Professional Documents
Culture Documents
Applied
Surfaces
Physics A ""
9 Springer-Verlag 1985
Abstract. Five commercial steels ranging from the martensitic stainless steel containing
12% chromium to the superferrite containing 29% chromium, 4% molybdenum, and 2%
nickel have been studied by XPS. In addition, a pure iron-chromium alloy containing 7%
chromium has been investigated. Armco iron and pure chromium (99.99%) were included
as references. The formation of the passive films (or corrosion)occurred in deoxygenated
0.1 M NaC1 solution (pH = 5.6), from which the samples were transferred directly to the XPS
chamber under controlled atmosphere (Ar). Concentration profiles (at.-%) of the alloy
constituents in their oxidized and metallic states have been determined separately from the
measured XPS depth profiles. For c > 12% chromium the passive films have the following
structure: there is a depletion of Cr in the inner region, followed by an enrichment
(concentration maximum) in the central region of the films. The height of this maximum
increases, and its position shifts towards the surface with increasing chromium content in
the alloy. The outermost monolayers are rich in water and hydroxyl groups. Various
significant properties of the films change drastically at the critical chromium concentration
of about 12%. This behaviour is rather independent of the other components (Mo, Ni, Cu)
present in the alloys and is discussed in terms of a phase transition in the films which is
controlled by the chromium concentration.
Detailed investigations of blade failures in lowpressure steam turbine stages have indicated that the
breakdown of passivity is a critical step in the damage
process [1]. As a first step in understanding passivity
breakdown, it is necessary to gain insight into the
structure and chemical composition of the passive
films which form on relevant technical alloys under
conditions chosen to simulate those found in practice.
The relevant environment within the low-pressure
steam turbine stages is the Wilson zone where first
condensation occurs. The exact composition of the
P. Briiesch et al.
4% Mo, and 2% Ni. In addition, a pure ironchromium alloy containing 7% chromium has been
investigated. As end members, pure Armco iron and
pure chromium have also been studied. In order to
simulate the conditions found in practice, the surface
films which were studied by XPS have been formed
under open-circuit conditions and not under potentiostatic control and the chloride electrolyte was deaerated. From XPS measurements alternating with Ar-ion
sputtering, depth profiles have been obtained for the
main alloying elements in both their metallic and
oxidized states, as well as for oxygen. From a semiquantitative analysis absolute concentrations in at.-%
have been derived. The distortions of the depth profiles
originating from the finite sampling depth of XPS have
been corrected. By this procedure we obtained "differential concentrations" which approximately reflect
the true concentrations as a function of depth. To our
knowledge only "integral concentrations" of the elements in the passive films have been obtained in the
literature. Such "integral concentrations" comprise
contributions from all levels below the surface; the
presence of steep concentration gradients in the passive films implies that depth profiles derived on the basis
of "integral concentrations" are considerably
distorted.
Additional information about the chemical nature of
the passive films has been obtained by angledependent XPS measurements. In contrast to ion
sputtering, this method is nondestructive and serves to
check the reliability of the results obtained by ion
sputtering. The combination of the two methods
yields, not only a detailed characterization of the
surface films but also a correlation of film properties as
a function of chromium content in the different
alloys.
The paper is organized as follows: Sect. 1 describes the
experimental procedure, including materials, electrochemical measurements, XPS measurements and data
reduction. In Sects. 2 and 3 we present the results of the
1. Experimental
1.1. Materials
Table 1 contains designations and structures of the
materials studied.
The compositions of the samples given in Table 2 have
been determined by optical emission spectroscopy,
x-ray fluorescence and wet-chemical analysis. The
alloys were studied in a heat-treated condition consistent with normal use. The surfaces were polished in the
manner usually practiced in metallography. This involves polishing them with ever finer polishing
material, terminating with alumina of less than 0.3 gm
size and a mirror-quality surface finish.
Commercial
designation
Our
designation
Structure
1
1A
2
Armco iron
X20CrMoV12
1
Fe
7Cr
12CrlMo
X7CrNiCuNb
15 6 2
15Cr6Ni
4
5
6
7
X3CrNiMol7 13 3
X4CrMnNiMoN2646
29-4-2
99.99Cr
17Crl3Ni
26Cr6Mn
29Cr4Mo
Cr
ferrite
ferrite
martensite
precipitationPH
hardened
austenite
duplex
ferrite
ferrite
Fe
99.85
1A
93.00
92.52
7.00
7.48
85.52
84.36
11.9
12.60
0.92
0.53
0.66
0.62
0.48
0.48
0.28
0.30
75.28
74.86
14.8
15.81
1.65
0.95
5.2
4.92
1.53
1.34
0.8
0.81
65.98
65.67
17.8
19.03
2.3
1.33
11,5
10,89
62.04
61.42
25.9
27.53
2.22
1.27
42
3.95
64.24
63.58
29.0
30.83
3.6
2.07
2,44
2.30
99.99
99.99
.
.
INSERTION
Cr
Mo
Ni
.
.
.
Cu
Si
0.24
1.09
0.23
0.14
0.06
0.27
0.45
0.89
1.7
1.72
0.09
0.10
0.05
0.03
0.029
0.13
0.55
1.09
5.6
5.63
0.039
0.18
0,07
0,07
0.12
0.13
0.05
0.03
0.005
0.02
0.48
0.95
.
.
.
.
Mn
.
.
.
.
.
.
.
.
.
.
LOCK
.
.
.
.
.
.
.
.
.
.
.
.
ELECTROCHEMICAL
PREPARATION
-
Auxiliary
Nb
.
.
CHAMBER
Por t
Sampleholder
to U H V - P r e p a r a t i o n
C h a m b e r and
Photoelectron
Spectrometer
g Electrode
Electrode Electrolyte
Contact
Platinum
Counter - Electrode
Reference - Electrode
(Sat. C a l o m e l - Electrode)
to Potentiostat
Glass Tube ~ _ ~
IIIIIIIIIIIIIIIIII
I
4
solution to be admitted. The working electrode is
mounted on a sample holder, which is a rod that can be
moved horizontally from the atmosphere through the
preparation chamber into the vacuum system (UHV
preparation, clean-sputtering) and back to the chamber. A glass tube mounted with its opening beneath the
electrode holds a certain volume of the electrolyte
(0.1M NaC1, pH about 5.6, room temperature, made
with BAKER organic-free water). This volume can be
lifted so that the meniscus of the liquid contacts the
electrode when desired. The electrolyte is deaerated in
advance by argon bubbling. A slight argon overpressure in the chamber keeps oxygen out during the
electrochemical measurements and film-forming exposure. Said glass tube also holds the reference electrode
with Luggin capillary. The counterelectrode is a wire
(Pt) wound around the Luggin capillary's thick portion. In view of the very small volume of electrolyte
used, the "deaerated" condition may not meet the
most rigorous criteria but is expected to be consistent
with conditions in the Wilson zone.
The three electrodes were connected to a PAR 123
potentiostat to record dynamic current-potential
curves. Open-circuit potentials (OCP) were monitored
via the same system and recorded as functions of time,
up to periods of 5 to 10ks.
All electrochemical measurements were performed
after surface preparation of the mechanically polished
electrode samples by argon-ion sputtering in U H V
(10rain, 4keV, 12 gA/cm 2, incidence angle 45~ The
dynamic current-potential curves were recorded with a
scan rate of 100mV/s. This unusually high speed was
selected in order not to mask the effect of the pretreatment by growth of secondary passivation films. In the
same way we could avoid the accumulation of perturbing concentrations of metal ions in the electrolyte
originating from the active-dissolution region. Repeat
curves were always recorded after repeated cleansputtering in UHV. By continuous cycling steady-state
current-potential curves could be obtained. All sweeps
were started from the cathodic region. The potentiostat was set close to the hydrogen evolution potential
before the circuit was closed by the surging electrolyte.
The sweep was triggered one or two seconds after
the meniscus touched the electrode.
The results obtained in these potentiodynamic current
measurements were checked in separate experiments.
A much larger volume of the deaerated electrolyte was
used. The electrodes were rotating disks pretreated
mechanically and electrochemically. The curves were
recorded at 100mV/s, as before, and at the much
slower scan rates of 20 and 2 mV/s. Without discussing
these results in further detail at this point, we wish to
point out that, (i) at 100 mV/s the shape of all curves
(Fe, Cr, and six alloys) is essentially the same as
P. Brfiesch etal.
reported here for the sputtered samples, (ii) at slower
scan rates, essential new features do not arise in the
forward scans (there are cases of considerable hysteresis in the reverse scans following transpassive dissolution which are not relevant to the present work), and
(iii) most conspicuously, the typical features of passivation curves, viz., a region of high currents (active
dissolution) followed, beyond a Flade potential, by a
region of drastically lower currents, are not evident in
the curves recorded in chloride solutions; sections
where the characteristic is negative are either totally
absent or quite insignificant. Hence all discussion
based on the results of Fig. 9 will be unaffected by the
unconventional procedure adopted, by necessity, in
the electrochemical cell of Fig. 1.
Prior to the XPS measurements the eight samples were
exposed to the electrolyte for a period of 15h. The
conditions were exactly the same as described above,
when measuring open-circuit potentials; the electrodes
were truly at open circuit to simulate practical conditions. After the exposure time the electrolyte was
separated from the electrode and the latter was
carefully rinsed with deaerated BAKER water while
keeping the electrochemical cell under argon atmosphere. The electrode with the surface film was then
transferred directly into the XPS spectrometer by
using the fast insertion lock. Residual water remaining
on the electrode, and the argon introduced from the
electrochemical cell, were pumped off after transfer in
the UHV system.
1.3. X P S Measurements and Data Reduction
XPS measurements were carried out in a KRATOS ES
300 Electron Spectrometer in the FAT mode of
operation using MgK~I,2 excitation (1253.6 eV). The
base pressure was a few times 10-9tort. Binding
energies of electrons were determined using a gold
standard; the overall resolution was about 1.3eV.
Samples having a surface area of 5 16mm 2 and a
thickness of 2ram were used. Depth profiles were
obtained by sputtering with argon ions (4keV,
12 jxA/cm 2, angle of incidence 45~ The sputter rate
depends on the composition and will, in general,
change with depth. As will be shown below, the passive
films on the alloys to a large extent consist of Cr203.
We therefore determined the sputter rate of Cr20 3 by
using a film of known thickness prepared by reactive
sputtering in a Balzers rf/dc machine. The thickness of
the film has been measured by an Alpha-Step Tencon
instrument. The sputter rate was about 30A/min; a
similar sputter rate has been obtained for Fe203.
The absolute concentrations ei(z) of atoms i at depth z
from the surface have been evaluated by means of
argon-ion sputtering alternating with XPS measure-
merits. By definition
c,(z) = n~(~)
Zjnj(z)'
Cr20 ~
Cr
(1)
20s
60s
aT'
(2)
120s
where
Ris(z ) = n~176
(3)
(4)
where Ri~(t)=n~176
and fi~=Xijf. The escape
depths for Ni2p, Fe2p, Cr2p, Ols, and Mo3d are
estimated to be 13, 15, 16, 17, and 19/k, respectively
[4, 5]. For the practical calculations we have assumed
a mean escape depth 2-=15A for all 2'~. In our
experiments ~ - 0 . 5 A / s giving i , ~ 3 0 s . The second
term in (2) and (4) corrects for the deformation of the
depth profile associated with the finite sampling depth
[6] (2-effect). In XPS 95% of the total photoelectron
peak intensity originates from a layer of depth
6=32-sinO, where O is the take-off angle of the
electrons; in our case O = 90 ~ and fi = 45 A. Neglecting
the second term one obtains "integral concentrations",
as mentioned in the Introduction. At t = 0 the slope
/~(0) in (4) usually is not well defined. For this reason
and because of unavoidable contaminations present at
l"~ 300s
~'q~
670
675
680
600 s
685
Eki n (eV)
"
P. Briiesch et al.
a
Mo 6+
Mo
Fe 2 p 3 / 2
f . . . . uo~ ud'f . . . . . . .
0s
540
545
550
20s
1015
t020
1025
Eki n (eV)
1030
675
680
Ni~p
Os
720
725
F: kin ( EV )
Fe s* Fe a+
60s
Fe
180s
595
400
405
Ekin(eV)
90*
Fig. 3a and b. Evolution of(a) the M03d, and (b) the Ni2p XPS
60*
45*
(5)
50"
t5"
54O
545
550
Ekin(eV)
Ri(O)~
= I~
I~
(6)
+ I.~(0) '
where I~
is the intensity observed for the total
oxide (Cr 3+, Fe 2+ + F e 3+) and I.~(0) is the intensity
observed for the metal (Cr, Fe) we obtain
c~
e -~z/,z, sinO d z
Ri(O)~,z~ = o
c~(z)e-~:"si"~
0
(7)
where q(z) = c~
+ cm(z). It should be mentioned that
Ri(O)obs is independent of sputter-induced effects
because the intensities in (6) have been measured
before sputtering; on the other hand, Ri(O)c,lc is
affected by sputtering via the concentrations c~(z).
Figure 6 shows a comparison between the Ri(O)obs and
Ri(O)~alc- The agreement is satisfactory. It should be
mentioned, however, that less satisfactory results have
been obtained especially for the iron profiles in the case
of very thin films. The deviations resulting in these
cases are related to effects such as preferential reduc-
i'ox
R (O)/
7
I
i~
-1oo
4.O
~ |
-zoo ~
0.9
0.8
O.i
R (o)
t.0
!
-
-400
'
'
5ooi-.,/
~-
"%
-~ooF
I,
0.9-
2000
0.7
0
I
15
I
30
I
45
I
60
75
I
9000
2. Electrochemistry
The surface films studied in the present work by XPS
were produced at open circuit. For this reason opencircuit potentials (OCP) of the samples were measured
under identical conditions. This was done in order to
simulate the conditions existing in the Wilson zone and
also in order to obtain the data required for comparison of our present results with those obtained by
other workers at films produced under potentiostatic
control.
The OCP-time curves show spontaneous passivation
for the chromium-containing samples. The values of
potential and the trends in the potential-time curves
provide a measure for nobility (stability against corrosive action) of a given alloy.
Potentiodynamic curves were recorded in order to
have a frame of reference (active/passive region) for the
open-circuit potentials. The absolute values of the
currents measured can be taken as a measure of
reactivity (electrochemical dissolution). It should be
pointed out that the double-layer charging currents in
our systems are of the order of 5 gA.
4000
TIME
0.8-
29 Cr
4Mo
'
<~
I
Cr
~A
6000
8000
/ s
P. Brfiesch et al.
t
0
-100
-2oo
Fe
;A T c ~
__
~
4
5
12
t5
17
26
29
Cr tMo
Cr 6 Ni
Cr,3Ni
Cr 6 M n
Cr 4Mo
++
J
+(~++~/""
+ . . - ~
iI
i
++~"/" J ~ " 7 ~
.........
: -300
>
E
... -400
o -500
-600
-700
t0 t
t02
TIME
~/PA/r
t03
/ s
~t500
/.." o
[/
..Tf ~
-500
500
t000
t500
U / mY vs SCE
-500
i/pA/cm2:1500
-t000
500
t04
/(ig)
=~
, i
3. X P S Results
7""
-tO
.~,~..~
.............
:56o
o
""J
500
1ooo
t5oo
U / mV vs SCE
-500
9
/k----
Ccr(t)
( at %)
50
.....
.o
._+';.'-:.
'_,;./2
. . . .
. . . . . . . . .
'10
I
0
40
I
20
I
80
I
t20
t80
I
40
60
90
Sputter time
I
(s) 5 0 0
Approx, depth
(~) t50
//~
600
/,,
I ,,~
300
/k---~
(t) i a
L-
(at % )
..../'
70
,i
60
50
40 ~
3oy / / /
"\\\~
/ Fe~
2O 10
I
40
80
4~.0
20
40
60
0
Ci
I -..we"
90
~ql---
]<600L-i/
I ~_
300
//--~
(t)
(at % ) - -
._..._.~/.'---~
-gO6O
5O
/"(
4O
Fgx
3O
2O
'
Or..
-"
l0
. . . .
crT-
t----/r
0
j
40
I
80
I
t~-0
I
//
600
I],,_
O
20
40
60
90 Approx. depth (~) t50 500
Fig. 1la and b. Depth profiles of (a) sample 1 (pure Armco iron)
and (b) sample 2 (12.6 Cr, 0.5 Mo, 0.6 Ni). Fe m, Cr'~: metallic iron
and chromium, Fe ~ = Fe z + + Fe 3 +, Cr ~ = Cr 3 +
10
P. Brfiesch et al.
lk-'--
cl (t)
ci (t) ]
(el % }F
/
(at % ) ' a
I/---"
,,,,-.---
70
60
60
50
50
,'I~
,~ F=m
40
40
30
20
%.
t0
0
I
cox
zog^i
Fl
~...~j.--.
Cr
2O
4.0
60
. . . . .
"r
t 8 0 Sputter
300
c; It}
80
i/-'-
I.
t20
%%0
20
40
60
90
(e) 3(~0
I
Approx. depth(n) t 5 0
I:
300
let % )
70
60
70
//
60
,,
40
(at % )
I~. w-.f.
--'I"-=- / / ~
time (s) ~ 0 0
600
1
//
I
c, ~
I\
IoI-/~ ".~-"
VJ'~Y-,_3"-.,--..,_.,
//---
//----
cl (t)
30
.Fe~
J
t~....~.-==~-~'~
~'F."
50
Fern
40
40
3~ / . / y c , ' "
.
3 0
--
. . . .
,i
t...
c~
20
rm
..-----~--
I J L-:~_
0
40
80
J_
420
20
40
60
t "'-.+-..,
I
I
t80 Sputter time (s) 300
I
/;v; :->_..
I ' " I " *---~-.1~
....
L5,,4 ",J
600
l/
~_
300
Fig. 12. Depth profiles of(a) sample 3 (15.8Cr, 0.9Mo, 0,4 Ni)
and (b) sample 4 (19 Cr, 1.3 Mo, 10.9Ni). Fe'~, Cr": metallic iron
and chromium, Fe~
2+ +Fe 3+, Cr~
3+
2o
40
60
80
420
600
ii
i=
]00
c; (t)
(It
'&
90
.f"
80
70
60
50
40
/F--
40
30
r,~ cSx
20
10
1
0
I
/'"~
40
l
20
"- ~
80
I
40
.. 4.---,~, . . . . . .
t20
I
60
4---
Fig. 13a~z. Depth profiles of(a) sample 5 (27.5Cr, 1.3 Mo, 4Ni,
5.6Mn), (b)sample 6 (30.8Cr, 2Mo, 2.3Ni), and (c) pure
chromium. Fem, Cr": metallic iron and chromium.
Feox=Fe z+ +Fe 3+, Crox=Cr 3+
11
Co It) /
tt---
,.,;3 a
40
1
20
BO
I
40
t20
t 8 0 Spulier
I
60
I
90
time (t) 3 0 0
I
Approx. depth(~) ~50
;;__
600
II
300
#---
c.o"(t )
(at %1
t.4
-/,--
t.2
t.0
./
0.8
.,,,m
f t . ~ |
0.6
0.4
,' ! - -
0.2
/ I
I I I
4080
I
t20
20
40
60
c/
0
c~p(t)
(at %
I
I
1 8 0 Spulter time Is) 300
I
I
9 0 Approx. depth (~) t 5 0
/,L_
600
I;
I_
300
#---
44
tZ
t0
8
6
/...----~>- . . . . . . . . . . . . . . . . . . .
l/_ _._'tit__
2
'I
0
I
I
40
I
20
I
80
I
40
I
420
I
60
I
I
t 8 0 Sputter time (e) 3 0 0
I
I
9 0 Approx. depthll) t 5 0
H--600
l/ I .~
300
Fig. 14a-c. Depth profiles of (a) oxygen, (b) metallic molybdenum, and (c) metallic nickel of selected samples @ pure
12
P. Brtiesch et al.
I1
12
0ts
2.0
1.8
t.6
t.4
t.2
t.0
0.8
0.6
0.4
0.2
t5
30
45
60
75
90 O
4. Discussion
qualitatively similar to the profiles observed for airoxidized iron-chromium alloys [21]. Only very few
indications are found in the literature for a minimum in
the chromium concentration at the interface between
the passive film and the underlying alloy [18]. A
possible explanation for this observation is discussed
at the end of Sect. 4.3.
Since in Figs. 11-14 we show absolute concentrations
of the elements, one might be tempted to derive the
stoichiometry of the passive films as a function of depth
below the surface. This is, in principle, possible, but it
should be kept in mind that the observed stoichiometry may deviate considerably from the true stoichiometry due to sputter-induced effects, in particular to
selective sputtering of oxygen. We have estimated the
stoichiometry in the central region of the surface films
(i.e., at the maximum of the Fe ~ or Cr ~ profiles in
Figs. 11-13) and have found a composition M20~
(M2= Fe~176
where x~1.8-2.3 for % < 2 0 %
and x ~ 3 for % > 2 0 % . These results agree qualitatively with Frankenthal's sputter experiments of Fe20 3
as discussed at the end of Sect. 1.3. To find the true
composition may require the use of significantly milder
sputter conditions. On the other hand, the ease of
sputter-induced reduction of the films with less than
20% Cr is a further indication for their insufficient
chemical stability.
Nickel and copper have been observed only in the
metallic state; these elements are strongly depleted in
the passive films. On the other hand, we observe an
accumulation of metallic nickel in the interface region
between the passive film and the alloy; this accumulation is most pronounced in the nickel-rich alloy 4
containing 13% nickel. An accumulation of nickel in
the interface region has also been observed by
Olefjord [22].
As expected, metallic molybdenum is strongly depleted
in the passive films. Molybdenum in oxidic states is
present before sputtering, similar to the results of
Olefjord and Brox [5]. The distribution of these species
in the passive films cannot be deduced since argon-ion
sputtering leads to instantaneous reduction [11-13].
An enrichment of molybdenum was found in the
passive film by Goetz and Landolt [23] for an alloy
containing 11% Mo; this concentration is considerably higher than the molybdenum concentrations in
our samples, so that a direct comparison with these
results is not possible. In contrast to Olefjord [22] but
in agreement with Lumsden and Staehle [24], we do
not find an enrichment of metallic molybdenum below
the passive film. This might be due to the fact that it is
difficult to detect such accumulations in narrow
regions by a method involving sputtering; in addition,
in comparing different results it should be borne in
mind that the preferential dissolution of alloying
13
(, a
+100
t.5 "-"...............
I
I
ul
0
-I00
>"
E
cn
-300
.%.
~0.5
-5oo
Z/
0
0
- - t
8
i
24
t6
i -70 0
52
ACc,
60.
12
5(> 9
40
I0
30
,o I j ,
0
~)
to
o,o
30
20
c,C':~176C
--.I---:
t.O
Fe 3+
Fe2++ Fe 3+
0.9
0.8
0.4
0.7
0,2
0,2
--,,4"
~
~'"
0
Ccrit.
I ~
10
20
30
C c r ( a t % )lnalloy
14
Sect. 4.1, the latter films do not constitute passive films,
since they were formed under OCP conditions not
leading to a point in the passive region at long
exposure times. This statement applies in particular to
the films formed on pure iron and alloy 1A whose film
thicknesses are not well reproducible and probably
also depend on the electrolyte [28]. The film thicknesses of samples 1 and 1A plotted in Fig. 16b are
estimated mean thicknesses with an uncertainty of at
least __20 A. We do not believe, however, that these
films were formed only after the end of exposure of the
samples to the electrolyte, because all manipulations
were carried out under controlled conditions (transfer
of the sample in argon atmosphere). We cannot rule
out that precipitation of corrosion products from the
solution has contributed to the films found on samples
1 and 1A and is responsible for some of the irreproducibility in film thickness. On the other hand, it is known
that the passive films (c>%it) formed under OCP
conditions after a long exposure time (about 15 h) are
quite stable [29], and for this reason their film
thicknesses are expected to be well reproducible and
unaffected by precipitation effects. At this point it
should be mentioned that a qualitatively similar
behaviour of film thickness as a function of chromium
concentration has also been found for pure ironchromium steels by means of ellipsometric
methods [30].
Figure 16c shows the normalized cation concentration
ofCr 3+, that is the ratio R = Cr~
~ + Fe~ as well
as the normalized concentration of Fe 3+, that is
P = Fe 3+/(Fe 2+ + Fe 3+), in the passive films, as functions of chromium concentration c in the alloys. The
values of P have been determined by deconvolution of
the Fe2p3/2 spectra before argon i o n sputtering
(Fig. 4a). Alloy 2 with c = 12.6 at.-% Cr is just at %~t
9 and R-~ 40%. For the true passive films with c > corotwe
obtain R > 50% in agreement with Fischmeister et al.
[31] and with Asami et al. [28]. A qualitatively similar
behaviour for P(c) has been found by Asami using
1N H2SO 4 as the electrolyte [32]; his absolute values
are, however, significantly different from our values,
possibly because of the different electrolyte or the
different method used for data evaluation. The fact that
alloy 2 is just at the limit between active and passive
behaviour is also reflected in Fig. 7 (compare the
corresponding remarks made in Sect. 2).
The general behaviour of the normalized concentration of Fe a +, that is of P(c), can be explained if one
assumes that Fe 3+ ions lost from the film by dissolution in the electrolyte are partially replaced by Cr 3
supplied from the alloy by diffusion. Note the relatively large deviation of the data point for sample 5
containing 27.5 at.-% Cr and 5.6 at.-% Mn (Table 2).
This deviation would be expected under the assump-
P. Brfieschet al.
tion that the substitution of Fe by Mn occurs mainly
in the divalent state. According to Pourbaix [33] the
system is just at the boundary between Mn 2+ and
Mn 3+.
It is very remarkable that the functions ACc~(C), d(c),
R(c), and P(c) shown in Figs. 16b and c are largely
independent of alloy structure and the presence of the
alloying elements Mo, Ni, and Cu (Table 2). This is
understandable if one remembers that Ni and Cu are
very strongly depleted in the passive films and that Mo
occurs only in very small quantities. The functional
dependences shown in Figs. 16b and c are therefore
almost completely determined by the main elements
iron and chromium. Deviations are expected to occur
only if the alloying elements are present in the oxidic
state in appreciable quantities, as is the case for
manganese in sample 5 (Fig. 16c).
15
is taken to mean resistance to pitting and crevice
corrosion in aqueous chloride solutions.
It is known that resistance to pitting corrosion is a
complex nonlinear function of both the chromium and
molybdenum contents. For example Horvath and
Uhlig [39], using the pitting potential as a measure of
pitting resistance, showed that the pitting resistance
increased very sharply, for Fe-Cr alloys, at a
chromium content of about 30%. They also showed
that increasing nickel contents in the range 0-60%
increased the pitting potential only very slowly, but
that small molybdenum additions had a very large
beneficial effect. Subsequently, the synergistic effect of
both chromium and molybdenum has been shown
repeatedly [40-44]. For some compositions of
F e - C r - M o - N i alloys (and alloy 5 would be expected
to be with this range), N additions can further increase
the pitting potential [45, 46]. No significant increases
of the pitting potential have been observed by additions of V, Si, Co, A1, Ti, Ag, Ce, La, Nb, Zr, and Cu
[40]. However, it has been often argued that the pitting
potential is in fact a poor predictor of actual corrosion
behaviour and that for this purpose the protection potential is to be preferred [44, 4749]. Unfortunately, there is less data available to record how the protection potential depends in composition. Although
a correlation between the pitting and protection potentials is expected, it has been shown [44] that alloys
with very noble pitting potentials can have quite active
protection potentials. Nevertheless, these data [44]
also indicate the beneficial effect of both chromium
and molybdenum as well as the synergistic effect when
both elements are present together in the alloy.
These electrochemical studies can be summarized as
predicting an increased resistance to pitting corrosion
as the chromium and molybdenum contents are increased. These can be correlated with observations of
corrosion behaviour during exposure tests which show
that alloys with higher chromium and molybdenum
contents are generally able to withstand higher temperatures [50, 51] and higher chloride concentrations
[43, 51-55] before becoming susceptible to pitting or
crevice corrosion. The actual rates of corrosion during
passive corrosion are usually very low and therefore
are very rarely measured. For these reasons the
expression % Cr + 3.3 x % Mo has evolved as a useful
guide to the corrosion resistance of stainless steels.
The stainless steels used in this study have been ranked
by this means, with the expectation that a higher
number reflects a higher corrosion resistance, manifest
by the ability to resist pitting in more concentrated
chloride solutions at higher temperatures.
The solution to which the steels were exposed was
chosen with the expectation that all the stainless steels
would exhibit passive corrosion behaviour with the
16
P. Br/iesch et al.
Table 3. Passive current densities for a wide range of stainless steels under a wide range of environmentalconditions
Material
Environment
Passive current
[ga/cm 2]
Scan rate
[mV/s]
Ref.
0.8-3
0.2-2
0.4-4
0.5
0.3
2-8
2-9
10
2
0.3
0.2
0.2
0.2
0.2
0.2
0.2
1
1
57
58
58
59
59
60
61
5
62
Appendix
Depth profiles have been obtained using the following procedure.
For photoelectrons of atoms i in state s the intensity is given by
17
surements. We also thank Drs. R. K6tz, S. Stucki, P. Pfluger, and
H. J. Wiesmann for interesting discussions and Dr. H. R. Zeller
for critically reading the manuscript. In addition we thank Prof. I.
Olet]ord, Prof. H. Fischmeister, and Dr. U. Roll for valuable
discussions during Conference meetings and Prof. H. J. Grabke
for providing us with the Fe7Cr-alloy.
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cc
and
oo
O
zl~,i~
0 -Ii~Kiln ~0 ~ e o
0
0
d z -_ _ K~n~2~s
o Idz)
Ri~(z)=ni
we obtain
1
~o
dz
! f(z')dz'= --f(z)
gives
18
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