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Abstract
The outstanding corrosion resistance of stainless steels results from the presence of a thin oxide */‘passive’ */film on the metal
surface, typically 1 /3 nm thick. The characterisation of the composition and structure of such thin films and the study of their
interaction with corrosive environments requires a combination of sophisticated experimental techniques. This paper reviews
progress in the characterisation and understanding of passive films on stainless steels achieved over the past two decades. During
this period, ex situ surface analysis methods have made substantial progress and new in situ methods for the study of passive films
with atomic resolution have been introduced, giving real time information on film chemistry and growth. It has been found that
whereas passive film growth occurs in seconds or minutes, long range film ordering is a considerably slower process that takes
several hours. In situ investigations indicate that at short times, charge transfer at the metal/film or the film/solution interface limits
the rate of film growth on stainless steels. In situ estimates of film composition confirm previous data obtained with ex situ
techniques.
# 2003 Elsevier Science Ltd. All rights reserved.
Keywords: Passive films; Stainless steel; Passivity; X-ray photoelectron spectroscopy; Scanning tunnelling microscope; X-ray absorption near edge
structure; Electrochemical quartz crystal microbalance
Table 1
Examples of recent commercial developments in the field of stainless steel with high impact on the surface behaviour of the material
654 SMO First 7% Mo austenitic stainless steel. Very high resistance to pitting corrosion at elevated temperatures Avesta Polarit
SAFUREX First 29Cr duplex stainless steel. Very high resistance to oxidising acids and localised corrosion, in particular stress Sandvik Steel
corrosion cracking.
UGICLEAN A special surface structure modified to resist bacterial adhesion Ugine
NSS AM1-4 Cu alloyed stainless steels with special heat treatment giving high resistance to bacterial adhesion Nisshin steel
Zeron 100 Duplex stainless steel alloyed with W Weir Materi-
als
DP3-W W alloyed stainless steel Sumitomo
concentration in the electrolyte. The dynamic properties Based on surface analysis, a three-layer model has
of the passive film provide the key to the high resistance been suggested for passive films formed on austenitic
of stainless steels to corrosive attacks. The state of stainless steels in acidic solutions: the outer part of the
knowledge of passive films on stainless steels as of 20 film consists of an hydroxide film on top of an oxide
years ago was thoroughly reviewed by Fischmeister and layer. The oxy-hydroxide film is formed on top of a
Roll [5]. The aim of this paper is to present an overview nickel enriched layer in the metal, the origin of which is
of new methods and results reported in the past two the selective oxidation of Fe and Cr during anodic
decades. One could say that whereas the keyword of the polarisation. This picture is obtained essentially from
70s and early 80s was ex situ surface analysis, recent XPS measurements on passive films, cf. Fig. 1 [9]. The
research has emphasised the use of different in situ film is enriched in chromium and the metal closest to the
methods.
metal/film interface shows a strong enrichment in nickel.
For an alkaline solution, the solubility is lower for Fe
and higher for Cr; this affects the level of chromium
2. Experimental methods for the study of passive films enrichment in the film. With angular resolved XPS
(ARXPS), it is also possible to obtain information on
Passive films are formed during an exposure of the the depth distribution of different species and oxidation
bare metal surface to an oxidising environment. Once a states, cf. Fig. 2, which illustrates the angular depen-
film is formed, the reaction rate between the metal and dency of different oxidation states of molybdenum in
the environment will be several orders of magnitude the passive film after immersion in a ferric chloride
lower. The original theory of film formation goes back solution [10]. Mo(VI) is enriched in the surface region,
to Michael Faraday, who in the 19th century studied the metal peaks show a buried layer appearance, and the
iron surfaces and found them ‘altered’. A review of the Mo(IV) oxide and Mo(IV) oxy-hydroxide show an
early days of passive film research has been written by angular distribution indicating a more homogeneous
Uhlig [6]. A general introduction to the theory of distribution through the passive film. The attribution of
passivity has been published by Sato [7], whereas the
electronic properties of passive films on different
materials have recently been reviewed by Schultze and
Lohrengel [8].
experiments have been performed by Courty et al. [22]. acquisition times of the order of one hour are used [28].
A direct estimate of the film change during transfer was A short introduction to XANES applied to passivity
obtained by comparing films formed in H18 2 O and related problems has been written by Schmuki and
transfer in 16O2 with films formed in H16 2 O and transfer Virtanen [31].
in 18O2. For low passive and cathodic potentials, both A XANES spectrum for Cr and Fe taken from an (Fe,
laboratories found a significant effect of sample transfer. Cr)2O3 sample is shown in Fig. 4. The height of the
Graham et al. reported a transfer influence also for the plateau at the high-energy side of the adsorption edge is
high passive region. However, when Courty et al. proportional to the respective amount of the element in
transferred samples in 18O2 atmosphere, no uptake of the sample, and the peak position reflects the oxidation
18
O in the film was seen, even though enrichment levels state. Quantification of XANES spectra is less straight-
close to those of Graham’s were observed for anodisa- forward than for AES and XPS. Davenport et al.
tion in H18 2 O and transfer in
16
O2. Thus, the direct introduced a formalism to separate the oxide and metal
measurement showed an absence of oxygen uptake signals from an oxidised sample [26]. This method was
during transfer for samples polarised to the high passive further developed by Oblonsky et al. for the quantifica-
region [22]. tion of film composition on Fe /Cr alloys [28], and later
The results indicate that caution is needed during the Ni /Cr [32]. The measurements confirm XPS and AES
sample transfer. However, by ensuring that the transfer results, i.e. for a certain polarisation and bulk composi-
is made consistently for all samples, it is possible to draw tion, the amount of Cr in the passive film surpasses 50%
valid conclusions from comparisons between series of of cations [33]. The XANES data also support the
measurements. Evidently, the only way to eliminate
enrichment of Cr in the passive film by selective
artefacts associated with sample transfer is to use in situ
dissolution of iron. It has also been possible to
techniques.
demonstrate the presence of Cr(VI) in the film [34].
In situ analysis of binary alloys can also be performed
2.2. In situ techniques by more conventional techniques. By solution analysis
with ICP-AES/MS (inductively coupled plasma atomic
A technique new to the study of passive films is X-ray emission spectrometry/mass spectrometry), it is possible
absorption near edge structure (XANES), which ac- to deduce composition changes in the passive film
quires in situ chemical information. It has been applied resulting from potential changes. This approach was
to the investigation of passive films on pure iron [23 / successfully employed by Castle and Qiu [35] and Hamm
27], iron /chromium alloys [28] and to the study of et al. [36]. For an Fe /Cr alloy in the passive region, both
sputter deposited iron /chromium oxides [29]. The papers concluded that the dissolved species consisted
sputter deposited oxide films were used as model almost solely of iron. Similarly, rotating ring-disc
systems for passive films. XANES puts strong demands electrode experiments with Fe /Cr alloys showed that
on the analysed material. The sample is a thin film of close to no Cr was emitted from the sample during a
about 10 nm thickness deposited on top of a gold potential change in the passive region [37], in good
contact layer. As substrate, a polymer carrier film that agreement with the ICP results. Annergren et al. used
ensures X-ray transparency is used. Sample character- the rotating ring-disc electrode in combination with
isation has been described by Stenberg et al. [30]. The electrochemical impedance to study the dissolution and
study of reaction kinetics is somewhat limited, since passivation behaviour of Fe /Cr alloys in sulphuric acid
Fig. 4. XANES spectra (Fe and Cr K edges) of a mixed (Fe, Cr)2O3 sample containing 50% Cr2O3 during anodic potential steps in 0.1 M H2SO4. The
potential was increased in 100 mV steps/15 min, which is illustrated with selected raw spectra. From Schmuki et al. [29].
C.-O.A. Olsson, D. Landolt / Electrochimica Acta 48 (2003) 1093 /1104 1097
solution with additions of chloride [38 /40]. They The composition and chemistry of the film also vary
calculated that ferrous ions were leaving the electrode with potential. For Fe /Cr alloys, enrichment of chro-
with a current efficiency even higher than unity for mium occurs in the film in the low passive region, but in
intermediate frequencies. The behaviour was explained the high passive region the chromium content decreases,
by postulating a concurrent chemical dissolution path of since the stability of iron surpasses that of chromium.
Fe(II) [39]. Chromium, in turn, may oxidise to its soluble hexavalent
state. At high passive potentials, Fe has a stabilising
action on the trivalent Cr, making Fe /Cr alloys stable
2.3. Environmental influence on the film composition over a wider potential range than pure Cr. Higher
oxidation numbers are also more dominant towards the
A passive film is in constant exchange of species with higher end of the passive region, as confirmed by
the electrolyte and consequently alters in thickness and XANES [34].
composition with the environment. Among the factors
that influence the passive film, one finds the potential, 2.3.2. Chlorides and sulphates
the presence of halides in the electrolyte, the pH, and the The presence of certain anions adsorbed on the
temperature. surface or incorporated in the passive film can be
detrimental to film stability and lead to pit initiation.
For chloride, there is a vast literature attempting to
2.3.1. Potential explain its effects on pitting. Three different models are
The thickness of passive films on stainless steels grows frequently quoted: adsorption leading to local film
linearly with the applied potential. This is illustrated in dissolution, penetration of anions in the film leading
Fig. 5 for a Fe15Cr alloy in an acidic sulphate [41] as to weakening of the oxide bonds, and film break down
well as Fe10Cr and Fe20Cr alloys in a sodium hydroxide at defects such as cracks and dislocations [46]. Con-
solution [42]. The basic solution gives considerably clusive analysis of the chloride content of passive films
thicker films, since dissolution is less pronounced. The has proven difficult, since it is rather low; frequently
observed increase in film thickness with potential in an quoted values range from 1 to 5%. Due to the very thin
acidic solution is due mainly to the oxide part; the passive film and the possible presence of structural
hydroxide part of the film is approximately independent defects, it is not easy to distinguish adsorbed from
of potential [43,44]. Development of the passive film incorporated anionic species. Using AES and XPS, it
with time has been investigated by, among others, has been shown that sulphates are present at or close to
Maurice et al. [45]. Between 20 min and 20 h of the film surface [47 /50]. Chlorides are enriched at the
polarisation, they found only a small change in the passive film surface, but the depth distribution is more
total film thickness; the oxide part of the film was found homogeneous than for sulphates [51], especially at
to grow at the expense of the hydroxide part. elevated temperatures [43]. Mischler et al. have shown
that alloying with molybdenum reduces the surface
enrichment of chlorides and sulphates [52]. Mitrovic-
Scepanovic et al. [53] found a higher tendency for
chlorides than sulphates to penetrate the passive film
on Fe /Cr alloys. Chloride penetration into an intact
passive film can be investigated by forming the film in a
non-chloride solution, followed by exposure to chlor-
ides. Such a series of experiments has been performed by
Hubschmid et al. for Fe /25Cr /X alloys. No incorpora-
tion was found when chlorides were injected after an
initial hour of film formation in a sulphuric acid
solution [54]. For films formed in chloride electrolytes,
on the other hand, chlorides were found distributed
through the film.
2.3.3. pH
The main effect of an increased pH is a lower
dissolution rate. This leads to a thicker passive film,
Fig. 5. Oxide layer thickness on a stainless steel as a function of
and a larger fraction of iron in the film, as iron oxides
potential for a Fe15Cr alloy in 0.5 M H2SO4, and for Fe10Cr and
Fe20Cr alloys in 1 M NaOH, estimated using XPS. The film growth are more stable in basic solutions. The pH effect is
region is considerably wider in the basic medium, which also gives illustrated by the data of Schmutz and Landolt, who
thicker films. After Haupt and Strehblow [41] and Hoppe et al. [42]. compared the response for two FeCr and FeCrMo
1098 C.-O.A. Olsson, D. Landolt / Electrochimica Acta 48 (2003) 1093 /1104
alloys to a potential change in basic and acidic solutions produced using PVD has been investigated by Hashi-
using the electrochemical quartz crystal microbalance moto et al. [59 /64] who underlined the extremely high
(EQCM) [55]. Increasing the potential in the passive corrosion resistance of amorphous alloys.
region lead to a mass loss in the acidic solution (0.1 M A showcase for the importance of microsctructure is
H2SO4/0.4 M Na2SO4) and to a mass increase in the the austeno /ferritic (duplex) stainless steels. Their two-
basic solution (0.1 M NaOH). A mass increase corre- phase structure makes them particularly sensitive to the
sponds to a net film growth and a low dissolution rate. formation of intermetallic phases. AES has been used to
The effect of pH on the passive layer of Fe /Cr alloys investigate the homogeneity of the passive film on the
have also been studied by Strehblow et al. [41,42]. The austeno /ferritic stainless steel 2205 (EN 1.4462) [65]. A
films were found to be thicker in basic solutions. In typical phase region for a commercial duplex stainless
addition, there was a marked increase of the amount of steel covers 10/20 mm. It has been demonstrated that
Fe(III) oxide. the passive film composition shows a comparatively
homogeneous composition, virtually independent of the
2.3.4. Temperature underlying phase structure. This homogeneity continues
The effect of temperature on the passive film was some Ångströms down in the metal phase where a nickel
studied by Jin and Atrens using XPS [56]. They found and nitrogen enrichment is found for the austenitic and
no differences in composition and thickness between the ferritic phases [65]. This enrichment would be
passive films formed at room temperature and at 90 8C sufficient to produce a fully austenitic structure in a
in a 0.5 M NaCl solution. Mischler et al. quoted slightly bulk material. Significant differences between phase
thicker values for films formed on Fe /Cr /Mo alloys at regions were found by Hubschmid et al. who studied a
65 8C when compared to room temperature [52]. The Fe /25Cr /11Nb model alloy with a considerably coarser
temperature effect on film thickness for a 6Mo stainless dendritic microstructure than for commercial 2205 [66].
steel has been quantified by Wegrelius and Olefjord It appears the lateral homogeneity of the passive film is
using XPS [43]. They compared film formation at 22 and linked to the lateral extension of different phases in the
65 8C in an acidic chloride solution. In spite of clear microstructure.
electrochemical indications of pitting attacks during the
exposure period at the higher temperature, the film was
found to be only 2 Å thicker for the higher temperature. 2.4.2. Fe
In acid solution, anodic polarisation of a Fe /Cr alloy
2.4. Influence of microstructure and alloying elements on in the passive potential region leads to selective dissolu-
passive film composition tion of iron, leaving chromium enriched in the passive
film. This behaviour is governed by the difference in
2.4.1. Microstructure diffusion rates of iron and chromium in the passive film
With classic metallurgical techniques, the composition [13,67]. When performing sputter depth profiles with
range of the bulk material is limited by the precipitation AES or XPS, there is normally an enrichment of iron in
of intermetallic phases. In addition, inclusions and the outer region of the passive film. This is possibly a
segregation cause defects in the passive film. For transfer artefact related to the higher diffusion rate of
detailed studies of passive films, the amount of inter- iron through the film. At about 0.58 VSHE, iron changes
metallic phases and other imperfections can be mini- valence from 2 to 3 [41] for an acidic solution; for a basic
mised by utilising thin film materials produced with solution, the corresponding potential is about/0.3
PVD (physical vapour deposition). Since PVD is a ‘cold’ VSHE [18].
technique */a typical deposition temperature is
400 8C */it is possible to obtain nanocrystalline or
amorphous material that is virtually free from inter- 2.4.3. Cr
metallic phases over a wide composition range. For moderate anodic polarisations in acidic solutions,
Inturi and Smialowska compared a nanocrystalline the passive film consists essentially of chromium in its
thin film alloy of the same composition with conven- trivalent state. As the potential increases above the
tional 304 material [57]. The breakdown potential of the stability limit of chromium III, (about 0.6 /0.8 VSHE),
nanocrystalline material in a near neutral NaCl solution the passive film will start to change composition and the
was found to be shifted anodically by about 850 mV, a fraction of trivalent iron in the film will increase. For
behaviour that was attributed to the smaller grain size acidic solutions, the cation fraction of Cr in the passive
and the high purity of the deposited thin film material. film normally amounts to 50/70%. For basic solutions,
Kraack et al. found a shift in the pitting potential to the solubility of Cr increases, resulting in a higher
more noble values when molybdenum was added to thin fraction of iron. The surface chemistry of pure chro-
film Fe/Cr alloys in agreement with the well-known mium has been studied by Björnkvist and Olefjord
behaviour of bulk material [58]. A wide range of systems [68,69]
C.-O.A. Olsson, D. Landolt / Electrochimica Acta 48 (2003) 1093 /1104 1099
on alloys with 24% Cr were amorphous, whereas 0/10% major part of the response is acquired. The structure
Cr in the bulk resulted in a spinel-like structure. With found was not a flat hydroxide layer, but resembled a
the invention of the STM in the early 1980s, it became buried island structure, much like the one suggested by
possible to study the crystal structure of the passive film Wegrelius and Olefjord based on XPS results [95]. STM
in situ with atomic resolution. studies of passive films on different materials have
recently been reviewed by Marcus [96].
3.1. Scanning tunnelling microscopy
3.2. Geometrical considerations
One of the first studies on the atomic arrangement of
Conjectures based on the geometrical arrangement of
active and passive stainless steel surfaces was performed
atoms in or near the passive film have been developed as
by Ryan et al. [91,92]. By studying iron in a borate
a possible explanation for some aspects of passivity. The
buffer solution and Fe /Cr alloys in sulphuric acid
simplest geometrical approach is to consider a bcc-
solutions, they confirmed the conclusion of McBee
lattice where every atom has eight neighbours. For
and Krueger [90] that the passive film is amorphous
iron /chromium, this means that if 1/8 (12.5%) of the
for Cr concentrations above 12 /19%. Marcus et al. have
atoms are Cr, at least 50% of the Cr atoms will have at
made detailed investigations on a series of single crystal
least one Cr as their nearest neighbour. This corre-
surfaces: Ni [93], Cr [94], Fe /Cr [48] and Fe /Cr /Ni
sponds to the onset of a continuous network of
[45]. The passive films were found to grow close to
chromium atoms in the bulk material. The fraction 1/8
epitaxially (Cr (110)) in small (3 nm diam) crystalline
also equals the lower limit of chromimum needed to
regions on iron /chromium alloys. Aging under polar-
make a steel stainless. Percolation theory is related to
isation led to growth of the crystallised regions, i.e. an
the 1/8 concept. It has previously been used in materials
enhanced long range order. The ordering process was
science to treat different phenomena in amorphous
observed to be slower for austenitics, which also showed
materials, e.g. phase transformations. A general treat-
a lower production rate of Cr2O3 on the surface. It was
ment of percolation has been presented by Zallen [97].
suggested that these effects were caused by the enrich-
Percolation is used to describe network connectivity.
ment of nickel at the metal/film interface which limited
For a one-dimensional system (e.g. a string with node
the access of chromium. An example of an STM image
points), the percolation limit is trivial, since the first
is given in Fig. 6, which shows the atomic arrangement
node cut will cause a break in connectivity between the
of a passive film on an austenitic Fe /Cr /Ni alloy [45].
end points. For a 2D structure, it is possible to find an
The STM can also be used to obtain depth informa-
exact percolation limit which will vary with the number
tion. This was demonstrated by Zuili et al. on Cr
of connections of each node (atom or molecule) in the
surfaces [94]. By varying the voltage of the scanning
network. For a 3D structure, the issue is more complex
tip, it is possible to control the depth from which the
and percolation limits become less well defined, since the
number of possible connections are much higher.
The connectivity of Fe /Cr matrices was studied for a
series of different compositions by Newman et al. For
their Monte Carlo simulations, they initially considered
a square two/dimensional lattice in which they ran-
domly placed iron and chromium atoms [98,99]. By
assuming a high dissolution rate for iron and zero
dissolution for chromium, they derived percolation
limits of 12% for onset and 17% for completed passivity.
These percentages are in good agreement with practical
experience.
Later, the percolation model was modified to incor-
porate pit initiation [100]. By assuming a low dissolution
rate for Cr, it was shown that an intermittent dissolution
of iron clusters at discrete times could be obtained. If
large enough, these clusters could serve as initiation sites
for pitting. Recently, the percolation results have been
compared to experimental data for Fe /Cr PVD films
exposed to acidic chloride media [101,102]. The percola-
Fig. 6. Topographic STM image of a passive film on a (100) Fe /
18Cr /13Ni substrate after passivation in 0.5M H2SO4 at 500 mVSHE tion approach has also been modified by assuming
for 2 h. An almost hexagonal lattice is superimposed to show the higher dissolution rates at defect sites on the surface, e.g.
directions of the close-packed rows. From Maurice et al. [45] kinks, or if one alloy component is restrained to the
C.-O.A. Olsson, D. Landolt / Electrochimica Acta 48 (2003) 1093 /1104 1101
Newman et al. considered the surface to be passive volume and valence, B is an oxide-specific constant, and
when a hydroxide or oxide chain can bridge the gap and U is the applied potential. For the HFM, the thickness
form a link between chromium atoms at the surface of the passive film is found in the denominator of the
[104]. Another approach is to consider the connectivity exponential.
between cations within the oxide film. This concept has The alternative to high field rate control is to consider
been applied to Fe /Cr [105] and other binary Cr alloys a rate limiting reaction at either the metal/film or the
[106] by McCafferty, who considered a series of binary film/electrolyte interface. A rate limiting reaction at the
systems following a formalism developed by Megirditch- metal/film interface is the base for the point defect
ian [107] and Randic [108]. For a certain ratio of Fe/Cr model (PDM) that was introduced in the early 80s. The
atoms in the oxide matrix, a connectivity between the PDM concept has since then been developed and
chromium atoms is obtained. Thus, for a certain discussed extensively in a series of publications by
Macdonald et al. [110,112/117]. A growth rate limiting
amount of iron, the continuous chromium network
reaction at the film/electrolyte interface has been pro-
through the oxide will be lost. The connectivity para-
posed by Vetter and Gorn [118]. It can be shown that
meter was successfully compared with parameters such
the form of the rate limiting reaction is independent of
as passivation currents, passivation potentials or experi-
which interface is considered [119]. Thus, the film
mental data on passive film compositions [105].
growth equation for the interface type models (IFM:s)
takes the form
@d Dd]
k1if ek2 [DUE0 (2)
4. Film growth kinetics @t
where kif1 and k2 are constants with different meanings
Passive films are constantly changing and adapting to depending on which model is represented [119]. For the
the environment. Thus, understanding film growth and IFM, the electric field E0 is usually assumed constant
dissolution is essential to the understanding of passive during the applied external potential change. The film
film stability in different and changing environments. will show a thickness change Dd until the potential
High reaction rates and small dimensions of the film (1 / applied across the film is balanced. For the IFM, the
3 nm thickness) make it difficult to obtain unique results thickness change is found in the nominator and the
for passive films on stainless steels. Some valve metals growth rate is not explicitly dependent on the absolute
show thicker films and are thus more easily studied. film thickness.
Numerous attempts to model film growth based on An attempt to unify the IFM and HFM conjectures
different concepts have been made; a recent review has was made by Kirchheim in 1987 [120], focussing on
been written by Macdonald [109]. More details on galvanostatic experiments on iron in acid environments.
earlier models for film growth dynamics have been Kirchheim divided the current into a growth and a
given by Chao et al. [110]. corrosion part: itot /icorr/igrowth. The growth current
For a passive film covering the entire surface, two was assumed to be controlled by an interface equili-
types of rate-limiting processes can be distinguished: brium, as previously suggested by Vetter and Gorn
high field assisted ionic transport through the film or [118,121], and the total current was assumed to be
charge transfer at either the metal/film or film/electro- limited by the HFM. The corrosion part can be
lyte interface. These models will be referred to as high estimated by solution analysis. Kirchheim showed that
field (HFM) and interface models (IFM), respectively. neither the interface equilibrium nor the high field
Most models presented in the literature give growth limitation for the total current on its own could
equations that reduce to either the IFM or the HFM successfully explain all experimental observations [120].
type. To understand steady-state dissolution in the passive
If the electric field is assumed to increase upon a region, Heusler introduced different diffusion rates for
change in potential, the film growth will be limited by the iron and chromium cations in the film. He found an
high field ion conduction through the oxide (HFM). An agreement with experimental data for diffusion rates of
early formalisation of this concept was made by Verwey iron eight times higher than for those of chromium [67].
[111]. The HFM is in widespread use for the modelling A similar approach was argued by Kirchheim et al., who
of passive currents, and can be respresented by an adopted different transport rates for cations in combi-
equation of the form nation with the concepts developed for iron [120].
1102 C.-O.A. Olsson, D. Landolt / Electrochimica Acta 48 (2003) 1093 /1104
Measurements of the passive current [122] as well as the HFM. The MCM has been successful in fitting
estimates of the amount of dissolved material [123] were impedance as well as passive film conductivity data.
both interpreted as a lower mobility for chromium in the Recently, the electrochemical quartz crystal micro-
passive film. Further investigations also included ellip- balance (EQCM) has been used to investigate passive
sometry [124], that was used to estimate the film growth film growth [55,133,134]. It gives in situ information
current igrowth. Another possibility is to use solution with a time resolution sufficient to provide real time
analysis to measure the dissolution current icorr. This growth curves of the passive film. This has been
approach was adopted successfully by Castle and Qiu illustrated by Olsson et al., who used the EQCM to
[35], who showed that the dissolved material was heavily study passive films on Cr [119], Fe /Cr [135], and Fe /
dominated by iron. Cr /Ni /(Mo/W) alloys [136]. The film growth during a
A combination of the above ideas was introduced in potential change in the anodic direction for a Fe /Cr /
an attempt to create a general theory for passive film Ni /Mo stainless steel PVD alloy is illustrated in Fig. 7a
[136]. The fit parameters for the IFM and HFM were
growth-the mixed conduction model (MCM), which has
fixed for a 304L type PVD material and it was assumed
been applied to pure Cr [125] as well as Fe /Cr [126 /
that the addition of Mo would essentially affect the
128], Ni /Cr [129], Fe /Mo [130], and Fe /Cr /Mo alloys
ability of the film to withstand an increased electric field,
[131,132]. The MCM includes a rate limiting step at an
a hypothesis supported by the difference in thickness
interface as well as transport through the film. It starts change between the alloys. As can be seen, the IFM
out from a diffusion equation, which for potential produces a satisfactory fit to the growth curve, whereas
sweeps in the anodic direction essentially reduces to less correspondence is found for the HFM. This experi-
ment was repeated for alloys with additions of Cr and
W. The electric fields in the film derived from the HFM
and IFM fits were then compared to that calculated
directly from dividing the applied potential change by
the experimental EQCM film thickness change, cf. Fig.
7b. The IFM fit values of the electric field gave a good
correlation with the direct estimates, whereas an oppo-
site trend was found for the HFM. In addition, it was
found that alloying with Mo and W gave considerably
higher mass losses than alloying with Cr. This indicates
that their presence renders the film more permeable to
ion transport, which would allow the film to reach an
equilibrium composition faster.
5. Concluding remarks
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