SCIENCE

1989 Whitney Award Lecture

The Whitney Award recognizes a contribution to science, such as the development of improvement of
a theory that provides a more fundamental understanding of corrosion phenomena and/or the
prevention of corrosion. An individual may qualify who hes made a recognized national or international
contribution to corrosion science through some form of education or works that lead to a better
understanding of the science of corrosion.

Toward a More Fundamental Understanding

of Corrosion Processes*
Norio Sato*

ABSTRACT

A review is given of some simplified concepts that will contribute
to a better understanding of corrosion fundamentals. The corro-
sion process involves not only electrochemical reactions but also
acid-base reactions, and it is the acid-base nature that diversifies
the corrosion phenomena. Anions either catalyze or inhibit the
anodic metal dissolution, and the passivation wilt result from the
hydroxide-catalyzed mechanism of metal dissolution. Corrosion
precipitates frequently control the selective mass transport in cor-
rosion processes. Anion-selective precipitates accelerate and cat-
ion-selective precipitates decelerate corrosion propagation. A bi-
polar precipitate film, if anodically polarized, undergoes
deprotonation and turns into a passive film. The electrochemical
stability of passivated metals is determined by the electron en-
ergy band structure of the passive film. The passiva film of n-type
semiconducting oxides appears electrochemically more stab/e
than the passiva film of p-type semiconducting oxides.
INTRODUCTION
Although it is apparently the past contribution to corrosion science
that should be acknowledged by the Whitney Award, 1 wish in the
present lecture to focus on the fundamental concepts of corrosion
that are somewhat oriented to the prospect, rather than the retro-
spect, of our research in corrosion science. Four subject areas of
fundamental interest wilt be examined: acid-base nature of corro-
sion, anodic metal dissolution in the active state, corrosion precipi-
tates leading to metal passivation, and electrochemical stability of
passivated metals.
ACID-BASE CHARACTERISTICS OF CORROSION
PROCESSES
Modern corrosion science sterns from the local cel] model
proposed by U.R. Evans' and the mixed potential model proved
° Presented at CORROSION/89, New Orleans, Louisiana, April 1989.
Electrochemistry Laboratory, Faculty of Engineering, Hokkaido University, Sap-
poro, Japan.
for the corrosion potential by C. Wagner and W. Traud. 2 These
two magnificent achievements have been combined into what is
called the electrochemical theory of corrosion. 3 The electrochemi-
cal theory describes the metal corrosion process as a combination
of an anodic oxidation, such as metal dissolution, and a cathodic
reduction, such as oxygen ionization or hydrogen ion discharge.
The corrosion process, however, involves not only electrochemical
oxidation-reduction reactions but also acid-base reactions. For in-
stance, the anodic metal dissolution is initiated with ionization of
surface metal atoms, and the metal ions thus produced on the sur-
face are transferred into aqueous solution to form hydrated metal
ions or metal-ion complexes associated with anions (Figure 1).
The ionization of surface metal atoms is an electrochemical oxida-
tion, whereas the hydration or complexation of metal ions is a
chemical process that belongs to what is called the Lewis acid-
base reaction.
Fundamentally, the electrochemical oxidation-reduction is
complete electron transfer from a species of electron donor (re-
ductant) to another species of electron acceptor (oxidant). The
complete electron transfer takes place Erom the frontier donor or-
bital (the highest occupied molecular orbital [HOMO]) of a reduc-
tant to the frontier acceptor orbital (the lowest unoccupied molecu-
lar orbital [LUMO]) of an oxidant, when the energy separation
between the two orbitals is large enough to prevent any significant
lowering of the energy due to orbital interaction, as shown in Fig-
ure 2. The probability of complete electron transfer is higher, when
the energy separation is greater between the donor and the ac-
ceptor orbitals. The acid-base reaction, on the other hand, is initi-
ated with the formation of the bonding, non-bonding, and
anti-bonding molecular orbitals due to the orbital interaction be-
tween the occupied frontier donor orbital of a species (a Lewis
base) and the unoccupied frontier acceptor orbitals of a reaction
partner (a Lewis acid), and proceeds with the population of elec-
tron pairs in the bonding molecular orbital lowering the energy, as
shown in Figure 2. According to the generalized Lewis definition, 4
a base is a species that employs a doubly occupied frontier orbital
in initiating a reaction, while an acid species employs an empty
orbital. The term species may mean a discrete molecule, a simple
or complex ion, or even a solid material exhibiting nonmolecularity.

0010-9312/89/000113/$3.00/0
354 © 1989, National Association of Corrosion Engineers CORROSION —May 1989
 SCIENCE

RELATIVE FRONTIER ORBITAL ENERGIES

METAL EDL SOLUTION
H 2 O ACTS
LUMO (Fe ) AS OXIDANT
HOMO_ 00

S.

MAM O O (H20)
(CI ) AS LEWIS ACID
W
C
O
(Fe'2) AS LEWIS BASE
/ 2e DOI O
W

( F 2 ) AS REDUCTANT
/ OHP

IQ OXIDATION FIGURE 3. Re/ative frontier orbital energy levels of species H2 O

and its reaction partners Fe, Cl - , Fe 2 +, and F2 .

Q HYDORATION
( LEWIS ACID- BASE REACTION ) TABLE 1
Reactions 1/lustrating the Amphoteric Nature of Water

FIGURE 1. Anodic metal dissolution comprising metal alom ioniza- 11 2 Is

tion (oxidation) and metal ion hydration (Lewis acid-base reaction).

oxidant 2H20 + Fe Fe` z + 20H + H 2 t
EDL = electrical double layer. acid nH20 + Cl - = CI(H 2 0)„
base 6H20 + Fe z = Fe(H20)é 2
reductant 2H20 + 2F2 = 4F - + 4H + 0 21

(A) Iron is in the activa state.

1) OXIDATION-REDUCTION
LUMO
HOMO
LUMO
HOMO
(OXIDIZING AGENT)
2) ACID-BASE
_____ LUMO
^, ^) 00- HOMO
LUMO K
BONDING ORBITAL
HOMO
(ACID) (BASE)
FIGURE 2. Frontier orbita/ energy levels of two reacting species
leading either to complete electron transfer (oxidation-reduction)
when their separation is large or to sharing electron pairs (acid-base
reaction) due to orbital interaction.
The orbital interaction becomes significant, only when the energy
of the two frontier orbitals are close to each other.
The acidity and basicity, as welf as the oxidant and reductant,
are of relative nature. For example, the frontier orbital energies of
H 2 O may be compared relatively with those of several reaction
partners, Fe, Cl - , Fee, and F, as shown in Figure 3. With re-
spect to Fe, complete electron transfer from Fe to H 2 O will be fa-
vorable, and H 2 O wilt act as an oxidizing agent. This is due not
only to the relative energies of the filled and empty orbitals but to
their large energy separation, which prevents any significant orbital
interaction. With respect to Cl - , the orbital interaction between the
filled orbit of Cl - and the empty orbit of H 2 O is the most favorable,
because of their small energy difference, and H 2 O will act as an
acid relative to Cl - , which wilt act as a base donating electron
pairs for the formation of covalent bands. With respect to Fe 2 +,
the orbital interaction between the filled orbit of H 2 O and the
empty orbit of Fee is the most favorable, and H 20 will act as a
base relative to F 2 , which will act as an acid. Finally, with
respect to F, complete electron transfer from H 2 O to F wilt be fa-
vorable, and H 2 O will act as a reducing agent. This extreme am-
photeric behavior of H 2 0 in chemical and electrochemical reac-
tions is illustrated in Table 1.
In metal corrosion, metal atoms on the surface are electro-
chemically oxidized by oxidizing agents to metal ions, which act as
a Lewis acid relative to water molecules and anions. The metal
Tons thus produced undergo an acid-base reaction to form aquo-
or aniono-complexes of metal ions. These electrochemical oxida-
tion-reduction and acid-base reactions are complicated quantum
processes. The simplest model will assume the ionization of ad-
sorbed metal atoms (ad-atoms), which takes place by donating
electrons from the frontier orbital of metal ad-atom to the Fermi-
level of solid metal, as schematically shown in Figure 4. The fron-
tier orbitals of metal ad-atoms will interact with the frontier electron
orbitals of the metal surface to form the bonding and antibonding
orbitals. The metal ad-atoms will be stable on the metal surface so
long as their bonding orbitals are occupied by electrons, whereas
they will be ionized and desorbed from the metal surface, if their
electrons are transferred from the bonding orbitals of metal ad-
atoms to the Fermi-level of the solid metal.
Anodic polarization, which lowers the Fermi-level of the
metal, will increase the probability of electron transfer from the ad-
atoms to the metal phase and hence will facilitate the desorption
of ionized metal ad-atoms (ad-ions), which then migrate across the
electrical double layer and form hydrated metal Tons. The hydra-
tion of metal ions results from the frontier molecular orbital interac-
tion between metal ions (Lewis acid) and water molecules (Lewis
base), which are configurationally coordinated around a metal ion

CORROSION—Vol. 45, No. 5 355

 SCIENCE

(M)ad
C7 1 1 I i 17Acm2
L Fe/0.5MH2SO4.
25 ° C o- -
w E E^ t I
F I I z+
M(H20)
2 0] n
Ó I I I H20
M2+
0.2Acm 2 ' frans-
LIJ ` ♦ 1 1 1 I ,,,, possive
W ^i I I N
^ I I I I 'E -2
W ^Oa^ I I I I á
> E
active passive OZgas^
jW (11 0) ad I ^^
cl
c l^
-4 !
METAL EDL VACCUM HYDRATED LIGAND
ION H 7µAcm2
IFe
[REDOX ] (ACID - BASE]
-6
POSSIBLE: i POSSIBLE
FIGURE 4. Frontier orbital interaction in metal ad-atom ionization, HYDROGEN , WATER STABLE 1 OXYGEN
desorption, and hydration. EVOLUTION; i EVO UTION
-0.5 0 0.5 1.0 1.5 2.0

to form the bonding and antibonding orbitals. The valence elec-
trons of coordinated ligand water molecules will occupy the bond-
ing orbitals leaving the antibonding orbital vacant, and a stable
aquo-complex of metal ion is formed.
The study of the metal dissolution mechanism from the view-
points of quantum electrochemistry may still be in its infancy 5 ,6 it
will certainly be one of the important subjects in the fundamentals
of corrosion science.
ANIONS IN ACTIVE METAL DISSOLUTION
Metal dissolution is known to occur in three different states of
the metal; the activa, the passive, and the transpassive states.
Figure 5 illustrates in the form of anodic polarization curve (disso-
E NHE / V
FIGURE 5. Anodic current-potential cure of iron in 0.5 M H 2 SO 4
showing anodic passivation and transpassivation. 7 JFe (—o—) is the
iron dissolution current density.
lution current-potential curve) these three states of anodic dissolu-
tion of iron in sulfuric acid solution. 7 The anodic iron dissolution in
the active state, which occurs in a potential region lower than the
passivation potential (Flade potential), takes place at the metal
surface covered with no superficial film and produces an etched
surface patter that differs in different crystallographic grains
(Figure 6). In the passive state the dissolution rate is extremely
small and the metal surface is covered with what is called the pas-

FIGURE 6. Microscopic appearance of /ron surface anodically polarized in the active, the passive,
and the transpassive potential regions. 8 8 is the surface layer thickness removed during anodic
polarization.

356 CORROSION—May 1989

 SCIENCE

Fe/0.5M C1, 25°C

b=230mV
disk, 2000rpm

-1.5

1 T
-2.0 °p
• ('1 -2
N p •
Q
-2.5 ó ;
a d %/ b= 53 mV
c7) -3
0
-3.0pH2.881 Q/

/
-3.5- /, Si2.32 -4
1 /'
-40 -
' /fl.03
ó •
,
-5
-0.3 -0.2 -0.3 -02 -0.1 0
E / VNHE E / VscE

FIGURE 7. Anodic current-potential curve of dissolution of a

FIGURE 8. Anodic current-potential curve of dissolution of a
rotating iron disk in the active state in acidic chloride solutions at pH rotating nickel disk in the active state in acidic chloride solution at
1.03, 2.32, and 2.88. 14 chloride concentrations 1 M, 2.5 M, and 5 M. 76

sive film, which is an iron oxide layer less than several nanome-
ters thick. The anodic dissolution current in the passive state is
independent of the metal electrode potential. The transpassive dis- Fe/ C
solution, which is potential-dependent, will take place in a potential
region more anodic than a threshold potential (the transpassivation
potential). Since the metal dissolution takes place in the presence
of a surface oxide film, there appears no etch patterns characteris-
tic of crystal grain orientation in the passive and transpassive S... yo
states. 8 We will discuss later the mechanism of transition from the N
0 5M[CI 1 .° 4.51M[CI ]
passive state to the transpassive state, and emphasize the role of á -2
degeneracy of the electron energy levels at the surface of the se- n -I
- si1
4.5M (cl]
miconducting passive oxide film. 9 n-
We now examine the role of anions in the active metal disso-
lution. It is widely recognized that the anodic dissolution rate of
ó -3
`\^' \®A 5[CI-]
M
iron and nickel in the active state is dependent on the hydroxyl ion
concentration (solution pH value) as well as the metal electrode N
potential. 10-13 Figure 7 shows the anodic polarization curves of a
-4
4.5M[CI7o...
rotating disk of iron in acid chloride solutions at different pH
values. 14 The iron dissolution rate at constant electrode potential
increases as the hydroxyl ion concentration increases in a rela-
-5 -I 0 +1
tively low potential region in the active state. Chloride ions have log (C H i / mol dm 3 )
also been found to affect the anodic metal dissolution. 15-18 Figure
8 shows the anodic polarization curve of a rotating disk of nickel in FIGURE 9. Effect of hydrogen ion concentration on the anodic
strong acid solutions of constant acidity at different chloride dissolution rate of iron at constant potential in the active state in
concentrations. 16 Again, the nickel dissolution rate at constant acidic chloride solutions. 17• 18 (1) -0.05 VNHE, (2) -0.15 VNHE. (3)
electrode potential in the active state increases with increasing 0.25 VNHE-
chloride ion concentration.
The anion-effects are not monotonous but are turned
depending on the range of anion concentration. Figure 9 shows, effect of chloride ion concentration on the rate of anodic iron dis-
as a function of hydrogen ion concentration and hence of hydroxyl solution in acidic chloride-perchlorate solutions at constant acidity.
ion concentration, the anodic dissolution rate of iron at constant Chloride ions act as an inhibitor in a low chloride activity range but
potential in chloride solutions of constant chloride act as a catalyst in a high-chloride activity range. 1 -1 ."" 19 Summa-
concentration."• 18 It appears that hydroxyl ions act as a catalyst rizing the above, we obtain schematic diagrams illustrating the ef-
for iron dissolution in weak acid solutions, 10, " whereas they inhibit fects of hydroxyl ions and chloride ions on the metal dissolution
rather than catalyze the iron dissolution in strongly acidic chloride rate, as shown in Figure 11.
solutions. The same effect of hydroxyl ions has also been The mechanisms of metal dissolution in the activa state that
revealed on the dissolution of nickel in acidic chloride solutions. 16 have been postulated in numerous publications do not in essence
Furthermore, chloride ions are found to function in much the same differ very much from one another so that we may develop a gen-
way as hydroxyl ions in metal dissolution. Figure 10 shows the eralized concept which includes within its framework all the postu-

CDRROSIDN—Vol. 45, No. 5 357



SCIENCE

Fe /Cl HYDROXIDE MECHANISM

OH --CATALYZED and C1 --INHIBITED
dO
II CHLORIDE MECHANISM
0
C1 --CATALYZED and OH --INHIBITED
0
N
-2 4. 5 M [ H t l/n=I.I 1
^E
V \^•^^ 0 4.5M [H + l 4— log [ 0W 1
® `.^ g^8
`.
`S ^M[H+l [ +I` II
'S ©8/ [H+ 1 .
a H
-° - /
.S o/o
Q08M[H+] `S-..
o/ 0
`. _0 0.08M (H)
o
OH -CATA.
- 01 OH - -INHIBITED
-4 -

-3 -2 -I Iog[H +] —r
log ( Ccj / mol dm 3

FIGURE 10. Effect of chloride ion concentration on the anodic

dissolution rate of iron at constant potential in the active state in I II
acidic Chloride solutions. 17• 18 (1) -0.025 VNHE, (2) -0.20 VNHE, (3)
0.00 VNHE, (4) -0.25 VNHE•
a [cl- l -
/ [cl- l
DI
O
CO \ ^
lated and anticipated mechanisms. The generalized concept of
metal dissolution thus developed wilt emphasize the important role
of adsorption of water molecules and anions on the metal surface, CI ANHIBITED %
- CI--CATA.
as illustrated in Figure 12. To understand the effects of hydroxyl
ion and chloride ion, we assume after a number of reaction paths log[Cr]
already postulated in the literature the following simplified
mechanisms: FIGURE 11. Effect of hydroxyl ion and chloride ion concentrations
on the rate of anodic metal dissolution via hydroxide mechanism (1)
1) Hydroxide mechanism
and chloride mechanism (11). [H±]* and [CI ]* denote the borderline
-

M + H 2 0 MOHed + H+ + e (1) concentrations for the two mechanisms.

MOH ad - MOH+ + e (2)

MOH+ -* M Z + + OH - (3)

2) Chloride mechanism j ads. I

M + Cl - - MCl ad + e (4)
v— H 2 0a q
MCl ad -* MCI+ + e (5)
H2Oad
,OHaq
MCI+ -* M 2 + + Cl - (6)
N OH. d -->t M0H: q
ç
/M - ► M ad -i M ad M2.
The hydroxide mechanism involves as an intermediate ad- a9
sorbed hydroxyl Tons, which catalyze the metal dissolution to pro- j -)r MCI; q ^
duce hydrated ions of metal hydroxide. Obviously, it is this type of
reaction mechanism involving adsorbed hydroxide that leads to the Cl aq
passivation of metals when subjected to increased anodic polar- H 2 OCIad
ization. In the presence of chloride ion, which is also surface ac- t- CIa4
tive, there is competitive adsorption between chloride and hydroxyl ads.
ions. Chloride adsorption at low chloride activity inhibits the metal
dissolution via the hydroxide mechanism.
Chloride adsorption tends to prevail over hydroxide adsorp-
tion at high chloride activity and high acidity (low hydroxide activ- METAL DOUBLE LAYER ELECTROLYTE
ity). The dissolution mechanism, therefore, will change from the
hydroxide mechanism to the chloride mechanism, as the acidity FIGURE 12. Reaction paths of anodic meta/ dissolution via hydrox-
and chloride activity increase over their threshold values. When ide mechanism and chloride mechanism.
the chloride mechanism prevails, hydroxide adsorption inhibits the
metal dissolution, as illustrated in Figure 11. It is apparent that the
chloride and hydroxide mechanisms compete with each other. No hydrogen ion and chloride ion, whereas the chloride-catalyzed and
passivation of metals will result from the chloride mechanism, hydroxide-inhibited mechanism will become predominant at high
which prevents the formation of an adsorbed oxygen or oxide activities of hydrogen ion and chloride ion. Accordingly, there will
layer on the metal surface. be a transition of the prevailing mechanism at the borderline activi-
As shown in Figure 11, the hydroxide-catalyzed and chioride- ties of hydrogen ion [H+]* and chloride ion [Cl ]*. Apparently, the
-

inhibited mechanism will prevail at relatively low activities of the borderline hydrogen ion activity will decrease with increasing chlo-

358 CORROSION—May 1989


CHLORIDE MECHANISM
(NON-PASSIVABLE)
*_
[H+ j [Cl - ]'
os
0
HYDROXIDE MECHANISM
(PASSIVATBLE)
log [cl-] -^
FIGURE 13. Borderline concentrations of hydrogen ion and chlo-
ride ion separating the two different dissolution mechanisms.
log [Cl -] --a
HYDROLYSIS
ACIDIFICATION
- !Q,!
PASSIVABLE NON-PASSIVABLE
rn
0
INITIAL [H + ]
INITIAL [Cl - ]
[ (M/n)CI ]
log [ (M/n) Cl ]-->
FIGURE 14. Borderline hydrogen ion and chloride ion concentra-
tion curve and acidification curve of anodically dissolved metal ion.
((M/n)CIJ* is the critical metal chloride concentration beyond which
no passivation wilt occur.
ride ion activity and the borderline chloride ion activity also de-
crease with increasing hydrogen ion activity. These borderline ac-
tivities are assumed to separate the region where the hydroxide
mechanism prevails from the region where the chloride mecha-
nism becomes predominant, as schematically shown in Figure 13.
Anodic metal dissolution in aqueous solution containing chlo-
ride ion generally leads to the accumulation of metal ions and
chloride Tons adjacent to the metal surface. In the case of iron
group metals, the accumulation of metal Tons gives rise to acidifi-
cation due to metal ion hydrolysis. In Pact the local pH within grow-
ing pits and other occluded corrosion celis is found acidic, even
when the bulk solution is neutral. 20 . 21 Here we examine the local-
ized dissolution within active corrosion pits and follow the compo-
sition of local solution within corrosion pit interiors. As the metal
dissolution progresses, both the metal Tons and the chloride ions
will be accumulated, and the acidification will begin to take place
when themetal chloride concentration exceeds a specific value.
Figure 14 conceptionally shows such a local change of solution
composition in a proton-chloride activity diagram, where the bor-
derline activities between the two types of dissolution mechanisms
CORROSION—Vol. 45, No. 5 359
SCIENCE
METAL / SOL. A+B B
/' pitting dil. B
rn A /
0
conc. B
0 A /
/ pitting
B
rn more conc. B
0
E —^
FIGURE 15. Schematic current-potential curve of anodic metal
dissolution in aqueous solutions containing nonaggressive, passi-
vating anion A and aggressive, depassivating anion B.
are also shown. As shown in Figure 14, there may be a case
where the metal chloride acidification curve intersects with the bor-
derline activity curve. This intersection indicates a critical metal
chloride activity [MCI]* for the transition from the
hydroxide-catalyzed dissolution mechanism to the
chloride-catalyzed mechanism.
Where the aqueous solution contains a passivating anion A,
such as sulfate or perchlorate, and a depassivating anion B, such
as chloride, the anodic polarization curve of metal dissolution is a
combination of the curves in the two solutions A and B. Figure 15
shows a gradual change of the anodic polarization of metal disso-
lution with increasing activity of depassivating aggressive anion B.
At relatively low activities of anion B the transition of the anodic
polarization curve from the passivating type A to the depassivating
type B takes place at an apparently specific potential, called the
pitting potential. It is recognized that the pitting potential is lower
when the chloride activity is greater. Al very high activities of ag-
gressive anion B, the anodic polarization curve shows no passiva-
tion and the transition from the A-type dissolution to the B-type
dissolution occurs in the active state of metal dissolution.
In pitting corrosion of passivated metals, the local passivity
breakdown first exposes to aqueous solution a certain area of the
fresh metal surface, where the active metal dissolution takes place
to form a microscopic corrosion pit. The freshly formed pit then is
either repassivated or continuously activated into a growing pit. At
pit sites there will be competitive metal dissolution between the
hydroxide-catalyzed mechanism and the chloride-catalyzed mech-
anism. The former may lead to repassivation, but the latter pre-
vents passivation giving rise to active pit growth. From the transi-
tion between the two types of dissolution mechanisms mentioned
above (Figure 14), it appears that the metal chloride activity in the
pit solution plays a decisive role in the stable growth of active pit-
ting. It the local metal chloride activity in a freshly formed micro-
scopic pit exceeds a critical value for the transition in dissolution
SCIENCE

mechanism, the microscopic pit would grow into an actively grow-

ing macroscopic pit on the passive metal surface.
Experimental observation 22 • 23 has revealed that the chloride
pitting of austenitic stainless steel in a sulfuric acid solution contin-
ues to grow so long as the concentration of metal chloride pro-
duced by the local dissolution within the pit interior is maintained
above a critical value of 1.8 Kmol m -3 This observation appears to
agree conceptionally with the criterion mentioned above of stable
pit growth.

SELECTIVE MASS TRANSPORT IN CORROSION

PROCESSES

When a metal corrodes in aqueous solutions, its surface is

frequently covered by a porous precipitate film of corrosion prod-
ucts consisting of hydrated metal oxides or other insoluble metal
salts. It is generally recognized that such a corrosion-precipitate
film, which is usually ion-permeable, either accelerates or deceler-
ates further corrosion of the underlying metal. A series of
studies 24-32 have been conducted in our laboratory to examine the
role of hydrated metal oxide precipitates in the corrosion
processes.
When the anodic metal dissolution takes place under a pre-
cipitate film, there must be some Tonic species migrating through
the precipitate film, namely cations migrating from the internal oc- FIGURE 16. Corrosion precipitates forming a surface film which
cluded solution under the film to the external bulk solution and an- either accelerates or decelerates further corrosion depending on
ions from the external to the internal solution, as shown in Figure their selective ion-permeability.
16. As a result, the occluded solution will undergo a composition
change. This composition change depends on which ion is prefer-
entially migrating through the precipitate film, i.e., on the selective
ion-permeability of the film. TABLE 2
Our studies 25 z 8 . 31 have revealed that hydrated oxides of iron- Point-of-Iso- Selectivity pH and Point-of-Zero-Charge pH
of Hydroxide Membranes in KCI Solution
group metals are anion-selective in acidic and neutral chloride so-
lutions, while they are cation-selective in basic solution. There is a Membrane pHPI. pH,
specific pH value, called the point of iso-selectivity pH, 32 at which
the ion selectivity is reversed. Table 2 31 shows for some Nickel(II) Hydroxide >13 9.6-11.3
Chromium(III) Hydroxide =11 6.5-7.4
iron-group metal hydroxide membranes the point of iso-selectivity
lron(II) Hydroxide >13
pH, as well as the point of zero charge at which metal hydroxide Hydrated Iron(II,III) Oxide 5.8
bears no surface charge. It has also been found that the ion-selec- Hydrated Iron(III) Oxide 10.3 8.6
tivity of hydrated metal oxide membranes depends not only on the
solution pH value but also on the specific desorption of foreign
ions to micropores of the membranes. Ferric hydroxide
mem-branes, for instance, are anion-selective in neutral chloride
solution, but they change to being cation-selective in the same =MOH(base site) + H 2 O -* =MOH 2 + OH - (8)
solution when molybdate anions Mo0 2- are adsorbed to their sMOH(acid site) -* =MO - + H+ (9)
micropores. 31
According to the membrane theory, the ion-selectivity is de-
In acid solution the base site is preferentially dissociated to form a
termined by the concentration C and mobility u of ionic species
positively charged site, while in basic solution the acid site is dis-
migrating through the micropores in the membrane. Besides mo-
sociated to form a negatively charged site. Accordingly, the fixed
bile cations and anions, there is an immobile electric charge at-
charge on hydrated metal oxides is positive in acid solution and
tached to the inner wall of the micropores, which is called the
negative in basic solution, and hence they are anion-selective in
fixed charge. The following electroneutrality is then established in
acid solution and cation-selective in basic solution.
the micropores:
The ion selectivity may be represented by the transference
number t ; of mobile species in membranes, which is the number of
n+C+ + fl__ + wX = 0 (7) moles of a mobile species transported by the charge flow of one
Faraday. The transference number can be determined by measur-
where n + (n_) and C + (C_) are the valency and concentration of ing what is called the membrane potential Ad>, which is the poten-
mobile cation (anion), and w and X are the sign and concentration tial difference across a membrane separating two solutions of dif-
of the fixed charge, respectively. It follows that if the sign w of the ferent mobile ion concentrations. In a simple case of
fixed charge is positive, the anion concentration C_ would be mono-monovalent ionic solution, the membrane potential may be
greater than the cation concentration C + and hence the expressed by the following equation:
membrane would be anion-selective. Obviously, a membrane wilt
be anion-selective if the fixed charge to the microporti is positive,
whereas it will be cation-selective if the fixed charge is negative. = FT Y~ i k In "k " (10)
The anion-selectivity is more pronounced when the concentration
of the positive fixed charge is greater.
Generally, the fixed charge arises from the acid-base dissoci- If the fixed charge concentration is much greater than the ion con-
ation of surface hydroxyl groups on hydrated metal oxides, as centration in the bulk solution, the membrane potential may also
shown in Figure 17: be expressed by the following equation:

360 CORROSION—May 1989



SCIENCE

10

Fe(OH) / KCI , NaCI

1.0

0.8
3
I _
F— ANION - SELECTIVE —) I tK+
0.6 S

0.4

E 0.2 CATION -
SELECTIVE Q1
0.0 0 l(
0

C -0.2 U

C -0.6 -5
(0 PZc
—. -0.8
N
-10.0
t ci • pis
-10
10 11 12 1S
pH
FIGURE 18. Dependence on pH of transference number i k + and
ic , in a hydrous iron (111) oxide precipitate membrane KCI solution 25
,

and of surface charge density a's on hydrous iron(lll) oxide in NaCI

FIGURE 17. Acid-base dissociation of surface functional groups of solution. 21
metal oxide or hydroxide in aqueous electrolyte.

(1) C I M NoCI/MEMBRANE/(II)C II MNoCI

T ) Iná°
^^= w(F (11) 60
C 1 n Ixt5 2 M .J
1
where t k is the transference number of mobile species, and a, and TNa` ` $'
a„ are the mean activities of the two solutions. Equations (10) and 40
(11) allow us to estimate the sign w of the fixed charge and the
transference number of mobile ions f k by measuring the
mem-brane potential as a function of the activity ratio of the two
solutions. 20
Fe(OH)3
Figure 18 shows the transference number of chloride and
potassium ions in a ferric hydroxide membrane as a function of pH E
in potassium chloride solutions. 25 This figure also shows the sur- 0
face charge density of a ferric hydroxide membrane in 0.01 M so-
dium chloride solution. 24 We see that the membrane is anion-se- d Fe(OH)3 Mo04 ad.
lective in acidic solution but cation-selective in basic solution. The
point of iso-selectivity pH (pH Pi9 ), which is estimated at pH 10.3, is
found to be more basic than the point of zero charge pH (pH pzc )
-20
estimated at pH 8.6; pH pis > pH 1, This difference is probably
caused by the specific adsorption of cation K+ at the negatively
charged surface sites, which apparently increases the positive S
fixed charge and gives rise to pH pi , more basic than
-40 S
S
Figure 19 shows the membrane potential of ferric hydroxide S
membranes with and without adsorbed molybdate anion Mo0 2- 5
as a function of the activity ratio of sodium chloride in the two neu-
-60 5
tral solutions separated by the membrane. 29 From Equations (10)
and (11), the negative slope of the membrane potential vs activity
ratio curve indicates that the moving ion is anion and hence that
the membrane is anion-selective, whereas the positive slope cor-
-1 0
responds to a moving cation and hence to a cation-selective mem-
brane. It is evident from Figure 19 that the adsorption of MoOá -
IOg(C 8 /C I )
anion changes the otherwise anion-selective ferric hydroxide mem-
brane into a cation-selective membrane. This ion-selectivity FIGURE 19. Membrane potential of hydrous iron(Ill) oxide mem-
change arises from the negative fixed charge created by MoO;+ branes with or without adsorbed molybdate anion in NaCI solution
adsorption, as schematically shown in Figure 20. Alternation in the as a function of the chloride concentration ratio of two chloride
ion-selective nature of ferric hydroxide membranes may also be solutions sepa rated by th e membrane. 29
caused by adsorption of oxyanions other than molybdate, such as
chromate CrO; and tungstate WOL. We note that this function of In the following, three simple cases will be examined in which
oxyanions to alter the ion-selective property of corrosion precipi- a corroding metal in an aqueous chloride solution is covered with
tates will play an important role in the corrosion of iron group met- an anion-selective, a cation-selective, or a bipolar membrane. Fig-
als. ure 21 shows the first case, in which an anion-selective precipitate

CORROSION—Vol. 45, No. 5 361

SCIENCE

FIGURE 21. Anion-selective corrosion precipitates accelerating

corrosion by accumulation of hydrogen ion and chloride ion in
occluded electrolyte under the precipitates.

2 _ 100 0
[C[ ] calc =
18•(-t w)

1c)
Y
0
E
FIGURE 20. Adsorbed ions to micropores in hydrous metal oxide
membranes, which provide the fixed charge whose sign determines
the ion-selectivity of the membranes. U
S-
[C[l obs
film is formed on the surface of corroding metal in neutral chloride 0
solution. When the anodic metal corrosion proceeds under such a
precipitate film, the internal occluded solution will become enriched 9
❑

in both metal ion and chloride ion, because the anodic current
through the anion-selective precipitate film is carried mainly by the
chloride ion migrating from the external bulk solution to the oc-
cluded solution. Since the concentrated metal chloride undergoes
hydrolysis to produce hydrogen ions the occluded solution will be-
come acidified, as has frequently been pointed out in the 0 1 2
literature. 33 Another important phenomenon worth noticing is the
electro-osmotic flow of water molecules accompanied by chloride
log -t ( w )
ion migration through the precipitate film into the occluded solu-
FIGURE 22. Maximum chloride ion concentration attainable in
tion. The rate of this electro-osmotic flow may be expressed by the
occluded electrolyte between a corroding metal and an anion-
transference number of water molecule f., which depends on the
selective corrosion precipitate film.
size and activity of the micropores in the precipitate film. This elec-
tro-osmotic flow of water wilt provide enough water for continuous
hydration of dissolved metal ions in the occluded solution.
The final chloride ion concentration to be eventually estab- chloride concentration, [CL] ai thus calculated from Equation (12)
, _ —1.
,

lished in the occluded solution can be estimated from the mole as a function of t W for an anion-selective membrane with fc
ratio of the transferring water due to electro-osmosis to the trans- Also shown in Figure 22 is the chloride concentration [Cl—], bs
ferring chloride ion with the anodic current: estimated experimentally with several hydrated ferric oxide mem-
branes of different t values. Agreement is fairly well between ex-
1,000 (12) periment and theory.
[Cl ]
- 1 = The transference numbers of water molecules and mobile
18(tW/t c1 -) ions, which are all characteristic of the corrosion precipitates, play
an important role in determining the final concentration of metal
,-
where t W and i c are the transference numbers of the water mole-
cule and chloride ion, respectively. Figure 22 shows the maximum
chloride in an occluded solution under an anion-selective precipi-
tate film. The metal chloride concentration in the occluded solution

362 CORROSION—May 1989

 SCIENCE

FIGURE 24. Bipolar corrosion precipitates consisting of an inner

anion-selective layer and an outer cation-selective layer, which
prevent anodic ion. transport and lead to metal passivation.

FIGURE 23. Cation-selective corrosion precipitates decelerating -2 FeCI 3 aq./Fe(III)oxide/NaCI aq.

corrosion by forming meta) hydroxide and depleting free water ' Na 2 Mo04 a .
molecules required for metal ion dissolution and hydration in
i
occluded electrolyte under the precipitates.

unipolar
will be more concentrated when f„, is smaller and hence when the N
porosity of the precipitate film is smaller. As stated in the preced-
U
1

ing section, there is a borderline of metal chloride concentration

beyond which the metal dissolution will proceed via the chloride-
catalyzed mechanism and hence will never lead to passivation.
Both the accumulation of metal chloride leading to acidifica-
Q -3
tion and the continuous electro-osmotic flow of water molecules
into the occluded solution will provide conditions favorable for lo- 0
calized corrosion to take place under an anion-selective corrosion
precipitate. Consequently, it follows that corrosion precipitates, if
anion-selective, will accelerate the propagation of metal corrosion
under the precipitates.
Figure 23 shows the second case in which the corrosion pre-
cipitate is cation-selective. In this case, chloride ions are cathodic ic
prevented from migrating into the occluded solution. Instead, the
anodic corrosion current through the precipitate film is carried by
m ranod
predominantly mobile cations such as hydrogen Tons, which mi-
grate outward leaving dissolved metal ions in the occluded solu-
tion. In addition, there is no inward electro-osmotic flow of water
-0.3 0 0.3 0.6
molecules. The only inward flow of water molecules is by diffusion
due to the activity gradient of water across the film, which presum- (a96—s9) /V
ably is incapable of providing enough water for metal ions to hy-
drate in the occluded solution. The eventual result will be the for- FIGURE 25. Current-potential curve of a bipolar membrane of
mation of metal hydroxide controlled by the inward diffusion of hydrous iron(l1l) oxide in chloride solution. 29
water through the corrosion precipitate film. Therefore, there is no
accelerated corrosion propagation and corrosion will rather be re-
tarded under a cation-selective precipitate film. of a bipolar ferric hydroxide membrane, which separates a ferric
The third case is a bipolar composite type of corrosion pre- chloride solution from a sodium chloride solution containing molyb-
cipitate film consisting of an anion-selective layer on the metal date anions. 29 The membrane surface facing the molybdate-con-
side and a cation-selective layer on the solution side, as shown in taining solution adsorbs molybdate anion to form a cation-selective
Figure 24. This type of bipolar precipitate film will be formed when layer about 4 x 10 -3 cm thick in the total membrane thickness of
an anion-selective precipitate film of hydrated ferric oxide adsorbs 1 x 10 -2 cm. The membrane surface of the other side facing the
molybdate ions on its surface facing the external bulk solution. ferric chloride solution, on the other hand, is intrinsically anion-
Both anion-selective and cation-selective unipolar membranes are selective with the positive fixed charge probably provided by ad-
ion-permeable irrespective of the direction of ionic current. But if sorption of ferric ions. In Figure 25 the anodic current is defined as
the membrane is made bipolar, its ion transport is made asymmet- a positive ionic charge transport from the ferric chloride solution to
ric and allowed to occur only in the forward direction. Figure 25 the molybdate-containing solution. We see that with this bipolar
shows the polarization curve (ionic current vs membrane potential) membrane the anodic current is greatly suppressed, while no cur-

CORROSION—Vol. 45, No. 5 363

 SCIENCE

NEUTRAL
LA VER
ANION- 1 1 CATION-
SELECTIVE 1 I SELECTIVE

+ + 1 I—
+ 1 _—

^I + + I ' -
0H H0 -iH*
+ / \ \++ I; __ W
I +++ I^
II
0
x- I:ó ':ó:) a• +++ i__ _
H+
OH < - HzO I
1 1 1

ANODIC CATION FLOW —+

41-- ANODIC ANION FLOW
cathodic anodic
FIGURE 27. Schematic potential distribution across bipolar mem-
brane under increased anodic polarization. 4) = inner potential, A4)
= membrane potential.
0
(ogb - ogs)
FIGURE 26. Schematic current-potential curve of bipolar mem-
brane.

rent blockage occurs in the cathodic direction. The bipolar mem-

brane thus proves ion-permeable in the cathodic direction but not
in the anodic direction.
Figure 26 shows a typical scheme of ionic current vs mem-
brane potential curve of bipolar membranes. This kind of rectifica-
tion of the ionic current arises from the contact of an anion-selec-
tive layer with a cation-selective layer. We may understand this
ionic current rectification by analogy with a semiconductor p-n
junction, which allows the electronic current in the forward direc-
tion only.
A bipolar corrosion precipitate film shown in Figure 24, there-
fore, blocks the flow of anodic ion transport and hence prevents
the anodic corrosion from taking place under the film. There is an
interfacial layer between the two ion-selective layers, and it is this
interfacial layer which holds most f the anodic bias potential in the
precipitate film. As the potential of corroding metal is made more
anodic, the electric field in this layer increases and eventually ex-
ceed a critical strength beyond which the decomposition of the
water molecule wilt occur. The final result will be the formation of
an inner dehydrated oxide layer covered by an outer hydrated ox-
ide layer facing the bulk solution. This is the passivation induced
by the bipolar nature of ion-selective corrosion precipitates. It is
therefore apparent that the corrosion precipitate of bipolar nature
is the most corrosion-resistance among the three types of ion-se-
lective precipitates mentioned above.
BIPOLAR MECHANISM OF PASSIVITY
As described above, a metal will be passivated when a bipo-
lar precipitate film is formed on its surface. We here discuss what
is expected to occur in a bipolar membrane, if subjected to an in-
creased anodic potarization. Figure 27 shows schematically the
potential distribution across a bipolar membrane subjected to an-
FIGURE 28. Current-potential curve of a bipolar lead sulfide mem-
brane and schematic membrane composition pro file at stages (1),
(2), and (3) in anodic polarization. 34
odic polarization. There occurs a high electric field in a neutral
layer between the two ion-selective layers. When this electric field
is made extremely high, the water molecule in the neutral layer will
dissociate into hydrogen ion and hydroxyl ion, and these two ions
then migrate in the anodic direction through the two ion-selective
layers. As a result, the bipolar membrane will be deprotonated and
the ionic transport will further be suppressed.
Figure 28 34 shows the ionic current versus potential charac-
teristics of a bipolar lead sulfate membrane, one side of which is
cation-selective facing a sulfuric acid solution and the other side of
which is anion-selective facing a lead nitrate solution. There is no
appreciable resistance against the ion transference in the cathodic
direction, but the ionic current is markedly suppressed in the an-
odic direction. As the anodic potential bias is increased, three dif-
ferent stages successively emerge in the anodic current-potential
curve. In the first stage, where the anodic current is a Ieakage flux
of ions, no compositional change is observed of the membrane. In

364 CORROSION—May 1989


FIGURE 29. Anodic current-potential curve of leed in 0.1 H 2SO 4
and schematic composition pro file of anodically formed surface
films on lead 34 in comparison with anodic current-potential curve of
a bipolar lead sulfide membrane shown in Figure 28.
the second stage where the anodic current increases beyond its
leakage current, the membrane undergoes dehydration and a lead
hydroxide Pb(OH) 2 or oxide PbO layer is formed on the anion-
selective side of the membrane. Further increase of the anodic
bias accelerates deprotonation in the third stage and eventually
produces a lead peroxide Pb0 2 layer on the anion-selective side
of the membrane.
In comparison with the anodic current-potential characteristics
of the bipolar lead sulfate membrane, Figure 29 shows the anodic
current-potential curve of a lead anode in sulfuric acid, where
again successively emerge three stages with increasing anodic
bias potential. In the first stage the lead anode is covered with a
lead sulfate film, which is usually bipolarized by both the positive
fixed charge due to the lead ion excess on the metal side and the
negative fixed charge due to the sulfate ion adsorption on the so-
lution side. Further increase of anodic polarization leads to the for-
mation of a lead oxide PbO layer on the lead metal surface pro-
ducing a bilayered film of oxide and sulfate in the second stage.
The third stage appears at furthermore anodic potentials, where
the bilayered oxide sulfate film is converted into a lead peroxide
Pb0 2 film. These three stages emerging in the anodic polarization
of lead anode in sulfuric acid solution are seen to agree well to the
three stages observed with a bipolar lead sulfate membrane.
We have examined above the bipolar mechanism of passivity
taking a lead anode as an example, in which the passive film is
sufficiently thick for analytical observation. This bipolar mechanism
will be applicable also to the passivation of iron-group metals, of
which the passive film is extremely thin. Figure 30 shows the suc-
cessive progress from the active metal dissolution to the passiva-
tion. As the active metal dissolution proceeds, metal ions will be
enriched near the metal surface and combined with hydroxyl ions
or non-aggressive anions to form gel-like or porous metal hydrox-
ide or salt precipitates, which are usually anion-selective in acid
and neutral solutions. When nonaggressive oxyanions are
adsorbed on the solution side of the precipitate film, its outermost
layer will be converted from an otherwise anion-selective into a
cation-selective phase, making the precipitate film bipolarized in its
ion-sectivity. Most of oxyanions in common use, such as sulfate
SO; , phosphate PO4 , borate B(OH)a , chromate CrO4 , molyb-
- a bipolar model consisting of an n-type semiconductive innermost
CORROSION—Vol. 45, No. 5 365
SCIENCE
FIGURE 30. Metal passivation via bipolar mechanism: (1) Metal
dissolution via hydroxide mechanism, (2) metal hydroxide precipi-
tation, (3) formation of bipolar precipitates due to oxyanion adsorp-
tion, (4) deprotonation under high electric field conditions, (5)
formation of an inner barrier oxide layer covered with an outer
cation-selective hydrous oxide layer.
date MoO;" and tungstate WO 4 , are capable of converting an-
ion-selective hydrated metal oxides to cation-selective phases by
their adsorption or incorporation into the phases. As described
above, the bipolarized precipitate film will be converted into a de-
hydrated metal oxide film covered with a hydrated outer layer,
which remains existing in neutral solution but dissolves vanishing
in acid solution. Observations 35 have shown that the passive film
formed on iron is composed of a thin barrier layer of dehydrated
oxide in acid solution, whereas it is a bilayered film consisting of
an inner barrier oxide layer and an outer hydrated oxide precipi-
tate layer in neutral solution. The outer hydrated layer frequently
includes oxyanions incorporated from the bulk solution. Auger
electron spectroscopic observations 36 have revealed that the pas-
sive film formed on iron in neutral borate solution contains in its
outer layer some amount of boron incorporated from the borate
solution.
The bipolar mechanism has also proved in the literature to be
applicable to the passive film formed on stainless steels. 37,38
While a chromium oxide layer is the primary means of stainless
steel passivation, the adsorption and incorporation of sulfate S0 2-
and chromate Cr02!ons bipolarize the anion-selective hydrous
chromium oxide film and enhance the deprotonation process to
proceed further growth in the chromium oxide barrier layer.
The passive film itself is bipolarized by the excess metal ions
or oxygen ion vacancies in the innermost layer, which provide the
positive ionic fixed charge, and the excess oxygen ions or metal
ion vacancies in the outermost layer, which provide the negative
ionic fixed charge, as shown in Figure 31. Accordingly, the passive
film may be regard as a bipolar film comprising an anion-selective
inner layer and a cation-selective outer layer. The anodic ion
transference, therefore, is restrained and a large potential drop
occurs in the passive film, which accelerates the deprotonation
and growth of the barrier layer. The outermost cation-selective
layer impedes the ingress of aggressive anions into the passive
film and hence makes the passive film highly corrosion resistive.
In the paragraphs above, we have examined the passive film
from the viewpoint of ion transference. If the passive film is exam-
ined from the electronic standpoint of view, we would reach again
SCIENCE
FIGURE 31. Bipolar nature of passive films with an anion-selective,
donor-rich, n-type inner layer and a cation-selective, acceptor-rich,
p-type outer layer, Vo = oxygen ion vacancy, VM = metal ion
vacancy, (+) = ionized donor, (—) = ionized acceptor, + _
positive hole, — = negative electron.
Iayer created by the excess metal ions or oxygen ion vacancies,
and a p-type semiconductive outermost layer resulting from the
excess oxygen Tons or metal ion vacancies, as shown in Figure
31. Such a semiconductor p-n junction generates a high potential
barrier for electrons in the passive film. Since the passive film of
iron-group metal is usually thinner than the electron tunneling Bis-
tance, the electron transfer across the passive film takes place
mainly via the tunneling mechanism. A similar model emphasizing
point defect structures for anodic passive films has been proposed
in the literature. 39
In conclusion, the passive film comprises an anion-selective
and n-type semiconductive inner layer, where the excess metal ion
or oxygen ion vacancy provides the n-type impurity levels for elec-
tron energy, and a cation-selective and p-type semiconductive
outer layer, where the excess oxygen ion or metal ion vacancy
gives the p-type impurity levels.
CORROSION IN PASSIVE AND TRANSPASSIVE
STATES
Metal dissolution in the passive and transpassive states takes
place through the passive and transpassive oxide barrier films
present on the metal surface. Consequently, the dissolution rate of
passive metals is apparently represented by the dissolution rate of
the passive oxide film. From the kinetics of metal oxide
366 CORROSION—May 1989
dissolution,40-42 it follows that the dissolution rate of passive oxide
films on metals is controlled by the potential difference across the
electrical double layer (the Helmholtz layer), b^ H , established at
the film-electrolyte interface. 43-45 The anodic dissolution current i d
of a passive metal, therefore, may be represented by the following
equation:
(13)
id= id exp( RT A4'")
where a is a kinetic parameter.
It appears that, as long as 04„ is constant, i d remains con-
stant, regardless of the metal electrode potential. This is in agree-
ment with observations that the anodic dissolution current of some
metals, such as passivated iron in acid solution (Figure 5), is inde-
pendent of the electrode potential in the the oxide-solution inter-
face is usually determined by the acid-base dissociation of the sur-
face functional groups and thus represented as a function of pH:
D^ H 2F (PH P ^^ — pH) (14)
where pH P ^0 is the point-of-zero-charge pH at which M4„ = o.
It is widely recognized that the passive oxide film on metals
can be regarded as a semiconducting oxide layer, in which the
electron energy level is characterized by the presente of a forbid-
den energy gap between the valence band and the conduction
band. If the passive film is highly detective or amorphous, the
band edge is broadened with the high density of localized electron
levels close to the edges and the forbidden energy gap is replaced
by the term called the mobility gap, 46 which is conceptionally
equivalent to the forbidden band gap.
The most marked difference between a metal electrode and a
semiconductor electrode is the distribution of potential across the
electrode-solution interface. In the case of metal electrodes, the
potential is distributed only at the Helmholtz layer and a linear re-
lationship can be established between 04„ and the electrode po-
tential E. In the case of semiconductor electrodes, the potential
distribution occurs not only to the Helmholtz layer at the interface
but also to a space charge layer in the semiconductor. The Helm-
holtz layer potential of semiconductive metal oxide electrodes, as
described above, remains constant in constant-pH solution, unless
the semiconductor surface is in the degenerate state for electrons.
Degeneracy of the electron energy levels converts the surface
Iayer from a semiconductor phase to a meta)-Iike layer, which is
capable of accommodating the excess electric charge to alter
AC H . The degenerate state of electron levels emerges, when the
Fermi-level at the semiconductor surface is located in the conduc-
tion band, at the dense surface state levels, or in the valence
band. Figure 32 shows the relationship between 04„ and the elec-
trode potential E for metal and semiconductor electrodes. We see
three potential regions (1, III, and V), where the semiconductor sur-
face layer turns into a metal-Iike Iayer giving rise to potential-de-
pendent OC H .
Here we consider a simple case where the passive oxide film
is intrinsic semiconductor with no impurity level within the forbid-
den energy band and hence the Fermi-level is located in the mid-
dle of the forbidden band. The Fermi-level of the oxide film is
equilibrated with the Fermi-level of the substrate metal. Figure 33
shows schematically the electron energy level and the potential
distribution of the passive film as functions of electrode potential. 9
At the flat-band potential E FB , there is no electrostatic poten-
tial gradient in the passive oxide film, and Od H at the film-solution
interface is determined solely by the solution acidity. If a small an-
odic or cathodic polarization is applied to the passive electrode,
the Fermi-level of the metal is lowered or raised to induce an elec-
tron energy band bending upwards or downwards in the film, while
AC H remains constant. Accordingly, the applied potential bias is
entirely localized at an increased potential drop in the passive film.

t SEMICONDUCTOR ELECTRODE
E
ESS
a F
Er E,--- Oi --- Ey
a E92 IV
1 1H EF - --
METAL ELECTRODE
____
'!ORE
Ep
d i ^
ELECTRODE POTENTIAL
FIGURE 32. Relationship between electrode potential E and inter-
facial Helmholtz layer potential H for metal and semiconductor
electrodes.
This mode of potential distribution is maintained as long as the
Fermi-level remains within the forbidden band of the film.
As the applied potential bias is further increased, the band
bending eventually becomes so great that the Fermi-level may be
lower than the valence band edge E„ or higher than the conduc-
tion band edge E c at the outermost surface layer of the film. This
corresponds to the degenerate state of electron energy levels at
the film surface. The electron tunneling then wilt take place
through the film, and the electrostatic charge carried by positive
holes or negative electrons accumulates at the densely degener-
ate electron energy levels in the outermost surface layer of the
film. The positive or negative charge accumulated in the degener-
ated energy levels at the surface layer contributes to a change in
04,,, giving rise to an anodic or cathodic overpotential at the film-
electrolyte interface.
Accordingly, as shown in Figure 33, AC H becomes dependent
on the electrode potential beyond a certain potential region (the
passive potential region) where 0d„ is independent of the elec-
trode potential. The anodic increase of O4 H thus accompanied
with increasing metal electrode potential will accelerate the rate of
metal ion transfer from the passive film to the solution and hence
will give rise to a potential-dependent dissolution of passivated
metals, i.e., transpassivation (Figure 33). The cathodic increase of
04„ with electrode potential will accelerate the rate of oxygen ion
transfer from the passive film to the solution, leading to a cathodic
destruction of the passive film, i.e., depassivation.
It follows that the passive potential region, where 0d„ is po-
tential-independent, is determined by the band structure of elec-
tron energy levels in the passive film. Figure 34 shows the anodic
polarization curves of iron' and nickel 47 in sulfuric acid solution
and the band structure of the passive oxide films at the flat-band
potential. 9 From the literature the flat-band potential is estimated
to be E FB = +0.43 V (normal hydrogen electrode [NHE]) for the
passive oxide film on iron, 48 and E FB = +0.8 V NHE for nickel
oxide 49 in acid solution of pH 0.7. The band gap has also been
reported to be E g = 1.6 eV for the passive oxide film on iron 4e and
51 ' 52
E g = 1.8 eV for nickel oxide. 50 Recent observations have
shown that there are two band gaps of 2 eV and 2.6 eV in the
passive oxide film on iron, probably corresponding to a band gap
of Fe3d-Fe3d transition and to a bandgap of 02p-Fe3d transition,
respectively. The Fermi-level E F appears to be located at 0.3 eV
below the conduction band for three-valent iron oxide. 53
As shown in Figure 34, the passive film on iron, which is of
n-type oxide, is electrochemically stable against anodic polariza-
tion, because there is a relatively large energy gap of about 1.3
eV between the Fermi-level E F and the valence band edge E v ,
within which the anodic polarization causes no potential-dependent
dissolution of the film. The passive film on nickel, which is of p-
CORROSION—Vol. 45, No. 5 367
SCIENCE
ELECTRON ENERGY LEVEL IN FILM ON METAL
Ec
v
EF . -- EF .:.: -- E --
POTENTIAL DISTRIBUTION
j YH
POTENTIAL AT FILM-ELECTROLYTE INTERFACE
FILM DISSOLUTION RATE y„„ i
im
' \ bx E
fb
CATHODIC — METAL POTENTIAL E — ANODIC
FIGURE 33. Schematic dia grams of electron energy levels, poten-
tial distribution, interfacial Helmholtz layer potential and film disso-
lution rate for a thin oxide semiconductor film on metals as functions
of metal electrode potential. 9
type oxide with a narrow energy gap of about 0.2 eV between E F
and E, is relatively unstable against anodic polarization and is
subject to the potential-dependent transpassive dissolution at com-
paratively less noble potentials.
It appears from the above discussion that the electrochemical
stability of the passiva film is related to the electron energy band
structure in the film. The potential region from the flat-band poten-
tial E FB to the transpassivation potential E TP , where the passive
film is stable against anodic polarization, corresponds to the elec-
tron energy gap between E F and E v in the film. Accordingly, the
passive oxide film of n-type appears to be more stable than the
p-type passive film in its anodic dissolution.
Thus far we have discussed the passive film dissolution in
which the metal ion and oxygen ion in the film dissolve without
changing their oxidation state. There is another mode of dissolu-
tion, which proceeds with an increase of the oxidation valency of
the metal ion or oxygen ion. This mode of oxidative dissolution is
an electron-donating or hole-accepting reaction and hence its rate
is obviously potential-dependent. The transpassive dissolution of
chromium and titanium belongs to this mode of dissolution as re-
presented by the following reactions:
Cr 2 0 3 + 5H 2 0 -> 2Cr0; + 1OH+ + 6e
- (15)
Ti0 2 — Ti °+ + 0 2 + 4e (16)
where the Cr(III) ions in the passive film on chromium are oxidized
to soluble Cr(IV) ions, while the oxygen ions in the passive film on
titanium are oxidized to oxygen molecules, both resulting in the
anodic destruction of the film. This mode of oxidative dissolution of
passive films is made thermodynamically possible, when the
Fermi-level of passivated metals is lower than the electron level of
the reaction, i.e., the metal electrode potential is more anodic than
the redox potential of the reaction. If the passive film is extremely
 SCIENCE
E/ V (NHE)
0 +0.5 +1.0 +1.5
M OX EL
-2t 1E e
-I.8ev
v O
Ef T. V ^
02 ev !
Ó E fb E i p
X02
Ni/0.5M 14SO4 V
-6 I 8.
,-o- M OX EL
O Ep
v 11.
-1.6 CV
IE -2 Í 3eV
V
Q EV r
O r
Q•
O
I 1.3V
Fe/0M H004 o o-o-o-o
-6 0 +0.5 +1.0 +1.5 +2.0
POTENTIAL E/ V (NHE)
FIGURE 34. Anodic current-potential curves of iron and nickel in
sulfuric acid solution and estimated electron energy band dia grams
of the passiva films at the flatband potential Efb . Etp is the
transpassivation potential. 9
thin, the oxidative dissolution will take place with the electron tun-
neling through the film. If the film is relatively thick, holes in the
valence band of the film will take part in the reaction. In the laffer
case, the oxidative dissolution may take place only when the elec-
tron level of the reaction is located within the forbidden band of
the passive film.
We have dealt herein with a few subject areas of important
corrosion fundamentals in a rather clear-cut approach. In reality,
however, the subjects discussed are obviously much more compli-
cated and are still open to further study. In examining these corro-
sion subjects we realize that corrosion scientists need, in addition
to the classical local cell theory, some new concepts, such as ac-
id-base, ion-permeability, and semiconductor concepts, to advance
further our fundamental understanding of corrosion processes and
its prevention.
ACKNOWLEDGMENTS
In my career of 37 years in corrosion research, 1 have been
very fortunate in having continuous encouragement and collabora-
tion from eminent scientists and highly talented coworkers. Most of
my contributions to various areas of metallic corrosion and passi-
vation have been made possible by their enthusiasm and their de-
votion to research. 1 am especially grateful to the following associ-
ates who have provided most of the laboratory work that
contribute to this lecture: Kiyokatsu Kudo, Masahiro Seo, Masao
Sakashita, Tetsugi Noda, Toshiaki Ohtsuka, Rokuro Nishimura,
Yoshiaki Shimizu, Yoshinori Yomura, and Kazuhisa Azumi. 1 also
acknowledge the contributions of many graduate students who
obtained their degrees in corrosion areas: Tokio Nakagawa, Hi-
roshi Tamura, Hisayasu Ohtake, Norio Arayama, Ryuichi Saito,
Nobuyuki Sato, Hitohi Murayama, Sakae Fujita, Yoshihisa Matsu-
mura, Tadashi Sakon, Fumio Baba, and Toshiaki Shimakura.
368 CORROSION-May 1989
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