consumption (nitrate, chromate and molybdate), pH
buffering (hydroxyl, phosphate and carbonate), and supporting electrolyte effects (sulfate, fluo-
ride and organic acids). Inhibitors which produce a resistive salt film on the alloy surface may
increase ∆Φ. This effect is significant only for large iCRIT values. Chromate, molybdate and
tungstate may act in this way.
Although it was proposed that the more mechanisms involved in the inhibition were indicative
of a higher efficiency of an inhibitor, the present review shows that an inhibitor may act strong-
er by a single mechanism than other acting by many mechanisms at the same time. There is a
need of a quantitative assessment of the considered mechanisms to account for the observed
effectiveness of the inhibitors.
AKNOWLEDGEMENTS
Financial support from the Agencia Nacional de Promoción Científica y Tecnológica of the Mi-
nisterio de Ciencia, Tecnología e Innovación Tecnológica and from the Universidad Nacional
de San Martín from Argentina is acknowledged.
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TX, USA, 2005).
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The Electrochemical Society 123, 464–474 (1976).
3. Galvele, J. R. Tafel’s law in pitting corrosion and crevice corrosion susceptibility. Corro-
sion Science 47, 3053–3067 (2005).
4. Rebak, R. B. Corrosion and Environmental Degradation Vol. II. Material Science and
Engineering. A Comprehensive Treatment (2000).
5. Rebak, R. B. Factors affecting the crevice corrosion susceptibility of alloy 22, Paper No
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Martín A. Rodríguez Ricardo M. Carranza

Keywords: Alloy 22, chloride, inhibitors, crevice corrosion, repassivation potential

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x·i > (x·i)CRIT (2)

ER,CREV = ECORR* + η + ΔΦ (3)

RESEARCH ON CREVICE CORROSION INHIBITORS

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MECHANISM OF CREVICE CORROSION INHIBITION

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Figure 2: Schematic polarization curves of Figure 3: Schematic polarization curves of

Figure 4: Schematic polarization curves of Figure 5: Schematic polarization curves of

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NO 3− + 6H+ + 5e − → N + 3H2O (4)

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©2013 by NACE International.

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MoO 24− + 4H + + 2e − → MoO 2 + 2H2 O (6)

Inhibitor Affected terms of Equation 3

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1. Szklarska-Smialowska, Z. Pitting and Crevice Corrosion. (NACE International: Houston,

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