Corrosion Science, Vol. 37, No. 9, pp.

141 l-1422, 1995

Pergamon Copyright 0 1995 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
0010-938X/95 $9.50 + 0.00

0010-938X(95)00048-8

THE EFFECT OF MICROCRYSTALLITES IN THE

AMORPHOUS MATRIX ON THE CORROSION BEHAVIOR
OF AMORPHOUS Fe-8Cr-P ALLOYS

B.-M. IM, M. KOMORI, B.-T. LEE, E. AOYAGI, E. AKIYAMA,

H. HABAZAKI, A. KAWASHIMA, K. ASAMI, K. HIRAGA and
K. HASHIMOTO

Institute for Materials Research, Tohoku University, Sendai 980-77, Japan

Abstract-The formation of a single amorphous Fe-Cr-P phase was strongly related to the amount of
phosphorus addition. The structure of the melt-spun Fe-8Cr-P alloys containing 16.5at% or more
phosphorus was confirmed to be amorphous by X-ray diffraction (XRD). However, high-resolution
transmission electron microscopy (TEM) revealed that a microcrystalline bee Fe phase was dispersed in the
amorphous matrix of the Fe-8Cr-16.5P and Fe-8Cr-18P alloys. The corrosion behavior of Fe-Cr-P alloys
is significantly sensitive to the presence ofmicrocrystallites in the amorphous matrix. A thick corroded layer
was formed on the Fe-8Cr-16.5P and Fe-BCr-18P alloys by immersion in 9M HsS04. A TEM image for the
thick corroded layer of the Fe-SCr-16SP alloy showed that the microcrystalline bee Fe phase was
preferentially dissolved away in the solution and that the amorphous Fe-Cr-P phase remained on the
surface of the alloy without dissolution. Accordingly, the thick corroded layer corresponds to the
amorphous Fe-C&P phase which is covered with the passive film. The addition of 20 at% phosphorus is
necessary to form an almost complete amorphous structure and to provide the high corrosion resistance
even in 9M HZS04.

INTRODUCTION

In amorphous transition metal-metalloid alloys, metalloids (B, C, Si and P) enhance

effectively the glass-forming ability and strongly modify the electrochemical behavior
of amorphous alloys. l-6 Phosphorus is the most beneficial metalloid element in
improving the corrosion resistance of the alloys,‘-9 especially if a film-forming element
such as chromium is present.‘-3,7m9 It has been shown’0p’3 that the presence of
phosphorus results in a rapid formation of highly protective passive film such as
hydrated chromium oxyhydroxide.
In a previous study,14 it was observed that the addition of 20 at% phosphorus to
Fe-8Cr-P alloy leads to a significant decrease in the corrosion rate as a result of
elimination of alloy dissolution, while the amorphous Fe-8Cr-13P-7C alloy dissolves
just after immersion in aggressive 9M H2S04 solution although spontaneous
passivation occurs later. It has also been reported” that carbon does not interfere
with the formation of the passive chromium oxyhydroxide film since carbonate is not
included in the passive -film. Accordingly, the addition of a large amount of
phosphorus is substantially effective in improving the corrosion resistance of
amorphous Fe-Cr-metalloid alloys.
Recently, the corrosion behavior of Fe-8Cr-P alloys with various contents of

Manuscript received 6 January 1995.

1411
1412 B.-M. Im et nl

phosphorus was investigated.‘” The corrosion behavior of amorphous Fe-8Cr-P

alloys is quite different with the alloy phosphorus content even though the corrosion
potentials of the amorphous Fe-8Cr-P alloys containing 16.5 at% or more
phosphorus are both ennobled to the passive region of chromium during immersion.
The amorphous Fe-Kr-16.5P and Fe-8Cr-18P alloys show high initial corrosion
losses. In addition, the corrosion losses of these two alloys increase with immersion
time. On the other hand, the corrosion loss of the amorphous Fe-8Cr-20P alloy is
hardly detected by a microbalance. These results indicate that the corrosion resistance
of Fe-8Cr-P alloys is largely affected by the change in the amount of phosphorus
addition, even though Fe-8Cr-P alloys containing 16.5 at% or more phosphorus were
found to be amorphous by X-ray diffraction (XRD). It is also observed that the
surface of the Fe-8Cr-16.5P and Fe-8Cr-I 8P alloys turns black after a short period of
immersion, such as 10 min, suggesting that the thickness of the corroded layer on these
two alloys is significantly high, such as of the order of pm. The film thickness estimated
by X-ray photo-electron spectroscopy (XPS) analysis is of the order of nm. It is
difficult to explain this disagreement of results obtained by eye observation of XRD
and XPS analysis.
Zhang et ~1.‘~ observed that the corrosion rate of the amorphous Cr-27Ni- 15P
alloy was about four orders of magnitude as high as that of the Cr-28.93Ni-15.14P
alloy, although these two alloys have very similar compositions. They explained the
difference in the corrosion resistance of these two alloys in terms of the fact that
microcrystalline phases undetectable by XRD are present in the amorphous matrix of
the Cr-27Ni-15P alloy, whereas the Cr-28.93Ni-15.14P alloy consists of a single
amorphous phase.
If microcrystalline phases are dispersed finely in the amorphous matrix in the Fe-
8Cr-16.5P and Fe-8Cr-18P alloys like the above-mentioned Cr -27Ni-15P alloy in
contrast to the formation of a single amorphous phase for Fe-XCr-20P alloy, the
difference of the corrosion behavior between the former two alloys and Fee8Cr-20P
alloy can be explained and may reveal the reason that the thickness of the corroded
layer formed on Fe-8Cr-16.5P and Fe-SCr-18P alloys estimated by XPS analysis is
very thin in comparison with actual thickness of the corroded layer. It is, however,
impossible to detect whether microcrystalline phases exist or not in the Fe-SCr-I 6.5P.
Fe-8Cr-I 8P and Fe-8Cr-20P alloys only by XRD.
In this work, an attempt was made tried to investigate the microstructure of the
Fe-8Cr-P alloys by means of high resolution transmission electron microscopy
(TEM). Particular attention was paid to the effect of the microstructure on the
corrosion behavior of the Fe-8Cr-P alloys.

EXPERIMENTAL METHOD
The alloys used have the following nominal compositions in at%: Fe- 80 16.5P, Fe-XCr- 15P and Fe-
8Crr2OP. Crystalline alloys were first cast into rod-shaped ingots by water quenching; mixtures of prescribed
amounts of commercially pure iron (99.9 wt%), pure chromium (99.3 wt%) and laboratory made iron-
phosphide were melted by high frequency induction melting under an argon atmosphere and then sucked up
into quartz tubes to get mother alloy ingots. The alloys were prepared by melt-spinning in the shape of
ribbons with a width of l-2 mm and a thickness of ICUO urn. By the conventional XRD method, all the
samples used in this study were apparently amorphous. The ultramicrotomed cross-sections of corroded
specimens were observed by a conventional 200 kV transmission electron microscope. In addition, the
structure of these alloys was examined in more detail by means of high-resolution TEM by using a 400 kV
 Amorphous Fe-8Cr-P alloys 1413

electron microscope (JEM-4000EX) with a resolution of 0.17 nm. Cross-sections of specimens for TEM
observations were prepared using a RMC MT-7 ultramicrotome.
The electrolyte used in this study was 9M H2S04 solution open to air, which was prepared from a reagent
grade chemical and de-ionized water. The concentration of the acid was chosen because the sulfuric acid of
this concentration is most aggressive for iron base alloys. Before immersion and electrochemical
measurements in the electrolyte, both sides of alloy specimens were polished in cyclohexane with silicon
carbide paper up to No. 1000, degreased with acetone and dried in air.
After immersion in the acid for different times, surfaces of Fe-ICr-P alloys were analysed by XPS
(Shimadzu ESCA-850 electron spectrometer with Mg K, excitation; hv = 1253.6 eV). Binding energies of
XPS were calibrated by the method described elsewhere.‘8,‘9 The compositions of the surface film and the
underlying alloy surface were quantitatively determined by the previously proposed method*“” by using
integrated intensities of the XPS spectra under the assumption of three layered structure: the outermost
contaminant hydrocarbon layer, the corrosion product (passive film) and the substrate alloy with X-ray
photo-electron spectroscopically infinite thickness, in each layer of which elements distribute
homogeneously.
Scanning electron microscopy (SEM) (Hitachi S-800) was used to observe the cross-section of the
specimen after immersion.

EXPERIMENTAL RESULTS

In a previous study, I6 it was reported that the amorphous Fe-8Cr-20P alloy

maintained metallic luster even after immersion for 168 h in 9M H$304. This indicates
that corrosion hardly occurred on the amorphous Fe-8Cr-20P alloy. By contrast,
amorphous Fe-8Cr-16.5P and Fe-8Cr-18P alloys became black by immersion for
about 10 min and the black color of the surface became deeper with immersion time,
suggesting that these two alloys are corroded severely in 9M H2S04 solution and
covered with a thick corroded layer.
Figure 1 shows a cross-section of Fe-Kr-16.5P alloy observed by the scanning
electron microscope (SEM) after immersion for 24 h. The thickness of the corroded

Corroded layer

,Subs tra te

Fig. 1. SEM image of cross-section of the amorphous Fe-8Cr-16.5P alloy after immersion
in 9M H2S04 solution at 30°C for 24 h.
1414 B.-M. Im et al.

Co/rroded pyer

(a) Fe-BCr- 16.5P (b) Fe-8Cr-16.5P (c) Fe-BCr- 16.5P

As-polished immersed for IOmin immersed for 24h
in 9M H,SO, in 9M H2S04

Fig. 2. TEM images of ultramicrotomed cross-sections of the amorphous Fe-8Crl6.5P

alloy polished mechanically (a) and after immersion in 9M H$SOh solution at 30°C for IO min
(b) and 24 h (c).

layer formed on the Fe-8Cr-16.5P alloy is significantly thick and is approximately

1 pm.
For a detailed observation of the corroded layer, the structure of ultramicrotomed
cross-sections of the Fe-8Cr-P alloys after mechanical polishing and immersion in the
acid was investigated by means of TEM. Figures 24 show cross-sections of Fe-8Cr-
16.5P, Fe-8Cr-18P and Fe-8Cr-20P alloys observed by TEM, respectively. The thick
corroded layer is formed on the surfaces of Fe-8Cr-16.5P and Fe-8Cr-18P alloys by
immersion for short times such as 10 min, as shown in Figs 2(b) and 3(b), respectively.
Prolonged immersion results in further thickening of the corroded layer, as shown in
Fig. 2(c). By contrast, as shown in Fig. 4, the corroded layer on the amorphous Fe-

(a) Fe-8Cr- 18P (b) Fe-8Cr- 18P

As-polished immersed for 1Omin
in 9M H,SO,
Fig. 3. TEM images of ultramicrotomed cross-sections of the amorphous Fe-SCr-18P alloy
polished mechanically (a) and after immersion in 9M HZS04 solution at 30°C for 10 min (b).
 Amorphous F&K&P alloys

(a) Fe-8Cr-2OP (b) Fe-8Cr-2OP

As-polished immersed for 1Omin
in 9M H *SO,
Fig. 4. TEM images of ultramicrotomed cross-sections of the amorphous Fe-8Cr-20P alloy
polished mechanically (a) and after immersion in 9M H$SOd solution at 30°C for 10 min (b).

8Cr-20P alloy after immersion is too thin to be detected by the TEM image of the
cross-section.
It has been well known20321that, in the XPS analysis, the film thickness is estimated
by intensities of photo-electrons from metallic species on the assumption of the
extinction of photo-electrons through the film. Because of the extinction the detectable
depth is less than 10 nm.
Figure 5 shows changes in photo-electron spectra of Fe-8Cr-16.5P alloy as a

Cr 2pJn
Fe-BCr- 16.5P Fe-ECr-16SP
9M H2SO4,3o”C

Immersed for dtfferent ttmes

r---l
mmemed for d/fferent Umes

Binding Energy / eV Binding Energy / eV Binding Energy / eV

Fig. 5. Fe 2~3,~ (a), Cr 2~3,~ (b) and P 2p (c) photo-electron spectra measured from the
amorphous Fe-8Cr-16SP alloy polished mechanically in cyclohexane and after immersion in
9M H2S04 solution at 30°C for different times.
1416 B.-M. Im et al.

function of time of immersion in 9M H2S04. All these spectra consist of two peaks
corresponding to a low binding energy peak of the metallic state and a high binding
energy peak of the oxidized state. In spite of the fact that the thickness of the corroded
layer on the Fe-8Cr-16.5P alloy exceeds 100 nm as shown in Fig. 2, the intensities of
the metallic signals of Fe and Cr 2psiZ electrons increase with immersion time.
Thicknesses of the surface films formed on these three alloys by immersion in 9M
H$04 were estimated from the integrated intensities of XPS spectra and were about
2 nm regardless of alloy composition.‘6 This cannot be explained if the thick corroded
layer on the Fe-8Cr-16.5P and Fe-8Crrl8P alloys is composed of oxidized corrosion
products.
From these observations, it can be considered that metallic elements such as iron,
chromium and phosphorus are dispersed in the thick corroded layer and hence the
photo-electrons from metallic species in the corroded layer seem to be measured
directly without a large extinction. In order to obtain further information on the

Fig. 6. High resolution TEM and selected area electron-diffraction (ED) pattern for Fe
SCr- 16.5P alloy before immersion.
 Amorphous Fe-80-P alloys 1417

corroded layer, ultramicrotomed cross-sections of the Fe-8Cr-16.5P alloy were

analysed by means of high-resolution TEM and corresponding selected area electron
diffraction (ED).
Figure 6 shows a high-resolution TEM image and a corresponding electron
diffraction pattern of the Fe-8Cr-16.5P alloy before corrosion. The high-resolution
TEM image and ED pattern of the Fe-8Cr-20P alloy are also shown in Fig. 7, for
comparison. As mentioned above, the structures of the Fe-8Cr-16.5P and Fe-8Cr-
20P alloys were characterized to be amorphous by XRD. However, as shown in Figs 6
and 7, the ED pattern and TEM image of the Fe-8Cr-16.5P alloy are quite different
from those of the Fe-8Cr-20P alloy. The ED pattern for the Fe-8Cr-16.5P alloy
shows the presence of a crystalline phase besides a halo pattern of an amorphous
phase. The strongest broad ring consists of two rings denoted as 110 and M. The outer
broad ring M corresponds to the first halo of an amorphous phase, and the 110 ring is
the most intense ring of the bee Fe phase. Accordingly, the Fe-8Cr-16.5P alloy

Fig. 7. High resolution TEM and selected area ED pattern for the matrix of Fe-8Cr-20P
alloy.
1418 B.-M. Im et al.

consists of a mixture of bee Fe and amorphous phases. The TEM image of this alloy
also shows microcrystallites dispersed finely in the amorphous matrix. This
microcrystallites seem to be the bee Fe phase identified by selected area ED.
The ED pattern of the Fe-8Cr-20P alloy shown in Fig. 7 is composed of no
diffraction rings for the bee phase but only a halo. Although the halo may be slightly
sharper than the typical amorphous halo, it is difficult to find the ordered structure
exceeding 1 nm in size in the TEM image. It can, therefore, be said that the Fe-K&
20P alloy is almost completely amorphous.
Figure 8 shows a high-resolution TEM image and a corresponding ED pattern for
the thick corroded layer of the Fe-8Cr-16.SP alloy after immersion for 24 h. The
selected area ED pattern of the corroded layer shows no diffraction of the
microcrystalline bee Fe phase although the halo ring corresponding to the
amorphous alloy can be seen in addition to some diffraction rings of corrosion

Fig. 8. High resolution TEM and selected area ED pattern for the cross-section of corroded
layer of Fe-Kr- 16.5P alloy after immersion in 9M H2S04 solution at 30°C for 24 h.
 Amorphous Fe-8Cr-P alloys 1419

products. The TEM image of the corroded layer is composed of a typical amorphous
structure. This result clearly indicates that the microcrystalline bee Fe phase dispersed
finely in the amorphous matrix is preferentially dissolved away by immersion in 9M
H2S04 solution. As a result of preferential dissolution of the microcrystalline bee
phase, only the amorphous phase remains on the surface of the Fe-8Cr-16.5P alloy
without dissolution. Accordingly, a black thick corroded layer formed on the
amorphous Fe-8Cr-16.5P alloy by immersion in 9M H$04 seems to be composed
of the amorphous phase and some corrosion products.
The corrosion loss of the Fe-8Cr-20P alloy is not detected by a microbalance’43i6
and the thickness of the corroded layer on the amorphous Fe-8Cr-20P alloy after
immersion is hardly detected by TEM observation as shown in Fig. 4. It can, therefore,
be said that the Fe-8Cr-20P alloy is covered by the thin passive film.

DISCUSSION

The structure and the corrosion behavior of the amorphous Fe-SCr-P alloys are
very much affected by the amount of phosphorus present. Demaree et ~1.~~examined
chemical and structural effects of phosphorus on the corrosion behavior of Fe-Cr-P
alloys prepared by ion beam mixing. They indicated that the resistance of the alloy to
anodic dissolution is not affected by the amorphous phase formation but is primarily a
function of the amount of phosphorus addition. In a recent study,16 the addition of
20 at% phosphorus to the Fe-SCr-P alloys was shown to lead to a significant decrease
in the corrosion rate and also to an elimination of initial active dissolution, while the
amorphous Fe-8Cr-P alloys containing 16.5 and 18 at% phosphorus suffer initial
active dissolution in aggressive 9M H2SO4 solution.
In the present study, SEM and TEM observations reveal that the black thick
corroded layer thicker than 100 nm is formed on the amorphous Fe-SCr-16.5P and
Fe-8Cr-18P alloys even after immersion for a short time such as 10 min in 9M H2S04
solution and becomes much thicker with increasing immersion time. Signals of the
metallic state are clearly seen. These become more intense in XPS spectra with
increasing immersion time after the thick corroded layer is formed on these two alloys.
This implies that the thickness of corrosion products covering the alloy phase is less
than 10 nm. According to XPS analysis after the formation of the thick corroded
layer, metallic elements such as Fe, Cr and P were found in the metallic state andthe
phosphorus contents for the Fe-8Cr-16.5P and Fe-SCr-18P alloys were generally
higher than the bulk alloy composition, suggesting the preferential dissolution of
alloying elements other than phosphorus.16
High resolution TEM reveals that the Fe-8Cr-P alloys with 16.5 at% phosphorus
consist of a very fine bee Fe phase dispersed in the amorphous matrix, even though
16.5P alloy has been confirmed to be amorphous by XRD.
A comparison of TEM images and ED patterns for the alloy matrix and for the
thick corroded layer of the Fe-8Cr-16.5P alloy shown in Figs 6 and 8 indicates that
the bee Fe phase is preferentially dissolved by immersion in 9M H2S04 solution while
the amorphous phase remains without dissolution. Accordingly, the preferential
dissolution of the microcrystalline bee Fe phase seems responsible for the high initial
active dissolution and the increase in the corrosion loss of Fee8Cr-16.5P and Fee8Cr-
18P alloys with immersion time.16 The phosphoru s c ontent of the bee Fe phase should
be lower than the amorphous Fe-Cr-P phase. Although the bee Fe phase contains
1420 B.-M. Im et al.

chromium, it is well known that a crystalline Fe-Cr alloy whose chromium content is
of the order of 8 at% is easily dissolved even in diluted acid. Consequently, immersion
of alloys consisting of a mixture of amorphous and bee Fe phases results in
preferential dissolution of the bee Fe phase, leaving the passivated amorphous phase
on the specimen surface.
By contrast, the TEM image of the Fe-8Cr-20P alloy is almost typical of the
amorphous structure. Because of no easily corrodible bee Fe phase, the Fe-8Cr-20P
alloy shows the undetectable corrosion loss and maintains the metallic luster even
after immersion for 168 h.14,16 Consequently, at least 20 at% addition of phosphorus
is necessary to form an entirely amorphous structure and to provide the high corrosion
resistance.
The film thicknesses formed on Fe-8Cr-I 6.5P and Fee8CrI 8P alloys estimated
by XPS” are quite thin even though the thick corroded layer is formed on these two
alloys by immersion. As mentioned above, the thick corroded layer of Fee8Cr-16.5P
and Fe-8Cr-18P alloys consists mostly of the amorphous phase.
In addition, it was reportedI that the open circuit potentials of the amorphous Fe-
8Cr-P alloys containing 16.5 at% or more phosphorus increased during immersion
from the active state to the passive state of chromium. Accordingly, the thickness of
the film on the Fe-8Cr-16.5P and Fe-8Cr-18P alloys detected by the XPS analysis
corresponds to the thickness of the passive film on the amorphous phase. Since the
thick corroded layer is composed of the passive amorphous alloy phase particles, the
XPS analysis detects strong signals of metallic elements in the amorphous alloy phase
in the outerpart of the thick corroded layer. Consequently, the thick corroded layer
consists of the amorphous Fe-Cr-P phase covered with the passive film. A schematic
drawing of this explanation is presented in Fig. 9. The microcrystalline bee Fe phase
dispersed in the amorphous matrix of Fe-8Cr-I 6.5P and Fee8Cr-18P alloys dissolves
preferentially by immersion in 9M H2S04 solution. As a result of the preferential
dissolution of microcrystallites, the amorphous Fe-Cr-P phase covered with a passive
film remains on the surface of these two alloys forming the thick corroded layer. The
Fe-8Cr-20P alloy consisting of a single amorphous phase does not suffer serious

metallic Fe,Cr and P metallic Fe,Cr and P

thickness of the

cc

P:
cl

h
microcrvstallites
:
Fig. 9. Schematic of surface on Fee8Cr- 16.5P and FekN320P alloys.
 Amorphous Fe-80-P alloys 1421

corrosion and is covered by a passive film. Accordingly, the metallic species found by
XPS analysis for the Fe-SCr-20P alloy are located in the alloy surface just under the
passive film.
The ennoblement of the open circuit potentials of these alloys from the active state
to the passive state of chromium has been attributed to the beneficial effect of
phosphorus which has been discussed previously.7,‘4,‘6,23

CONCLUSIONS

The relationship between the microcrystalline phase and the corrosion behavior of
Fe-8Cr-P alloys is investigated. The following conclusions are drawn:

(1) High resolution TEM reveals that a microcrystalline bee Fe phase is dispersed
finely in the amorphous matrix of Fe-8Cr-16.5P and Fe-8Cr-18P alloys. This
microcrystalline bee phase cannot be detected by XRD. The microcrystalline bee Fe
phase is preferentially dissolved into 9M H2S04 and the spontaneously passivated
amorphous Fe-Cr-P phase remains on the surface of Fe-8Cr-16SP and Fe-8Cr-18P
alloys as a thick corroded layer. The preferential dissolution of the microcrystalline
bee phase in the amorphous matrix is responsible for an initial high corrosion rate of
the Fe-8Cr-16.5P and Fe-8Cr-18P alloys.
(2) TEM observation shows that the Fe-8Cr-20P alloy with extremely high
corrosion resistance in aggressive 9M H2S04 solution is amorphous.
(3) The corrosion behavior of Fe-8Cr-P alloys is quite sensitive to the
microcrystalline phase dispersed in the matrix. In addition, it is necessary to form a
single amorphous phase for extremely high corrosion resistance. The addition of a
large amount of phosphorus is quite effective in forming a complete amorphous phase.
(4) In conclusion, in the case of Fe-8Cr-P alloys, the addition of at least 20 at%
phosphorus is necessary for forming an amorphous structure and for high corrosion
resistance.

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