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ELSEWER Solid State Ionics 86-88 (1996) 865-871
IONICS

Fe,O, as part of the passive layer on iron

D. Rahner
Dresden University of Technology, Institute of Physical Chemistq and Electrochemistry, D-01062 Dresden, Germany

Abstract

A short overview concerning the nature of the passive layer on iron will be given. It will be shown by the rotating split
ring-disc technique that the experimental conditions, especially during the processes of Fe,O, reduction, play an important
role for the establishment of a “passive” layer model. The current efficiencies of various Fe,O, reduction reactions will be
discussed. During the electroreductive dissolution of iron oxides, clusters of Fe(II)oxy-hydroxides or hydroxylated Fe(I1)
ions leave the oxide surface.

Keywords: Passive layer; Iron oxide; Magnetite

1. Introduction secondary-ion mass spectrometry and others) or in-

situ experiments (SERS, reflection spectroscopy,
The passivity of metals in the presence of aqueous ellipsometry or electrochemical reduction of the
solutions is caused by a more or less thin oxide film). To date the number of layers is controversially
layer, formed by reactive interactions between the discussed. Most information concerning the number
metal surface and the solvent, sometimes involving of layers have been drawn from electrochemical
anions. In the case of passive iron [l] two different reduction experiments of the surface film. Therefore,
models have been discussed: the purpose of this work is to show

(1) a two-layer model on the basis of the scheme (1) the strong influence of the experimental con-
Fe/Fe,O,ly-Fe,O, [2-71 with variable stoichi- ditions on the electrochemical processes during
ometry in the different layer parts [S-lo], and galvanostatic cathodic film reduction, and
(2) a single layer model on the basis of the scheme (2) the electrochemical behaviour of magnetite as a
Fe/Fe,O,-FeOOH [11,12] with a wide stoi- part of the passive layer on iron and its main
chiometry range of the Fe(III)oxy-hydroxide. influence on the suggested number of layers in
the above discussed models.

It was found that the film composition and the

number of layers depends on the formation con-
ditions [11,13,14] and the film may contain Fe,O,,
y-Fe,O,, y-FeOOH or Fe(II)Fe(III)(OH), with vary-
ing ratio X. The above discussed models have mainly
been developed on the basis of ex-situ (ESCA, AES,
2. Experimental
The influence of the experimental conditions was
studied using rotating disc electrodes. The amounts

0167-2738/96/$15.00 Copyright 01996 Elsevier Science B.V. All rights reserved

PII SO167-2738(96)00196-8
866 D. Ruhnrr I Solid
of Fe*+ species formed during the reduction process
and of hydrogen evolved during electrochemical
side-reactions have been determined in-situ by the
demountable split ring-disc electrode during polari-
zation and galvanostatic cathodic reduction experi-
ments.
By means of the ring-disc technique one is able to
determine reaction products in a qualitative and
quantitative way. For instance, in the case of a
metallic iron disc electrode, the metal corrodes in an
acid solution according to the following overall
reaction scheme:
Disc electrode:
Fe+Fe’+ + 2e
2H’ + 2e-- + H, .
The amounts of formed reaction products can be
determined analytically at the platinum ring electrode
by an electrochemical oxidation process at different
ring potentials.
Ring electrode:
potential 1: H,+2H++2e-,
potential 2: Fe*+ + Fe3+ + e- .
From the theory of ring-disc electrodes [ 15,161 it is
known, that a certain part of the reaction products is
detectable by the ring electrode reaction. This part is
called collection efficiency N and is given as
&kqE,
nR' 'D
where n, and IZ~ are the electrons consumed in the
disc and ring reaction, and i, and i, the current
density of the disc and ring reaction.
In the case of the stable products, the collection
efficiency N is normally independent of the rotation
velocity and corresponds within the error limit to the
theoretical collection efficiency N,, which only de-
pends on the electrode geometry. It can be calculated
from the radius r, of the disc and the radii t-z and r3
of the inner and outer part of the ring electrode [ 151.
Measurements were carried out on pure iron (discs
with 7.98 mm diameter). A demountable split ring-
disc electrode (r, = 3.99 mm, r2 = 4.50 mm and rj =
6.02 mm) with half-rings made of platinum was
Stute lonics X6-88 (1996) X65-871
used. The collection efficiency of each half-ring was
19.8%. Measurements were performed at 298 K in
de-aerated solutions. The potential values are given
with respect to the saturated calomel electrode
(SCE). For more experimental details see [ 17- 191.
3. Magnetite as part of the passive layer on
iron
Most of the information concerning the composi-
tion and the structure of the passive layer have been
collected by the method of galvanostatic cathodic
reduction of the surface film. For the electrochemical
reduction of y-Fe,O, and Fe,O, the following
overall reactions can be assumed to occur:
Fe,O, + 6H+ + 2eP -+ 2Fe*’ + 3H,O, (1)
Fe,O, + 8H+ + 2e- + 3Fe*+ + 4Hz0, (2)
Fe,O, + 8H+ + 8e- + 3Fe + 4H,O. (3)
Side-reactions in the potential region of Fe,O,-re-
duction may occur:
2H+ +2e-+H,, (4)
2Fe’+ + 2e- +2Fe. (5)
The reduction process of the surface film (disc) and
the monitored reduction products (ring) are shown in
Fig. 1. A constant cathodic current density i was
applied to the passive iron disc electrode. The
electrode potential U vs. the consumed charge q = i. t
was monitored. The U(t)-q transients can be inter-
preted in terms of the two-layer model [4], with an
outer layer of y-Fe,O, and an inner layer of Fe,O,.
The consumed charge q for the reduction process of
y-Fe,O, is rotation independent (Fig. 2). The de-
tected amount of Fe2+ species at the ring electrode
during the first potential plateau corresponds to Eq.
(l), with a current efficiency qFe2+ = 100% which is
in accordance with most of the collected data. The
reduction of the second layer part (magnetite) de-
pends strongly on the rotation speed of the electrode
(Fig. 2). In this potential region the reactions de-
scribed by the Eqs. (2-5), may occur simultaneously
depending on the experimental conditions. Thus, a
 D. Rahner I Solid State Ionics 86-88 (1996) 86.5-871 867

04

0 1 2 3 4 5 6 0 1 2 3 4 5 6

q [mCcm-*] 9 ImCct+l

ou 0 Fe= n H, 0 u 0 Fe= n H,

Fig. I. Galvanostatic cathodic reduction of the passive film on iron in buffered borate solution (pH 8.4, U,_ = 800 mV, t,,_ = 30 min,
l,,d = -SO p,A/cm2, f= 16.7 s-‘, addition of lo-’ mol/l EDTA). (a) High hydrogen overvoltage, (b) low hydrogen overvoltage.

the Fe,O, part of the passive film depends, at a

0 ment of the iron disc (hydrogen overvoltage). There-
.
Fig. 2. Consumed amount of charge 4 for different parts of the
passive film, dependent on the rotation speed (experimental
conditions see Fig. 1).
high convection will avoid the reduction of formed
Fe*+ species during the reduction process of magne-
tite (Eq. (5)). The current efficiency according to
Fe*’ (Eq. (2)) was found in this potential region to
be between O-40%. The consumed total charge q for
given pH and passivating potential, on the rotation
speed of the electrode, the Fe*+ concentration, the
reduction current density, and the surface pretreat-
fore, the layer thickness d, of the Fe,O, part of the
passive film can be calculated only with the actual
current efficiencies of the reduction processes (see
Fig. 3). This can only be achieved when monitoring
the reduction products (Fe’+, Hz) at the ring elec-
trodes simultaneously.
A high hydrogen overvoltage (the overvoltage for
hydrogen on Fe and Fe,O, is different) leads to a
reduction curve e.g. Fig. la. A low hydrogen over-
voltage gives curves e.g. Fig. lb. Sometimes only the
first plateau (y-Fe,O, reduction) is visible. In this
case, however, the ring electrodes indicate the sec-
ond “shielded” plateau by monitoring the Fe*+-
current and a pronounced hydrogen evolution due to
the low hydrogen overvoltage. Under these con-
ditions the reduction reaction according to Eq. (3)
also takes place.
868 D. Rahnrr I Solid State Ionics 86-88 (1996) 865-871

Cl
-800 -600 -400 -200 0 ml 400 600 800
U vs. SCE [mv]
-i-U-curve (arbitrary) 0 dl=Fe304 n d2=Fe203
0 dl+& +q (peroxide) * q (hyperoxide)
Fig. 3. Layer thickness d of the different parts of the passive film on iron in buffered borate solution (experimental conditions see Fig. I).

These findings show that the controversy con- FelFe,O,ly - Fe,O,/oxide part of higher valence
cerning magnetite reduction, and the experimental state.
findings of only one reduction plateau, leading to the
single-layer model, can be explained clearly by the
experimental conditions. By monitoring the U(t)-q
transients combined with in-situ analysis of the 4. Electrochemical behaviour of Fe,O,
reduction products (Fe’+ and Hz) one gets infor-
mation on a two-layer composition of the passive The investigations concerning the Fe,O, part of
film (Fig. 3). the passive film have shown, that, depending on the
experimental conditions, the reduction to Fe2+ ions
(Eq. (2)) is not the only process. Therefore it was
3.1. Oxide part of higher valence state
considered interesting to study the electrochemical
behaviour of pure magnetite (single crystal’) by the
At passivation potentials U( SCE) > 200 mV in the
same technique.
beginning of the reduction process, a lack in the
There is some controversy as to the reduction
detection of Fe*+ ions at the ring electrode is
reactions on magnetite surfaces. Depending on the
observed (Fig. 1). The amount of charge consumed
experimental conditions, Fe2+ ions, Fe(II)oxy-hy-
in this region is small and corresponds to 0.1-0.8 of
droxides, or metallic iron have been found to be
a monolayer. The potential dependence (Fig. 3) can
formed [22-261. It was predicted that the elec-
be discussed in terms of an oxidation of 02- ions in
troreductive dissolution process of oxides is accom-
the passive oxide via peroxide and hyperoxide ions
panied by a change in the surface stoichiometry
to form an oxide part of higher valence state [20,21].
[27,28]. According to the findings during the reduc-
tion of the passive layer one should assume that the
OfO$ + H,O a O&,, + 2H’ + 2e
electroreduction of compact Fe,O, will also depend
on the experimental conditions. The electrochemical
0 &,,, + H,O w O& + OH- + e behaviour of the Fe,O, single crystal is shown in
Fig. 4 and Fig. 5.
From this estimation of the layer thickness by the Starting at the rest potential Fe,O, is reduced to
galvanostatic reduction of the layer parts and moni- Fe’+-ions (Eq. (2)) with a current efficiency
toring the Fe2+ concentration at the ring electrode, Q,Z+ z 100% (region 1). With increasing overvoltage
one can assume the passive layer on iron to consist
of a layered structure according to the following ‘Museum of Mineralogy and Geology, Dresden (Germany), Nr.
scheme: 486912915, (1 11).face.
 D. Rahner I Solid State
Fig. 4. Current voltage curve of a magnetite single crystal in a
model solution (1 M Na,SO, solution with pH 2.74, sweep rate
20 mV/s, starting at the rest potential, 0.23 V, into cathodic
direction).
100
Fig. 5. Cathodic reduction of a Fe,O, single crystal and current
efficiency n for different reactions (pH 4, sweep rate 3.3 mV/s).
(1) i-U curve. (2) Current efficiency n for the reduction process
Fe,O, +8H’ +2e +3Fe*’ +4HZ0. (3) Current efficiency n for
the reduction process Fe,O, +4H’ +2ee+2Fe(OH)Z +Fe*‘.
the current efficiency for this reaction decreases due
to the different potential dependence of the charge
transfer processes of 02- ions and Fe2+ ions in the
crystal lattice. Thus, in region 2 only one third of
Fe 2f ions is formed when considering the overall
reaction according to Eq. (2). This process is better
expressed by the following overall reaction
Fe,O, + 4H+ + 2e + 2Fe(OH), + Fe2’ (6)
and the current efficiency of this reaction (curve 3 in
Fig. 5) is increasing up to about 100%. In region 3
‘onics 86-88 (1996) 865-871 869
metallic iron is formed on the magnetite surface
accompanied by a hydrogen evolution [20].
The reduction current density in region 1 de-
creases with increasing pH and the cathodic maxi-
mum is shifted to more negative values. At pH>8
the magnetite reduction occurs in the potential region
of hydrogen evolution (Eq. (4)) and of reduction of
Fe 2+ ions to metallic iron (Eq. (5)). These findings
are in accordance with the electrochemical behaviour
of the Fe,O, part in the passive film.
In the potential region 4 the formed layer of
metallic iron is dissolved and in the potential region
5 the magnetite surface is oxidized to y-Fe,O, or
y-FeOOH. The process in potential region 6 is
always coupled with the processes in potential region
3 and 4. It seems to be the oxidation of Cr3+ out of
the oxide surface to CrOt- (enrichment of chromium
impurities in the host material). In potential region 7
the oxygen evolution takes place.
5. Electroreductive dissolution of y-Fe,O, and
Fe304
During the reduction experiments of the passive
film and the Fe,O, single crystal a rotation depen-
dence of the Fe’+ -ring currents was observed (Fig.
6). The lower the rotation speed, the higher the
detected amount of Fe2+ ions at the ring electrode.
The extrapolation to & = 0 corresponds in all cases
to the theoretical value N, of the collection efficiency
of the ring-disc electrode and equals the current
efficiency vFe2+ G 100% for Eq. (1) and for Eq. (2).
0 4 8 12 16 277
Jii [h-y
Fig. 6. Fe’+ ring current during reduction experiments in depen-
dence on the rotation speed.
870 D. Rahner I Solid State Ionics 86-88
This interesting behaviour can be explained by two
assumptions.
During the reduction of the Fe(II1) ions in the
oxide lattice, clusters of two-valent iron-oxy-
hydrates are formed and leave the surface. On the
way to the ring the clusters are decomposed
chemically to hydrated ions [25]. Thus, the lower
the rotation speed the longer the time before
reaching the ring electrode, and the probability of
detecting the Fe ” ions at the ring electrode is
greater.
The rate determining step in the reduction process
of the oxides is the protonation of oxygen ions
0:; or hydroxide ions OH, at the surface. The
formed [Fe(OH),]‘2~“‘+ -species will cover part of
the surface and leave the surface according to
assumption 1.
was found [20] that the rate determining
during the oxide reduction is the reaction
OH, + H,‘g + H,O,, . (7)
Simultaneously to the charge transfer reaction (Eq.
(7)) [Fe(OH),]‘*-“’ species or clusters will leave
the surface and transform to hydrated Fe(I1) ions,
detectable at the ring electrode, via the overall
reaction in the solution
[Fe(OH),]‘2~“‘f + xH+ + Fe,,*+
depending on the existing pH-equilibria.
6. Conclusions
The above experimental findings show that the
controversy concerning the establishment of the
passive layer model from iron-leading to the single-
layer or two-layer model, can be explained clearly by
the experimental conditions. By monitoring the U(t)-
4 transients combined with in-situ analysis of the
reduction products (Fe’+ and Hz) one gets infor-
mation on a two-layer composition of the passive
film.
At passivation potentials U(SCE)>200 mV in the
beginning of the reduction process, a lack in the
detection of Fe’+ ions at the ring electrode is
(1996) 865-871
observed. In this potential region an oxide part of
higher valence state is growing. The amount of
charge consumed in this region and the potential
dependence can be discussed in terms of an oxida-
tion of 02- ions in the passive oxide via peroxide
and hyperoxide ions as a prerequisite for the oxygen
evolution at higher anodic potentials.
From the estimation of the layer of thickness by
the galvanostatic reduction of the layer parts and
monitoring the Fe’+ concentration and the evolved
hydrogen in the side reaction at the ring electrode,
one can assume the passive layer on iron to consist
of a layered structure according to the following
scheme:
FelFe,O,ly - Fe,O,/oxide part of higher valence
state
During the electroreductive dissolution of iron ox-
ides, clusters of Fe( II)oxy-hydroxides or hydroxy-
step lated Fe(B) ions leave the oxide surface and are
transformed in a slow reaction to hydrated Fe(B)
ions.
Acknowledgments
The author wishes to thank Prof. W. Forker for
helpful discussions. The technical assistance by Dr.
G. Ludwig is also acknowledged.
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