Journal of Nuclear Science and Technology

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Effect of nitrate on corrosion of austenitic

stainless steel in boiling nitric acid solution
containing chromium ions

Satoshi Hasegawa, Seong-Yun Kim, Tetsunari Ebina, Haruaki Tokuda,

Tatsuya Ito, Nobumichi Nagano, Keitaro Hitomi & Keizo Ishii

To cite this article: Satoshi Hasegawa, Seong-Yun Kim, Tetsunari Ebina, Haruaki Tokuda,
Tatsuya Ito, Nobumichi Nagano, Keitaro Hitomi & Keizo Ishii (2016) Effect of nitrate on corrosion of
austenitic stainless steel in boiling nitric acid solution containing chromium ions, Journal of Nuclear
Science and Technology, 53:9, 1332-1341, DOI: 10.1080/00223131.2015.1107514

To link to this article: https://doi.org/10.1080/00223131.2015.1107514

Published online: 08 Jan 2016.

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JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY, 
VOL. , NO. , –
http://dx.doi.org/./..

ARTICLE

Effect of nitrate on corrosion of austenitic stainless steel in boiling nitric acid

solution containing chromium ions
Satoshi Hasegawaa,b , Seong-Yun Kima , Tetsunari Ebinaa,b , Haruaki Tokudab , Tatsuya Itoa , Nobumichi Naganoa ,
Keitaro Hitomia and Keizo Ishiia
a
Department of Quantum Science and Energy Engineering, Graduate School of Engineering, Tohoku University, ---
Aza-Aoba-Aramaki, Aoba-ku, Sendai, Miyagi -, Japan; b Japan Nuclear Fuel Limited, - Aza Okitsuke, Oaza Obuchi,
Rokkasho-mura, Kamikita-gun, Aomori -, Japan

ABSTRACT ARTICLE HISTORY

The oxidation behavior of chromium and the corrosion behavior of austenitic stainless steel in Received  July 
boiling nitric acid solution containing highly concentrated nitrates were investigated using UV- Accepted  October 
visible spectroscopic measurements, Raman spectral measurements, immersion tests, and poten-
KEYWORDS
tiodynamic polarization measurements. The oxidation rate measurement of chromium from Cr(III) Stainless steel; corrosion;
to Cr(VI) was performed by 1 M boiling nitric acid solution containing each highly concentrated reprocessing; nitric acid;
nitrates: Al(NO3 )3 , Nd(NO3 )3 , Ca(NO3 )2 , Mg(NO3 )2 , and NaNO3 as a simulant of uranium nitrate in chromium; nitrate; salt-effect
uranium concentrator in reprocessing plants. As a result, the rate of chromium oxidation was dif-
ferent depending on the added nitrates even at the same nitric acid concentration. In addition,
the oxidation rate of chromium was increased with increasing the calculated partial pressure of
nitric acid in consideration of the hydration of cation of nitrates. Furthermore, the corrosion rate
of type 310 stainless steel was accelerated by the solution having a high chromium oxidation rate
containing nitrates. These results indicated that the acceleration of the corrosion rate in the solu-
tions depending on the oxidation rate of chromium, and the rate is affected by the salt-effect of
nitrates.

1. Introduction are present in the spent fuel from nuclear reactors [6–
12]. Cr(VI) is generated as a corrosion product of stain-
The reprocessing of nuclear spent fuel by the plu-
less steels during processing, and Cr(III) does not accel-
tonium and uranium recovery by extraction process
erate the corrosion of stainless steel [13,14]. In previ-
uses nitric acid as the dissolution reaction medium.
ous study, it is reported that the Cr(III) is oxidized to
In this process, severe corrosive environment to the
Cr(VI) more than 4 M (M = mol·L−1 ) boiling nitric
equipment material is caused by heating operation
acid solution, and pointed out the accelerating corro-
(e.g. dissolver and evaporator) of the nitric acid solu-
sion of stainless steels [15]. Our previous study reported
tion. The ultra-low-carbon (ULC) austenitic stainless
that the oxidation of chromium ion is affected by the
steels (R-SUS304ULC, R-SUS316ULC, R-SUS310ULC,
boiling phenomena of nitric acid, and that is related to
R-SUS310Nb) were developed in Japan, which con-
the decrease in HNO2 concentration due to the forma-
tain less than 0.02 wt% carbon and reduced amounts
tion of NOx gas [16,17].
of other impurity elements [1]. These stainless steels
In addition, Arai et al. [18] evaluated that the effect
have high corrosion resistance and are employed in
of nitrate on corrosion behavior of 304L stainless steel
Rokkasho reprocessing plant or Tokai reprocessing
in nitric acid solution containing Fe(III) ions using
plant [2,3]. In addition, the SUS310EHP® (EHP: extra-
Al(NO3 )3 . They reported that the corrosion rate of
high-purity) austenitic stainless steel was developed in
stainless steel was increased by the addition of the
Japan recently [4]. This stainless steel has more high-
nitrate due to the increase of NO3 − concentration.
corrosion resistance for intergranular corrosion than
However, the effect of nitrate on corrosion behav-
the ULC stainless steel by increasing the purity. The
ior of stainless steel in nitric acid solution contain-
research and development of SUS310EHP® has been
ing chromium ions is unknown. In reprocessing plants,
advanced towards the application to reprocessing plants
uranium concentrator and high-level liquid waste con-
[5].
centrator are typical example of the solution environ-
Corrosion of stainless steels is known to be acceler-
ment including highly concentrated nitrates. Therefore,
ated by ions having high oxidizability in nitric acid solu-
an evaluation of the relationship between the corrosion
tion. Such ions, Ce(IV), Ru(III), Pu(VI), and Np(VI),
of stainless steel and the oxidation behavior of Cr(III)

CONTACT Seong-Yun Kim kim@qse.tohoku.ac.jp

This article was originally published with errors. This version has been corrected. Please see Erratum (http://dx.doi.org/./..).
©  Atomic Energy Society of Japan. All rights reserved.
 JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY 1333

Table . Composition of test solutions.

Type of solution H+ (M) Nitrate (M) Total NO − (M) Cr(III) (M) Cr(VI) (M)

Soln. A  Al(NO )    or .  or .

Soln. B  Nd(NO )    or .  or .
Soln. C  Mg(NO )    or .  or .
Soln. D  Ca(NO )    or .  or .
Soln. E  NaNO    or .  or .
Soln. F  − −   or .  or .
Soln. G  − −   or .  or .

in solution containing nitrates will provide useful infor-
mation for lifetime extension of the equipment in repro-
cessing plants.
In this study, we investigated that the oxidation
behavior of Cr(III) in boiling nitric acid solution con-
taining each highly concentrated nitrates: Al(NO3 )3 ,
Nd(NO3 )3 , Ca(NO3 )2 , Mg(NO3 )2 , and NaNO3 as a
simulant of uranium nitrate in uranium concentrator
in reprocessing plants; then, the relationship between
the corrosion of stainless steel and this behavior was
determined.
Table 2 shows the chemical composition of
SUS310EHP® specimen. The specimens for the immer-
sion tests were plate-type (30 × 15 × 2t mm) and
the specimens for the potentiodynamic polarization
measurements were flag-type (measurement part: 20 ×
5 × 1t mm, cross section of lead part: 1 × 1 mm).
Each specimen was wet ground up to #800 using emery
papers. The specimen surfaces ultrasonically cleaned
with ultrapure water followed by ultrasonic cleaning in
acetone to remove the surface contaminants: air-dried
and then used immediately for the immersion tests and
potentiodynamic polarization measurements.

2. Experimental
2.1. Materials
Table 1 shows the solutions for the experiments. The
five nitrates were used, i.e., Al(NO3 )3 ·9H2 O (Wako
Pure chemical Industries, Ltd.), Nd(NO3 )3 ·9H2 O
(Alfa-Aesar), Ca(NO3 )2 ·6H2 O (Wako Pure chemi-
cal Industries, Ltd.), Mg(NO3 )2 ·6H2 O (Wako Pure
chemical Industries, Ltd.), and NaNO3 (Wako Pure
chemical Industries, Ltd.). They have only one oxida-
tion state of cation and no redox couple in nitric acid
solution [19–23]. Thus, these cations do not accel-
erate the corrosion in the solutions as with uranium
[11]. Cr(III) was dissolved Cr(NO3 )·6H2 O (Nacalai
Tesque, Inc.) for Cr(III) oxidation rate measurements,
immersion tests, and potentiodynamic polarization
measurements. Cr(VI) was dissolved CrO3 (Wako
Pure chemical Industries, Ltd.) for potentiodynamic
polarization measurements. The 1 M nitric acid con-
centration was established with respect to the literature
value of 0.8 M reported for the uranium concentration
in the Rokkasho reprocessing plant [2]. The nitrates
concentration was adjusted so as to equalize total NO3 −
concentration in the test solutions. All chemicals were
of reagent grade. Ultrapure water with a resistivity of
18.2 M cm was used in the experiments.
2.2. Cr(III) oxidation rate measurements
The generation rate of Cr(VI) as a function of
the run time of the experiment was measured for
the each test solutions under boiling conditions at
atmospheric pressure. Cr(VI) concentration was ana-
lyzed by UV-visible spectrophotometry (Shimadzu
UV-2550). The test solution (430 mL) was intro-
duced into a 500-mL Pyrex flask, and heated with
a mantle heater. The condensate was total-refluxed
by an open type Allihn condenser. The test solu-
tion sampled every 48 h and measured Cr(VI) con-
centration for 288 h, after the solution reaches the
boiling temperature.
2.3. Raman spectral measurements
The Raman spectral measurements were obtained
using a JASCO RMP-200 spectrometer. An excit-
ing light source is Nd-YVO4 laser of 532 nm. Test
solutions for Raman spectral measurements were Solns.
A–G containing no Cr(III) and Cr(VI) shown in
Table 1. The direct measurement of the test solutions
was performed at room temperature before the immer-
sion test of SUS310EHP® stainless steel shown in the
next section.

Table . Chemical composition of SUSEHP® specimen (wt%, B: ppm).

C Si Mn P S Cr Ni B Fe

. <. <. . . . . . Bal.

1334 S. HASEGAWA ET AL.

Potentiostat
W.E.
(SUS310EHP®)

PC

C.E. (Pt)

Solution bridge
(69% HNO3) Thermocouple
Thermocouple
R.E.
(SSE)
Temperature
1 M HNO3 controller
Specimen Stirring bar
(SUS310EHP®) Mantle heater
Temperature
Glass holder controller Figure . A schematic diagram of apparatus for potentiody-
Mantle heater namic polarization measurements.
Stirring bar

Figure . A schematic diagram of apparatus for immersion tests.
2.4. Immersion tests of SUS310EHP® stainless steel
Figure 1 shows the apparatus for the immersion tests.
The specimens were settled in a glass holder, and the
test solution (430 mL) was introduced into a 500-mL
Pyrex flask. The ratio of the solution volume to the sur-
face area of the specimen was about 40 mL cm−2 . The
tests were carried out for a total of 200 h (100 h/batch ×
2 batches). The specimens and the test solutions were
not changed throughout the test. After the immersion
of each batch for 100 h, the specimens were weighed to
evaluate the corrosion rate.
2.5. Potentiodynamic polarization measurements
To investigate the electrochemical corrosion behavior of
SUS310EHP® in each test solution, the potentiodynamic
polarization measurement was performed. The correla-
tion diagram of the potential and current density (com-
monly referred to as a “polarization curve”) is obtained
from the responding current by scanning of the poten-
tial of stainless steel.
potential was stable (about 1 h after reaching the boil-
ing point). The scan rate was 1 mV s−1 . Measurements
were carried out to the cathode direction from the
open-circuit potential initially. About 10 min after the
measurement of cathode direction, the measurement of
anode from the open-circuit potential was performed.
3. Results
3.1. Oxidation rate of Cr(III)
Figure 3 shows the time variation of Cr(VI) concentra-
tion with respect to the initial concentration of Cr(III).
In Solns. A and C, the generation amount of Cr(VI)
exceeds that of Soln. G of 7 M HNO3 . The molar ratio
of Cr(VI) to initial Cr(III) after 288 h in Solns. A, C
and G were 17%, 26%, and 13%, respectively. In con-
trast, the generation amount of Cr(VI) was less than 5%
in Soln. D and E. No Cr(VI) was observed in Solns. B
and F. From the results, we determined the rate con-
stant of pseudo-first-order oxidation under each test
solution. The rate constants were calculated by the
Molar ratio of Cr(VI) to initial Cr(III) (%)

Figure 2 shows the apparatus for the potentiody- 30

Soln. A
namic polarization measurements. The potentiostat Soln. B
25
was a Hokuto Denko Corp. HZ-5000 electrochemi- Soln. C
Soln. D
cal analyzer. A three electrode system was utilized: 20 Soln. E
SUS310EHP® working electrode (surface area: 2.5 cm2 ), Soln. F
15 Soln. G
a Hokuto Denko Corp. HX-C7 Pt counter electrode,
and DKK-TOA Corp. HS-305DS referenece electrode
10
(SSE: silver-silver chloride electrode, Ag/AgCl in sat-
urated KCl). A solution bridge was used to support 5
an ionic conductive path between the working elec-
trode and the reference electrode. The test solution (100 0
0 50 100 150 200 250 300
mL) was introduced into a 300-mL Pyrex flask. The Test time (hr)
ratio of the test solution volume and the surface area
of the SUS310EHP® specimen was about 40 mL cm−2 . Figure . Time variation of Cr(VI) generation amount. Initial
Measurements were performed after the open-circuit Cr(III) concentration:  mM; Atmospheric pressure boiling.
 JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY 1335

Table . Rate constants of pseudo-first-order oxidation of Cr(III) (k) and boiling point of test solutions.
Soln. A Soln. B Soln. C Soln. D Soln. E Soln. F Soln. G

k (s− ) . × − − . × − . × − . × − − . × −
b. p. (K)       

following equation [16]: the Nernst equation can be written as [25]:

[Cr(III)]0 − [Cr(VI)] NO− + −
3 + 3H + 2e = HNO2 + H2 O
ln = −kt (1)  0 
[Cr(III)]0 E = 0.934 V vs. SHE (2)
where [Cr(III)]0 , [Cr(VI)], k, and t are the initial con- 2.303 × 3 × RT RT [NO−
3]
E = E0 − pH + ln (3)
centration of Cr(III), Cr(VI) concentration, rate con- 2F 2F [HNO2 ]
stants for first-order oxidation and test time, respec-
where R, T, and F are the gas constant (8.3145
tively. Table 3 shows the k values for each test condition
J·mol−1 ·K−1 ), temperature (K), and Faraday constant
and boiling point (b. p.) of test solutions. We see from
(9.6485 × 104 C·mol−1 ), respectively. Equation (3)
Table 3 that the rate constant k becomes larger by the
shows that the redox potential of nitric acid is raised
addition of specific nitrates (especially, Al(NO3 )3 and
by the increase of NO3 − concentration. This is indicate
Mg(NO3 )2 ) even at the low nitric acid concentration.
that the oxidation reaction of Cr(III) becomes easy to
However, the rate constant k is different about one order
occur in the solutions from view point of equilibrium
of magnitude, depending on the type of nitrates. There-
theory.
fore, we considered that the rate constant k is affected
However, in Soln. B, the intensity of NO3 − is smaller
not only by solution temperature but also the salt-effect.
than other solutions. There is a possibility that the rea-
son is complexation of specific to the lanthanide: in gen-
3.2. Raman spectrum eral, a lanthanide complex of large coordination num-
ber (n = 10–12) is formed in the case of containing
Figure 4 shows the Raman spectrum of each test solu- NO3 − [26].
tion. In general, the peak of undissociated nitric acid
is not observed in the low nitric acid concentration,
and the peak of NO3 − is confirmed as in the Soln. 3.3. Corrosion rate of SUS310EHP®
F. Additionally, the peak of undissociated nitric acid is stainless steel
observed in the high nitric acid concentration as in the The results of immersion tests of SUS310EHP® in each
Soln. G [24]. We see from Figure 4 that the NO3 − inten- test solutions were illustrated in Figure 5. Tests were
sity of Solns. A–E is stronger than that of Soln. F of performed by two conditions at each solution: no addi-
1 M HNO3 . It is estimated that the reason is increase tion of Cr(III) and addition of Cr(III). If the no addi-
of NO3 − concentration by the addition of nitrates. In tion of Cr(III), no increase of the corrosion rate was
addition, the intensity of NO3 − is about seven times of observed from first batch (∼100 h) to second batch
the Soln. F with the exception of Soln. B. We will discuss (100–200 h) in each test solution. While the corrosion
about consideration of Soln. B in the last paragraph of
this section. Now, the redox reaction of nitric acid and

8
-
NO3

6
Intensity (a.u.)

NO2 (stretch) HNO3

4
G
F
2 E
D NO2 (bend)
C
B
0 A
2800 2400 2000 1600 1200 800 400
-1
Wave number (cm )

Figure . Raman spectra of test solutions at room temperature. Figure . Corrosion rates of SUSEHP® in various test solutions.
An exciting light source: Nd-YVO laser; Incident wavelength: Initial Cr(III) concentration at addition condition of Cr(III):  mM;
 nm. Error bars were obtained from error of electronic balance.
1336 S. HASEGAWA ET AL.

Table . Corrosion potential (Ecorr ) and corrosion current den- to the case of no addition of chromium. If the addition
sity (icorr ) obtained from polarization curves of SUSEHP® . of Cr(VI), the Ecorr was shifted to the noble direction
Type of solution Ecorr (V vs. SSE) icorr (A·cm− ) significantly, and the icorr was increased for any of the
test solutions. However, there was no significant differ-
Without Cr
Soln. A . . × − ence of the Ecorr and the icorr depending on the type of
Soln. B . . × − nitrates.
Soln. C . . × −
Soln. D . . × −
Soln. E . . × −
Soln. F . . × −
4. Discussion
Soln. G . . × −
With Cr(III) 4.1. Salt effect on oxidation of Cr(III)
Soln. A . . × −
Soln. B . . × − Despite there was no significant difference in the inten-
Soln. C . . × −
Soln. D . . × −
sity of NO3 − in Raman spectrum of Solns. A, C, D, and
Soln. E . . × − E, the difference was observed in the oxidation rate of
Soln. F . . × − Cr(III) in Figure 3. Hence, we considered that the oxi-
Soln. G . . × −
With Cr(VI) dation rate of Cr(III) is affected not only by NO3 − con-
Soln. A . . × − centration but also cation of nitrates. To investigate this
Soln. B . . × −
factor, we carried out the vapor–liquid equilibrium cal-
Soln. C . . × −
Soln. D . . × − culation in consideration of the hydration of nitrates.
Soln. E . . × − Takahashi et al. [27] proposed the modeling for vapor-
Soln. F . . × −
Soln. G . . × −
liquid equilibria of nitric acid containing highly con-
centrated nitrates. In this model, modification of the
stoichiometric molar fraction of nitric acid is as fol-
rate was decreased in second batch, we considered that lows:
the reason is the formation of the passivity film on the X
surface of stainless steel in nitric acid solution. On the X = (4)
1 − nM XM
other hand, if the addition of Cr(III), the significant
increase of corrosion rate was observed in Solns. A and where X  , X, nM , and XM are the modified molar frac-
C. In addition, the total corrosion amount of first batch tion of nitric acid, stoichiometric molar fraction of
and second batch was in order of Soln. F < Soln. B < nitric acid, hydration number, and stoichiometric molar
Soln. E < Soln. D < Soln. G < Soln. A < Soln. C. This fraction of nitrates, respectively. Equation (4) defines
order is consistent with the results of chromium oxida- the effective molar fraction of nitric acid in considera-
tion rate measurements as already described in Figure 3 tion of the reduction of water molecules by hydration of
and Table 3. Therefore, the results indicate that the cor- cation. The value of PNA was calculated from Rault’s rule
rosion rate of SUS310EHP® is accelerated by Cr(VI) as follows:
generated in the solutions. It should be noted, we con- PNA = PNA
0
· γ · X (5)
sider that the corrosion rate is accelerated in the case of
where PNA , P0 NA , and γ are the partial pressure of
high initial Cr(III) concentration even if the oxidation
nitric acid, vapor pressure of pure nitric acid, and ratio-
rate of Cr(III) is low.
nal activity coefficient, respectively. The rational activ-
ity coefficient was curve fitted as functions of X  and T
3.4. Polarization curve of SUS310EHP® (in degrees kelvin).
stainless steel 
5
 n
log10 γ298.15 K = an 1 − X  (6)
Potentiodynamic polarization measurements were car-
n=1
ried out on three conditions of each test solutions: no
addition of chromium, addition of Cr(III), and addi- where a1 , a2 , a3 , a4 , and a5 are −0.857011, 10.4040,
tion of Cr(VI). Figure 6 shows the polarization curves −41.7371, 55.0937, and −27.1588, respectively, with:
of SUS310EHP® in each test conditions, and measured log10 (γ /γ298.15 K ) = − (1/T − 1/298.15) (7)
parameters of the corrosion potential (Ecorr ) and the 3
n
corrosion current density (icorr ) are listed in Table 4. log10  = bn X  (8)
The icorr is obtained by the Tafel extrapolation method. n=0
If the no addition of chromium, the Ecorr of Solns. A– where b0 , b1 , b2 , and b3 are 3.240, −0.670, −0.637, and
E (added nitrates) were shifted to the noble direction −7.332, respectively. The vapor pressure of pure nitric
(>0.8 V) as compared with Soln. F (no addition of acid is calculated as follows:
nitrates), and the increase of the icorr was observed. The  0 
icorr of Solns. A and C was close to the Soln. G. If the log10 PNA /mmHg
addition of Cr(III), the polarization curves were similar = 7.5119 − 1406/ (221.0 + T − 273.15) (9)
 JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY 1337

0 0
10 10
-1 Without Cr Soln. A -1 Soln. B
10 10

Current density (A·cm )

Current density (A·cm )

With Cr(III): 10 mM

-2

-2
-2 -2
10 With Cr(VI): 10 mM 10
-3 -3
10 10
-4 -4
10 10
-5 -5
10 10
-6 -6
10 10
-7 -7
10 10
-8 -8
10 10
0.2 0.4 0.6 0.8 1.0 1.2 1.4 0.2 0.4 0.6 0.8 1.0 1.2 1.4
Potential (V vs. SSE) Potential (V vs. SSE)
0 0
10 10
-1 Soln. C -1 Soln. D
10 10

Current density (A·cm )

Current density (A·cm )

-2
-2

-2 -2
10 10
-3 -3
10 10
-4 -4
10 10
-5 -5
10 10
-6 -6
10 10
-7 -7
10 10
-8 -8
10 10
0.2 0.4 0.6 0.8 1.0 1.2 1.4 0.2 0.4 0.6 0.8 1.0 1.2 1.4
Potential (V vs. SSE) Potential (V vs. SSE)
0 0
10 10
-1 Soln. E -1 Soln. F
10 10
Current density (A·cm )

Current density (A·cm )

-2

-2

-2 -2
10 10
-3 -3
10 10
-4 -4
10 10
-5 -5
10 10
-6 -6
10 10
-7 -7
10 10
-8 -8
10 10
0.2 0.4 0.6 0.8 1.0 1.2 1.4 0.2 0.4 0.6 0.8 1.0 1.2 1.4
Potential (V vs. SSE) Potential (V vs. SSE)
0
10
-1 Soln .G
10
Current density (A·cm )
-2

-2
10
-3
10
-4
10
-5
10
-6
10
-7
10
-8
10
0.2 0.4 0.6 0.8 1.0 1.2 1.4
Potential (V vs. SSE)

Figure . Polarization curves of SUSEHP® in each test solutions at atmospheric pressure boiling.

Table 5 shows the values of X , X, nM , and XM for described in Figure 7 because the nitric acid concen-
the calculation of partial pressure of nitric acid. The X tration of Soln. G is different from other test solutions.
and XM were calculated from the mass of added nitrates, Previous studies reported that as the concentration of
mass of added nitric acid, and density of solutions. The the nitric acid increases, the partial pressure of nitric
nM value used the literature values [28–31]. In addi- acid increases with increasing nitric acid concentration
tion, we calculated the case of the uranium nitrate for [33], dissociation degree of nitric acid decreases with
comparison with other solutions. The X and XM of increasing nitric acid concentration [34], and the NO2
the uranium nitrate solution were calculated from the concentration increases with increasing nitric acid con-
Spencer’s equation [32]. centration [24]. Hence, we considered that the Soln.
Figure 7 shows the calculated results of tempera- G is unable to simply compare with other test solu-
ture variation of the partial pressure of nitric acid in tions when evaluating the effect on oxidation rate of
each test solution. It should be noted, Soln. G is not Cr(III), because it is necessary to consider the presence
1338 S. HASEGAWA ET AL.

Table . Modified molar fraction of nitric acid.

Type of Uranium
solution A B C D E F solution∗

X . × − . × − . × − . × − . × − − . × −
X . × − . × − . × − . × − . × − . × − . × −
XM . × − . × − . × − . × − . × − − . × −
nM . []  []  [] . [] . [] −  []
∗  M HNO +  M UO (NO ) .


3.0
Partial pressure of nitric acid (mmHg)

2.5 Soln. A
Soln. A
Soln. B

Rate constants (k) (×10 s )

Soln. B

-7 -1
Soln. C
2.5 Soln. C
2.0 Soln. D
Soln. D
Soln. E
Soln. E 2.0 Soln. F
Soln. F
1.5 1 M HNO3 + 3 M UO2(NO3)2
1.5
1.0
1.0

0.5 0.5

0 0
290 310 330 350 370 390 0 0.5 1.0 1.5 2.0 2.5 3.0
Temperature (K) Partial pressure of nitric acid at b.p. (mmHg)

Figure . Calculated partial pressure of nitric acid using the Figure . Relationship between rate constants of Cr(III) oxida-
modified molar fraction of nitric acid. tion (k) and calculated partial pressure of nitric acid at boiling
point.
state of the nitrogen oxides in the solution in addition to
the partial pressure of nitric acid. We see from Figure 7 2.303 × RT RT pNO2
E = E0 − pH + ln (11)
that the partial pressure of nitric acid is increased with F F [HNO2 ]
increasing of the temperature; however, the degree of HCrO−
4 + 7H +
+ 3e −
= Cr3

pressure increase is different depending on the type  

+ 4H2 O E 0 = 1.350 V vs. SHE (12)
of solution. The effect on the partial pressure of nitric
acid was increased as: Soln. F < Soln. B < Soln. 2.303 × 7 × RT RT [HCrO− 4]
E = E0 − pH + ln 3+
E < Soln. D < Soln. A < Soln. C. This order is con- 3F 3F [Cr ]
sistent with the order of the oxidation rate constant of (13)
Cr(III) in Table 3. The partial pressure of nitric acid in NOx gas is generated as a thermal decomposition
the case of uranium nitrate solution was close to the cal- product of nitric acid with HNO3 gas by boiling of
culated result of Soln. B (neodymium nitrate). nitric acid solution [24], and the redox potential of E is
increased with increasing of the partial pressure of NO2
4.2. Relationship of oxidation rate of Cr(III) and as shown in the Equation (11). Therefore, the oxidation
partial pressure of nitric acid behavior of chromium in boiling nitric acid solution is
affected by the partial pressure of NOx gas components
Figure 8 shows a plot of the rate constant of Cr(III) in addition to the solution temperature. We have eval-
oxidation versus the calculated partial pressure of uated that the generation amount of Cr(VI) increases
nitric acid at boiling point (b. p.) of each solu- with the decrease of HNO2 concentration by the gener-
tions. Soln. G is not described in Figure 8 because ation of NOx gas with HNO3 gas in boiling nitric acid
of the same reason explained in the Section 4.1. solution using the thermodynamic calculation [16,17].
We see from Figure 8 that the rate constant of In addition, we can draw the following equations from
Cr(III) oxidation tend to increase linearly with increas- the Equations (2) and (12):
ing the partial pressure of nitric acid. Motooka
et al. [35] evaluated that the generation amount of 2Cr3 + 3NO−3 + 5H2 O = 2HCrO4 + 5H
− +
 0 
Cr(VI) is increased by the formation of NO2 with ther- + 3HNO2 E = 0.416 V (14)
mal decomposition of nitric acid using the following 2.303 × 5 × RT
equations: E = E0 − pH
6F
    2
NO2 (g) + H+ + e− = HNO2 E 0 = 1.093 V vs. SHE RT HCrO− 4 [HNO2 ]3
+ ln  3 (15)
(10) 6F [Cr3+ ]2 NO− 3
 JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY 1339

considered that the generation rate of NO2 gas such as

Stainless steel Solution
Equation (10) is accelerated by the thermal decompo-
NOx (g)
sition of nitric acid. If the reaction of Equation (10) is
Cr3+ HNO2 accelerated, it is considered that the reduction reaction
of NO3 − in the Equation (2) is also accelerated. Thus,
M 3e- 2e- we considered that the generation reaction of Cr(VI) as
Cr6+ NO3- a counter-reaction of the reduction reaction of NO3 −
(Equation (14)) is accelerated, and the corrosion rate
Fe3+, Cr3+, Ni2+ of the stainless steel is accelerated by the generated
NOx (g) Cr(VI).
H2O
HNO2 Mn+
5. Conclusions
M 2e- Hydration of cation
of nitrate To investigate the effect of nitrate on corrosion of
M= metal NO3- austenitic stainless steel in nitric acid solution contain-
ing chromium ions, we carried out the measuring the
Figure . Model for the corrosion mechanism of stainless steel time dependence of chromium concentration, Raman
in boiling nitric acid solution containing highly concentrated
spectral measurements, immersion tests, and potentio-
nitrates with chromium ions.
dynamic polarization measurements using the various
nitrates: Al(NO3 )3 , Nd(NO3 )3 , Ca(NO3 )2 , Mg(NO3 )2 ,
and NaNO3 as a simulant of uranium nitrate in ura-
From the Equation (14), we consider that the oxida-
nium concentrator in reprocessing plants. The rate of
tion rate of Cr(III) is increased (the reaction shifts to
chromium oxidation was different depending on the
the right direction) with decrease of HNO2 concentra-
added nitrates even at the same nitric acid concentra-
tion due to the generation of NOx gas.
tion. Raman spectrum showed the increasing of the
These results indicate that the oxidation rate of
NO3 − concentration by the addition of nitrates. How-
Cr(III) is affected by the change of vapor–liquid equilib-
ever, we could not explain the difference of the oxi-
rium in nitric acid solution due to the hydration of the
dation rate by just only the Raman spectrum. There-
cation of nitrates, and this salt-effect shows that the cor-
fore, we evaluated the partial pressure of nitric acid
rosion rate of stainless steel is accelerated by the coexis-
on oxidation rate of chromium using the modified
tence of chromium ions even in the nitric acid solution
molar fraction of nitric acid in consideration of the
containing highly concentrated nitrates with no accel-
reduction of water molecules by hydration of cations.
eration of the corrosion.
There was a positive correlation to the oxidation rate of
chromium and the calculated partial pressure of nitric
4.3. Corrosion mechanism acid. This indicated that the oxidation rate of chromium
was increased with increasing the partial pressure of
The cathodic reaction on the surface of stainless steel
nitric acid by the hydration of cation of nitrates. In
can be represented by the Equation (2) (cathodic
addition, the corrosion rate of SUS310EHP® was accel-
reaction of NO3 − ) and Equation (12) (cathodic reac-
erated by the solution having a high chromium oxi-
tion of Cr(VI)). The anodic reaction of the dissolu-
dation rate containing nitrates. The order was con-
tion reaction of the stainless steel can be written as
sistent with the results of measuring the time depen-
follows:
dence of Cr(VI) concentration. Furthermore, the polar-
Fe = Fe3+ + 3e− (16) ization curve of SUS310EHP® in the nitric acid solu-
− tion containing nitrates showed that the corrosion
Cr = Cr 3+
+ 3e (17)
− potential and the corrosion current density was largely
Ni = Ni 2+
+ 2e (18)
increased by the addition of Cr(VI), regardless of the
The corrosion rate of the stainless steel is acceler- type of nitrates. This result indicates that the corro-
ated by the Cr(VI), that is generated by the re-oxidation sion rate of the stainless steel is depending on the
reaction from Cr(III) to Cr(VI) in nitric acid solution. amount of generation of Cr(VI) in the solution, and the
Figure 9 shows the schematic diagram for the corro- important point is the oxidation kinetics of chromium
sion mechanism of stainless steel. From the test results in consideration of the salt-effect in nitric acid
of Figures 3 and 5, we considered that the corrosion solutions.
rate of the stainless steel is accelerated by the increase of These conclusions can be given as the useful infor-
the generation rate of Cr(VI) due to the addition of the mation for the corrosion control of reprocessing plants
nitrates. As described in Section 4.1., the partial pres- handling a coexistence solution of highly concentrated
sure of nitric acid increased by the hydration of cation nitrates with chromium ions as a corrosion prod-
due to the addition of the nitrates. In this case, it is uct. However, the corrosion behavior of stainless steel
1340 S. HASEGAWA ET AL.
must be evaluated by irradiation environments, or
using radioisotope. This is an important area for future
investigation.
Disclosure statement
No potential conflict of interest was reported by the
authors.
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