Materials Chemistry and Physics 73 (2002) 252–258

Chemical composition and corrosion resistance of passive chromate films

formed on stainless steels 316 L and 1.4301
D. Stoychev a , P. Stefanov b , D. Nicolova a , I. Valov a , Ts. Marinova b,∗
a Institute of Physical Chemistry, Bulgarian Academy of Sciences, Sofia 1113, Bulgaria
b Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Acad G. Bochev Str. B1 11, Sofia 1113, Bulgaria
Received 15 August 2000; received in revised form 3 May 2001; accepted 4 May 2001

Abstract
The chemical composition and corrosion behavior of the natural and formed by chemical treatment in chromium-containing solution pas-
sive films on 316 L and 1.4301 stainless steel surfaces have been investigated by means of X-ray photoelectron spectroscopy and electrochem-
ical in situ method of anodic polarization curves. It have been established that the oxide films formed by the chemical treatment have different
chemical composition (Cr-enriched), color and reduced corrosion resistance compared to the natural passive films on both steels. The results
have shown that the lower part of the oxide layer represents a uniform modified passive film and the upper one is a porous Cr3+ -enriched film
with an island-like structure. The latter permits a direct contact of the solution with the modified passive film which controls the corrosion
resistance by the dissolution of the Fe3+ oxides present in the lower thinner layer. © 2002 Elsevier Science B.V. All rights reserved.
Keywords: Stainless steel; Passive films; Chemical composition; Corrosion resistance

1. Introduction polarization curves enables one to compare quantitatively

It is known that the corrosion behavior of stainless steels
depends directly on the composition, structure and thick-
ness of the passive films on their surface [1]. On this basis,
it can be assumed that additional chemical, electrochemi-
cal, thermal and other treatments of stainless steel surfaces,
which lead to changes of these characteristics of the natu-
ral oxide films, can affect the corrosion resistance of these
materials. It is assumed that the chromium-enriched surface
films formed on stainless steel can maintain the stability of
the steel [2–11]. In this connection it is of special interest to
study the changes which occur in the chemical composition
and morphology of the natural passive films on stainless steel
surfaces when they are subjected to chemical and other treat-
ments aimed at enhancing the concentration of chromium
and chromium oxides, respectively. In some cases, this treat-
ment is used with a view to achieving the desired color or
obtaining an intermediate layer on which functional (e.g.
catalyst supports) coatings should be deposited.
One of the most convenient ex situ methods of such inves-
tigation is X-ray photoelectron spectroscopy (XPS). Com-
bining it with the electrochemical in situ method of anodic
∗ Corresponding author. Tel.: +359-2-971-28-59;
fax: +359-2-971-28-59.
E-mail address: marinova@igic.bas.bg (Ts. Marinova).
the changes in nature of the passive film, on the one hand,
and its corrosion resistance, on the other.
The present investigation is aimed at modifying the pas-
sive films on two widely used kinds of stainless steels by
chemical treatment and studying the effect of the induced
changes on the corrosion resistance.
2. Experimental
The chemical composition of stainless steels 316 L and
1.4301 is given in Table 1. Specimens with a width of 1 cm
and a length of 5 cm were cut from standard stainless steel
sheets with a thickness of 0.5 mm.
The samples obtained were subjected to standard pre-
liminary treatments (successive decreasing with organic
solvents, Vienna lime and hot alkaline decreasing solutions
[12]). Some of the samples were additionally roughened
according to a method described in [13]. After careful wash-
ing with distilled water, the samples were immersed for
different times in a solution containing 250 g CrO3 , 300 ml
H2 SO4 (ρ = 1.84), and distilled water needed for 1000 ml.
In this way, oxide films of different colors (dark-blue, violet,
green–yellow and deep-yellow) were formed on the steel
surfaces depending on the duration of immersion treatment
(5 s–30 min) and the solution temperature (65, 70 or 80 ◦ C).

0254-0584/02/$ – see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 2 5 4 - 0 5 8 4 ( 0 1 ) 0 0 3 7 6 - 5
 D. Stoychev et al. / Materials Chemistry and Physics 73 (2002) 252–258 253

Table 1
The chemical composition of the steels studied
Steel Chemical composition (wt.%)

Cr Ni Mn Mo Si C S Fe

SS 316 L 18.0 12.0 2.0 2.5 ≤1.00 ≤0.03 ≤0.045 Bal

SS 1.4301 18.2 8.1 1.5 – 0.37 0.044 0.004 Bal

The change in electrode potential (E) of the steel samples

as a result of the chemical treatment was followed by a
calomel reference electrode and a high-sensitivity digital
millivoltmeter (RFT 401a, Germany) whose inlet voltage
was 2.10 V. The E–t curve was recorded with a Y–t recorder
(Endim 621.02, Germany) at a rate of 600 mV min−1 for
short durations and 60 mV min−1 for long durations of the
immersion treatment.
The chemical composition of the surface films formed was
investigated with XPS. The XPS studies were performed in
an Escalab II system using Mg K␣ radiation with an en-
ergy of 1253.6 eV. The pressure in the chamber was 10−7 Pa.
The photoelectron spectra were quantified using the peak ar- Fig. 1. Variation of the electrode potential (E) of smooth (1) and rough-
eas and Scofield’s photoionization cross-sections. The depth ened (2) (according to [13]) stainless steel 1.4301 vs. the time of immer-
profiles were obtained using 3 keV Ar+ ions and a current sion (1–30 min), (2–15 min). The temperature of the chromium-containing
density of 16 ␮A cm−2 . solution was 65 ◦ C.
The anodic polarization curves were obtained in a poten-
tiodynamic regime (Wenking Standard Potentiostat Model
and its value is about +1.30 V. The results obtained (Fig. 3)
68 TS 1, Voltage Scan Generator Wenking Model WSG 72)
indicate that the formation of a oxide film on the surface of
at a scan rate of 10 mV s−1 in a thermostated (T = 298 K)
stainless steel 316 L (at a working solution temperature of
glass three-electrode cell with a volume of 100 ml. The steel
65 ◦ C) occurs at a potential which is by about 20 mV more
samples with a chemically modified surface had a surface
positive than that of steel 1.4301.
area of 1 cm2 . The cathodes were made of platinum and the
The anodic behavior (Fig. 4) of steels 316 L (curve 1) and
reference electrode was a standard saturated calomel elec-
1.4301 (curve 2) depends on the composition of their natural
trode. The potential values in the plots are normalized to-
passive films. The natural passive film richer in chromium
wards the scale of the standard hydrogen electrode. The
(316 L > 1.4301) possesses a higher corrosion resistance.
working electrolyte (simulating a highly aggressive corro-
This is confirmed by the data in Fig. 4 which concern the
sion medium) was 0.1N H2 SO4 .
treatment in 0.1N H2 SO4 . The potential of maximum ac-
tive dissolution (Ecor ), and the current of maximum ac-
tive dissolution (Icor ), respectively, amount to 1.225 V and
3. Results and discussion

Fig. 1 shows the E–t curves obtained during immersion

treatment of a smooth (curve 1) and a roughened [13] (curve
2) stainless steel 1.4301 surface. It is evident that the elec-
trode potentials for both kinds of samples change practically
in the same way, except at the beginning (up to the second
minute of immersion). The passive layers on the smooth
and roughness steel surfaces, which differ negligibly from
each other in composition and structure [14], become prac-
tically identical as a result of the immersion treatment. Af-
ter the treatment, the surface film formed determines the
practically constant electrode potential of the steel (about
+1.28 V). Analogous measurements on stainless steel 316
L (Fig. 2) have shown that irrespective of whether the sur-
Fig. 2. Variation of the electrode potential (E) of stainless steel 316 L vs.
face is smooth or roughened, the electrode potential does the time of immersion in chromium-containing solution. The temperature
not change with both short and long durations of treatment of the solution was 65 ◦ C.
254 D. Stoychev et al. / Materials Chemistry and Physics 73 (2002) 252–258

Fig. 3. Variation of the electrode potential (E) of smooth 316 L Fig. 5. Potentiodynamic anodic polarization curves (V = 10 mV s−1 ),
(1) and 1.4301 (2) stainless steels vs. the time of immersion in obtained in 0.1N H2 SO4 , for smooth stainless steel 1.4301 chemically
chromium-containing solution. The temperature of the solution was 65 ◦ C. treated in chromium-containing solution at 65 ◦ C and times of immersion:
15 min (curve 1); 30 min (curve 2).

47 mA cm−2 for 316 L and to 1.200 V and 61 mA cm−2

for 1.4301. The relatively narrow regions of passive and
transpassive states of the two kinds of steel practically co-
incide.
The anodic behavior of these steels after the correspond-
ing chemical treatment in chromium-containing electrolyte,
i.e. after modification of their passive surface film, is pre-
sented in Figs. 5–10. Fig. 5 shows the anodic polarization
curves of steel 1.4301 treated chemically in a chromium
electrolyte heated at 65 ◦ C for 15 min (curve 1) and 30 min
(curve 2). The color of the samples treated for 15 min is
light-blue, and of those subjected to a 30 min treatment,
dark-blue. This change of color is probably associated with
the change in thickness of the oxide layer formed and with Fig. 6. Potentiodynamic anodic polarization curves (V = 10 mV s−1 ),
the change in concentration of Fe and Cr oxides in the sur- obtained in 0.1N H2 SO4 , for smooth stainless steel 316 L chemically
treated in chromium-containing solution at 65 ◦ C and times of treatment:
face layer. This assumption is confirmed by the analysis of
15 min (curve 1); 30 min (curve 2).
the anodic curves.
For samples whose oxide layer is formed within 15 min,
Icor is 40 mA cm−2 , whereas after a 30 min treatment, the acterizing the thicker oxide films (1.340 V). This is proba-
Icor value drops to 24 mA cm−2 . It is interesting that with bly associated with a higher porosity of the film formed for
the thinner oxide layer, the potential of active dissolution 30 min due to which the steel itself influences the Ecor and
(Ecor ) is more positive (1.380 V) as compared to that char- Icor values. During the transition in the region of passive and

Fig. 7. Potentiodynamic anodic polarization curves (V = 10 mV s−1 ),

Fig. 4. Potentiodynamic anodic polarization curves (V = 10 mV s−1 ), obtained in 0.1N H2 SO4 , for smooth stainless steel 1.4301 chemically
obtained in 0.1N H2 SO4 , for smooth untreated in chromium-containing treated for 30 min in chromium-containing solution at temperatures: 65 ◦ C
solution stainless steels 316 L (1) and 1.4301 (2). (curve 1); 70 ◦ C (curve 2); and 80 ◦ C (curve 3).
 D. Stoychev et al. / Materials Chemistry and Physics 73 (2002) 252–258 255

Fig. 8. The same as in Fig. 7 for smooth stainless steel 316 L.

transpassive state, the anodic curves practically coincide, i.e.

at potentials more positive than about 1.5 V, there is no dif-
ference in the anodic behavior of the oxide films formed.
The behavior of steel 316 L after an analogous chemical
treatment is different (Fig. 6). When the oxide film is formed
for 15 min, E cor = 1.20 V, whereas after 30 min, a shift in
the positive direction is observed and the value of E cor =
1.45 V is reached. A similar shift is found with respect to
the potentials of the passive state (Ep ) which are about 1.25
and 1.52 V, respectively. The corrosion currents, Icor , how-
ever, are 63 and 68 mA cm−2 , respectively, while for the
passive state the values are 47 and 53 mA cm−2 . These val-
ues indicate that the oxide film formed on steel 316 L has a
higher dissolution rate than is the case of steel 1.4301. Al-
though Ecor is shifted in the positive direction (from 1.20 to
1.45 V), Icor and Ipas , respectively, increase. Since the Cr and
Fe concentrations in the surface film after treatments for 15
and 30 min are practically the same, and that of Si increases
Fig. 9. Variation in the surface composition of the oxide layer formed on
316 L (a) and 1.4301 (b) stainless steels depending on the duration of
chemical treatment.
almost two times (Fig. 9), it can be assumed that the en-
hanced concentration of non-metal inclusions around which
more intense dissolution of the film and the substrate is ob-
served, determines the higher dissolution rate and porosity,
respectively.
Comparison of the results in Figs. 5 and 6 with those
in Fig. 4 shows that the chemical treatment of the stain-
less steels aimed at changing the oxide layers composition
and thickness (and color, respectively), leads to an essential

Fig. 10. Changes of Cr 2p3/2 , Fe 2p3/2 and O 1s photoelectron peaks with the time of ion sputtering of an oxide layer formed on chemically treated SS
316 L.
256 D. Stoychev et al. / Materials Chemistry and Physics 73 (2002) 252–258

decrease in the corrosion resistance of the two kinds of steel.
The corrosion current of steel 1.4301 increases from six to
nine times, while with steel 316 L, the increase amounts to
about one order of magnitude. The currents in the passive
state increase about 3 times for 1.4301 and 2.6 times for
316 L.
The change in the corrosion parameters of the chemically
treated stainless steels is also affected by the temperature of
the chromium electrolyte in which the chemical treatment
takes place. This effect is illustrated in Figs. 7 and 8 present-
ing the anodic curves of samples treated for the same time
(30 min), but at different temperatures (65, 70 and 80 ◦ C).
The increase in temperature of the chromium solution results
in a shift of the corrosion potential to the negative region
and an increase of the corrosion current, i.e. an increase in
porosity of the films on the surface of steel 1.4301. With
steel 316 L the changes are more specific. The increase in
temperature of the immersion solution up to 70 ◦ C leads to
the formation of an oxide film characterized by a more neg-
ative corrosion potential but a lower corrosion current as
compared to that at 65 ◦ C. With films obtained at 80 ◦ C, Icor
increases and Ecor is shifted to the positive region, reach-
ing an intermediate value with respect to Ecor characterizing
the corrosion potentials of layers obtained at 65 and 70 ◦ C
(Table 2).
Judging by the results discussed above, it is obvious that
the optimum conditions, with respect to the corrosion re-
sistance of the oxide films formed on the two steels, are a
temperature of 65 ◦ C and a treatment duration of 30 min for
steel 1.4301, while for steel 316 L the optimum temperature
is 70 ◦ C and the treatment duration, 30 min.
The essential changes in the corrosion resistance of the
steels under consideration are associated with the changes
in the chemical composition and/or the peculiarities of the
morphology of the passive films formed during the chemical
treatment. The effect of pronounced surface accumulation
of Cr on Fe/Cr steels in acid electrolytes is well known.
The better solubility of Fe3+ ions facilitates the elimination
of Fe-rich surface films. In addition, enrichment in Cr is
localized on the surface [15,16] although a very thin Fe-rich
film exists on the surface according to [1]. The accumulation
of Cr in the passive film of the iron alloys is due to the very
low dissolution rate of Cr2 O3 .
The composition and structure of the surface films were
determined by XPS. Fig. 9 shows the change in surface com-
position of the oxide layer formed depending on the duration
of chemical treatment. It is evident that the oxide film con-
sists mainly of chromium and iron oxides and small nickel
and silicon inclusions. The general trend of the film compo-
sition is that the content of Cr oxide increases with the pas-
sivation time. The prolonged exposure up to 30 min causes
an increase in Cr(ox) concentration from 17 to 22% for both
steels. Simultaneously, the Fe(ox) concentration decreases
gradually from 18 to 7%. The concentration of other species
(Si, Ni, Mo) is almost independent of the passivation time
and remains within the limits of several percents.
In a previous study [14], where one of the steels used here
(SS 316 L) was treated in the same way (15 min immersion
in a CrO3 -based electrolyte), the oxide film was found to
have a bilayered structure in which the topmost layer was
composed of chromium hydroxide or oxy-hydroxide fol-
lowed by an inner part of a Cr2 O3 phase. The thickness of
the film was estimated to be about 50 nm. Besides, the anal-
ysis made showed that the Ni, Mo and Si inclusions as well
as most of the registered Fe did not participate in the oxide
film formed. Their signals were associated with some areas
where part of the underlying steel surface was exposed to
XPS analysis. The latter is illustrated in Fig. 10 where the
XP spectra recorded during depth composition profiling of
the Cr oxide film deposited on a SS 316 L surface are shown.
The Fe 2p3/2 spectra feature similar shapes and intensities
during prolonged sputtering. Moreover, after a 20 min ion
bombardment, a metal component appears in the Fe 2p3/2
spectrum. It cannot be attributed to ion-induced reduction of
iron oxide to metal because no such data are to be found in
the literature. We suppose that the Fe0 signal originates from
some areas of the surface where the sputtering eliminates the
passive film, thus revealing the underlying steel surface. On
the other hand, a Cr0 signal was observed after prolonged
sputtering of the film. The depth profile of the Cr oxide film
deposited on a SS 1.4301 surface showed that the films on
this steel have a similar structure and thickness. This charac-

Table 2
The values of the potentials and currents for the steels studied and the colors observed
Potential/current Steel type After chemical treatment in chromium electrolyte at the following conditions
(V mA−1 cm−2 )
1.4301 316 L 1.4301 316 L 1.4301 316 L 1.4301 316 L
(65 ◦ C) (65 ◦ C) (70 ◦ C) (70 ◦ C) (80 ◦ C) (80 ◦ C)
15 min 30 min 15 min 30 min 30 min 30 min 30 min 30 min

Eeq 0.500 0.600 0.700 0.700 0.180 0.230 0.700 0.230 0.150 0.150
Ecor 1.220 1.180 1.380 1.340 1.200 1.450 1.250 1.250 1.260 1.330
Epas 1.470 1.520 1.560 1.560 1.290 1.380 1.420 1.420 1.420 1.520
Icor 4.5 6.2 40 25 63 68 24 37 35 62
Ipas 2.3 2.0 6.5 4.0 47 53 60 20 13 55
Color – – Light- Dark- – Light- Purple–yellow– Violet–green– Yellow– Yellow
blue blue blue green yellow purple (old gold)
 D. Stoychev et al. / Materials Chemistry and Physics 73 (2002) 252–258
ter of the spectra cannot be explained within the framework
of a model of dense, uniformly deposited oxide layer.
The enrichment in Cr of the surface film presupposes en-
hancement of the corrosion resistance of the steels, whereas
the experimental results obtained indicate just the opposite.
A possible explanation can, according to us, be given on the
basis of the two-layer model of Atrens et al. [9] concern-
ing the formation of secondary passive films in acid me-
dia. According to this model, on the surface of the modified
natural oxide film (“modified passive film”), an additional
porous film is formed by the products of chemical inter-
action of the steel with the solution in which it has been
treated. This “corrosion product film”, which is enriched in
Cr3+ , increases the total thickness of the oxide film, but has
practically no contribution to the electrochemical stability
of the system. “The corrosion product film could be in the
form of mounds separated by areas where the modified pas-
sive film is in direct contact with the solution. The overall
composition of the secondary passive film is most probably
of a mixed Fe/Cr oxide/hydroxide enriched in Cr3+ , with a
composition quite similar to a primary passive film” [9].
Probably in our case, the chromium film is not dense
and has an island-like structure due to which the aggressive
medium is also in direct contact with the lower part of the
modified passive film on the steel surface. This assumption
is also based on the angular-dependent XPS measurements
made at two different take-off angles: 90◦ (normal emission)
and 30◦ (with respect to the surface). In the latter case, there
is a higher sensitivity towards the film surface because at
this angle the escape depth of the photoelectrons decreases
almost twice. Fig. 11 shows the change in the Fe/Cr ra-
tio at both take-off angles. Prior to the chemical treatment
these two ratios coincide, which evidences that the natu-
ral passive film consists of mixed iron and chromium ox-
ides. The chromium concentration in the subsurface layer
Fig. 11. Intensity ratio Cr/Fe measured at take-off angles 30 and 90◦ .
257
Fig. 12. An illustration of the model of the bilayer film discussed in the
text.
considerably increases with the duration of chemical treat-
ment, which is indicated by more pronounced increase of
the Cr30 /Fe30 ratio. The character of this change could be
explained using a model of the passive film similar to that
given above [9]. Fig. 12 shows schematically a section of the
oxide film formed during the treatment. Due to island-like
character of the oxide film formed, some areas of the modi-
fied passive film are revealed. The three-dimensional struc-
tures increase with the duration of chemical treatment. Ac-
cording to the XPS results these structures consist, above
all, of chromium oxides, the iron oxide concentration being
lower, whereas the modified passive film contains more iron
and less chromium oxides. This explains why after changing
the take-off angle from 90◦ (normal emission) to 30◦ (sur-
face sensitive emission), the Cr/Fe ratio increases almost two
times (after 15 min treatment). This change of angle causes
an essential decrease of the contribution of the secondary
modified passive film.
On the basis of this type of structure, i.e. this type of Fe
and Cr oxide distribution, it is possible to explain the higher
values of Icor and Ipas , respectively, as well as the shifts of
Ecor and Epas .
This model may also be used for explaining the different
colors of the films obtained after chemical treatment. Al-
though having practically the same chemical composition,
they may differ in thickness and color. This is also confirmed
by the essential color change of the surface films depending
on the time and temperature of drying. The porous overlayer
formed by precipitation (probably gel-like) contains, in ad-
dition to Cr oxides, also Cr hydroxides and structured water
[10,11,14,17]. Thermal treatment will lead to a color change
of the overlayer passive film as a result of decomposition of
the hydroxides and elimination of the structured water.
4. Conclusions
The present investigation has shown that the formation
of chromium-enriched surface films on the stainless steels
1.4301 and 316 L as a result of chemical treatment in
chromium-based solutions alter (decrease) substantially
their corrosion resistance in strongly acid media. The ob-
258 D. Stoychev et al. / Materials Chemistry and Physics 73 (2002) 252–258
served Cr3+ enrichment, on the one hand, and the decrease
in corrosion resistance of the steels, on the other hand, per-
mits assuming that the oxide film consists of two layers. In
agreement with the bilayer model proposed in [9], the lower
part of the oxide layer represents a uniform modified pas-
sive film and the upper one is a porous Cr3+ -enriched film.
Probably the latter has an island-like structure, which per-
mits direct attack (dissolution) of the Fe3+ oxides present in
the lower thinner modified passive film, and, consequently
an accelerated corrosion of the steels.
Acknowledgements
This work is financially supported by European Com-
mission through the Environment and Climate Project
ENVA-CT97-0633 and by the National Scientific Council
of Bulgaria under contract no. X-828.
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