Journal of Nuclear Science and Technology

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Effect of Oxygen Partial Pressure on Oxidation of

Iron at 573 K

Hitoshi SAKAI , Toshihide TSUJI & Keiji NAITO

To cite this article: Hitoshi SAKAI , Toshihide TSUJI & Keiji NAITO (1984) Effect of Oxygen
Partial Pressure on Oxidation of Iron at 573 K, Journal of Nuclear Science and Technology, 21:11,
844-852, DOI: 10.1080/18811248.1984.9731123

To link to this article: https://doi.org/10.1080/18811248.1984.9731123

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Journal of NUCLEAR SCIENCE and TECHNOLOGY, 21(11], pp. 844-852 (November 1984).

Effect of Oxygen Partial Pressure on

Oxidation of Iron at 57 3 K
Hitoshi SAKAI, Toshihide TSUJI and Keiji NAITO

Department of Nuclear Engineering,

Faculty of Engineering, Nagoya University*

Received july 4, 1984

The oxidation of iron was investigated by Rutherford backscattering spectroscopy at

573 K under the oxygen partial pressure from 10- 1 to 105 Pa for 3-24 h. In the first stage
of oxidation, thickness of the oxide film reached the maximum around 1 Pa. In the second
stage the oxidation obeyed the parabolic rate law. From 10- 1 to 10- 0 • 5 Pa the parabolic rate
constant increased with increasing oxygen partial pressure due to the growth of magnetite,
whereas from 1 to 10°· 5 Pa hematite covered magnetite but the parabolic rate constants were
kept still high values possibly due to the presence of grain boundaries. Between 10 and
10u Pa the protective hematite coverage over magnetite kept the parabolic rate constants
low regardless of oxygen partial pressure. At 105 Pa a sharp increase of the parabolic rate
constant was observed due to the simultaneous growth of hematite and magnetite. The
oxygen concentration in water for the inhibition of the corrosion may correspond to the
oxygen partial pressure for the formation of protective film in gas phase around 573 K.
KEYWORDS: Rutherford backscattering spectroscopy, oxidation, iron, oxygen
partial pressure, coolants, corrosion, oxygen concentration, high temperature,
pressure dependence, protective films

I. INTRODUCTION
The radioactivity buildup in the primary coolant systems of water reactors has been
increasing year by year, which is caused by the deposition of the corrosion products re-
leased from the structural materials. Videm <1 l showed that the addition of small amount
of oxygen gas into the coolant water reduced the corrosion of carbon steel in the simulated
BWR environment effectively due to the formation of protective oxide film. The details
of the behavior of the corrosion, however, have not been understood quantitatively yet.
Water as a coolant has such a low electrical conductivity that the growth of the oxide
film as well as the metal dissolution plays a major role as the corrosion process. From
this point of view the study on the oxidation behavior of iron at 573 K under the various
oxygen partial pressures was expected to assist us to clarify the effect of oxygen concentra-
tion on the corrosion of carbon steel in the coolant.
The oxidation of iron below 673 K has been studied by many investigators<zJ-< 1 <) mainly
under reduced pressures, and some authors revealed that two-stage oxidation took
place<sJ <5 J <sJ <•J : In the first stage the iron was oxidized very rapidly and then rather slowly
in the second stage. The occurrence of the transition from the first stage to the second
stage was delayed as temperature decreased; a few ten minutes at 623 K and several hours
at 523 K. The behavior of oxidation in the first stage being very complex, the loga-
rithmic <2 J-(5), the double-logarithmic <l3J o•J or the parabolic rate law< 5 J-< 12 J was suggested for
various oxygen partial pressures and temperatures. The logarithmic rate law seemed to
* Furo-cho, Chikusa-ku, Nagoya 464.

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Vol. 21, No. 11 (Nov. 1984) 845

be obeyed at lower temperatures and lower oxygen partial pressures although it was not
the case in some investigators<•> <l2>. It was shown that the oxidation rate in the first stage
depended very much on the oxygen partial pressure at 543< 8 >, 623 and 673 K< 9 >.
In the second stage several investigators reported that the oxidation proceeded para-
9
bolically<•: <•> <7>< ~. The parabolic rate constant in the second stage was reported by Graham
et at.< 9 > to be almost independent of oxygen partial pressure in the range of I0- 2"-'1 Pa at
623 and 673 K, however, both reported values of the parabolic rate constant around 573 K
by Caule et at. <7 > at 10'·' Pa and Davies et at. w at 10'·' Pa seemed to be different, indicat-
ing the dependence of oxygen partial pressure. The effect of oxygen partial pressure in
wide range upon the rate constant has not been clear so far partly dt.:e to the scattering
of the data.
The scattering of the data of parabolic rate constants below 673 K may be originated
from the sensitivity limit of the microbalance which has been used by most of the investi-
gators. The optical method <•> was suitable for measuring the very thin oxide (less than
50nm). The manometric method<•>ooo 2 > was able to be applied to the thicker oxide as
well as the very thin oxide, however unable to maintain the oxygen partial pressure con-
stant during oxidation. The application of conversion electron backscattering Mossbauer
spectroscopy (CEMS) o•> may be difficult to determine the oxide thickness precisely when
both magnetite and hematite are formed.
The Rutherford backscattering spectroscopy (RBS) is one of the useful techniques for
the determination of thickness, which can measure the thickness directly by way of stop-
ping power of the thin layer for ion beam. It has already been proved that RBS was very
useful for measuring the thickness of the oxide film between 50 and 500 nm <m (18).
In the present study the thickness of the oxide formed on iron under the oxygen
partial pressure ranging IQ- 1 "-'10 5 Pa controlled precisely at 573 K is measured by RBS in
order to clarify the oxidation behavior and the effect of oxygen partial pressure on it.
The oxide films formed are detected by CEMS and X-ray diffractometry.

ll. EXPERIMENTAL
The iron specimen used was 2 mm-thick sheet with 99.5% purity. The specimen was
cut from a cold-rolled sheet (thickness 0.50 mm) to a size of 15 X 15 mm. After abrading with
a 800-grit silicon carbide and degreasing with ethyl alcohol, the specimen was polished for
5 min in an oxalic acid (10.0 g)-hydrogen peroxide (20 m/)-water (270 ml) mixture at 315 K,
followed by 1 min electropolishing in an acetic acid (190 ml)-perchloric acid (10 ml) solution.
Then the specimen was annealed in vacuum at 970 K for 2 h. The chemical- and eiectro-
polishings were repeated again just before use.
The apparatus is shown schematically in Fig. 1. The flowing gas was purified by
passing through 5A molecular sieves column cooled with a dry ice-acetone solution as a cold
trap 09 >. The oxygen, the air and the argon-oxygen mixture gases were used for control-
ling the oxygen partial pressures. For the oxygen partial pressures from IQ- 1 to 102 Pa,
the amount of oxygen in argon gas was regulated with a stabilized zirconia solid-electrolyte
cell at 1,023 K as an oxygen pump< 2o>. The oxygen partial pressure was determined and
monitored continuously by nonstoichiometric cobaltous oxide oxygen sensors< 20 •
After a constant oxygen partial pressure and a constant temperature were maintained,
the suspended specimen was inserted into the furnace by means of a magnet. It was
confirmed by oxygen sensors placed before and after the specimen that the change in
-41-
846 ]. Nucl. Sci. Techno/ ..

............... Ar,Ar-0 2 ,
Molecular sieves Air or 02
,.---- in dry ice-acetone E - -
Magnet
180K

L-?
1~1
Zr0 2(CaO)
o2 pump
1023K
~
::""'' "=11
1~1
Co1-xO
o2 sensor
1273K
Fe sheet
15x1 5x0.5mm

~
I:::::::==<:::::1 I~ Sample

I~ I 573 K

Flow Co 1_x0

out
Meter
1.2-14.1 ml/s
r- o2sensor
1273K

I~ I ....._
Fig. 1 Schematic diagram of experimental apparatus

oxygen partial pressures was negligibly small during the oxidation, which indicated that
the oxidation took place in a constant oxygen partial pressure. After the oxidation for a
certain time the specimen was raised out of the furnace and cooled without changing the
oxygen partial pressure. The thickness of the oxide film formed was determined by RBS,
and the oxides were analyzed by means of CEMS or X-ray diffractometry. The specimen
was again brought back to the apparatus to be oxidized further, which meant one specimen
was oxidized repeatedly in the same oxygen partial pressure. Finally the surface of the
oxide was observed by scanning electron microscopy (SEM).
In RBS a 1.5 MeV 'He+ and a 1.0 MeV 1 H+ ion beams were impinged vertically on the
specimen for thinner and thicker oxide films than 300 nm, respectively. The size of the
ion beam spot on the specimen was about 1 mm in diameter. Ions backscattered at an
angle of 160° were measured with a silicon surface barrier detector. The current on the
specimen was about a few ten nanoampere so that the counting time could be shortened
20 min or less. The following equation was used to calculate the thicknesso.;>:
L1E=(Ks(E 0 )+ c(K£ 0 ) / Icos(} I )Nt, (1)
where ilE is the energy loss between incident and backscattered beams, K the kinematic
factor, Eo the incident beam energy, (} the scattering angle ( = 160°), t the thickness, s(E)
the stopping cross section per atom at energy E and N the number of atoms per unit
volume. The stopping cross sections of the oxides, magnetite and hematite, were estimated
by applying the Bragg's rule of additivity with the stopping cross sections of iron and
oxygen<zz>. It has already been provedm>~<zs> that the Bragg's rule is valid for the iron
oxides if the effective oxygen stopping cross section is adopted. Since the difference be-
tween stopping cross sections of magnetite and hematite is less than 1.5%, the oxide thick-
ness was determined assuming the oxide consisting of only magnetite regardless of the
oxide ratio of magnetite to hematite.
In CEMS the conversion and Auger electrons emitted from the surface of the oxide
film were detected by a He/CH 4 gas flow proportional counter. The only outermost peak
was used to calculate the peak area for hematite or magnetite, since others were too much
-42 ·-
Vol. 21, No. 11 (Nov. 1984) 847

superimposed by iron, hematite and/or magnetite to discriminate one another precisely.

m. RESULTS
Figure 2 shows the typical Rutherford backscattering spectra when a 1.5 MeV 'He'
beam was impinged on the oxide formed on iron after 6 h in various oxygen partial pressures
at 573 K. The energy width between the midpoints of the slopes can correspond to the
thickness in terms of Eq. ( 1 ). The accuracy of the calculated thickness depended mostly
on that of the stopping cross section of the oxide as long as the metal-oxide interface was
clearly determined in the spectrum. Since the error of the stopping cross section was less
than 5%, the error of the calculated thickness was considered to be less than 5% except
the case for the oxide thinner than 100 nm because of the difficulty of the precise deter-
mination of the metal-oxide interface in the spectrum. Since the difference in the thick-
nesses from position to position was often more than 5%, it was shown that the surface
was not so smooth. The boundary between oxide layers was unable to be found in the
spectra although the oxide was supposed to consist of two layers, magnetite and hematite.
This is because the values of stopping cross sections of both oxides 'i'ke so close to each
other that it was beyond the resolution limit of the detector to distinguish them.
The thickness of the oxide film formed under various oxygen partial pressures at 573 K
is plotted against square root of time in
Fig. 3. The error bar stands for the ex-

242 nm 12 24
300
log(Po,JPa)=
0.0

0.5
5.0
2.0
-0.5

E
c

4.3

Incident beam: 1.5 MeV 'He+ 00~------~------~--------~--~

Scattering angle detected: 160°
Sample current: -30 nA
Counting time: -15 min
Fig. 2 Rutherford backscattering spectra
of oxides formed on iron after 6 h
between 1 and 103 Pa at 573 K
100 t, 121 5112 200 l:>O
- · - · - Boggs et al. at 543 K"'
------ Gulbransen at 573 KC2l
-··-··- Hussey et al. at 573 K""
Fig. 3 Growth of oxide film on iron at various.
oxygen partial pressures at 573 K

~ 43 ~
 848 ]. Nucl. Sci. Techno!.,

tent of the scattering of the thicknesses measured at a few different positions in the same
sample. It is seen from the figure that the thickness at all oxygen partial pressures in-
~reased linearly with square root of time
during the measured oxidation time, which (0)

indicates that the oxidation obeyed the par-

abolic rate law in the second stage. The
0
.
validity to· obey this law will be discussed
later. The thickness at 3 h increased with
increasing oxygen partial pressure from IQ- 1
to 1 Pa, whereas it had a tendency to decrease 0
with increasing oxygen partial pressure fur-
ther. The latter trend was consistent with
the results obtained in the first stage at ~1.0 (b)
<!
:S43 K by Boggs et at.<sJ as shown in Fig. 3. 0::
1n oxygen, 105 Pa, the slight deviation from ~0.5
w
the straight line was noticeable and the z
<>xidation proceeded most rapidly although ~ o~~--~L---~--~~--~--~~--~~
the thickness of the oxide film at 3 h was
relatively thin. Fig. 4(a) (above) Parabolic rate constant
The parabolic rate constant obtained vs. oxygen partial pressure at 573 K
from the slope in Fig. 3 is shown as a func-
<• Caule et al. at 569K<7l, 'Y Davies
et al. at 573 K<•J, • Lustman at 573
tion of oxygen partial pressure in Fig. 4(a). K<•J and 0 this work at 573 K)
Figure 4(b) indicates the ratio of the mag- (b) (below) Ratio of magnetite peak
area to total oxide peak area of oxide
netite peak area to the total oxide area for
formed after 24 h by CEMS ¢ and
the specimen after 24 h oxidation at each X-ray diffractometry D.

~a) IQ- 0 •5 Pa, thickness 181 nm

(b) 1 Pa, 277 nm (c) 102 Pa, 181 nm (d) 105 Pa, 184 nm
Photo. 1 Surface photography of oxide tormed after 24 h in
various oxygen partial pressures at 573 K by SEM

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Vol. 21, No. 11 (Nov. 1984) 849

oxygen partial pressure by means of CEMS and X-ray diffractometry. The intensity of
the peak detected by X-ray diffractometry was so weak that the results could be regarded
as supplements. However, the results by X-ray diffractometry still have good correspondence
with those by CEMS, and enabled us to estimate the magnetite ratio approximately when
the results by the latter are lacked, for example, at 105 Pa. The parabolic rate constant
increased from 10- 1 to 10- 0 • 5 Pa where the oxide consisted mainly of magnetite. Around
1 Pa there appeared a maximum where both hematite and magnetite existed in about equal
amount. A similar maximum was observed around 1 Pa at 773 K as reported previously< 26 >.
Considering the reproducibility of the data, the parabolic rate constant was nearly inde-
pendent of oxygen partial pressure between 10 and 10'·" Pa. In this region the ratio of
magnetite to the oxides tended to decrease with increasing oxygen partial pressure. At
105 Pa a sharp increase of the parabolic rate constant was observed where both oxides
were detected by X-ray diffractometry. The agreements with the results by Lustman<"> in
air and those by Caule et al. <7 >at 10"·' Pa were fairly good, however those by Davies et al. <•>
in air was larger than ours.
The surface photography of the oxide formed at various oxygen partial pressures after
24 h oxidation was observed by SEM and shown in Photo. 1.
IV. DISCUSSION
1. Oxidation in Gas Phase
The parabolic rate constant k P is usually defined as
W 2 =kpt or W=v'iipv' (, ( 2)

where W is the weight gain and t the oxidation time. However in such a case that the
oxidation in the second stage started at a time t 0 and a weight gain W0 , the parabolic rate
constant should be defined as
( 3)

Although t 0 was not determined in the present study, it was estimated to be around 1 h
which was small enough to allow us to assume that t 0 =0 for the determination of the
parabolic rate constant with Eq. ( 3 ). In fact if t 0 =1 h, the oxidation kinetics still obeyed
the parabolic rate law and the differences of the parabolic rate constants between t 0 =1 h
and t 0 =0 h were less than 15%.
In the first stage the thickness at 3 h showed a maximum around 1 Pa as seen from
Fig. 3. The thickness had a tendency to decrease as the oxygen partial pressure increased
from 1 Pa. This tendency was consistent with the results at 543 K reported by Boggs
et al. <s>, who suggested that more rapid coverage of hematite as a protective film over
magnetite should occur with increasing oxygen partial pressure above 1 Pa. Below 1 Pa the
thickness decreased with decreasing oxygen partial pressure. It is considered that the
growth of magnetite may proceed slowly at lower oxygen partial pressures due to the
smaller gradient of the oxygen potential in the oxide layer as was suggested by Graham
et al. <9 > for the results in 10- 2 to 1 Pa at 623 K.
In the second stage the proposed mechanism will be divided into four oxygen partial
pressure regions as follows :
(a) 10- 1 to 10-o.s Pa : In this region, the oxide consisted mostly of magnetite even after
24 h oxidation. If the growth of magnetite is dominant, the increase of the parabolic rate
constant with increasing oxygen partial pressure can be expected, since the diffusion in
-45-
850 ]. Nucl. Sci. Techno/.,

the oxide increases with increasing oxygen partial pressure. However the slope obtained
was very large, although this was determined only from the two experimental points. The
parabolic rate constants at the oxygen partial pressure lower than I0- 1 Pa are necessary to
discuss the mechanism of oxidation from the slope. The surface of the oxide observed by
SEM shown in Photo. 1 (a) showed little lateral growth of hematite compared with Photo.
l(b) where lateral growth of hematite from grain boundaries is observed clearly.
(b) 1 to 10°· 5 Pa: Judging from the ratio of magnetite to total oxide determined by
CEMS, hematite can cover magnetite completely. However the oxidation was not retarded
so much as expected. The surface of the oxide observed by SEM in this region showed
the existence of grain boundaries as shown in Photo. l(b). It may be expected that hema-
tite could cover magnetite laterally on each grain to reduce the rapid growth of magnetite,
however grain boundaries existed to allow the grain boundary diffusion. The previous
results at 773 K (26 > showed a similar maximum around 1 Pa due to the competitive reactions
with increasing oxygen partial pressure between the faster growth of magnetite and the
quicker formation of hematite as a protective film. On the contrary, Graham et al. (9 >
suggested that the parabolic rate constants of the second stage were almost independent of
oxygen partial pressure between I0- 2 and 1 Pa at 623 and 673 K. This discrepancy may be
originated from the fact that their parabolic rate constants for the second stage were cal-
culated from the data obtained in very short time period ; around 1 h.
(c) 10 to 104.3 Pa: As shown in Photo. 1(c) there existed no grain boundaries. It is
thought that hematite could cover magnetite so uniformly that the grain boundary diffusion
would be reduced much. The uniformity of the oxide layers formed around 573 K at
103 •4 Pa was suggested by Caule et a!. (7 ) from the cathodic reduction curve. The tendency
to decrease of the ratio of magnetite to total oxide with increasing oxygen partial pressure
in this region is explained by the fact that amount of growth of magnetite in the first
stage decreases with increasing oxygen partial pressure. The fact that the parabolic rate
constant was nearly independent of oxygen partial pressure makes it possible to assume
that the diffusion in hematite was not so affected by oxygen partial pressure.
(d) 105 Pa: The surface of the oxide observed by SEM revealed the occurrence of many
pittings as seen in Photo. 1(d). The exact parabolic oxidation behavior was not observed,
and both magnetite and hematite grew simultaneously as indicated by X-ray diffractometry.
It is therefore considered that the uniform oxide layers could not be formed. At 773 K a
similar sharp increase of the parabolic rate constant was observed at 10 Pa due to the crack
formation of the oxide as shown in the previous work( 26 >.
2. Comparison with Corrosion in Water
The effect of oxygen concentration on the corrosion of iron and mild steel in high-
temperature and high-pressure water around 573 K has not been investigated very well
because of the difficulty of the experiment. The kinetics of the corrosion of mild steel
around 573 K was reported at several oxygen concentrations between "degassed" and 10
ppm, showing that the corrosion rates obeyed the parabolic rate law roughly(!) (28 >(29 >.
Ruther et a!. (so> showed that iron suffered severe pitting at 35 and 50 ppm, and formed
protective films at 290 and 540 ppm at 588 K. Videm (1) suggested that the corrosion be-
havior of carbon steel in water around 573 K was divided into three regions; 'inhibition',
'pitting' and 'passivation', depending on the oxygen concentration in water.
The corrosion rate of iron in water can be compared with the oxidation rate in a gas,
provided that the amount of metal lost due to the corrosion in water would be converted
-46-
 Vol. 21, No. 11 (Nov. 1984) 851

to the amount of the oxide to be gained. The film growth rate in water, which is obtained
by subtracting the release rate from the corrosion rate, can also be converted in the same
manner. Considering that the oxygen in water is in equilibrium with the oxygen gas over
water, the oxygen partial pressure equilibrated with the oxygen concentration in water is
evaluated with Henry's constant at 573 K <27 >. As a result 1, 10 and 100 ppb correspond to
about 1, 10 and 10 2 Pa, respectively. The comparison of the parabolic rate constant with
the corrosion rate and the film growth rate in water is shown in Fig. 5. The oxygen
concentration described to be "degassed" in their papers 0 ><zs> was equal practically to 10
ppb. The regions for the corrosion behavior of carbon steel suggested by Videm o> are
also shown by the converted scale in the figure. Although the corrosion behavior did not
obey the exact parabolic rate law, the corrosion rate was estimated to be the average
value between the beginning (10-100 h) and the final (1,000 h-) of the corrosion. As seen
from Fig. 5, the corrosion rate in water is larger than the oxidation rate in gas phase by
about two orders of magnitude although the specimens used and the temperature corroded
are different among authors. The sharp increase in gas phase oxidation at around 10 5 Pa
just corresponds to the boundary between
the 'inhibition' and the 'pitting' regions in ,....__'INHIBITION'~ I

water corrosion. The increase of the cor-

9
t 'PITTING' !• i
rosion rate with decreasing oxygen concen- 'PASSIVATION'TI

tration in water was found to be the same

10
trend as the parabolic rate constant at the ~

low oxygen partial pressure region. Al-

7
Ill

'E
~
I '
though it is difficult so far to compare the
water corrosion with the gas phase oxida-
~11
N

I
Q.
tion quantitatively, the oxygen concentra- ""'Cl I
tion for the 'inhibition' region of the water .S!
corrosion may correspond to the oxygen
I 12
\
\

\
I
0 \
partial pressure range for the formation of 0
\
\
\
\
I
protective film in gas phase oxidation. judg-
ing from the condition of the formation of
13 \
\
\
\
i\
\
protective oxide film in gas phase, it is
suggested that the oxygen concentration in
water should be controlled between 10 ppb
and 10 ppm, and the corrosion rate in
water would be reduced much at oxygen 4 5 6
concentration less than 0.1 ppb. In the
present reactors the oxygen concentration .&L'. Tackett et al. at 573 K"'>, aD Videm
is maintained to be 20rv60 ppb by addition at 588 K'll, +<> Vreeland et al. at 558 K""
and 0 this work at 573 K.
of oxygen gas into the coolant water,
Fig. 5 Comparison between corrosion (solid) and
which corresponds to the lower oxygen film growth (open) rates in water and
concentration side in the suggested region. parabolic rate constant in this work

V. CONCLUSION
(1) The thickness of the oxide film formed on iron at 573 K was determined by means
of RBS together with CEMS techniques more precisely than the previous techniques.
(2) In the first stage the thickness showed a maximum around 1 Pa oxygen partial pres-
-47-
852 ]. Nucl. Sci. Techno!.,

sure at 573 K.
(3) In the second stage the oxidation obeyed the parabolic rate law. The proposed
mechanism of the oxidation was divided into the following four regions depending on
the oxygen partial pressure.
(a) I0- 1 to I0- 0 • 5 Pa: The growth of magnetite was dominant, and the parabolic
rate constant was strongly dependent on oxygen partial pressure.
(b) 1 to 10°· 5 Pa: Hematite covered magnetite, but the presence of grain boundaries
enhanced the diffusion in oxide, keeping the parabolic rate constants to be high.
(c) 10 to 10'· 3 Pa: Hematite as a protective film covered magnetite uniformly so as
to keep the parabolic rate constants low regardless of oxygen partial pressure.
(d) 10 5 Pa: The sharp increase of the parabolic rate constant occurred due to the
simultaneous growth of hematite and magnetite.
(4) The oxygen concentration in water for the inhibition of the corrosion may correspond to
the oxygen partial pressure for the formation of protective film in gas phase around 573 K.

AcKNOWLEDGMENT

The authors are indebted to Prof. N. Itoh and Prof. H. Sakao of Nagoya University
for the use of RBS and SEM, respectively.
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