Corrosion Science. Vol. 36, No. 2, pp.

327-359, 1994
Pergamon Copyright © 1994 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
0010-938X/94 $6.00 + 0.00

THE MECHANISM OF THE OXYGEN REDUCTION ON

RUST-COVERED METAL SUBSTRATES

M . STRATMANN a n d J. M O L L E R *

Max-Planck-lnstitut fiir Eisenforschung, D~isseldorf, G e r m a n y

A b s t r a c t - - O x y g e n reduction is a major cathodic partial reaction during the corrosion of iron. The reaction
is greater than the H + reduction reaction for pH values >4. In the same pH range the iron surface is
covered by insoluble oxide layers like rust scales. As rust scales are reduced in the potential range of the
oxygen reduction, it was the aim of this study to analyse the relation between the kinetics of the oxygen
reduction and the reduction of the rust layer. The results presented in this paper show that oxygen is
predominantly reduced within the rust scale and not at the metal/electrolyte phase boundary. In order to
allow any oxygen reduction, the rust layers have to be reduced. Oxidized rust scales, which are nearly free
of Fe 2+ states, inhibit the reduction of oxygen completely.

INTRODUCTION
IN ORDERto allow any corrosion reaction to occur, the anodic metal dissolution has to
be balanced by a cathodic partial reaction. Considering the solubility of oxygen in
aqueous electrolytes (2 x 10 -4 moll 1 in equilibrium with Po~ = 0.2 atml), the
oxygen reduction has to be regarded as the major cathodic partial reaction in
comparison to the hydrogen evolution reaction at pH values >4. In the same pH
range the solubility of Fe 3+ ions which are formed during the corrosion process is
rather small. Therefore under nearly all corrosion conditions where the oxygen
reduction is the major cathodic reaction, the metal surface is covered by an oxide
layer. This layer may be a dense, adherent and only some nm thick passive layer but
under most circumstances rather thick and porous rust layers are formed. In order to
understand the kinetics of corrosion reactions the mechanism of the oxygen re-
duction has to be studied on oxide-covered iron surfaces, as the kinetics of this highly
catalytic reaction will strongly depend on the chemical composition of the substrate.
The oxygen reduction takes place at electrode potentials lower than 0 V(SHE).
The primarily formed Fe(III) oxihydroxides are not stable in this potential range. 2
They will be reduced, generating Fe(II) states within the oxide m a t r i x ) It has been
shown in previous studies that such phase transitions have a great influence on the
corrosion kinetics, 4 especially when the corrosion conditions are changing period-
ically with time. Examples of such changing corrosion conditions are indoor and
outdoor atmospheric corrosion, 5'6 the periodic immersion of metals in the splash-
zone of sea water v and the change between flow and stagnation of aerated water in
pipes. 8 In all these cases the corrosion potential varies periodically with time and
simultaneously the composition of the oxide scale is changed from an oxidized to an
Fe 2+ enriched state. Such phase transitions have been studied in detail by many
different techniques. 3"6'9"12 The oxidized rust layer is reduced in two steps: at first
7 - F e O O H is reduced within the given crystal structure: Fe 3+ ions are reduced to
* Present address: Thyssen Edelstahl, Krefeld.
Manuscript received 4 May 1993,

327
328 M. STRATMANNand J. MOLLER

(a) 6

4
o

jO2
i
1 ~ o v
i ~-0.1 V

-O.2 V
0 o--o-0.3 V
0~0-0.4 V

_ i J t i i i
-110_5 ' 10' 3 ' 10_~ 10~ 103 105
Frequency [Hz]
(b) 8I I
I

I
6 Formafion of Fe 2+-
E
o
a ' ~ in y-FeOOH
i,
E 4
Formation of \
o 2 Fes04 [] aXX~

O-- i i i B i i

-0.5 -0.3 -0.1 0.1

Potential [VsHE]

Fro. 1. (a) Impedance spectra of 7-FeOOH-electrode in 0.2 M NazSO 4. Electrode poten-

tials as indicated. (b) The potential dependence of the pseudo-capacity of y-FeOOH as
derived from (a).

Fe 2+ and at the same time this charge is compensated by the diffusion of protons
from the aqueous phase into the oxide lattice transforming O 2- ions into O H -
species. This fast redox reaction is clearly shown in impedance spectra of pure 7-
F e O O H films (d = 400 nm), which have been prepared according to Cohen 13 on gold
electrodes (Fig. la). At low frequencies a pseudo capacity Ccp shows up, which is
due to the reversible reduction and re-oxidation of 7-FeOOH. 9 The pseudo capacity
is rather high (some mF cm -2) and strongly potential dependent (Fig. lb), as with
increasing cathodic overpotential larger amounts of Fe 2+ states are created within
the v-FeOOH lattice. Below - 0 . 3 V the pseudo capacity is nearly potential indepen-
dent and then the formation of a new phase (Fe304) is observed. 3,9 The formation of
a new phase is proven by Fig. 2, which shows the open circuit potential of a rust
electrode as a function of the cathodic charge, by which this rust layer had been
 Oxygen reduction on rust-covered substrates 329

0.3
H-0.2 v
:> ~I 0.3 v
-~ -0.4 v
tp
c

o
Q- -0.1

(J

(D
-0.5
££
O "• --A • • tit •- • •

i i i i
-0"50 0.02 0.04 0.06 0.(}8 0.1
Mole f r a c f i o n of Fe 2+
(n! e +/nre~,+nFe@

F1G. 2. Equilibrium potentials of a rust electrode as a function of the mole fraction of Fe z+

states, 0.2 M N a : S O 4, pH = 6.

reduced at different electrode potentials (for details see Ref. 14). The open circuit
potential is clearly a function of the reduction charge and not a function of the
electrode potential at which the reduction has taken place. If up to 2% of the Fe 3+
states are reduced to Fe 2+, the open circuit potential strongly decreases with
increasing reduction charge. This is explained by a solid solution of Fe 2+ states within
the Fe 3+ matrix, the resulting open circuit potential being given by the Fe 2 ~/Fe 3+
redox potential. For a reduction charge > 2 % , below - 0 . 3 V(SHE) the formation of
the new phase magnetite is observed, e.g. by magnetic techniques ~) or in situ
M613bauer-spectroscopy. 3 The open circuit potential is no longer a function of the
reduction charge, as it is now given by the equilibrium between two phases of
constant activity. The Fe 2+ states within the 7 - F e O O H matrix can be re-oxidized
reversibly, whereas once formed Fe304 is oxidized to Fe3_oO4 .3'')
These potential dependent redox reactions within the rust layer should have
consequences on the kinetics of electron transfer reactions: during the first stage of
rust reduction the donor concentration in the oxide matrix increases dramatically up
to 2%. This should increase the electron density of the n-type semiconductor and
therefore increase the rate of electron transfer reactions. During the second stage of
rust reduction a new phase (magnetite) is formed. This should change the local
electronic conductivity, as magnetite has a specific conductivity close to a metal. In
addition the morphology of the corrosion layer is altered, which could result in a
different grain size and pore structure. This would change the transport of electro-
active species from outside to the site of the electron transfer reaction.
Taking these facts into account, the following questions should be answered by
this study:
(1) Where does the electron transfer reaction take place on a rust-covered iron
surface? Is oxygen reduced only at those parts of the metal surface, which are not
covered by corrosion products or is the electron density at the oxide surface due to
the rust reduction high enough, so that the reaction can take place at the phase
boundary oxide/electrolyte?
330 M. STRATMANNand J. MOLLER

(2) Does a correlation exist between the amount of rust reduction, which is
characterized by the Fe 2+ content of the oxide phase, and the kinetics of the oxygen
reduction?
There have been numerous papers published on the kinetics of the oxygen
reduction on passive iron as well in alkaline 15'16 as in neutral electrolytes. 17-19 In
addition, the oxygen reduction has been studied on well defined iron oxides. 2°'21
However, detailed investigations concerning the oxygen reduction on rust-covered
iron substrates are largely missing (see only Refs 22 and 23), due to the complexity of
this electrochemical system. Studies on passive metals cannot be directly applied to
rust-covered metals, as for the latter system the oxide film is highly porous, rather
thick and at the metal/rust interface bare metal is in coexistence with an oxide-
covered surface.

EXPERIMENTAL METHOD
Electrochemical experiments
All electrochemical experiments have b e e n performed on rust layers of well defined composition. In
the beginning of each experiment, the rust layer is oxidized (minimum concentration of Fe 2÷ states) and
the layer is prepared on noble metal electrodes (Au) such, that it contains no metallic iron. 24 Then during
an electrochemical polarization only redox reactions within the rust layer and other electron transfer
reactions (ETR) like the oxygen reduction have to be considered and anodic partial reactions like the
dissolution of metallic iron can be neglected. Such rust scales show very anodic open circuit potentials of
about +0.2 V(SHE) (see Fig. 2). In order to simulate real corrosion conditions and corrosion potentials of
typically - 0 . 3 to - 0 . 4 V(SHE) 6 the oxidized rust layers are polarized cathodically. At a given electrode
potential the rust layer will be reduced and Fe 2+ states are formed until, according to Fig. 2, the new
equilibrium is approached. The rate of E T R is analysed during rust reduction at the given electrode
potential in order to derive the relation between the kinetics of the ETR and the amount of rust reduction.
It is of major importance for such experiments, to distinguish at .a given electrode potential between
currents due to rust reduction and currents due to oxygen reduction.

Sample preparation. For all experiments, isolated rust layers have been prepared on top of Au
electrodes. 9,24 At first iron is galvanostatically electrodeposited from a N 2 purged 0.3 M (NH 4 )2 Fe(SO4)2
solution of pH = 7 with a current density of i = 7.5 m A c m -2. After deposition, the iron layer is
completely corroded in a humid and contaminated atmosphere. 9 The humidity is adjusted by a 0.5 M NaC1
solution to 99% relative humidity; as contamination, about 1 g SO 2 per m2 surface area is added to the
atmosphere. Under these conditions an iron layer of 10/~m thickness is completely corroded in
approximately 14 days.9 The corrosion layer is about 70/~m in thickness and nearly free of Fe2+ states, as
during the corrosion process the surface is covered only by extremely thin electrolyte layers. The oxygen
supply is rather high and very positive corrosion potentials are observed, which inhibit the formation of
Fe 2+ states. 25 As a result, rust layers are formed with the major constituents 7-FeOOH and a-FeOOH.
The surface area of these corrosion layers is approx. 50 m2 g-1 rust,14 the real surface area of the sample
under investigation approximately 0.6 m 2.
For many experiments such rust layers are prepared on the ring of a Au-disc/Au-ring electrode. As
leakage currents and crevice corrosion proved to be a severe problem for ring/disc studies, which run over
weeks, a special preparation technique is used. Ring and disc electrodes could be demounted from the
rotating head (Jaissle). The sides of each electrode are first sealed by a two-component epoxy and then
mounted in a special device, such that the disc is centred within the ring and the surface of both electrodes
is adjusted in height carefully. The remaining gaps between ring, disc and an outer Teflon shield are filled
in a vacuum system with a rapidly curing two-component epoxy. Then, the vacuum line is aerated, the
epoxy is firmly squeezed into the gap and crevice corrosion is no longer observed.

Measurement of the current transients. Current transients are recorded after a sudden change of the O z
activity in front of the rust layer. The transients are analysed with regard to their time lag, rise time and
their final values. The transients are recorded as a function of the electrode potential, the amount of rust
reduction and the thickness of the corrosion layer.
 Oxygen reduction on rust-covered substrates 331

ruTe )

~ I I "04<yg a n reduction

iring

02-evolutioln
idisc

time

FIG. 3. A schematic plot of current transients on ring and disc electrode for the modu-
lation technique used to separate the rate of rust reduction from the rate of oxygen
reduction.

For these experiments a rotating ring-disc electrode is used. The rust layer is prepared on the ring
electrode with a thickness between 35 and 175/~m and polarized potentiostatically. The direct current is
due to the reduction of the corrosion layer and the formation of Fe 2+ states (see schematic drawing of Fig.
3). At the A u disc electrode the flux of oxygen is modulated galvanostatically in the form of a square wave.
This causes a modulation of the 02 concentration in front of the corrosion layer. Due to the modulation of
the activity, oxygen will diffuse in and out of the corrosion layer and this causes a modulation of the current
at the ring electrode. The modulated current can easily be distinguished from the non-modulated current
and corresponds to the oxygen reduction within the oxide scale. This electrochemical experiment
therefore allows the currents of oxygen and oxide reduction to be separated (Fig. 3), as long as the time
scale for both reactions is different. The transients due to oxygen reduction can now be analysed as a
function of the composition of the rust scale.
A major drawback of this type of experiment is given by the fact that any modulation of the disc current
causes a modulation of the electrode potential at the rust ring. 26 The potentiostat, which controls the
potential of the ring electrode, also senses via the c o m m o n electrolyte an IR drop, which is due to a current
flux to the disc electrode. In order to keep the ring potential constant, the ring potentiostat will change the
potential drop at the ring electrode/electrolyte interface by a voltage difference, which is identical but
opposite in sign to the IR drop. As the rust electrode shows an extremely large capacity (some mF, see Fig.
lb), this modulation of the potential drop at the interface causes a large modulation of the ring current,
which is not correlated to the oxygen reduction and is observed also for a non-rotating electrode. In order
to prevent this, a voltage-signal identical to the IR drop caused by the disc current is added to the potential
of the ring potentiostat. 27 As the disc galvanostat is operated isolated from ground, an isolation amplifier
has to be used (Fig. 4). In order to find the correct value of the external resistance R', which is necessary to
compensate the IR drop caused by the disc current at the ring potentiostat, the A C current at the disc is
modulated with a high frequency (10-100 Hz) and/or the rotation of the R R D E is stopped. T h e n any
current modulation at the ring potentiostat is caused by the described electronic coupling of the two
potentiostats via the c o m m o n electrolyte, as there is no time for any electroactive species to diffuse from
the disc to the ring causing a real electrochemical current modulation at the ring potentiostat. The external
resistance R' is chosen such that the modulated current vanishes. Figure 5 shows the typical current
transient observed at the ring for a galvanostatic current modulation at the disc. It is obvious that the
current value of the external resistance (5.4 ,(1 for the given position of the reference electrode) is
determined with high accuracy.
For most electrochemical experiments a borate buffer is used as an electrolyte (0.07 tool I i Na 21340 7 ,
0.15 mol 1- l H3BO 3 and 0.2 tool 1- l Na2SO4, pH = 8.7). The use of a buffer is necessary, because the
332 M. STRATMANNand J. MULLER

I~nl~tit~n

+o
/ R'

- 0

Disc
galvanostat iostat

Counter electrodes

FIG. 4. A circuit diagram of the experimental arrangement.

modulation of the flux of oxygen at the disc causes a modulation of the p H value according to equation (1)
in an unbuffered electrolyte:

4 O H - ~ 02 + 2 H 2 0 + 4 e - . (1)

D u e to the p H modulation in front of the rust ring the rate of rust reduction would be modulated, too, and
this modulation could not be separated from the modulated current of the oxygen reduction. Unfortu-
nately, unlike unbuffered electrolytes, no magnetite is formed during rust reduction in buffered solutions,
as a p H shift inside the corrosion layer is necessary for the formation of magnetite from a thermodynamic
standpoint of view. 2'9 The investigation of samples containing magnetite requires the following pro-
cedure: first the corrosion layer is reduced at potentials of - 0 . 2 to - 0 . 3 V(SHE) in a borate buffer and the
kinetics of the oxygen reduction are analysed as a function of the reduction of the rust layer. For such
reaction conditions only Fe 2+ states are formed within the lattice of v - F e O O H . T h e n the rust layer is
reduced in an unbuffered 0 . 2 m o l l -1 NazSO 4 solution at a potential of - 0 . 4 V ( S H E ) . Magnetite
formation is observed u n d e r these conditions. After formation of magnetite the electrolyte is replaced by
borate buffer again and the oxygen reduction is studied on magnetite rich corrosion layers. A n
investigation of the 02 reduction during the formation of Fe304 is not possible for the reason described
above (unbuffered electrolyte).
The oxygen activity in front of the rust ring can be calculated according to equation (2)as for the
boundary condition that the rate of oxygen reduction at the ring is much smaller than the diffusion limited
reduction rate, which is given by the hydrodynamics of the R R D E [io2(ring) ---*0]:
0.641/6 v
Co2 = ND[o( o2) ]2/3col/2nFerr2D iD (2)

for: N D = current efficiency of the given R R D E (0.31);

v= viscosity of the electrolyte;
D(02) = diffusion coefficient of oxygen;
m= rotation frequency of the R R D E ;
rD = radius of the disc electrode;
iD = current (oxygen evofution) at the disc electrode;
n = n u m b e r of electrons transferred at the disc.

This condition is fulfilled, since for most rust scales the rate of oxygen reduction is only a small fraction
of the diffusion limited rate observed, e.g. on a Pt ring electrode. The validity of equation (2) has in
addition been tested by a m e a s u r e m e n t of the rotation dependence of the oxygen activity. According to
equation (2) the oxygen activity in front of the ring electrode is given by the disc current iD . For most
 Oxygen reduction on rust-covered substratcs 333

2ol R':4'.sa

I I

2O
R'=3.Q

:::L
-20
Zq~ I i I

o 40
Ob
R'=O~
. _C

-40
i i i i

0 20 40 60 80 100
Time [ m s ]
FIG. 5. ]'he determination of the correct IR compensation (see Fig. 4). R ' = (I,Q,
R' = 3 fL R' = 4.5 1). Modulation of the disc current: 10 Hz; no rotation of the R R D E .

experiments a disc current of I mA and a rotation frequency of 900 rpm is chosen. The oxygen activity is
then Co: = 8.7 x 10 5 m o l l 1.
Additional experiments have been performed with [Fe(CN)6] 3 as an example of an outer sphere
reaction. The reduction of [Fe(CN)6] 3 follows a much more simple mechanism than that of 02 and the
reaction is diffusionally controlled on noble metal electrodes at potentials more negative than
+0.2 V(SHE). An investigation of the reduction of [Fe(CN)6] 3 is therefore possible at electrode
potentials at which the oxidized rust layer free of Fe e+ is stable, whereas the reduction of oxygen is
possible only at potentials at which the rust layer is also reduced. For these experiments K4 [Fe(CN)6 ] is
added to the electrolyte in a concentration of 3 x 10-3 mol I 1. Again, the reducible species [Fe(CN)6 ~s
is formed at the disc electrode with a rate of 1 mA. The transients of the reduction of IFe(CN)6]3 to
[Fe(CN)6] 4 within the rust layer are measured and analysed as described above.

The measurement of polarization curves. It is expected that the kinetics of the electron transfer depend
on the number of Fe 2 + states within the rust l ayer.J 5 Therefore polarization curves of the oxygen reduction
should bc measured only for a given composition of the rust scale. Steady state current voltage curves arc
difficult to interpret since the number of Fe 2+ states changes for each potential. If, on the other hand,
polarization curves are measured by non-stationary techniques, then currents due to redox reactions
within the oxide scale have to be separated from currents due to oxygen reduction.
334 M. STRATMANNand J. MOLLER

The following technique is used in this study to measure polarization curves on a 7-FeOOH electrode
of given composition: the oxide layer is prepared on the disc of the rotating ring~lisc electrode and the
electrode is purged by oxygen, the 0 2 concentration being 10-3 moll 1 (P02 = 1 atm). The Pt-ring
electrode is polarized to a potential of - 5 0 0 mV(SHE). The oxygen reduction is diffusionally controlled,
its rate being given by i02.ring if no oxygen reduction occurs at the disc electrode (equation 3): 29
i(~2,ring = 0.62 z F zt[~ - ~]2/3[D02 ]2/31'1/% 1/2Co2 (3)

where F = Faraday's constant;

z= number of electrons for the oxygen reduction (=4);
ra = inner radius of ring electrode (=0.66 cm);
ri = outer radius of ring electrode (=0.87 cm);
Co2 = oxygen activity in the electrolyte.

If oxygen is reduced also at the oxide disc with a rate of/O2.disc, then the oxygen activity in front of the Pt
ring drops and the ring current decreases to io2,ring. The rate of the oxygen reduction at the disc electrode
can easily be calculated from the decay of the current at the Pt disc and the known current efficiency of the
rotating ring-disc electrode, No (equation 4): 29

i _ i~2,ring -- iO2,ring,
02,di,c - (4)
No
With this shielding experiment it is possible to measure the rate of the oxygen reduction at the 7-FeOOH
disc electrode even immediately after a potential jump at the disc. This is not possible by a modulation
experiment as described above, since immediately after a jump of the electrode potential the currents due
to redox reactions within the rust layer are much larger than those of the oxygen reduction.
Before measuring a polarization curve, the oxide layer is polarized at electrode potentials between
+0.3 and - 0 . 4 V(SHE) until the composition approaches its equilibrium as shown in Fig. 3. Then the
potential of the oxide disc is changed stepwise as shown in Fig. 6. The currents at the oxide electrode are
large due to oxide reduction but the ring electrode only shows changes which are due to the changing

---']I ~ +0.4V
EdJsc
-0,2 V

-0.4 V

i i iiiiat°n
t"

iringI iO2,dng

0.998mAI . . . . . . . . . . . . . . . . . . . . ~ i02,ling

f
FIG. 6. A schematic plot of current transients on ring and disc electrode for the modu-
lation technique used to measure polarization curves on a rust layer of constant compo-
sition.
 Oxygen reduction on rust-covered substrates 335

oxygen reduction at the disc. The current-voltage curve is constructed by plotting the initial rates of the
oxygen reduction versus the electrode potential after each jump. It is a problem of this technique,
however, that the diffusion-limited current at the ring electrode is of the order of some m A . A change of
this current can be observed only with an accuracy of 1BA and so the detection limit of the oxygen
reduction at the rust electrode is about 3 u A .

Non-electrochemical experiments
In order to analyse the transport of species through the rust m e m b r a n e and the site distribution for the
E T R within the rust layer, additional non-electrochemical experiments have been performed. T h e
transport of electro-active species is followed through isolated rust m e m b r a n e s , which are placed between
two separated electrolyte chambers. Thin iron foils have been corroded completely in a h u m i d and
SOz-containing atmosphere until no metallic iron could be detected any more. Then the pure rust
m e m b r a n e (approx. 6 0 ~ m in thickness) is placed between two electrolyte reservoirs (Fig. 7). On the right

-L l-
I iiiiii [Fe(CN6]3 iiiili
/kh

iiiiii
...... iiilii
iii~i!
~i~!ii
iiilii
......
ili iii

~ o i!i!ii iiiiii?iiii!i!!iii!i! OWE

~ ~nce
Ii t electrode ORE

[Fe(CN)6]4 ,....... ~ .....

OCE

© /// / \ \\
oxidation of [Fe(CN)6]4/ /
'\ \ \ \ l
to [Fe(CN)6] 3 / / \ \
\ \
/ \
\ \
Pt-electrode

rust p i a/s t i c dilfusio: ol

layer cover [Fe(CN)6]a-

FIG. 7. The a r r a n g e m e n t for permeation m e a s u r e m e n t s on isolated rust layers for a well

defined pressure difference between the two electrolyte reservoirs.
336 M. STRATMANN and J. MOLLER

side of the membrane the electrolyte is nearly static and a Pt-electrode is placed very close to the rust
membrane. The electrode is polarized such that [Fe(CN)6] 3- will be reduced under transport control. On
the left side a flow system is used which contains the reduced species [Fe(CN)6] 4-. At t = 0 a
concentration of 8 x 10 -5 mol 1-1 [Fe(CN)6] 3- is adjusted in the left chamber by galvanostatic oxidation
of [Fe(CN)6]4-• At the Pt-electrode in the right chamber the transient of the reduction of [Fe(CN)6]3 is
measured and the transport of [Fe(CN)6] 3- through the rust membrane can be analysed. Unlike the
ring-disc studies described before, the electroactive species has to diffuse through the membrane, as a
reduction inside the oxide scale is impossible. Some calibration experiments have been performed with an
organic membrane (pore diameter 2 # m , thickness 140#m) instead of the rust membrane. These
experiments have shown that, in addition to diffusion, convection is important in considering the flux of
[Fe(CN)6] 3- through the membrane. Therefore a variable pressure difference is adjusted between the two
chambers in order to analyse the diffusion process for a pressure difference equal to zero.
The distribution of electro-active sites is further marked by the electrodeposition of silver. For these
experiments the rust electrode is partially reduced and then Ag + ions are added to the electrolyte up to a
concentration of 10 4 M. Ag is electrodeposited within the rust layer and the distribution of Ag crystals is
later analysed by secondary electron spectroscopy. The time of electrodeposition has to be rather short,
since otherwise the pore system will be completely filled with silver and the original nuclei will not be
found.

Experimental equipment
A rotating ring-disc electrode (Jaissle) with mercury contacts of the following dimensions is used:
diameter of the d i s c = 0.56cm, inner diameter of the r i n g = 0.61cm, outer diameter of the
ring = 0.83 cm. The disc is controlled by a battery powered potentiostat (Jaissle, IMP 83), the ring by a
grounded potentiostat (Jaissle, IMP 83/100, Fig. 4). For most experiments the disc potentiostat operates
as a galvanostat whereas the ring potentiostat uses a Hg/HgSO 4 reference electrode. All potentials in the
following part refer to the standard hydrogen electrode (SHE). Each potentiostat is connected to an
individual counter electrode. The counter electrodes are composed of a disc and ring, respectively, which
are situated in front of the rotating ring/disc head. The electrolyte usually is purged by nitrogen and
thermostated to 25°C.

EXPERIMENTAL RESULTS
Oxygen reduction transients after a sudden jump of the oxygen activity
Figure 8 shows a transient due to the reduction of oxygen at a clean Au-ring
electrode after a sudden change of the oxygen activity. The change of the oxygen
activity is caused by a jump of the disc current (oxygen evolution). Due to the

©
Idisc
~ImA

C3
0 -

-400 g A
i k i
r i 1 i
-0.4 -0.2 0 02 0.4 0.6 0.8 I 1.2
Time is]
FIG. 8. The rate of the transport of oxygen between disc and ring. Disc: Au, galvanostatic
oxygen evolution, 1 mA; ring: Au, potentiostatic oxygen reduction, - 0 . 4 V(SHE); electro-
lyte: borate buffer, pH = 8.9,900 rpm, N2-purging.
 Oxygen reduction on rust-covered substrates 337

geometry of the rotating ring-disc electrode the onset of the current rise at the ring
electrode is observed 80 ms after the change of the disc current, and after about
600ms a stationary state is reached. These data show the best possible time
resolution with the given arrangement at 900 rpm, as the Au ring electrode is not
covered by any additional diffusion barrier besides the Nernst diffusion layer.
Unlike the results presented in Fig. 8 the transients of the oxygen reduction
observed on a rust covered Au-ring after a sudden change of the oxygen activity are
much slower. As an example Figs 9 and 10 show typical results which have been
obtained with a rust layer of 70/~m in thickness. In Fig. 9 the rust layer has been
reduced at a constant electrode potential of - 0 . 2 V ( S H E ) (upper part: rust re-
duction + oxygen reduction) and the transients of the oxygen reduction have been
measured after different times of rust reduction (lower part: oxygen reduction,
only). The onset of the reduction current occurs within the time scale given by the
hydrodynamics of the rotating ring-disc electrode (see Fig. 8), yet a steady state
reduction rate is observed only for a time of oxygen reduction which exceeds 31) rain.
The shape of the oxygen reduction transients shown in Fig. 9 cannot be described by

200

[ ~ Oalvanostatic oxygen
E evolution at disc
u

sf reduction
=L
100

\'~. oxygen reduction

J
b~ -7<____
/
/
/

/ / / )ooo
,

0.1
Time of rust reduction [rain] /
/ / / / /
E
o
R 2o

s
)

>,
£
o

b T:
,l< 2,} 40

r ,rr:e 3f o~ 7gen reduction [rrun]

FIG. 9. Upper part: The rate of rust reduction and rate of oxygen reduction during
galvanostatic oxygen evolution at disc. Lower part: The transicnts of O2 reduction for
different times of rust reduction. Disc: Au, oxygen cvolution l m A , [02] = 8.7 x
10 S m o l l I; ring: rust layer, thickness 70/~m; electrolyte: N2-purged borate buffer.
pH = 8.9, electrode potential at rust ring: - 0 . 2 V(SHE).
338 M. STRATMANNand J. MOLLER

E
150
< -0.2 V -0.3 v -0.4 v

C- /
.0 / /
100 //

-o

C
o~
>, 50
x
o

0 1000 2000 3000 4000 5000

cc
Time of rust reduction [min]

E
150
<
-0.2 V -0.3 V
c-
O
100 -

C
01
>,
X 50 "
Y
0

~ o-
a3 0.00 0.05 0.10 0.15
n-
Mole fraction of Ve 2+ r~,~+r~o~
FIG. 10. The final rate of oxygen reduction as a function of the time of rust reduction
(upper part) and as a function of the mole fraction of Fe2+ within the rust layer (lower part)
(data from Fig. 9 lower part and Fig. 9 upper part). Disc: Au, oxygen evolution 1 m A ,
[02] = 8.7 x 10 -5 mol 1-1; ring: rust layer, thickness 70/zm; electrolyte: N2-purged borate
buffer, p H = 8.9.

a single diffusion process of a given diffusion length, as then the time of the current
onset (time lag tD) should be 0.17 times the time necessary for approaching 95% of
the final value. Final values of the oxygen reduction reaction are observed only after
30 min and therefore a rise of the current should have been observed only for times
exceeding 5 min. The measured times of the current rise, however, are in the order of
some seconds. This implies that a wide distribution of diffusion paths has to be taken
into account, which will directly be correlated to the pore structure of the rust layer
(see Discussion).
In Fig. 10 the final values of the oxygen reduction transients are plotted versus the
time of rust reduction for electrode potentials of - 0 . 2 , - 0 . 3 and - 0 . 4 V (upper
part). At - 0 . 4 V the borate buffer is intermediately exchanged to the unbuffered
Na2SO4 electrolyte in order to allow the formation of magnetite (see Experimental
Method). After about 15 h the electrolyte is changed to borate buffer again and a
 Oxygen reduction on rust-covered substrates 339

transient of the oxygen reduction reaction is measured on the magnetite-containing

rust electrode. In the lower part of Fig. 10 the final values of the transients are plotted
versus the number of Fe 2+ states within the rust layer. The number is directly given
by the rust reduction charge. Figure 10 shows clearly that a correlation exists
between the rate of oxygen reduction and the amount of Fe 2+ states within the rust
layer. This correlation cannot be explained by a model which would take into
account only the reduction of oxygen at the interface metal/electrolyte. Instead of
this a predominant oxygen reduction at the oxide/electrolyte interface has to be
proposed. The correlation between the rate of oxygen reduction and the number of
Fe 2+ states is nearly linear up to very high concentrations of the Fe 2+ states (Fig. 10:
15%). This cannot be explained by an increasing conductivity of single oxide crystals
only, as the conductivity of semiconductors does not increase linearily for such high
donor densities. It is more likely that the major effect of rust reduction is given by an
increasing area of oxides which show a sufficient conductivity, so that the increasing
rate of oxygen reduction is directly coupled to the increasing electroactive area
within the rust layer (see Discussion).
Previous in situ M613bauer studies have shown that reduced rust layers may be re-
oxidized reversibly as long as no magnetite has been formed during reduction. 3
During re-oxidation the Fe 2+ states are re-oxidized back to Fe 3+. Figure 11 shows
the final values of the oxygen reduction transients as a function of the time of rust
reduction before and after an oxidation of the rust layer at +0.8 V. The dependence
of the rate of oxygen reduction on the number of Fe 2+ states within the rust layer is
quite similar and it is therefore evident that after a re-oxidation of the rust layer at
+0.8 V the electrocatalytic activity of the rust layer is lost and the rust electrode has
to be reduced for some time again in order to allow any oxygen reduction to occur.
Figure 11 excludes the fact that the effect of rust reduction on the rate of oxygen
reduction is given by a change of the rust morphology (size and distribution of oxide
particles), as the size distribution of oxide particles should not be changed reversibly
by an electrochemical reduction and re-oxidation. This is confirmed by a normalized
plot of the oxygen reduction transients observed for different amounts of the Fe 2+

=L
//
[] [] //
DE]~
L~
E]

q; 2 []

o3 +800 mVsHE ~
>-.

--300 lqq V SHE --300 mVsH z

C~
Pr" t i i
20 40 60 80 100
Time of rust reduction [h]
FIG. 11. The final rate of oxygen reduction as a function of the time of rust reduction
before and after a reoxidation of the rust scale at +0.8 V(SHE).
340 M. STRATMANNand J. MULLER

states within the rust layer (Fig. 12). Whereas the final values of these transients
[io2(t = oo)] strongly depend on the amount of Fe 2+ states (see Fig. 9), the transients
normalized with respect to their final values show no relation to the number of Fe 2+
states at all. This result, which could be proven many times in this study, is surprising
since the shape of the normalized transients of Fig. 12 is determined mainly by the
diffusion of oxygen through the rust scale. Clearly, the distribution of diffusion paths
is not altered significantly by the reduction of the oxide scale. This excludes the
possibility that the rate of oxygen reduction is changed during rust reduction due to
changes of the rust morphology, as this should have strong effects on the distribution
of the diffusion paths. It also can be excluded from Fig. 12 that the main effect of rust
reduction is the shift of a zone of electron-conducting oxides from the metal surface
towards the outer boundary of the rust layer, which would increase the diffusion
limited current density of the oxygen reduction by a shorter diffusion length. For a
shift of the reaction plane the rise time of the transients (r) should be inversely
proportional to the square root of the final rate of the oxygen reduction [io~(t = oo)]:

io2(t oo) 4FDo2~

= = (Ref. 30) (5)
d2
r~ (Ref. 31)
6Do2

= 2.66F2Do2c22 1
[io2(t = 00)]2

This is not observed in Fig. 12.

The results presented up to now have shown that the current rise after the sudden
change of the 02 activity is unusually slow. Two reasons may account for this result:
first, the long rise time of the transients is given by the distribution of diffusion paths
within the rust layer. Very long diffusion lengths would have to be taken into

~. 0.8
8
f!

-~'°°6i
.30.4
0--0-0.2 V
0.2 ~-0.3 v
-0.4 V

O0 10
' 20
' 5'0 40
' 50
' 6'0 70
Time of oxygen reduction [min]
FIG. 12. Transients of the oxygen reduction normalized on to their final values for
different amounts of Fe 2+ states within the rust layer (data from Fig. 10, ~7-FeOOH
+ = 0.03
(0), 0.07 (zx), 0.13 (E~)).
 Oxygen reduction on rust-covered substrates 341

account. T h e second possibility is that oxygen is t r a p p e d by adsorption or chemical

reaction within the oxide layer before it reaches the site of the E T R . In this case one
should assume that the adsorption sites are saturated with increasing oxygen activity
and the normalized transients should show decreasing rise times with increasing
oxygen activity. This has never been observed. As an example, Fig. 13 shows two
transients normalized on to their final values. T h e first transient i~+ is m e a s u r e d after
a j u m p of the oxygen activity from 0 to 4.4 x 10 5 mol 1 l, the second transient i~')~
after the activity has been additionally increased by a factor of 2. B o t h transients are
identical and give no hints, that the rise time is d e t e r m i n e d by trapping of oxygen.
The transients of the oxygen reduction reaction have also been analysed as a
function of the thickness of the oxide scale. In these experiments different oxide
electrodes have to be c o m p a r e d . Identical pore distributions cannot be p r e p a r e d
reproducibly even for a given thickness and therefore some scatter has to be
expected. Figure 14 shows the final values of the 0 2 reduction transients for different
electrode potentials plotted versus 1/d (d = thickness of the rust layer). Included in
Fig. 14 is a theoretical line, which describes the diffusion limited rate of oxygen
reduction according t o : 3°

/cliff ~ 4FDo+ Co___~2

d (6)

with: D(O2)=2.2x 10 5 c m 2s J
c(O2) = 8.7 x 1 0 - S m o l 1 - 1 ,

if the metal surface below the rust layer is fully accessible for the oxygen reduction.
Figure 14 shows that the rate of the 0 2 reduction is i n d e p e n d e n t of the thickness of
the rust layer at - 0 . 2 V. This m a y be explained by a rate determining charge transfer
reaction. At - 0 . 3 and - 0 . 4 V the rates are nearly inversely p r o p o r t i o n a l to the
thickness of the rust scale, taking the large scatter into account. This points to a
diffusion-limited reaction. The currents at these electrode potentials are close to the

1 ~ i02 I

I£ 0.6

--20.4
•- II ,oimn I I '

0.2'
it
o
½ t

O0 20
' 4'0 60
' 8'0 100
' 120
' 140
' 160
Time [rain]
FIG. 13. Normalized transients of the oxygen reduction for two subsequent increments of
the oxygen activity. A: jump of disc current from 0 to (1.5 mA; [02] = 4.4 x 10-s mol F ~;
O: jump of disc currcnt from 0.5 to 1 mA; [O21 = 8.7 × 10-5 mol I-l .
342 M. STRATMANNand J. MOLLER

250-

oE 200-
///y
v,/ ,,
150

~, 100
o
"6
0~ .3 V
~- 50-

. . . . . . . .

0 0

1/175 1/70 1/35

Thickness of rust layer [prn]
FIG. 14. Final values of the transients of oxygen reduction as a function of the thickness of
the oxide scale for electrode potentials of - 0 . 4 V ( 0 ) , - 0 . 3 V (A), - 0 . 2 V (©). Disc: Au,
oxygen evolution 1 mA, [02] = 8.7 x 10 -5 mol 1-]; ring: rust layer, thickness as indicated;
electrolyte: Ne-purged borate buffer, pH = 8.9.

theoretical rates, which are calculated for a free metal surface and a diffusion length
which is identical to the thickness of the oxide scale. However, major parts of the
metal surface are covered by an adherent oxide film and the electro-active area of the
metal can be only a small fraction of the geometric surface area. The observed rates
therefore are far too high. Figure 14 proves that the thickness of the rust scale has a
strong influence on the rate of the oxygen reduction. This implies that oxygen has to
diffuse into inner parts of the oxide scale before any E T R can occur.
The E T R cannot take place at the metal/electrolyte interface. Figure 15 shows
those transients which have been recorded at - 0 . 3 V ( S H E ) for varying thicknesses
of the rust layer. The transients are normalized on to their final values. Even for the
thickest rust layer no time lag to is observed between the sudden change of the
oxygen activity and the current rise. For a 175 # m thick rust layer a minimum time lag
of 800 ms would be expected according to equation (7), if the thickness of the
corrosion layer is regarded as the minimum diffusion distance: 31
d2
to - - - (7)
20Do2
The observed time lag has always been much shorter than this expected value. Only
the rise time r, which describes the approach to the final reduction rate, clearly
depends on the thickness of the rust layer. This is in agreement with Fig. 14, since for
thicker rust scales the diffusion length increases, which results in a decrease of the
final rate of oxygen reduction (Fig. 14) and an increase in the rise time (Fig. 15).
There is a strong discrepancy between Figs 14 and 15 which proves that oxygen
reduction does not occur at the metal surface but inside the rust scale. Let it be
assumed that oxygen is reduced at the metal surface and the diffusion limited rates of
 Oxygen reduction on rust-covered substrates 343

0.8
H
6~ 0.6

&~ 0.4
E2~-[3 .35 ~m

&--~ 70 p.m
0.2 175 ~zm

i i i i i i ~ i J
O0 10 20 30 40 50 60 70 80 90 100
Time of o x y g e n r e d u c | i o n [rain]
FIG. 15. Normalized transients of the oxygen reduction for an oxide thickness of
35/~m (E]), 70/~m (G), 175/~m ( ~ ) . Disc: Au, oxygen evolution I mA,
[ O 2 ] = 8 . 7 x 1 0 - S m o l l 1; ring: rust layer, thickness as indicated; - 0 . 3 V ( S H E ) ;
electrolyte: Nz-purged borate buffer, pH = 8.9.

Fig. 14 are given by the diffusion of oxygen through the oxide layer. In order to
explain the rates of Fig. 14, the diffusion length must be nearly identical to the
thickness of the rust layer (see solid line in Fig. 14). Then the rise time r, which is
necessary to approach (1 - l/e) of the final reduction rate can be calculated directly
according to equation (8): 32
c2
T - (8)
6Do2
Figure 16 shows the calculated rise times as a function of the thickness of the rust
layer in comparison to the experimental values (data from Fig. 15). It is quite obvious
that the experimental rise times are orders of magnitude longer than the values which
would result if oxygen is directly reduced at the metal surface. There is only one
explanation for this discrepancy: the real diffusion length is much longer than the
thickness of the oxide layer and the electroactive area is much larger than the
geometric area of the metal surface. This would account as well for a long rise time
(Fig. 15) as well as for the high rate (Fig. 14). The metal surface cannot be the
reaction site. Instead, the reaction occurs on the reduced oxide crystals deep inside
the highly porous rust layer, which has a real surface area of approx. 0.6 m 2 (6000
times the geometric area of the metal!). Figure 16 also shows that the slope of the plot
log r vs log d is not linear, whereas a slope of 2 is expected for the theoretical line.
With increasing thickness of the rust layer the plot deviates to faster rise times. This,
in accordance to Fig. 14, proves that the reaction site is shifted outwards if the
thickness of the rust layer is increased. In summary a large distribution of diffusion
paths has to be considered, taking into account distances which are shorter than the
thickness of the rust layer (short time lag), and distances which are much longer (long
rise time).

Transients of the reduction of [Fe(CN)6] 3

The rate of oxygen reduction cannot be investigated on oxidized rust layers, as
344 M. STRATMANNand J. MULLER

3 5 IJm 70 p m 1 7 5 IJm
1000

experimental
100 • rise time
p-
Q)
E 10 theoretical
(D
rise t i m e , ~ ~
rr (slope=2)

0.1
10 100 lO00

Thickness of rust layer [pm]

FIG. 16. Experimentally measured rise times of the oxygen reduction transients for a
thickness d of the rust layer of 35, 70 and 175/~m. Broken line: theoretical rise time for the
diffusion of oxygen through a diffusion barrier of thickness d; disc: Au, oxygen evolution
1 mA, [02] = 8.7 x 10-s tool 1-1; r!ng: rust layer, -0.3 V(SHE); electrolyte: N2-purged
borate buffer, pH = 8.9.

the oxygen reduction occurs only at those electrode potentials at which the rust layer
is also reduced. The reduction of [Fe(CN)6] 3- has therefore been investigated since
the rate of this reaction is already diffusionally controlled at potentials of +0.2 V on
noble metal electrodes. At these anodic potentials the n u m b e r of Fe z+ states within
the rust layer is extremely small (see Fig. 2).
Figure 17 shows the reduction transients of [Fe(CN)6] 3- after a sudden increase
of the [Fe(CN)6] 3- activity at potentials of the rust electrode of +0.2, 0 V (oxidized
rust-layers) and - 0 . 2 and - 0 . 3 V (reduced rust layers). The thickness of the rust
layer is 35 p m . For potentials of +0.2 and 0 V, extremely small final reduction rates
of 0.2/~A c m - 2 are observed. The rise time of these transients is in the order of some
seconds and therefore much smaller than the rise time observed for the oxygen
reduction at m o r e negative electrode potentials. At both potentials the reduction of
[Fe(CN)6] 3- at the gold surface is seen for those parts of the surface which are not
covered by a rust layer. Comparing these results with rates which have been
measured on a Au-ring electrode not covered with rust (300 p A cm -2) it has to be
concluded that less than 0.1% of the Au electrode is not covered by a rust layer and
more than 99.9% of the electrode surface are blocked by the dense oxide film! If the
corrosion layer is reduced at more negative potentials ( - 0 . 2 , - 0 . 3 V), then the final
rates as the rise times of the transients are comparable to those measured with
oxygen (Fig. 17). At, e.g., - 0 . 3 V the rate of the reduction of [Fe(CN)6] 3- is
increased by more than a factor of 1000 with respect to the oxidized rust layer. This
proves that the electronic properties of the oxide layer are of ultimate importance for
the rate of E T R and therefore also for the corrosion rate in neutral aqueous
electrolytes.

Current density-potential curves

The current density-potential curves have been mainly determined for the
reduction of 02 on a thin 7 - F e O O H layer, as rust layers proved to be too porous to
 Oxygen reduction on rust-covered substratcs 345

180

,,~ <, [F~(CN)d~- '~-******

140
.~¢~/- -os v
100
/,'
/' ,,
~p
6O
*d.

2O / ~ V
0.~
1D

(b
h
0.2 [

+0.2 V#,
0.1
/

~ov
0
0.0 o.1 i ' 10
' lOO
Time [rain]

FIG. 17. Transients of the reduction of [Fe(CN)6] B ( V ) and oxygen ( 0 ) on the rust
electrode at +0,2 V, 0 V, - 0 . 2 V and - 0 . 3 V(SHE). Disc: Au, formation of oxygen or
[Fc(CN)6] 3 with i = 1 mA; ring: rust layer, thickness 35 !~m; electrolyte: Ne-purged borate
buffer, pH - 8.9.

apply the potential step experiments described in the Experimental section. The
amount of Fe 2+ within the )'-FeOOH electrode layer is given by the potential at
which the measurement of the polarization curve is started. At a starting potential of
+0.4 V(SHE), ~-FeOOH is almost oxidized (Fig. 18a). If the oxide layer is stepwise
reduced up to - 0 . 4 V , Fe 2+ states are formed within the crystal structure of
7'-FeOOH (Fig. 18b), whereas a direct potential jump to - 0 . 4 V leads to the
formation of magnetite. All polarization curves have been measured by a compli-
cated sequence of potential jumps (see Experimental section) in order to keep the
composition of the oxide nearly constant for the time of the measurement. The y-
F e O O H layer is prepared on the disc of a rotating ring-disc electrode, the rate of the
oxygen reduction is measured on the ring in a shielding type of experiment.
Figure 19 shows the resulting polarization curves for O2 reduction on ~-FeOOH
layers of different composition. It is quite obvious that the composition of the oxide
scale has a strong influence on the rate of the ETR. For oxidized scales no oxygen
reduction is observed at potentials positive to 0 V(SHE). At more negative poten-
tials oxygen is reduced at increasing rates but simultaneously some ~-FeOOH will be
reduced, although the experiment is designed in such a way that oxide reduction is
minimized during the measurement of the polarization curve. On reduced oxide
346 M. STRATMANNand J. MOLLER

(a) ++ + ,+ . . . . 4-
100

99

r"

•69
£ 98

69
c0 97

-6
a: 96

95
'5 (~ i
-10 - 5 10
Velocity [mm//s]

(b)
+
4 +,+4~_, 4~- + +

100

t-
O

69

E
69
c-
O
k-
99

-6 + Experimental data
Pr" - - Theory
- - y-FeOOH
• - re(OH)2

-10 - '5 0 5 1()

Velocity [ m m / s ]

Fro. 18. M613bauerspectra of ~/-FeOOHat +0.4 V(SHE) (upper part) and -0.4 V (lower
part) 0.2 M Na2SO4.

electrodes oxygen is reduced much m o r e rapidly. Even at 0 V ( S H E ) the rate of the

oxygen reduction is close to the diffusion-limited rate if the },-FeOOH layer contains
a high n u m b e r of Fe 2+ states• It has therefore to be concluded that E T R is strongly
inhibited on oxidized electrodes and a reduction of oxygen is possible only by the
incorporation of Fe 2+ states into the oxide crystal. 15
For some experiments a rotating ring-ring-disc electrode is used to follow the
formation of H202. Only very small amounts of H202 could be detected and
therefore the oxygen reduction mainly proceeds according to the four-electron
reduction mechanism or by a fast chemical decomposition of H202 inside the oxide
scale. 15
 Oxygen reduction on rust-covered substratcs 347

-2

A--'
E
o \ ~ -0.4 V
4:
-4
Ob
0 -0.2 V
\
-5 i +0.4 V

i r i i i i

-0.6 -0.4 -(3.2 0 012 0.4

Polenfiol [VsHE]

Fro. 19. The polarization curve of oxygen reduction on a y-FeOOH electrode of different
stochiometry: v-FeOOH oxidized at +0.4 V(SHE) (&); y-FeOOH reduced at -0.2 V (½);
y-FeOOH reduced at -0.4 V (~).

Non-electrochemical experiments
Permeation of [Fe(CN)6] 3- through isolated rust membranes. As described in the
Experimental section an arrangement has been used where two electrolytes are
separated by a rust m e m b r a n e (Fig. 7). At the left electrolyte a concentration of
8 x 10 --5 mol l - l [Fe(CN)6]3- is adjusted by a galvanostatic current and in the right
electrolyte the p e r m e a t e d species are detected by a Pt electrode polarized at
0 V ( S H E ) . Figure 20 shows the permeation rate for an organic m e m b r a n e (pore size
2 # m ) and the rust m e m b r a n e as a function of the pressure difference between the
two compartments. The sensitivity of the detection is 0.08/~A cm -2. It is quite
obvious that the permeation of [Fe(CN)6] 3 can be followed easily for the m e m -
brane. The diffusion is enhanced by convective transport for a positive pressure
difference and retarded by a negative pressure difference. For the rust film, however,
no transport of [Fe(CN)6] 3 is observed even for a very large positive pressure
difference. The permeation rate is smaller than 0 . 0 8 # A cm -z and therefore much
smaller than the rate observed for the oxygen reduction on rust covered gold
electrodes (more than 100 # A cm -2, see Fig. 11). This proves that oxygen is reduced
within the oxide scale and not at the metal/oxide interface.

The determination of the reaction site by markers. As described in the Experimen-

tal section, rust layers have been prepared on top of Cu plates and Ag has been
electrodeposited on to this electrode. After deposition of some silver the sample is
polished at a very small angle with respect to the Cu surface (Fig. 21) so that on the
right side of Fig. 21 the oxide scale is completely removed, whereas on the left side
the rust layer is almost intact. 14 From left to right the distance to the outermost rust
layer increases. As indicated in Fig. 21, Ag nuclei have been found only in a zone,
which corresponds to deeper parts of the rust layer. Figure 22 shows an SEM analysis
of these silver nuclei: they are formed on top of ~ - F e O O H crystals. This proves that
the E T R takes place deeply inside the rust layer on reduced and therefore electron-
conducting iron oxides.
348 M. STRATMANNand J. MULLER

diffusion diffusion
-convection +convection

5 /
L~ polymer
uE 4 membrane/
<~

q.)
I
1

I rust layer
I
,0- .... @ . . . . . . @. . . . . ©
0 -15 -10 -5 0 5 10 15
P r e s s u r e d i f f e r e n c e b e t w e e n fhe fwo
c o m p a r t m e n t s Ah [ m b a r ]

FIG. 20. The permeation rate of [Fe(CN)6] 3- through a polymer membrane ([3, thickness
120~m, pore-size 2~m) and an isolated rust membrane (O, thickness approx. 60~m) as a
function of the pressure difference between the two compartments (see Fig. 7). Concen-
tration of [Fe(CN)6] 3- in the left chamber: 8 x 10 _5 real I 1.

DISCUSSION
All experiments have shown that the rate of electron transfer reactions like the
reduction of oxygen is strongly influenced by the reduction of rust layers. Two
extreme models may be discussed to explain this correlation between rust reduction
and oxygen reduction:

Model I
The 02 reduction takes place only at the metal/electrolyte interface at those parts
of the metal surface, which are free of corrosion products.
If the rate of the O2 reduction is determined by the charge transfer reaction, then
the rust reduction changes the rate of 02 reduction only, if the area of the uncovered
metal surface is changed, e.g. by reductive dissolution of FeOOH crystals. Obvi-
ously, the rate of inner sphere ETR like 0 2 reduction should differ by orders of
magnitude from fast outer sphere ETR like the reduction of [Fe(CN)6] 3-.
If the rate of the 0 2 reduction is transport-controlled then the rust layer would be
a diffusion barrier and the current of oxygen reduction should be inversely pro-
portional to the thickness of the rust layer. Rust reduction may alter the rates of outer
sphere and inner sphere ETR in the same way by a change of the rust morphology.
Current transients, which are recorded after a stepwise change of the oxygen
concentration, should show a clear time lag between the sudden activity change and
 rust layer pores with Ag Cu
FIG. 21. Micrograph of a rust covered Cu-electrode, polished at a small angle. Left: rust
layer not removed at all; right: rust layer eomplctely removed: deposition of Ag as
indicated.

349
 white spots = Ag-crystals
FIG. 22. SEM picture of a pore inside the rust scale, Ag nuclei as indicated.

350
 Oxygen reduction on rust-covered substrates 351

the onset of the reduction current. The rise time, the time lag and the final value of
the current transients should be a function of the thickness of the oxide layer. The
time lag is given by the diffusion length of the shortest pore through the rust scale
whereas rise time and final value of the current transient are determined by the
distribution of the pore lengths and pore diameters.

Model II
The 02 reduction takes place at the oxide/electrolyte interface on reduced and
therefore electron conducting iron oxides.
If the mobility of the electrons in the lattice of 7 - F e O O H is low, then the
transport of the electrons through the oxide scale can be rate determining for the
overall reaction. The rust reduction would change the conductivity in the oxide scale
by increasing the number of donor states.
The kinetics of the 02 reduction could be determined by the concentration of
Fe 2+ ions at the outermost part of the oxide surface. This may be due either to the
formation of catalytic active complexes between these Fe 2+ ions and the oxygen
molecule or due to a chemical reduction of oxygen by the Fe 2+ ions followed by an
electrochemical reduction of the Fe 3+ ions generated during the chemical reaction
(CE reaction sequence). 15
The site of the electron transfer reaction may be shifted during the reduction of
the oxide scale from the metal/oxide interface towards the bulk electrolyte, as the
reduction of the corrosion layer starts at the phase boundary metal/oxide. If the
transport of the electro-active species within the rust layer is rate determining for the
overall reduction reaction, then a shift of the reduced zone within the rust layer
would result in a shorter diffusion distance between the electrolyte and the site of the
E T R and hence in a larger diffusion limited current density.
The kinetics of the 0 2 reduction reaction may be determined by the area of
conductive oxides. During rust reduction the amount of Fe 2+ containing oxides and
therefore the area, is increased significantly at which the O~ reduction reaction may
take place. If the rate of the E T R is controlled by the charge transfer reaction, then
the current increases with the area of the conducting oxides, the current density
being constant. If the rate of the E T R is controlled by diffusion of electroactive
species, then an increasing area of electron conducting oxides only leads to increas-
ing currents if new diffusion paths (e.g. new pores) are now accessible.
The first model can be ruled out for the following reasons. For thick rust layers
the oxygen reduction rate is too large in comparison to the theoretical rate which
would result if the rust film is considered as a simple diffusion barrier, At the same
time the observed time lag is too small in comparison to the expected time lag if
oxygen would have to diffuse through the oxide layer. High rates of oxygen reduction
would be reasonable within model I only, if the metal surface is fully accessible for
the E T R . This would result in rise times which are orders of magnitude Smaller than
the observed ones. Long rise times may be explained by a large diffusion distance but
then the electro-active surface area has to be much larger than the geometric surface
of the metal. For anodic electrode potentials no E T R can happen within the rust
scale and the reduction proceeds at the metal/electrolyte interface. The reduction of
[Fe(CN)6] 3- has shown that at anodic potentials, a short time lag and correspond-
ingly a short rise time is observed (Fig. 17), yet the currents are orders of magnitude
smaller than the currents observed for the E T R at more negative potentials. This
352 M. STRATMANNand J. MULLER

proves that only negligible parts of the metal surface are accessible for any charge-
transfer reaction. These electrochemical results are supported by the negligible
permeation of electroactive species through the rust membrane and the marker
experiments which proved the oxide surface to be the electrochemically active sites.
The oxygen reduction reaction therefore has to occur within the rust scale on
electron-conducting oxides (model II). The observation that the final rate of oxygen
reduction is proportional to the number of Fe z+ states within the oxide excludes any
model which regards the electronic conductivity of the oxide as the rate determining
step, as the electronic conductivity no longer is proportional to the number of Fe z+
states for very high doping levels. The observed reversibility between the rate of
oxygen reduction and the reduction and re-oxidation of the oxides excludes a major
influence of morphological changes on the rate of the ETR, as a change of the rust
morphology should not be reversible. It has also been shown that the site distribution
of the ETR is unchanged during rust reduction, as otherwise the shape of the 02
reduction transients would have been altered (Fig. 12). It has to be concluded
therefore, that the rate of the oxygen reduction is directly coupled to the number of
Fe 2+ states at the surface of the oxide crystals and/or the inner surface area of the
reduced rust scale. The shape of the transients is given by the distribution of diffusion
paths through the oxide scale.

Mechanism of oxygen reduction

A major complication in the interpretation of the electrochemical data is given by
the observation that the rate of the oxygen reduction is very comparable to the rate of
reduction of [Fe(CN)6] 3- and that both rates are accelerated in a similar way by rust
reduction (Fig. 17). The reaction scheme for the reduction of oxygen is most
probably given by the following sequence:

O2(electrolyte) Diffusion,Oa(rust) (9)

Fe2+
(y-FeOOH) -t- H + -~ 0 2 ~ Fe3+OOH(~_FeOOH) (10)
Fe3+OOH(y_FeOOH) + e - + H +--~ F~3+
~(~,-FeOOH) + H202 (11)
F~3+
~"(?,-FeOOH) nt- e - ~ F-2+
~(?,-FeOOH). (12)
If the heterogenous reaction and not diffusion is rate determining for the overall
reaction, then the observed dependence of the reaction rate on the number of Fe 2+
states requires equation (10) to be rate determining. However, a consequence would
be that the rate of the chemical oxidation of the Fe 2+ by oxygen is comparable to the
oxidation rate by [Fe(CN)6] 3-. If diffusion is rate determining (equation 9), then the
similarity of the rates of both reduction reactions (02 and [Fe(CN)6] 3-) is obvious.
The dependence of the reduction rate on the number of Fe 2+ states, however, is not
easily explained. It has to be assumed that during rust reduction the area of electron
conducting oxides deep inside the rust scale is increased and as a consequence new
diffusion paths are accessible, which will increase the rate of mass transport.
The polarization curve of the oxygen reduction on pure y-FeOOH shows
diffusion-limited rates below electrode potentials of -0.2 V(SHE) whereas the
reduction of [Fe(CN)6] 3- proved to be diffusionally controlled already below
 Oxygen reduction on rust-coveredsubstrates 353

+0.35 V(SHE). 14 In this study, E T R on rust electrodes has been investigated mainly
in the potential range between - 0 . 2 and - 0 . 4 V. At these potentials both reduction
reactions should be diffusionally controlled according to the polarization curves
described before and the major effect of rust reduction seems to be the increase of the
area of electron conducting iron oxides. Nevertheless it cannot be excluded that the
acceleration of the charge transfer reaction (9) due to an increasing concentration of
Fe z+ states within the v - F e O O H may also be of some importance.

The transport of oxygen

The transients of oxygen reduction observed after a sudden change in the oxygen
activity are attributed to the transport of oxygen to the reaction site. It has to be
explained why time lags are observed, whereas the time necessary to approach
steady state is rather long. It is assumed that the shape of these transients is
determined by the distribution of diffusion paths through the oxide scale.
In the most simple model, the rust layer may be represented by a distribution of
cylindrical pores of length l i and diameter ri (area of cross section Ai = Jrr2) and it
may be assumed that an electrochemical reaction is possible only after a diffusion
distance li. The pores may be classified according to their length and then the overall
area of electro-active surface Ato t can be divided into the areas Ag, which belong to a
certain group of pores of common length li. If the oxygen activity at the outermost
part of the pore is suddenly increased from 0 to e(o~ 0 and oxygen will be reduced
completely after a diffusion distance 6 of the pore (diffusion limited oxygen
reduction), then the oxygen concentration profile can be calculated as a function of
time according to: 33

= cO x 2 C~o_,)cos (n~) sin exp (13)

The current transient of this class of pores (represented by li) is given as:

ii = A i z F D ( o : ) ~ (14)
O~ x=O

{, 1 cos tt] /
= AizFD(°:)c{°'~l " ~ + -Jr li exp \ l~ )]1" (15)

Figure 23 shows current transients ji = li/Ai, which have been calculated according to
equation (15). As expected, short pores will show high currents and short rise.times,
whereas long pores show small currents and long rise times. Real transients of the
oxygen reduction on rust electrodes are therefore dominated over short times by
short pores and over long times by long pores. The total current is now given by a
summation of the currents of the different classes of pores:

iges = 2 {i(li)Ai} (16)

i=1
354 M. STRATMANNand J. MULLER

8 . t 0 -5

I i ---- 1 0 0 #.m

6.10 -5 .
E
o
<

'5 4.10 -5
c .......................................... ~I I I~ 0 0 ~ m
"0 ,,,'"
L 2,10 -s . / //" .......... :_400 p.m
0
y. //// = 1000 p.m

0
--.// ..........'_ j/ ................. 50oo
i I I ' I I I
10 - 2 10 -1 1 101 10 2 10 3 10 4 10 5

Time [s]
FIG. 23. The calculated current transients for pores of different length, as indicated.

Atot = y , A i. (17)
i=l

An experimental transient may now be fitted by equation (16) and as a result the area
Ai of a certain class of pores can be derived as a function of the length /~. A
comparison between the experimental data and the fitted transient is shown in'Fig.
24(a), the corresponding pore length distribution in Fig. 24(b). It is quite obvious
that for a reasonable agreement very long pores have to be taken into account. For
rust layers of 70~tm thickness the length of the major class of pores is appox. 3 mm
(Fig. 24b). The labyrinth factor, describing the difference between geometric
diffusion length and real diffusion distance, would therefore approach unusually
high values of 40. The total surface Ato t (equation 17) is calculated to be approx.
5 cm 2. This value is high in comparison to a geometric surface area of the metal of
i cm 2 but it is rather small considering a real surface area of the rust electrode of
5000 cm 2. The deposition of silver, however, was observed on only a few sites. A
large portion of the inner surface of the rust electrode seems to be not accessible for
the electrolyte or not conductive enough, in order to allow any ETR.
Figure 25 shows similar analysis for the oyxgen reduction transients measured on
rust layers of different thickness (see Figs 15/16). It is quite clear that the mean
diffusion distance increases with increasing thickness of the rust layer (see also
transients of Fig. 16). The distribution of pore lengths is wider for thicker rust layers.
Most remarkable, however, is the decreasing effective surface area of the rust
electrode with increasing thickness of the rust layer and therefore increasing absolute
surface area. Figure 25 shows that inner parts of the rust electrode which are reduced
and therefore show high electronic conductivity are less accessible as the film
thickness increases. This corresponds to an increasing corrosion protection of the
surface by a more dense rust layer.
 Oxygen reduction on rust-covered substrates 355

(a)

o4
E
1E-5

x e x p e r i m e n t a l data
S
" 8E-6

c
0
6E-6
qD
@

4E-6
Q~
>..
x
o

"~ 2E-6-
@
"6
C12
O- __ X ;(

I I I I I I I
5 10 50 100 500 1OO0 SO00

Time of oxygen reduction Is]

(b) 1.2

0.8

c~ 0.6
E
o

©
@
04 ~/.,q
<~ ////,+
//~-'. 4
// //~.

°2
////•
////,
"/ // //// / 4 ///,

0 , / / i / / /4J - ,
"W,A
1/ /' / "" ] '1
0.1 0.2 0.5 0.4 0.5 0.6 0.7 0.8 0.9

Pore length [cnq]

Fie. 24. (a) The transient of the reduction of oxygen on a rust electrode ( x , data similar to
Fig. 9, lower part) and best possible fit (- ) with a pore size distribution model. (b) The
pore size distribution, which results from the best possible fit of (a).

In an alternative model a distribution of diffusion coefficients rather than just

one may be assumed. Again, the experimental data can be fitted by equations (15)
and (16) perfectly, but n o w the diffusion length is fixed (e.g. 200ffm, labyrinth factor
of 3) and a distribution of the diffusion coefficient results. In order to explain within
this model the very long rise times rather small diffusion coefficients (e.g.
3 x 10 -8 cm 2 s -1) have to be taken into account for the most important class of
pores. This value is by a factor of 1000 smaller than the diffusion coefficient of oxygen
356 M. SrRaTMANN a n d J. MOLLER

/~ Thickness 35 kLm
A~ot=21 cm 2

1 ~ . . . . .

Thickness 70 lain
/ A~o1=15 cm 2

E
o
o
a)
L.
<
~-.~ Y / ~ ~ , , , ~ ......

8 Thickness 175 p.m

Atot=8 cm 2
7
6
5
4
3
2-
1-
O-
0.2 0.8
Pore lengfh [cm]

Fro. 25. The pore size distribution for a thickness of the rust layer of 35, 70 and 175/~m
(data of Fig. 15).

in water and such a deviation would make sense only if oxygen diffuses not only
through water filled pores but also through thin membranes of 7-FeOOH, as has
been discussed for N i O O H electrodes. 34
A last explanation for the observed transients of the oxygen reduction may be
given by the shape of the pores. The previous calculations are based on a simple
cylindrical pore size. SEM investigations of rust cross sections always have shown a
rather complex pore shape (see e.g. Fig. 22). Typically, a few large pores or caverns
are found, which are connected by very thin tunnels. Under these circumstances a
bottle-neck type of diffusion would occur, and oxygen would diffuse rather slowly
through the bottle neck into large pores. The oxygen activity inside the large pore
would rise slowly and therefore also the rate of oxygen reduction. The first current
rise will be noticed, however, as soon as the first oxygen has passed the bottle neck.
Short time lags and long rise times are therefore likely. In order to calculate oxygen
reduction transients a detailed knowledge of the exact pore shape is required but this
 Oxygen reduction on rust-coveredsubstrates 357

knowledge is not available up to now. Further studies therefore have to concentrate

on the detailed morphology of the oxide scale, in order to obtain a more detailed
understanding of the transport of oxygen through rust layers.

SUMMARY
The results of this study have shown that oxygen is mainly reduced within the rust
scale at those oxide crystals, which are highly doped by Fe 2+ states, and not at the
metal surface. After a sudden jump of the oxygen activity in front of the rust
electrode the oxygen reduction starts nearly immediately, yet long rise times are
observed until the final reduction rate is reached. The rate of oxygen reduction
strongly depends on the number of Fe e+ states. On oxidized rust electrodes no E T R
are observed. The rise time is not affected by the rust reduction. This demonstrates
that the distribution of diffusion paths is not changed significantly by the reduction of
the iron oxides, but the area of electron conducting oxide crystals deep inside the
corrosion layer is significantly increased. The thickness of the rust layer also
determines the final rates of oxygen reduction but with increasing thickness the rate
of oxygen reduction decreases less than expected from a simple diffusion model. This
is explained by a shift of the reaction site to the outer boundary of the rust structure.
Transients of the reduction of [Fe(CN)6] 3 have confirmed the results described
before for the oxygen reduction. The reduction rate is extremely small on oxidized
rust layers. This proves that the E T R nearly exclusively happens within the oxide and
not at the metal surface. On reduced rust layers the reduction rate of [Fe(CN)6] 3 is
nearly identical to the rate of the oxygen reduction. This implies that the rate is
mainly controlled by the diffusion of the electro-active species into the rust film and
the area of electron conducting oxides.
The main question in the interpretation of the experimental data presented in this
study is the shape of the reduction transients. Very short time lags are observed
between a change in oxygen activity outside the rust layer and the onset of the current
rise but simultaneously rise times are quite long. Three models are discussed to
interpret these results. The transients may be explained by a distribution of simple
cylindrical pores. Very long pores of some mm length have to be considered in order
to interpret long rise times. Also a distribution of the diffusion coefficient of oxygen
is discussed, which may result from the diffusion through pores of some nm in
diameter (frequent oxygen l wall collision) or from the diffusion of oxygen through
F e O O H membranes. The diffusion coefficient of oxygen has to be some orders of
magnitude smaller than the one in water in order to explain the observed long rise
times. Last, but not least, the influence of the shape of the pores is discussed, which
may deviate significantly from a simple cylindrical shape. Bottle-neck type diffusion
may occur, but this transport cannot be described theoretically in an adequate
manner, as long as the detailed pore shape is unknown.
It should be mentioned that this work is quite important for the understanding of
the corrosion of steel in neutral electrolytes. For the first time it has been shown that
oxygen is reduced within the oxide scale and not at the metal/electrolyte interface.
This implies that the electronic structure of the oxides will strongly influence the
reduction of oxygen and therefore also the corrosion rate. Many alloys of technologi-
cal importance contain elements like Cu or Cr, which are dissolved during corrosion
and incorporated into the corrosion layer. 35 For of a homogenous solution of these
cations inside the iron oxide lattice, strong changes of the electronic conductivity
358 M. STRATMANNand J. ML/LLER

m a y b e e x p e c t e d . A s an e x a m p l e m a g n e t i t e ( F e 3 0 4 ) is a m e t a l l i c c o n d u c t o r , w h e r e a s
the spinel F e z C u O 4 is an i n s u l a t o r . A l s o c a t i o n s a n d a n i o n s o r i g i n a t i n g f r o m t h e
e l e c t r o l y t e like c a r b o n a t e s m a y b e p r e c i p i t a t e d inside the rust l a y e r a n d m a y
influence t h e r a t e of o x y g e n r e d u c t i o n at t h e o x i d e / e l e c t r o l y t e interface. T h e results
o f this p a p e r a r e o f significance also for t h e u n d e r s t a n d i n g o f the a t m o s p h e r i c
c o r r o s i o n o f i r o n a n d steel. 6 It has b e e n s h o w n t h a t in a large p o t e n t i a l r a n g e o x y g e n
is r e d u c e d u n d e r diffusion c o n t r o l . If n o w t h e t h i c k n e s s o f t h e e l e c t r o l y t e inside t h e
p o r e s d e c r e a s e s d u r i n g d r y i n g , t h e diffusion o f o x y g e n is a c c e l e r a t e d a n d the
r e d u c t i o n r a t e increases. A t the s a m e t i m e t h e c o r r o s i o n p o t e n t i a l is shifted
a n o d i c a l l y , h o w e v e r , a n d t h e o x y g e n r e d u c t i o n is no l o n g e r diffusionally c o n t r o l l e d
for v e r y thin e l e c t r o l y t e films, b u t its r a t e is d e t e r m i n e d by the c h a r g e t r a n s f e r
kinetics ( e q u a t i o n 10). 25'36 This rate is d i r e c t l y p r o p o r t i o n a l to the surface o f iron
o x i d e s e n r i c h e d in F e z+ a n d e x t r e m e l y high r a t e s o f o x y g e n r e d u c t i o n result, as
o x y g e n is r e d u c e d on a large a r e a c a t h o d e . If o x y g e n w o u l d be r e d u c e d o n l y at the
m e t a l / e l e c t r o l y t e i n t e r f a c e , m u c h s m a l l e r c o r r o s i o n rates c o u l d be a c h i e v e d . T h e rate
o f the a t m o s p h e r i c c o r r o s i o n is d e t e r m i n e d for thin films by t h e e l e c t r o n i c p r o p e r t i e s
o f t h e rust l a y e r a n d the c o r r o s i o n r a t e i m m e d i a t e l y d e c r e a s e s as t h e s e o x i d e s a r e
r e - o x i d i z e d . 25

Acknowledgements--These studies have been funded by the Deutsche Forschungsgemeinschaft as part of

the "Schwerpunktprogramm Korrosionsforschung". The financial support is gratefully acknowledged.

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