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Corrosion Science, Vol. 19, pp.

3 to 14
Pergamon Press Ltd. 1979. Printed in Great Britain

A N X-RAY PHOTO-ELECTRON SPECTROSCOPIC S T U D Y ON


THE ROLE OF M O L Y B D E N U M IN INCREASING THE
CORROSION RESISTANCE OF FERRITIC STAINLESS
STEELS IN HC1
K. HASHIMOTO,K. ASAMIand K. TERAMOTO
The Research Institute for Iron, Steel and Other Metals, Tohoku University, Sendai, Japan
Abstract--X-ray photo-electron spectroscopy has been used to investigate the correlation between
composition of surface films and the beneficial effects of molybdenum addition to high purity, 30Cr
ferritic stainless steels in improving the corrosion resistance properties in HCI. It has been found that
the passive films formed consist mainly of hydrated chromium oxy-hydroxide and the composition
of the films on 30Cr and 30Cr-2Mo stainless steels is essentially the same, except for the existence
of a small amount of hexavalent molybdenum on the latter steel. The surface film formed in the
active region contains a large amount of hexavalent molybdenum. The beneficial effects of molybdenum have been interpreted as follows: molybdenum eliminates the active surface sites through
the formation of molybdenum oxy-hydroxide or molybdate on these site, on which it is difficult to
form the stable passive film. This leads to the appearance of a homogeneous steel surface and to the
formation of a homogeneous passive film.
INTRODUCTION

HIGH PURITY, high chromium ferritic stainless steels with molybdenum b_ave been
developed as corrosion-resistant alloys, resistant in particular, to halide solutions.
Since ferritic 30Cr stainless steels with high hot-workability have easily been prepared
by vacuum-calcium refining instead of electron-beam refining, x the commercial use
of the ferritic stainless steels is further stimulated. The improved corrosion resistance
is derived mainly from the addition of molybdenum. The beneficial effect of molybdenum is further increased by increasing the chromium content in the steels, z
Horvath and Uhlig 3 have explained the beneficial effects of molybdenum and
chromium in chloride solutions in terms of competitive adsorption of oxygen and
chloride on the steel. It has been reported by many investigators that molybdenum
increases the thickness of passive films on the steels 4,5 and changes the protective
properties of the passive films by including molybdenum. 5-s However, Lumsden
e t al.S, 1 in reporting the Auger electron spectroscopic study have stated that the
improved corrosion resistance obtained by the addition of molybdenum cannot be
explained by its enrichment in the protective film. As has been reported previously, n
the composition and thickness of passive films formed on 30Cr and 30Cr-2Mo ferritic
stainless steels in 0.5 M H2SO4 are essentially the same as each other.
The present work herein has been carried out to determine the role of molybdenum
in improving the corrosion resistance of high purity 30Cr ferritic stainless steels in
HCI. X-ray photo-electron spectroscopy has been applied to determine the composition and thickness of the surface film formed on the steels as a function of polarization
potential.
Manuscript received 5 October 1977; in revised form 15 March 1978.

K. HASHIMOTO,K. ASAMIand K. TERAMOTO

EXPERIMENTAL METHOD
High purity Fe-30Cr-0-2Mo ferritic stainless steels were prepared by vacuum-calcium refining.
The steels were rolled and then cut to specimens of 20 x 20 x 2 mm for the electrochemical polarization measurement and 16 x 6 x 0.4 mm for X-ray photo-electron spectroscopy. The chemical
compositions are given in Table I. The specimens were solution-treated for 1800 s at 1143K in
vacuum and subsequently water-quenched. Prior to polarization, the specimens were mechanically
polished with emery paper to No. 2000, rinsed ultrasonically in carbon tetrachloride, cleaned with
methyl alcohol and finally dried by air blasting.
TABLE 1. CHEMICALCOMPOSITIONOF FERRITICSTAINLEssSTEELS(wt ~/~
Specimen
30Cr
30Cr-lMo
30Cr-2Mo

Cr

Mo

Mn

Si

30.8
31.2
29.6

-1.00
1.71

0.01
0.01
0.023

0.01
0.01
0.13

0.003
0.010
0.004

N
0.007
0.007
0.0097

O
0.0039
0.015
0.0012

Polarization was carried out in 1M HCI which was open to the air. Anodic polarization curves
were measured after holding the potential for 60 s at each setting, which was successively increased
in steps of 20 mV from the corrosion potential. In order to clarify the effect of the molybdenum
addition on the rate of passivation, the change in current density with time was measured after
abrading the specimen surface during anodic polarization at various constant potentials. The abrasion of the specimen surface was performed by a rotating abrasive rod made of a resin solidified with
No. 2000 silicon-c,arbide powder which was attached as a bit to a bench drilling machine. A constant
weight was applied to the arm of the drilling machine. The steel specimen was embedded in a resin,
so as to expose the area of specimen smaller than the cross-section of the abrasive rod in the electrolyte. Immediately before the cessation of abrasion the measurement of current was commenced by
a digital memory with a clock rate of 1 ms/word through a logarithmic amplifier.
Surface films were formed potentiostatically by polarization for 3600 s at various potentials.
After removal from the electrolyte, the specimens were rinsed with de-ionized water and placed
immediately in the vacuum system. X-ray photo-electron spectra were measured by AEI-ES200
electron spectrometer with Mg Kctl.2 excitation (1253.62 eV). Binding energies of electrons were
determined by a calibration method described elsewhere.12,~3 A quantitative determination of the
composition and thickness of the passive films and substrate steels by X-ray photo-electron spectroscopy was carried out by the same method as reported in the previous papers 1~,x5by using integrated
intensities of Fe 2pst2, Cr 2pair, Me 3d, O ls, CI 2p and C ls spectra scanned in the narrow bindingenergy ranges. Photo-electron-cross-section-ratios used for the quantitative determination have
been reported previously,n except for CI 2p electrons. The ratio of photo-electron cross-section of
the latter to the O ls electrons was estimated by using integrated intensities of X-ray photo-electron
spectra of sodium chloride, sodium chromates and sodium tungstate and was 1.017.
EXPERIMENTAL RESULTS
Figure 1 shows anodic p o l a r i z a t i o n curves o f ferritic 30Cr stainless steels cont a i n i n g 0 - 2 w t % M o in 1 M HCI at 293 K. Because of the high c h r o m i u m content,
a n a b r u p t rise in the c u r r e n t caused by pitting does n o t appear o n these steels u p to
the potential in the transpassive region. 5 The a d d i t i o n of m o l y b d e n u m decreases the
c u r r e n t density in b o t h the active a n d passive regions. The current density for the
30Cr steel in the passive region is fairly high, a n d hence electrochemical passivation
o f the steel w i t h o u t m o l y b d e n u m also takes place b u t is incomplete i n the aggressive
hydrochloric acid.
The passivation behaviour for the 3 0 C r - 2 M o steel has been c o m p a r e d with that for
the 30Cr steel, t h r o u g h the change in the c u r r e n t density with time, immediately after
a b r a d i n g the steel surface d u r i n g anodic p o l a r i z a t i o n in 1 M HCI as s h o w n in Fig. 2.
The c u r r e n t density in the passive region for b o t h steels decreases asymptotically
due to film f o r m a t i o n . A sharp decrease in the c u r r e n t density with time corresponds

Spectroscopic study on the role of molybdenum

lO3

11~
I

HCl , 20*C

~10 2

~ 3 0 C r -IMo
YOCr

I0

i lO-t

:r-2Mo

IG
-03

0.5

Potential,

1.0

1.5

V (5CE)

FIG. 1. Anodic polarization curves of Fc--30Cr-2Mo ferritic stainless steels in


1 M HCI.

104

lo 3
E

5
~ I 0,~

00.l

0.2 04 04 0.5 0.6 0.7 0.8 0.9


Time

I0 20 30 40 50 60 70 80 90 100
SeC

FIG. 2. Change in current density with time after abrading the steel surface during
polarization in 1 M HCI at various potentials relative to the saturated calomel electrode
which are indicated in the figure.

to rapid decrease in the reactivity of bare surface i.e. rapid formation of a protective
film. Immediately after removal of the rotating abrasive rod from the steel surface, the
film formation takes place simultaneously with the wetting of the surface with the
electrolyte. Accordingly, the current density observed immediately after cessation
of the abrading does not correspond to the reactivity of the steel itself without the
surface film. It is assumed from the extrapolation of the current density vs time

K, HASmMOTO, K. ASAMI and K. TEKAMOTO

curve to the time zero that the reactivity of the bare surface for the 30Cr-2Mo steel
is not greatly different from that for the 30Cr steel or even higher than that for the
30Cr steel. The current density for the 30Cr-2Mo stainless steel decreases rapidly
with time, and hence the addition of molybdenum to the ferritic stainless steel increases
the rate of protective film formation in 1 M HCI. In particular, at -- 0.3 V (SCE)
which is close to the Flade potential in the passive region, the current density of the
30Cr-2Mo stainless steel decreases continuously and finally shows negative current
at 8 s. On the other hand, at the same potential, the 30Cr stainless steel exhibits a
current density of ca. 4 l0 s A/m a but suddenly decreases after 25 s to the order of
3 102 A/re. 2
X-ray photo-electron spectra were measured for the 30Cr-2Mo and 30Cr stainless
steels after polarization for 3600 s in 1 M HCI. The Fe 2p8/~, Cr 2p31~ and Mo 3d
spectra consisted of two peaks corresponding to the oxidized state in the surface
film and the metallic state in the substrate steel. The Fe 2p~/2 spectrum for the oxidized
state was further composed of spectra for ferrous and ferric states} 6-~s Chromium
in the passive film was in a trivalent state. 13 The majority of oxidized molybdenum
was in the hexavalent state, but a small amount of tetravalent molybdenum was also
included in the pasive films. 19 In the O Is spectrum, a low binding energy peak
assigned to oxygen in metal-O- metal bond (OM oxygen) was superimposed upon a
high binding energy peak for oxygen in metal-OH bond and/or bound water (OH
oxygen)Y T M The latter two kinds of oxygen could not be separated on the O ls
spectrum. A small amount of chloride ions was also found in the surface film. After
the integrated intensities were separately obtained for oxidized and metallic states of
Fe, Cr and Mo and for OM and OH oxygen, a quantitative, simultaneous determination of the composition and thickness of a surface film and the composition of the
substrate steel immediately under the surface film was performed.
Figure 3 shows the thickness of surface film as a function of polarization potential.

-o

O~Q

?
3

Q.
0

=.

30Or

30Cr-2Mo
in IM HCI

4
tJ

-0.6

-0.4

-02

0.2

0.4

0.6

0.~

I.O

Potential , V (SCE)

FIG. 3. Change in the thickness of surface film formed on 30Cr and 30Cr-2Mo ferritic
stainless steels by polarization at various potentials for 3600 s in I M HCI.

Spectroscopic study on the role of molybdenum

The thickness of passive film increases gradually with an increase in polarization


potential in the region higher titan 0.2V (SCE). There is no difference in the thickness of passive films on the 30Cr-2Mo and 30Cr stainless steels. Consequently, the
addition of molybdenum to the ferritic stainless steel does not affect on the growth of
the passive film.
The weight fraction of cations which constitute the surface films on the 30Cr2Mo and 30Cr stainless steels is given as a function of polarization potential in Fig. 4.
In the passive region, a remarkable enrichment of chromium occurs in the passive
films on both stainless steels through selective dissolution of iron. Oxidized molybdenum is also found in the passive film on the 30Cr-2Mo stainless steel, but the
ratio of molybdenum to chromium in the passive film is smaller than that in the bulk
steel. Therefore, molybdenum is deficient in the passive film. The ratio of ferrous
species to total iron species decreased with an increase in polarization potential in the
passive region but was of the order of 0.4 throughout the passive region. Because
the content of oxidized molybdenum is small, the cationic compositions of the passive
films formed on both 30Cr-2Mo and 30Cr stainless steels at a given potential in 1 M
HCI are not essentially different from each other. Accordingly, the addition of
molybdenum to the ferritic stainless steel does not change the composition of passive
film formed in hydrochloric acid.
The most interesting feature of film composition in the active state is the existence
of a large amount of hexavalent molybdenum in the surface film on the 30Cr-2Mo
stainless steel as seen in Fig. 4. The amount of the hexavalent molybdenum species

l.o

I.

o.8
~ o.e

.~ o.4

~o.e

r-

'\!!-

-0

-0.4

-0.2

0.2

Potential ,

"

'--0--0--0--e--0--

0.4

0.8

1.0

Y (5CE)

FI~. 4. Weight fractions of cations in surface films formed on 30Cr and 30Cr-2Mo
stainless steels in I M HCI. Asterisks indicate results for the specimen which was
polarized at -- 0.4 C (SCE) for 3600s and subsequently passivatexl at + 0.2 V (SCE)
for 3600 s.

K. HASmMOTO,K. As~a~nand K. TERAMOTO

in the active region changes similarly to the current density with potential. The ratios
of chromium to iron in the surface films formed at a given potential in the active
region on both 30Cr-2Mo and 30Cr stainless steels are nearly equal. As has been
reported previously, ~s this ratio in the active region was also nearly the same as that
in the bulk steel. Consequently, the hexavalent molybdenum preferentially remains,
without dissolving, in the surface film in the active region on the molybdenumbeating ferritic stainless steel as is also the case with trivalent chromium in the
passive region. An EPMA examination reveals that molybdenum was not localized
but distributed uniformly, regardless of microstructure, in the surface film formed
on the 30Cr-2Mo stainless steel polarized in the active potential region.
Immediately after polarizing the 30Cr-2Mo stainless steel for 3600 s at -- 0.4 V
(SCE) to form a large amount of hexavalent molybdenum on the specimen surface,
the polarization potential was switched to + 0.2 V(SCE) and polarization was further
continued for 3600 s to form a passive film. The results of analysis of this specimen
are also included in Figs. 3-5 as indicated by asterisks. The thickness and composition
of the passive film thus formed coincide exactly with those of the films on stainless
steels polarized only at + 0.2 V (SCE). It can be said that, when the stainless steel
dissolves rapidly in the active region, the rate of dissolution of molybdenum is slower
than those of iron and chromium, with a consequent enrichment of hexavalent
molybdenum species on the steel surface. However, when the active dissolution is
stopped by switching the potential to the passive region, the majority of the molybdenum species formed is dissolved into the electrolyte prior to the passive film formation. Accordingly, the protective quality of the hexavalent molybdenum species is
not high as compared with that of the passive film.
Figure 5 shows the composition of substrate steel immediately under the surface

o
30Cr
~ 30Cr-2Mo
~
in IM HCl

0.8
eo-

'

O---|~----'-8=!

.I

g o.4
'-- --i'~

-i---

--I~

0 ~___~___4L.----'-----0

-0.4

-02

-- -'% -t--

| -t-

A-;

_e_e_e_e_e_'--

0.2
0.4
Potential , V ( $ C E )

0.6

0.8

I,0

FzG. 5. Composition of substrate steel immediately under surface film. Included


for comparison is composition of bulk steels which is indicated by dotted lines.

Spectroscopic study on the role of molybdenum

film. The dotted lines indicate the result of chemical analysis of bulk steels. In spite
of significant enrichment of chromium in the passive film, the compositions of
substrate steels immediately under the passive film are nearly the same as those for
bulk stainless steels. This fact also indicates that the enrichment of chromium in
the passive film occurs through selective dissolution of iron and molybdenum.
Numbers of OM and OH oxygen per cation in the passive film are given as a
function of polarization potential in Fig. 6. The amount of OM oxygen does not
~2

!__[.

__L._!
.

0
~

u~

!"
zo

T
!

.0.6

-0.4

-0.2
0
~2
0.4
Potential , V ($CE )

~6

~6

~0

FIG. 6. Numbers of OM (in metal-O-metal bond) and OH (in metal-OH bond and
bound water) oxygen per cation in the surface film formed on 30Cr and 30Cr-2Mo
stainless steels in ! M HCI.

significantly change with polarization potential, while the amount of OH oxygen in


the passive film on the 30Cr-2Mo steel tends to decrease with an increase in polarization potential. The OH oxygen consists of oxygen in metal-OH bond and bound
water which are indistinguishable in the O ls spectrum. Since the number of OM
oxygen per cation is almost independent of polarization potential and since the average
valence of cations does not become lower with increase in polarization potential, the
decrease in the number of OH oxygen arises from the decrease in the concentration
of bound water in the passive film with the increase in polarization potential. The
concentration of bound water in the surface film is given as a function of polarization
potential in Fig. 7. The concentration of bound water in the surface films formed in
the active region on the 30Cr-2Mo stainless steel is low. With an increase in potential

K. HASHIMOTO,K. ASAMI and K. TERAMOTO

10

in the passive region, the concentration of bound water increases once and then
decreases through the maximum. The concentration of bound water in the passive
film on the 30Cr stainless steel varies widely from potential to potential and showed
poor reproducibility.

O - -

30Cr-2Mo

(~

....

I-

in I M H C l

.Q

ellA_
-0

FIG. 7.

-0.4

o
-0.2

0
02
0.4
Potential , V ( $ C E )

0.6

0.8

Number of bound water per cation in the surface film formed on 30Cr and
30Cr-2Mo stainless steels in 1 M HCI.

Small amounts of chloride ions were found in the passive film. The concentration
of chloride ions was not different in both passive films on 30Cr and 30Cr-2Mo
stainless steels and tends to decrease slightly with the increase in polarization potential
in the passive region.
From the above analytical results the average composition of the passive film can
be estimated, for example on the 30Cr-2Mo stainless steel as
(.Felol.!1 Feo.12ui ",-'0.75c'IIIMoVl2). C10.14 Oi.02 (OH)0.77. 1.09H20
at 0.2 V(SCE),
and
II

HI C . I I I
VI
~'0.70 Mo.ol)
C1o.12 Ol.13 (OH)0.52" 0.4H20
(Fro.J3 Feo.16

at 0.8 V(SCE).
Consequently, the passive films formed on both 30Cr-2Mo and 30Cr stainless steels
in 1 M HClconsist mainly of hydrated chromium oxy-hydroxide, CrOx(OH)a_2.~'nH20.
An example of the average composition of the surface film formed in the active region
is:
11

I~-I11

c-Ill

Vl

(Feo.22 1~0.37 -~0.27 M0o.14) C1o.02 O1.3o (OH)0.46" 0.61H20


at -- 0.55 V(SCE).
In general, with an increase in the content of total iron in surface films, the content

Spectroscopic study on the role of molybdenum

11

of OM oxygen and the ratio of ferric species to total iron in the film tend to increase
and both OH group and bound water decrease.

DISCUSSION
Scatter appears in the concentration of bound water in the passive film on 30Cr
stainless steel. Some of the bound water analyzed may exist on the film surface as
adsorbed water. If a large amount of water is adsorbed on the film surface, the film
thickness analyzed must be affected and vary widely similarly to the concentration of
bound water analyzed. The film thickness and the concentration of bound water in
the surface film on the 30Cr stainless steel in the active region show some scatter.
This scatter arises mainly from the adsorbed water, suggesting non-uniformity of the
surface on the 30Cr stainless steel in the active region. Conversely, the major proportion of bound water in the passive films on both stainless steels is not adsorbed
water but true bound water in the passive films, inasmuch as the thickness of passive
films on both steels coincide with each other and change continuously with polarization potential. The concentration of bound water in the passive film formed on the
30Cr-2Mo stainless steel tends to decrease with an increase in polarization potential.
This tendency is in agreement with the result of analysis of bound water with the aid
of tritiated water as a tracer by Okamoto e t al. 2,21 They have reported that the
content of bound water in passive films depends upon the degree of development of
the films--that is, the concentration of bound water is low in the well-developed
passive film formed by polarization at higher potential and/or for longer time. In the
present work, the continuous decrease in the concentration of bound water in the
passive film formed on the 30Cr-2Mo stainless steel with the rise of potential suggests
that the passive film is stable and hence possesses the good protective quality.
Okamoto 21 has also suggested the following dual function of the bound water: the
boundwater may react to give various species or be replaced by the other ions coming
from surroundings, resulting in degradation of passive film. On the other hand, the
bound water acts as the beneficial species to capture the dissolving metal ions with
consequent formation of the new film resisting against further attack by surroundings.
The bound water detected on the 30Cr stainless steel is distributed throughout the
entire passive film, inasmuch as the thickness of passive film on the stainless steel
does not vary widely from potential to potential. It cannot be said, however, that all
of the bound water detected on the 30Cr stainless steel does correspond to the bound
water proposed by Okamoto. Some of it is not beneficial in maintaining a protective
property of the passive film and are responsible for inhomogeneity of the passive film,
resulting in a leakage of current through the passive film.
The passive films on both 30Cr and 30Cr-2Mo stainless steels include a small
amount of chloride ions which tends to decrease with the increase in polarization
potential. The concentration of chloride ions in the passive film may depend on the
degree of development of the film, similar to the concentration of bound water. In
general, the addition of molybdenum to stainless steels improves resistance against
chloride attack. Nevertheless, the concentration of chloride ions is not different in
the passive films on 30Cr and 30Cr-2Mo stainless steels. Accordingly, contamination
of passive films by chloride ions may not be necessary or sufficient to bring about

12

K. HASmMOTO,K. ASAMIand K. TERAMOTO

pitting but inhomogeneity of the passive films must also be presumed to play an
important part for pitting.
The fact that the main constituent of the passive films on the 30Cr-2Mo and
30Cr stainless steels is hydrated chromium oxy-hydroxide agrees with the results for
these steels in H2SO4,11 a series of Fe-Cr alloys in H~SO4,15 amorphous Fe-Cr-P-C
alloy in HC122 and amorphous Ni-Cr-P-B alloys in HC1 and H2SO4.28 The question
is raised why corrosion resistance properties are improved by the addition of molybdenum despite the fact that the main constituents of the passive films formed on the
30Cr-2Mo and 30Cr stainless steels are not different from each other. There are two
recent papers interpreting the role of molybdenum addition to stainless steels in
improving corrosion resistance properties in terms of compositions of passive films
on stainless steels. Yaniv e t al. 1 have stated that the improved corrosion resistance
properties obtained by the addition of molybdenum cannot be explained by its
endctunent in the protective film and have suggested that the beneficial effects of
molybdenum arise from improving the quality of the bonding at the metal-oxide
interface creating a barrier layer. Sugimoto and Sawada 5 have stated that the thickness
of passive film increases with an increase in the molybdenum content and hexavalent
molybdenum oxide, which exists in the passive film, improves the protective quality
of passive chromium hydroxide film, due to its high stability in acidic chloride
solutions.
In the present work, molybdenum is deficient in the passive film and the composition of passive films on both 30Cr-2Mo and 30Cr stainless steels is essentially the
same except for scatter of the content of bound water in the film on the 30Cr stainless
steel. The thickness of passive film is also unchanged by the addition of molybdenum.
Nevertheless, the addition of 1.7 ~oMo to the 30Cr stainless steel decreases the current
density in the passive region two orders of magnitude in 1 M HCI.
In general, once pitting and crevice corrosion initiate concentrations of hydrogen
and chloride ions within the pit and crevice increase and the potential at the dissolving
front within the pit and crevice is no longer in the passive region.24'25 Accordingly,
to study the effect of alloying elements on pitting and crevice corrosion, attention
'must be given to the behaviour of the alloys in the active region in acidic solutions
containing concentrated chloride ions. The ratio of chromium to iron in surface
films formed in the active region is almost the same as that in the bulk steels. However, marked enrichment of hexavalent molybdenum occurs in the surface films on
the 30Cr-2Mo stainless steel in the active region and the amount of molybdenum
varies with polarization potential. This dependence confirms that XPS analysis is
representative of the film formed during polarization in the active region and is thus
not an artifact of the sampling process. As seen in Fig. 1, the addition of molybdenum
to the ferritic stainless steel decreases significantly the current density in the active
region, although the reactivity of bare surface without surface film is not decreased
by the addition of molybdenum as seen in Fig. 2. It can be said from the above consideration that Mo(VI) oxy-hydroxide or iron or chromium molybdate is formed by
polarization in the active region on the steel surface, including the active surface sites,
with consequent inhibition of active dissolution.
In general, passivation occurs through active dissolution of metals at the initial
time period36"~7 Sato and Okamoto 26 have stated that, even if the potential is set

Spectroscopic study on the role of molybdenum

13

in the passive region, an increase in the concentraion of soluble metals or hydroxyl


ions in the vicinity of the electrode surface, i.e. active dissolution, is a necessary
precursor for passive film formation. Because the composition of passive films formed
on the 30Cr and 30Cr-2Mo ferritic stainless steels by polarization for 1 h is not
different from each other, the accumulating species in the vicinity of the surface
must be the same for both stainless steels. However, the time difference for the onset
of passivity of 30Cr and 30Cr-2Mo stainless steels is too big to assume the same
passivation process for both stainless steels, in particular, at -- 0.3 V (SCE). Therefore, inhibition of active dissolution during polarization in the passive region occurs
on the 30Cr-2Mo ferritic stainless steel before the accumulation of species necessary
for the film formation. It can be said that some of molybdenum oxy-hydroxide or
molybdate remain, without dissolving, on the surface of the 30Cr-2Mo stainless steel
during initial active dissolution by polarization in the passive region. Although
the molybdenum species themselves do not have a high protective quality as
compared with the passive hydrated chromium oxy-hydroxide film, the molybdenum species may decrease the activity of the active surface sites prior to the
passive film formation. This would be consistent with the sharp decrease in the
current density with time for the 30Cr-2Mo ferritic stainless steel as compared to the
30Cr stainless steel immediately after abrading the steel surface during anodic polarization in the passive region. From the point of view of the formation of passive
hydrated chromium oxy-hydroxide film, the decrease in the activity of active sites,
on which it is difficult to form the stable passive film, would correspond to the
appearance of a homogeneous steel surface and hence lead to the formation of a
uniform passive film. The importance of alloy homogeneity has been illustrated by the
extremely corrosion-resistant amorphous alloys, which are chemically homogeneous,
single phase alloys without crystal defects that act as active sites for corrosion.2s

CONCLUSION
From XPS study of the passive films formed on 30Cr and 30Cr-2Mo ferritic
stainless steels by polarization for 1 h in 1 M HCl the following conclusions can be
drawn:
The thicknesses of the passive film are not different from each other. Molybdenum
is deficient in the passive film on tbe 30Cr-2Mo ferritic stainless steel and the passive
films on both 30Cr and 30Cr-2Mo ferritic stainless steels consist mainly of hydrated
chromium oxy-hydroxide. The composition of passive films on both stainless steels is
essentially the same except for scatter of the content of bound water in the film on the
30Cr ferritic stainless steel. This scatter results from non-uniformity of the passive
film containing weak points filled with water, which are responsible for a leakage of
current through the passive film.
The beneficial effects of the molybdenum addition to ferritic stainless steel in
improving corrosion resistance properties can be interpreted in terms of the decrease
in the activity of active surface sites by molybdenum through the formation of
molybdenum oxy-hydroxide or chromium or iron-molybdate on these sites. This
leads to the appearance of a homogeneous steel surface and hence to the formation
of a uniform passive film.

14

K. HASHIMOTO,K. ASAMIand K. TERAMOTO

REFERENCES
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