Accepted Manuscript

Characterization and prediction of carbon steel corrosion in diluted seawater

containing pentaborate

Yuichi Fukaya, Yutaka Watanabe

PII: S0022-3115(17)31252-7
DOI: 10.1016/j.jnucmat.2017.10.032
Reference: NUMA 50564

To appear in: Journal of Nuclear Materials

Received Date: 8 September 2017

Revised Date: 11 October 2017
Accepted Date: 11 October 2017

Please cite this article as: Y. Fukaya, Y. Watanabe, Characterization and prediction of carbon steel
corrosion in diluted seawater containing pentaborate, Journal of Nuclear Materials (2017), doi: 10.1016/
j.jnucmat.2017.10.032.

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 ACCEPTED MANUSCRIPT

Characterization and prediction of carbon steel corrosion in diluted seawater containing

pentaborate

Yuichi Fukaya a and Yutaka Watanabe b

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a Tokyo Electric Power Company Holdings, Inc., 4-1, Egasaki-cho, Tsurumi-ku, Yokohama 230-8510, Japan
b School of Engineering, Tohoku University, 6-3, Aoba, Aramaki, Aoba-ku, Sendai 980-8578, Japan

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*Corresponding author. E-mail address: Fukaya.yuichi@tepco.co.jp (Y. Fukaya)

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ABSTRACT

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This study addresses the influence of Na2B10O16, which may be used for criticality control of fuel
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debris in the Fukushima Daiichi Nuclear Power Station, on the corrosion behavior of carbon steel in
diluted artificial seawater. The corrosion forms of carbon steel were categorized as uniform corrosion,
localized corrosion, and passivity based on the balance between the dilution ratio of artificial seawater
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and the concentration of Na2B10O16. The changes in corrosion forms were arranged on a water quality
region map. Passivity was maintained by adding 3.7 × 10−2 M or more of Na2B10O16 to artificial seawater
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with a dilution ratio of 100-fold or more. The criticality control of the fuel debris and corrosion mitigation
of the carbon steel components may be achieved simultaneously in the water quality. The prediction of the
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corrosion form of carbon steel was attempted by the extended Larson–Skold Index (LSI) = ([Cl−] +
2[SO42−])/([HCO3−] + 2[B10O162−]). However, because the passivating action of B10O162− was remarkably
stronger than that of HCO3−, the prediction was difficult under the simple addition of equivalent
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concentrations. The localized corrosion of carbon steel under the addition of Na2B10O16 preferentially
occurred from the crevices of the test specimens, as was the case in stainless steel.
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Keywords:
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Fukushima Daiichi Nuclear Power Station, Uniform corrosion, Localized corrosion, Passivity,
Carbon steel, Sodium pentaborate, Criticality control

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1. Introduction

1.1 Fukushima Daiichi accident

On March 11, 2011, the Great East Japan Earthquake with a magnitude of 9.0 occurred off the Pacific

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coast of the Tohoku region. The tsunami that followed the earthquake destroyed the power sources to
units 1 to 4 of the Fukushima Daiichi Nuclear Power Station; without power, the cooling of the nuclear
fuel was lost. As an emergency measure, fuel cooling was accomplished by injecting seawater into the

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nuclear reactors and spent fuel pools. However, the reactors in units 1 to 3, which were in operation at the
time of the earthquake, experienced core meltdowns. It is thought that parts of the reactor pressure vessels

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(RPVs) and primary containment vessels (PCVs) were damaged at this point.
When seawater was injected into the reactors and spent fuel pools, the related components were
exposed to a highly corrosive environment. In order to prevent further leakage of the cooling water and

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radionuclides, corrosion mitigation of the components became urgent. Since the Fukushima Daiichi
accident, many corrosion mitigation measures have been attempted, including deoxygenation treatments
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and desalination of the cooling water [1]. At present, no critical issues caused by the corrosion of the
components have been identified. However, during the decades-long removal of fuel debris from the
reactors, maintaining the functionality of the components such as the PCVs, RPV pedestals, and cooling
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water piping after temporary exposure to high-temperature seawater is necessary.

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1.2 Current conditions within the PCVs [2,3]

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While six years have passed since the accident, the internal conditions of the PCVs of units 1 to 3 have
not yet been verified because of the hindrance of exposure to strong radiation. However, it is estimated
that the fuel debris generated by the core meltdown during the accident is present at the bottom of either
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the RPVs or the PCV drywell. Because both the RPVs and PCVs lost airtightness under damage caused
by the core meltdown, the cooling water injected into the RPVs to cool the fuel debris leaks out, and
accumulates in the PCVs or reactor building basements. The accumulated water is currently being
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pumped out to water treatment facilities located away from the buildings and decontaminated. The
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decontaminated water is recycled for use as the coolant. The temperature inside the PCVs is kept at
<40°C.
Most of the components inside the PCVs comprise carbon steel or low-alloy steel; some use stainless
steel. The aqueous corrosion rates of these steel materials are mainly determined by the concentration of
dissolved oxygen (DO) in the water. Therefore, the removal of oxygen from the system is the most basic
corrosion mitigation method. The removal of salt, which promotes galvanic corrosion of carbon steel and
localized corrosion of stainless steel, is also effective. Therefore, after the seawater injection immediately
following the accident, de-aerated fresh water was injected into the reactors for fuel-debris cooling, the

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inside of the PCVs was filled with nitrogen, and the accumulated water in the PCVs was desalinated and
sterilized by injection with hydrazine to mitigate the corrosion of the components [1]. The findings from
the water-quality analysis of the accumulated water in the PCVs [2] and the concentration of oxygen gas
inside the gas phase section inside the PCVs [4] conducted after these treatments are shown in Tables 1
and 2. The concentration of chloride ions in the accumulated water is purified to a level equivalent to, or

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purer than, that of tap water. The concentration of oxygen gas inside the PCVs is ~0.3 vol%, which is
approximately 0.1 mg/L of DO concentration at 50°C by the equilibrium calculation. The DO in pure
water in equilibrium with the atmosphere at 1 atm is 5.5 mg/L at 50°C [5]; the DO inside the PCVs is

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approximately 1/60 relative to atmospheric conditions, and thus it is expected that the corrosion rate of
the components comprising carbon steel is reduced to approximately 1/60 as well. However, the corrosive

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environment most unique to Fukushima Daiichi is the highly radioactive interior of the PCVs; in the PCV
vapor-phase area, dose rates of 0.75 to 73 Sv/h have been observed so far. Radiation could cause adverse
effects, such as increased corrosion rates by the radiolysis of water [6,7] or deteriorated corrosion

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inhibitors [8]. AN
1.3 Anticipated future changes in conditions

One of the major issues with the decommissioning of Fukushima Daiichi is the removal and safe
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storage of the fuel debris within the PCVs. Currently, the inside of the PCVs is being treated with nitrogen
injections, intended to prevent hydrogen explosions and component corrosion. However, the PCVs may
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be opened when fuel debris removal is conducted; oxygen may, during this period, dissolve into the
cooling water and increase the risk of corrosion. Furthermore, during fuel debris extraction, in order to
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prevent the fuel debris reaching criticality by changes in the water level, the addition of a neutron
absorber has been considered. With the addition of soluble borate to the cooling water as a neutron
absorber, the electrical conductivity of the water is increased, and with it, the risk of the galvanic
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corrosion of carbon steel is also increased. Therefore, it is important to prepare and implement a corrosion
mitigation measure to replace the current deoxygenation treatment.
Using corrosion inhibitors in the current transient water injection method used for cooling the fuel
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inside the PCV would be difficult. However, if cooling through a circulation loop became possible, as
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long as the water quality is similar to that of tap water, corrosion inhibitors could potentially be applied.
Therefore, the International Research Institute for Nuclear Decommissioning (IRID) is engaging in
extensive examinations [9–12] on the application of corrosion inhibitors in actual plants under radioactive
environments.

1.4 Influence of neutron absorbers on carbon steel corrosion

Boric acid (H3BO3) and sodium pentaborate (Na2B10O16) are potential soluble neutron absorbers for the

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criticality control of fuel debris in the decommissioning of the Fukushima Daiichi [13]. In the accident of
Three Mile Island Unit 2 reactor, the coolant water was borated with concentrations of >4350 mg/L as
boron to secure the subcritical condition, overcoming some uncertain situation [14]. Similarly, in the
Fukushima Daiichi, the concentration of boron added to the cooling water may be several thousand mg/L
to overcome various uncertain situation [13,15]. Sodium tetraborate (Na2B4O7) passivates carbon steel

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[16], but little is known about Na2B10O16. However, as seen in the following equation, Na2B10O16 can be
expressed as a reactant of H3BO3 and Na2B4O7, so Na2B10O16 may also have a passivating effect.

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6H3BO3 + Na2B4O7 = Na2B10O16 + 9H2O (1)

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If Na2B10O16 has sufficient passivation capabilities, it may achieve both the corrosion mitigation of the
carbon steel components in the PCVs and the criticality control of the fuel debris. However, depending on
the concentration balance between aggressive ions, such as chloride ions, and passivators, localized

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corrosion (e.g., pitting corrosion, crevice corrosion, and stress corrosion cracking) can occur in passivated
carbon steel [17–23]. The rate of localized corrosion is generally much higher than that of uniform
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corrosion; thus, localized corrosion often causes penetration leakage in a short period. Therefore, creating
and studying the correlation diagram between water quality and corrosion forms such as uniform
corrosion, passivity, and localized corrosion is very important. In this paper, “passivity” and “passivation”
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are distinguished depending on the following means: Passivity is the state of a metal in which a low
corrosion rate is brought about by a chemically stable and protective film, usually an oxide; Passivation is
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the process by which the condition of passivity is obtained on the surface of a metal.
Many reports [17–28] describe the threshold conditions for passivation and localized corrosion of
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carbon steel in carbonate solutions, but few reports investigate these in borate solutions. Sawochka et al.
[29] conducted weight-change measurements of carbon steel in a 12 wt% Na2B10O16 solution at 35°C to
assess the corrosion of boiling water reactor (BWR) Na2B10O16 injection systems. They reported weight
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loss rates of <0.17 mg/dm2·day (mdd) after two months of exposure. However, the water in the case of
Fukushima Daiichi contains 0.1–200 mg/L of Cl− and 0–0.1 mol/L of Na2B10O16, which is not fully
covered by past findings [29].
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From the above background, the purposes of this study are to quantitatively evaluate the influence of
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Na2B10O16 on the corrosion forms of carbon steel in a wide range of water quality conditions and to
explore the possibility of simultaneous criticality control of fuel debris and corrosion mitigation of carbon
steel components.

2. Experimental

2.1 Test material

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The chemical composition of the carbon steel used in the examination is shown in Table 3. The PCV
drywell in Fukushima Daiichi was made of ASME SA-516 Grade 70-specification carbon steel. The
actual plant data range in the Table was extracted from the 49 material test reports published during the
construction of Fukushima Daiichi, calculated based on the range of µ ± σ, where µ is the average
concentration of C, Si, Mn, P, and S and σ is the standard deviation. The 20-mm-thick test material was

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fabricated by combining these elements in ratios within the designated concentration ranges; after vacuum
melting, forging, and hot rolling, they were normalized (at 600°C × 0.5 h, air cooling). The concentrations
of other trace elements in the table were included with reference to the representative component values

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of commercially available SA-516 carbon steel.

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2.2 Corrosion immersion test

Flat test specimens measuring 30 × 20 × 2 mm were cut by machining. After the surfaces of the test

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specimens were wet-polished with 220-grit and 600-grit SiC abrasive paper, they were washed with pure
water and degreased in ethanol. Silicone tubes with external diameters of 3.2 mm were inserted into
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3-mm through-holes drilled into the top sides of the test specimens, as seen in Fig. 1.
The test solutions were diluted artificial seawater with Na2B10O16 added at different concentrations. The
original undiluted artificial seawater was prepared using chemical reagents according to ASTM
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D1141-2003. The chemical composition of the artificial seawater (g/L) was NaCl: 26.5, MgCl2: 2.4,
MgSO4: 3.3, KCl: 0.73, NaHCO3: 0.20, NaBr: 0.28, and CaCl2: 1.1; the pH was 8.3. The artificial
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seawater was then diluted from 1 to 10,000-fold with ion-exchanged water having an electrical
conductivity of less than 0.1 µS/cm to create the diluted artificial seawater solutions. Sodium pentaborate
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decahydrate (Na2B10O16·10H2O) of 99.57% purity, was added at concentrations between 3.7 × 10−4 and
3.7 × 10−2 mol/L (hereinafter, the molar concentration is abbreviated as M). Converting these to boron
concentrations, they are equivalent to 40–4,000 mg/L.
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Five liters of each test solution was poured into a Pyrex glass flask, and the solution temperatures were
adjusted to 25°C or 50°C with a thermostatic chamber or mantle heater. After laboratory air was bubbled
through the test solutions’ liquid-phase portion at 10 cm3/min for 24 h, the pH and DO concentrations of
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the test solutions were measured using a pH meter (HORIBA D-51) and an optical DO instrument
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(YSI/Nanotech ProODO). The test specimens were then immersed in the test solutions by suspending the
specimens from nylon strings threaded through the silicone tubes, as seen in Fig. 1. Seven test specimens
were immersed per solution condition. The wetted area per specimen was 13.9 cm2, and the solution
volume-to-specimen area ratio was 51.4 mL/cm2. The air bubbling into the liquid phase was continued
after test specimen immersion. After 500 h immersion, the test specimens were removed to determine the
corrosion forms. The corrosion products were removed from the test specimens by 2 to 6 min of
ultrasonic cleaning in a 40°C, 20% diammonium hydrogen citrate aqueous solution, and then the weights
of the test specimens were measured. The corrosion rate was evaluated by subtracting the amount of

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weight change after the immersion test from the wetted area of the test specimens. Finally, the depth of
the corrosion on the surface areas of 30 × 20 mm on both surfaces of the test specimens was measured
using a 3D shape measurement system (Keyence VR-3000), and the ratio of the corroded area to total
area of both surfaces was defined as the corroded area ratio. During this evaluation, the side surfaces of
the test specimens were disregarded.

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The test conditions (temperature, dilution ratio of artificial seawater, addition concentrations of typical
anions in test solution) of the corrosion immersion tests are shown in the numbers from a to r in Table 4.

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2.3 Measuring the polarization curve

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Flat test specimens of 10 × 10 × 3 mm were cut from the test material by machining. As in section 2.2,
the specimens were wet-polished, washed, and degreased. Afterward, the test specimens were immersed
in concentrated nitric acid at 25°C for more than 24 h and then passivated. Coated copper wire was

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soldered to the test specimens, which were then embedded in a cylindrical epoxy resin to expose only the
10 × 10 mm test surfaces. Just before testing, the test surfaces were wet-polished using 600-grit SiC
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abrasive paper once more and washed with pure water.
The test solution was a Na2B10O16 aqueous solution prepared by mixing the Na2B10O16·10H2O reagent
into ion-exchanged water with an electrical conductivity of less than 0.1 µS/cm and a sodium bicarbonate
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(NaHCO3) aqueous solution prepared using the same ion-exchanged water as a special-grade reagent.
Four solute concentrations of 3.7 × 10−4, 3.7 × 10−3, 3.7 × 10−2, and 1.0 × 10−1 M were prepared.
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Pyrex glass flasks were filled with 0.8 L of each test solution, and the solution temperatures were
adjusted to 25°C in a thermostatic chamber. After the test solution was de-aerated by bubbling 99.999%
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pure nitrogen gas into the liquid-phase portion at 10 cm3/min for 2 h, the test specimens were immersed in
the test solution. De-aeration with nitrogen gas was switched from the liquid phase to the gas phase and
the open-circuit potentials of the test specimens were measured for 1 h. Then, the potential applied to the
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test specimens was swept in the anodic direction starting from 50 mV below the open-circuit potential 1 h
after immersion at a rate of 20 mV/min, and the current density was recorded. The measurement was
terminated either when the current density reached 50 A/m2 or when the potential reached 1.396 V vs. a
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standard hydrogen electrode (SHE). The measurement was conducted three times per condition, as
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determined by the concentration. The potential was measured with reference to Ag/AgCl electrodes in
saturated KCl solution at 25°C, but in this report, the potential values have been converted to values with
reference to SHE. To measure the open-circuit potential and polarization curve, Solartron 1280Z was used.
A platinum plate was used as the counter electrode. Before the measurement of the polarization curve, the
solution resistance values were obtained by measuring the impedance at 50 mV AC amplitude under
open-circuit potential, and the IR drop was corrected accordingly.
The test conditions of the measurements of polarization curves are shown in the numbers from s to z in
Table 4.

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3. Results

3.1 Corrosion immersion test results

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The results (pH, DO concentration, corrosion rate, corroded area ratio, and corrosion form) of the
corrosion immersion tests are shown in Table 5. The values of mean and standard deviation of the
corrosion rate were calculated from the results of seven specimens per condition. The corroded area ratio

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was defined as the ratio of the corroded area to the total area per specimen, and the values in the table
were the mean values per seven specimens. The detail of the categorization of the corrosion form is given

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below.
The influence of the addition of Na2B10O16 on the pH of 25°C diluted artificial seawater is shown in Fig.
2. The pH of the undiluted artificial seawater solution was 8.2, but increasing solution dilution

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corresponded to an increasingly acidic solution; the pH of the 100-fold diluted artificial seawater was 6.3.
When 3.7 × 10−4 M of Na2B10O16 was added to the 100-fold diluted artificial seawater, the pH shifts from
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6.3 to 8.6 and alkalized, but when the concentration of the added Na2B10O16 was increased, the solution
tended to acidify slightly. The influence of the added Na2B10O16 remained approximately consistent
within the range of 100- to 10,000-fold diluted artificial seawater.
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Fig. 3 shows the influence of adding Na2B10O16 to 25°C diluted artificial seawater on the DO level. The
DO in undiluted artificial seawater was 7.1 mg/L, but increasingly diluted artificial seawater showed
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increased DO levels. In the 100-fold diluted artificial seawater, the DO was measured at 8.3 mg/L.
Conversely, increasing the concentration of the added Na2B10O16 caused decreases in the DO levels of the
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100- to 10,000-fold diluted artificial seawater.

Fig. 4 shows the typical photo of corroded samples in solutions of 100-fold diluted artificial seawater
with various concentrations of added Na2B10O16. When the Na2B10O16 concentration was zero or 3.7 ×
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10−4 M, the entire surface of the test specimens gradually became covered in a corrosion product with a
two-layered structure in which the inner layer was black and the outer layer reddish-brown in color. After
the test, the corrosion product was removed from the surfaces of the test specimens, revealing corrosion
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over the entire surface area. In this study, this form of corrosion, in which the entire surface area of a test
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specimen was corroded, was defined as uniform corrosion. When the Na2B10O16 concentration was 3.7 ×
10−3 M, corrosion initiated between the through-holes and the silicone tubes used to hang the test
specimens; from these points, corrosion spread to the surrounding area. After 500 h the test specimens
were entirely reddish-brown with large tuberculation. However, when the corrosion product was removed
and examined, the corrosion was limited to the bottom portion of the tuberculation, with the corroded area
ratio of 23.9%. This type of corrosion, in which a part of the surface area of a test specimen was corroded,
was defined as localized corrosion. When the concentration of Na2B10O16 was 3.7 × 10−2 M, the test
specimens experienced no corrosion over the 500-h period, retaining their metallic shine. This form with

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no corrosion was defined as passivity.

The categorization of corrosion forms in each water quality was summarized in Table 5. When all the
seven specimens per condition showed uniform corrosion, the corrosion form was categorized as “U:
Uniform corrosion” in the table. When all the seven specimens showed passivity, the corrosion form was
categorized as “P: Passivity” in the table. The condition neither U nor P was categorized as “LC:

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Localized Corrosion” in the table.
Fig. 5 shows the relationship between the corrosion rate in diluted artificial seawater with Na2B10O16
added and the Na2B10O16 concentration ([Na2B10O16]), organized based on the dilution ratio. For

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convenience, the results of [Na2B10O16] = 0 are shown at the location of 1 × 10−5 M. With 100-fold diluted
artificial seawater (represented with □), unlike the corrosion rate of 24.7 mdd when [Na2B10O16] = 0, as

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[Na2B10O16] increased, the corrosion rate increased to 54.2 mdd. However, when [Na2B10O16] was
increased to 3.7 × 10−2 M, passivation occurred, and the corrosion rate decreased to <0.1 mdd. In the
dilution ratio of 10- and 100-fold, the corrosion rates when [Na2B10O16] = 3.7 × 10−3 M became the

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maximum values. AN
3.2 Polarization curve measurement results

Fig. 6 and Fig. 7 each shows an example of the anodic polarization curves of carbon steel measured in
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Na2B10O16 aqueous solutions and NaHCO3 aqueous solutions at various concentrations. In Na2B10O16
aqueous solutions of various concentrations, passivation behavior occurred regardless of the added
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concentration, with the anodic current density suddenly decreasing after increasing. The peak current
densities were observed at two points, one at −0.4 V and the other at 0–0.1 V. The passive current density
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was approximately 2–4 × 10−2 A/m2. For 3.7 × 10−4 M, after showing passivation behavior, the current
density recovered to ~2 A/m2. After the measurements, only the 3.7 × 10−4 M solution system showed
slight pitting corrosion on the surfaces of the test specimens; no signs of corrosion appeared on other
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samples.
In the NaHCO3 aqueous solutions, the specimens tended to passivate at concentrations >3.7 × 10−3 M,
but not at 3.7 × 10−4 M, and the anodic current density increased monotonically. At concentrations
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between 3.7 × 10−2 and 1.0 × 10−1 M, as with the Na2B10O16 aqueous solution, the anodic current density
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peaked twice. The surfaces of the test specimens after the measurements showed no corrosion with the 1.0
× 10−1 M solution; all other specimens showed either localized or uniform corrosion.
The passivation of carbon steel occurs when the peak current density in the active area of the anodic
polarization curve decreases below the reduction current density of the DO. This peak current density is
called the critical current density for passivation (icrit). The potential showing icrit is called the primary
passivation potential (Epp). Examples of these parameters are shown in Fig. 6. The reduction current
density of the DO increases for decreases in potential; as the potential reaches the diffusion limit, the
reduction current becomes nearly constant. Therefore, lower icrit or Epp values correspond to easier

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passivation. The effects of the Na2B10O16 or the NaHCO3 concentration on the mean values of icrit and Epp
in three polarization curves per condition are shown respectively in Fig. 8 and Fig. 9.
As can be seen in Fig. 8, in the low-concentration range, the icrit in the Na2B10O16 aqueous solution was
one to two digits smaller than that in the NaHCO3 aqueous solution. The icrit in the NaHCO3 aqueous
solution greatly decreased at 1.0 × 10−1 M to a value approaching that in Na2B10O16 aqueous solution. As

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seen in Fig. 9, on the low-concentration side, the Epp in Na2B10O16 aqueous solution was significantly
lower than that in the NaHCO3 aqueous solution. At 1.0 × 10−1 M, the Epp in a NaHCO3 aqueous solution
closely matched that in Na2B10O16 aqueous solution.

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4. Discussion

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4.1 Prediction of corrosion forms

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In the criticality control of the fuel debris at the Fukushima Daiichi, the important point is to prevent
localized corrosion of the carbon steel when the Na2B10O16 is added as a neutron absorber. This is because,
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generally, the propagation rate of localized corrosion in the depth direction is 10 to 1000 times higher than
the uniform corrosion rate, which increases the risk of leakages in the PCV drywell and water injection
piping. Therefore, for practical use, the correlation diagram between water quality and corrosion forms is
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particularly important.
The Larson–Skold Index (LSI) [28] is widely used to express the corrosiveness of water of a given
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quality toward carbon steel. LSI is expressed by the following equation, as the ratio of the equivalent
concentration sum of Cl− and SO42− to the sum of the equivalent concentrations of HCO3− and CO32−.
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Here, [x] represents the molar concentration of the species x (mol/L).

LSI = ([Cl−] + 2[SO42−])/([HCO3−] + [CO32−]) (2)

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The judgement criteria of the corrosiveness based on LSI have been interpreted in many ways.
Generally, LSI < 0.2 indicates no corrosiveness; LSI = 0.2 can be regarded as a boundary condition as to
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whether passivation can occur. Ozawa et al. [30] showed that the M-alkalinity determined by the titration
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experiment using a mixed solution of NaHCO3 and Na2B10O16 was equal to the sum of the blended
concentrations of both. This indicates that Na2B10O16 can also be a component of the denominator of
equation (2). Therefore, the LSI can be extended by adding the equivalent concentration of Na2B10O16 to
the denominator of equation (2), as seen in the following equation. Here, in the pH = 6.3–8.6 targeted by
this research, the [CO32−] is negligibly small, and can therefore be excluded from the equation.

Extended LSI = ([Cl−] + 2[SO42−])/([HCO3−] + 2[B10O162−]) (3)

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The corrosion form of the test specimens after the corrosion immersion test as shown in Table 5 is
arranged in Fig. 10, with the horizontal axis of [HCO3−] + 2[B10O162−] and the vertical axis of [Cl−] +
2[SO42−]. The boundary line of the extended LSI = 0.2 is shown as a broken line within the diagram.
Considering that localized corrosion (represented with ▲) is occurred as a result of passivation, the
border of carbon steel passivation is represented as in the solid line in the diagram. The slope of the solid

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line is clearly greater than that of the borderline of extended LSI = 0.2, indicating that higher values in the
concentrations of the horizontal axis correspond to increases in the passivity region as well. The
experiment shown in Table 5 is, in every case, [B10O162−] >> [HCO3−]; therefore, the values in the

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horizontal axis of Fig. 10 are practically expressed as 2[B10O162−]. As seen in Fig. 8 and Fig. 9, with
Na2B10O16, the decrease in both icrit and Epp occurs at low concentrations; the passivation effect is

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significantly greater compared to that in NaHCO3. Therefore, when the values of the horizontal axis are
increased, the passivity range is also expanded upward. While Na2B10O16 and NaHCO3 have components
with the same M-alkalinity, they are significantly different in their passivation effect; thus, the corrosion

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form of carbon steel cannot be easily predicted by the simple extension of LSI.
Based on Fig. 10, Na2B10O16 addition to more than 100-fold diluted artificial seawater ([Cl−] < 200
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mg/L) at a boron concentration >4,000 mg/L (equivalent to more than 3.7 × 10−2 M) allows the
maintenance of passivity without initiating localized corrosion. The same occurs at 50°C, as shown in
Table 5. Therefore, if criticality control of the fuel debris in the Fukushima Daiichi is conducted under
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these water quality conditions, corrosion mitigation of the carbon steel components inside the PCV could
be achieved simultaneously. However, because Fig. 10 is based on 500-h corrosion immersion test results,
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it is not guaranteed that localized corrosion would not occur over longer terms than that measured by this
test, as localized corrosion occurs probabilistically and requires some incubation time to occur. Therefore,
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it is necessary to use an evaluation method based on the critical potential for localized corrosion, which is
not time-dependent; this remains as a future task.
In this study, most localized corrosion attacks began at the crevices between the through-holes and
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silicone tubes used to hang the test specimens. The preferential occurrence of corrosion in crevices is
similar to that in stainless steel. These results suggest that the method of determining critical potential for
localized corrosion of stainless steels such as JIS G 0592 [31] can be applied to passivated carbon steel.
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4.2 Passivation effect of pentaborate

As shown in Fig. 5, the addition of Na2B10O16 promotes the passivation of carbon steel. In strong
alkaline conditions, for example pH = 12–14 as in concrete, carbon steel can be passivated. However, the
pH after the addition of Na2B10O16 is weakly alkaline in the range of 7.9–8.2, as shown in Fig. 2.
Therefore, the passivation as seen in Fig. 5 is not due to the pH increase, but rather to the passivation
effect of Na2B10O16.
The phase diagrams of aqueous borate solutions are complex with many aspects of the solution

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chemistry remaining unknown. In particular, little information exists on the solution chemistry of
Na2B10O16. H3BO3, which constitutes the Na2B10O16 in equation (1), is a Lewis acid; by interacting with
water, it creates the tetrahydroxyborate ion B(OH)4−, as seen in equation (4). The equilibrium constant Ka
of the reaction is represented by equation (5), and pKa is 9.24 at 25°C [32].

H3BO3 + H2O = B(OH)4− + H+

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(4)
Ka = [B(OH)4−][H+] / [H3BO3] (5)

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Based on equations (4) and (5), the fraction diagram of aqueous boron species is as shown in Fig. 11.
The Na2B4O7 aqueous solution is also complex. Once Na2B4O7 is dissolved to generate B4O72−, this
species further decomposes into B(OH)4− [33]. The sum of moles of chemical species generated by the

SC
dissolution of Na2B4O7 in water is seven times larger than that of Na2B4O7 added to the water [34]. As a
reaction formula satisfying these reports, the following equation can be considered:

U
Na2B4O7 + 8H2O = 3B(OH)4− + H3BO3 + H+ + 2Na+ (6)
AN
Here, 1 M of Na2B10O16 aqueous solution is assumed as a combined solution comprising 6 M of H3BO3
and 1 M of Na2B4O7 to determine its pH. Based on equation (5),
M

pH = pKa + log ([B(OH)4−] / [H3BO3]) (7),

D

but since H3BO3 hardly dissociates, [B(OH)4−] is almost equal to 3 M, as generated in equation (6).
TE

Conversely, [H3BO3] is 6 M added as H3BO3 plus 1 M generated as equation (6) to become 7 M.

Therefore, the [B(OH)4−] / [H3BO3] in equation (7) is approximately 3/7, and the pH is calculated as 8.9.
The pH of the aqueous solution of Na2B10O16 added to the diluted artificial seawater, as seen in Fig. 2, is
EP

~8.6, near this calculated value. Therefore, the Na2B10O16 added to the diluted artificial seawater may
undergo the reactions in equations (1), (4), and (6), and may therefore be present in the aqueous solution
as both H3BO3 and B(OH)4−. Since H3BO3 has no direct influence on corrosion, it is thought that B(OH)4−
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has the passivation effect. However, based on Fig. 11, the fraction of B(OH)4− when the pH is 7.9–8.2 is
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0.04–0.08. This value is too small to show the strong passivation effect of Na2B10O16 shown in Fig. 8 and
Fig. 9. These findings suggest the generation of other borate species with strong passivation effects in the
Na2B10O16 solution.

4.3 Effect of pentaborate on corrosion rate

As seen in Fig. 2 and Fig. 5, as the concentration of added Na2B10O16 in 100-fold diluted artificial
seawater is increased from 0 to 3.7 × 10−3 M, the corrosion rate is increased by approximately 2.2 times

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for some time and the pH is increased from 6.3 to 8.5. Similar concentration dependencies in corrosion
rate have also been observed with other passivators such as nitrite ions [35]. Because DO hardly changes
in Fig. 3, it is not a factor in the increase of the corrosion rate. Fujii et al. [36] reported that the corrosion
rate was linearly increased by approximately 1.7 times when the pH was increased from 6.5 to 8.5 in an
aqueous carbonate solution system. Larson et al. [28] also reported that the corrosion rate of carbon steel
was maximized at a pH of ~8 when the [Cl−]/[HCO3−] was in certain carbonate aqueous solutions. The

PT
findings of this study are in good agreement with these reported cases. Aqueous solutions of both
carbonate and borate are buffer solutions, another point of agreement. Regarding the increased corrosion

RI
rate, Fujii et al. [36] assumed that it was associated with the decrease in the buffering capacity of the
carbonate solution as the pH was increased from 6.5 to 8.5. However, for the borate solutions in this study,
the buffering ability is the highest at pH = 9.24, at which [B(OH)4−]/[H3BO3] in equation (7) is 1; thus, the

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increase of pH from 6.3 to 8.5 seems instead to increase the buffering capacity against acid. Therefore,
while the pH dependence of the corrosion rate matches these findings, further studies are required to

U
determine the contributing factors. AN
5. Conclusions
M

Using corrosion immersion tests, Na2B10O16, which may be used as a neutron absorber for the criticality
control of fuel debris in the Fukushima Daiichi, was evaluated for its influence on the corrosion form and
D

rate of carbon steel as an additive in diluted artificial seawater. The obtained findings are summarized
below.
TE

(1) The addition of Na2B10O16 to diluted artificial seawater increased the pH to weak alkalinity and
changed the corrosion form of carbon steel from uniform corrosion to either passivity or localized
corrosion. These corrosion form changes were arranged on the water quality region map.
EP

(2) Passivity was maintained by adding 3.7 × 10−2 M or more Na2B10O16 to artificial seawater with a
dilution ratio of 100-fold or more. It became clear that the criticality control of the fuel debris and
corrosion mitigation of the carbon steel components could be achieved simultaneously. However, it
C

remains necessary to determine whether probabilistic localized corrosion will occur.

AC

(3) The prediction of the corrosion form of carbon steel was attempted by the extended Larson–Skold
Index (LSI) = ([Cl−] + 2[SO42−])/([HCO3−] + 2[B10O162−]) . However, the passivating action of
B10O162− was much stronger than that of HCO3−; therefore, it was difficult to predict the corrosion
form by simply adding the equivalent concentrations.
(4) It was suggested that the strong passivation effect of Na2B10O16 was caused not by well-known
B(OH)4−, but by other borate species.
(5) The localized corrosion of carbon steel under added Na2B10O16 preferentially occurred from the
crevices of the test specimens, similar to that of stainless steel.

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Acknowledgements

The authors would like to thank Mr. Masami Miyano and Mr. Takuma Yokomori of Tokyo Power
Technology, Ltd., for their assistance in the experiment.

PT
References

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[1] Y. Fukaya, T. Hirasaki, K. Kumagai, T. Tatsuoka, K. Takamori, S. Suzuki, An overview of corrosion
mitigation activities after Fukushima-Daiichi accident, Proc. 17th Int. Conf. Environ. Degrad. Mater.

SC
Nucl. Power Syst. – Water React., CNS (2015), 1321–1337.
[2] Tokyo Electric Power Company Holdings, Inc. Web site, http://www.tepco.co.jp/en/index-e.html
[3] Nuclear Damage Compensation and Decommissioning Facilitation Corporation, Technical Strategic

U
Plan 2016 for Decommissioning of the Fukushima Daiichi Nuclear Power Station of Tokyo Electric
Power Company Holdings, Inc. July 13, 2016.
AN
[4] Nuclear Regulation Authority, Japan Web site, https://www.nsr.go.jp/english/index.html
[5] B. Benson, D. Krause, Jr., The concentration and isotopic fractionation of oxygen dissolved in
freshwater and seawater in equilibrium with the atmosphere, Limnol. Oceanogr., 29 (1984) 620–632.
M

[6] J. Nakano, Y. Kaji, M. Yamamoto, T. Tsukada, Effects of hydrazine addition and N2 atmosphere on
the corrosion of reactor vessel steels in diluted seawater under gamma-rays irradiation, J. Nucl. Sci.
D

Technol., 51 (2014) 977–986.

[7] M. Yamamoto, T. Sato, A. Komatsu, J. Nakano, F. Ueno, Estimation method for corrosion rate of
TE

carbon steel in water with gamma-ray irradiated condition, Proc. Europ. Corros. Congr. 2015, Graz,
1008–1014.
[8] T. Hirasaki, Y. Fukaya, T. Tatsuoka, Proceedings of 61st Japan Conf. Materials and Environments,
EP

Japan society of corrosion engineering (2014) 179–182. (in Japanese)

[9] T. Kaneko, N. Tanaka, T. Yamaoka, H. Masaki, Y. Masuda, M. Iwanami, S. Ishioka, K. Fujii, Y. Goto,
K. Saito, Y. Yokoyama, R. Umehara, K. Kumagai, Y. Fukaya, Evaluation of corrosion behaviors for
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reactor pressure vessels/primary containment vessels in Fukushima Daiichi units 1–3 nuclear power
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plant, J. Nucl. Sci. Technol., 52 (2015) 773–783.

[10] T. Kaneko, N. Tanaka, T. Yamaoka, H. Masaki, Y. Masuda, M. Iwanami, S. Ishioka, K. Fujii, Y. Goto,
K. Saito, Y. Yokoyama, R. Umehara, K. Kumagai, Y. Fukaya, Corrosion and corrosion protection for
reactor pressure vessels /primary containment vessels in Fukushima Daiichi unit 1-3 nuclear power
plant, Proc. 17th Int. Conf. Environ. Degrad. Mater. Nucl. Power Syst. – Water React., CNS (2015),
1254–1272.
[11] S. Ishioka, M. Iwanami, K. Fujii, N. Tanaka, T. Yamaoka, T. Kaneko, Y. Yokoyama, R. Umehara, K.
Kumagai, Y. Fukaya, Evaluation of corrosion behavior for PCV material with various anionic species

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in diluted simulated seawater, Proc. 17th Int. Conf. Environ. Degrad. Mater. Nucl. Power Syst. –
Water React., CNS (2015), 1310–1320.
[12] Y. Yokoyama, R. Umehara, N. Tanaka, T. Yamaoka, T. Kaneko, S. Ishioka, M. Iwanami, K. Fujii, K.
Kumagai, Y. Fukaya, Evaluation of corrosion behavior of piping material in flowing dilute seawater,
Proc. 17th Int. Conf. Environ. Degrad. Mater. Nucl. Power Syst. – Water React., CNS (2015), 1338–

PT
1356.
[13] IRID Annual Research Report 2015, International Research Institute for Nuclear Decommissioning
(2016) 26-27.

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[14] W. R. Stratton, Review of the state of criticality of the Three Mile Island Unit 2 core and reactor
vessel, DOE/NCT-01, LLNL (1987).

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[15] K. Tonoike, H. Sono, M. Umeda, Y. Yamane, T. Kugo, K. Suyama, Options of principles of fuel
debris criticality control in Fukushima Daiichi reactors, Nuclear Back-end and Transmutation
Technology for Waste Disposal, Springer, Tokyo (2015) 251–259.

U
[16] M. Nagayama, M. Cohen, The anodic oxidation of iron in a neutral solution, J. Electrochem. Soc.,
109 (1962) 781–790.
AN
[17] G. P. Marsh, I. W. Bland, J. A. Desport, C. Naish, C. Westcottand K. J. Taylor, Corrosion assessment
of metal overpacks for radioactive waste disposal, European Appl. Res. Rep. -Nucl. Sci. Technol., 5
(1983) 223–252.
M

[18] K. Ohba, N. Hara, K. Sugimoto, A. Honda, H. Ishikawa, Passivation and depassivation behavior of
carbon steel in water in contact with bentonite, Zairyo-to-Kankyo, 45 (1996) 209–216. (in Japanese)
D

[19] T. Fukuda, M. Akashi, Effect of [HCO3-+CO32-] on corrosion crevice repassivation potential of

carbon steel in simulated bentonite environment, Mat. Res. Soc. Symp. Proc., 412 (1996) MRS 597–
TE

602.
[20] G. Nakayama, Y. Fukaya, M. Akashi, The effects of carbonate-bicarbonate concentration of empirical
corrosion diagram of mild steel as a material of geological disposal package for high level nuclear
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wastes, Mat. Res. Soc. Symp. Proc., 451 (1997) MRS 567–572.
[21] Y. Fukaya, M. Akashi, Passivation behavior of mild steel used for nuclear waste disposal package,
Mat. Res. Soc. Symp. Proc., 556 (1999) MRS 871–878.
C

[22] T. Haruna, K. Domoto, T. Shibata, Effect of sulfate ion on corrosion of carbon steel in
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carbonate/bicarbonate solutions, Zairyo-to-Kankyo, 51 (2002) 350–355. (in Japanese).

[23] Y. Fukaya, M. Akashi, Passivation behavior of carbon steel in aqueous carbonate solutions,
Zairyo-to-Kankyo, 56 (2007) 521–528. (in Japanese)
[24] T. E. Larson, R. M. King, Corrosion by water at low flow velocity, Corrosion, 10 (1954) 110–114.
[25] T. E. Larson, R. M. King, Corrosion by water at low flow velocity, J. AWWA, 46 (1954) 1–9.
[26] N. Sato, The stability of localized corrosion, Corros. Sci., 37 (1955) 1947–1967.
[27] R. V. Skold, T. E. Larson, Measurement of the instantaneous corrosion rate by means of polarization
data, Corrosion, 13 (1957) 139–142.

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[28] T. E. Larson, R. V. Skold, Laboratory studies relating mineral quality of water to corrosion of steel
and cast iron, Corrosion, 14 (1958) 285–288.
[29] S. G. Sawochka, M. R. Miller, M. A. Leonard, Corrosion of A193 grade B7 bolt material in BWR
sodium pentaborate solutions, STP-NU-068, ASME standards technology, LLC (2014) 1–62.
[30] M. Ozawa, M. Akashi, Proceedings of 62nd Japan Conf. Materials and Environments, Japan society

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of corrosion engineering (2015) 25–28. (in Japanese)
[31] JIS G 0592, Method of determining the repassivation potential for crevice corrosion of stainless
steels, 2nd edition, Japanese Standards Association (2016) 1–9.

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[32] Douglas A. Skoog, Donald M. West, F. James Holler, Stanley R. Crouch, Analytical Chemistry : An
Introduction - 7th edition, Saunders College Division (2000).

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[33] F.A. Cotton, G. Wilkinson, C.A. Murillo, M. Bochmann, Advanced Inorganic Chemistry 6th Edition,
Wiley-Interscience, p. 171 (1999).
[34] A. Apelblat, E. Manzurola, Solubilities and vapour pressures of saturated aqueous solutions of

U
sodium tetraborate, sodium carbonate, and magnesium sulfate and freezing-temperature lowerings of
sodium tetraborate and sodium carbonate solutions, J. Chem. Thermodynamics, 35 (2003) 221–238.
AN
[35] KURITA water industries LTD., KURITA handbook of water treatment, Second English edition,
(1999).
[36] T. Fujii, T. Kodama, H. Baba, Influence of water quality and flow conditions on corrosion of carbon
M

steel pipes in fresh water, Boshoku Gijutsu (Presently Zairyo-to-Kankyo), 31 (1982) 637–642. (in
Japanese)
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Captions for the Figures and Tables

Table 1 Results of water quality analysis of the accumulated water inside the PCVs.
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Table 2 Results of the O2 gas concentration analysis of the gas-phase section and the Dissolved oxygen
(DO) concentration in the water accumulated within the PCVs, estimated by the equilibrium
C

calculation at 50°C.
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Table 3 Chemical composition of the test material. The actual plant data range in the table is µ ± σ,
where µ is the average concentration and σ is the standard deviation thereof, calculated based
on the material test reports published during the construction of the Fukushima Daiichi.

Table 4 The test conditions (temperature, dilution ratio of artificial seawater, and addition
concentrations of typical anions in test solutions).The numbers from a to r are for the corrosion
immersion testing. The numbers from s to z are for the measurements of polarization curves.

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Table 5 The results of the corrosion immersion testing. The values of mean and standard deviation of
the corrosion rate were calculated from the results of seven specimens per condition. The
corroded area ratio was defined as the ratio of the corroded area to the total area per specimen,
and the values in the table were the mean values per seven specimens. The corrosion forms are

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abbreviated as U: Uniform corrosion; LC: Localized corrosion; P: Passivity.

Fig. 1 The shape of the test specimens and immersion method.

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Fig. 2 The influence of adding Na2B10O16 on the pH of diluted artificial seawater (ASW) at 25°C.

SC
Fig. 3 The influence of adding Na2B10O16 on the Dissolved oxygen (DO) concentration in diluted
artificial seawater (ASW) at equilibrium with the atmosphere at 25°C.

U
Fig. 4 The typical photo of corroded samples of carbon steel in solutions with Na2B10O16 added to
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100-fold diluted artificial seawater (ASW) at 25°C.

-
M

-
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Fig. 5 The influence of the concentration of the added Na2B10O16 in diluted artificial seawater (ASW) on
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carbon steel corrosion rate at 25°C.

Fig. 6 Examples of anodic polarization curves of carbon steel in Na2B10O16 aqueous solutions of various
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concentrations at 25°C. The icrit and Epp in the figure mean the examples of the critical current
density for passivation and the primary passivation potential, respectively.
C

Fig. 7 Examples of anodic polarization curves of carbon steel in NaHCO3 aqueous solutions of various
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concentrations at 25°C.

Fig. 8 The influence of Na2B10O16 or NaHCO3 concentration on the mean value of the critical current
density for passivation icrit, as observed on the anodic polarization curves at 25°C.

Fig. 9 The influence of Na2B10O16 or NaHCO3 concentration on the mean value of the primary
passivation potential Epp, as observed on the anodic polarization curves at 25°C.

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Fig. 10 Corrosion form diagram of the carbon steel in diluted artificial seawater with added Na2B10O16
aqueous solution organized by water quality, evaluated by corrosion immersion testing for 500 h
at 25°C. The extended LSI = ([Cl-] + 2[SO42-])/([HCO3-] + 2[B10O162-]).

Fig. 11 The fraction diagram of aqueous boron species at 25°C.

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U SC
AN
M
D
TE
C EP
AC

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Unit Date of pH Conductivity Cl- Cs-134 Cs-137

sampling (mS/m) (ppm) (Bq/cm3) (Bq/cm3)
1 10/12/2012 7.2 8.8 19 1.9 x 104 3.5 x 104
2 8/7/2013 7.4 2.5 2.9 2.1 x 103 4.4 x 103

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3 10/22/2015 6.8 1.4 <1 4.0 x 102 1.6 x 103

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U SC
AN
M
D
TE
EP
C
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Unit Date of sampling O2 gas Estimated DO

(vol%) (mg/L)
1 3/28/2013 0.30 to 0.35 0.08 to 0.09
2 4/3/2013 0.38 to 0.62 0.10 to 0.16

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U SC
AN
M
D
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Material Composition, mass%

C Si Mn P S Al Cr
Tested material 0.17 0.29 1.07 0.015 0.012 0.011 0.10
Actual plant data range 0.135 to 0.185 0.24 to 0.32 0.96 to 1.20 0.009 to 0.019 0.007 to 0.015 - -

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ASME SA516 Gr.70 ≤ 0.28 0.13 to 0.45 0.79 to 1.30 ≤ 0.035 ≤ 0.035 - -

Composition, mass%

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Cu Ni Mo Nb Ti V
0.10 0.10 0.02 0.005 0.01 0.011
- - - - - -

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- - - - - -

U
AN
M
D
TE
C EP
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No. Temperature Dillution ratio Addition concentration of typical anions in test solutions
[Cl-] [SO42-] [HCO3-] [B10O162-]
(°C) (-fold) (mol/L) (mol/L) (mol/L) (mol/L)
a 25 1 5.6 x 10-1 2.9 x 10-2 2.4 x 10-3

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b 25 10 5.6 x 10-2 2.9 x 10-3 2.4 x 10-4
-3 -4
c 25 100 5.6 x 10 2.9 x 10 2.4 x 10-5
-3 -4
d 25 100 5.6 x 10 2.9 x 10 2.4 x 10-5 3.7 x 10-4

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e 25 1000 5.6 x 10-4 2.9 x 10-5 2.4 x 10-6 3.7 x 10-4
-5 -6 -7
f 25 10000 5.6 x 10 2.9 x 10 2.4 x 10 3.7 x 10-4

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g 25 10 5.6 x 10-2 2.9 x 10-3 2.4 x 10-4 3.7 x 10-3
-3 -4 -5
h 25 100 5.6 x 10 2.9 x 10 2.4 x 10 3.7 x 10-3
-4 -5 -6
i 25 1000 5.6 x 10 2.9 x 10 2.4 x 10 3.7 x 10-3

U
j 25 10000 5.6 x 10-5 2.9 x 10-6 2.4 x 10-7 3.7 x 10-3

AN
-1 -2 -3
k 25 1 5.6 x 10 2.9 x 10 2.4 x 10 3.7 x 10-2
l 25 10 5.6 x 10-2 2.9 x 10-3 2.4 x 10-4 3.7 x 10-2
-3 -4 -5
m 25 100 5.6 x 10 2.9 x 10 2.4 x 10 3.7 x 10-2

M
-4 -5 -6
n 25 1000 5.6 x 10 2.9 x 10 2.4 x 10 3.7 x 10-2
o 25 10000 5.6 x 10-5 2.9 x 10-6 2.4 x 10-7 3.7 x 10-2
-3 -4 -5
p 50 100 3.7 x 10-2

D
5.6 x 10 2.9 x 10 2.4 x 10
q 50 1000 5.6 x 10-4 2.9 x 10-5 2.4 x 10-6 3.7 x 10-2

TE
-5 -6 -7
r 50 10000 5.6 x 10 2.9 x 10 2.4 x 10 3.7 x 10-2
s 25 − − − − 3.7 x 10-4
t 25 − − − − 3.7 x 10-3
EP
u 25 − − − − 3.7 x 10-2
v 25 − − − − 1.0 x 10-1
w 25 − − − 3.7 x 10-4 −
C

x 25 − − − 3.7 x 10-3 −
AC

y 25 − − − 3.7 x 10 -2
−
z 25 − − − 1.0 x 10 -1
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No. pH DO Corrosion rate (mdd) Corroded area ratio Corrosion form

(mg/L) Mean Standard (%)
deviation
a 8.2 7.1 26.0 0.4 100 U
b 7.2 8.1 21.6 2.2 100 U

PT
c 6.3 8.3 24.7 2.3 100 U
d 8.5 8.2 43.2 1.0 100 U

RI
e 8.5 8.2 43.3 2.6 100 U
f 8.6 8.2 43.3 1.5 100 U

SC
g 8.5 8 44.3 2.1 100 U
h 8.5 8.2 54.2 5.9 43.9 LC
i 8.5 8.1 7.4 3.4 3.9 LC

U
j 8.5 8 0.3 0.4 0.1 LC
k 7.9 6.4 6.9 1.8 0.7 LC

AN
l 8.2 7.6 2.4 0.4 0.8 LC
m 8.2 7.6 < 0.1 < 0.1 0 P
n 8.2 7.5 < 0.1 < 0.1 0 P

M
o 8.2 7.5 < 0.1 < 0.1 0 P
p 8.2 5.4 < 0.1 < 0.1 0 P

D
q 8.1 5.4 < 0.1 < 0.1 0 P
r 8.2 5.3 < 0.1 < 0.1 0 P

TE
C EP
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Nylon string (Unit: mm)

Silicone tube

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φ3

SC
2
30

U 20
AN
M
D
TE
EP
C
AC
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0
10
Uniform corrosion

PT
Localized corrosion
-1 Passivity
10
[Cl-] + 2[SO42-] (Molarity)

Uniform corrosion Passivity or

RI
-2 Localized corrosion
10

SC
-3
10

-4
Extended LSI
10

U
= 0.2 AN
-5
10
-5 -4 -3 -2 -1 0
10 10 10 10 10 10
[HCO3-] + 2[B10O162-] (Molarity)
M
D
TE
EP
C
AC
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1
pKa = 9.24

PT
0.8 [H3BO3]
Fraction of species

RI
0.6

SC
0.4

[B(OH)4-]
0.2

U
AN
0
6 7 8 9 10 11 12
pH
M
D
TE
EP
C
AC
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10

PT
9

RI
pH

SC
ASW dilution ratio
1-fold
7 10-fold

U
100-fold
1000-fold
10000-fold
AN
6
-5 -4 -3 -2 -1
0
10 10 10 10 10
[Na2B10O16] (Molarity)
M
D
TE
EP
C
AC
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10
ASW dilution ratio

PT
1-fold
10-fold
100-fold
9 1000-fold
10000-fold

RI
DO (mg/L)

SC
7

U
AN
6
0 -5
10 10
-4 -3
10 10
-2 -1
10
[Na2B10O16] (Molarity)
M
D
TE
EP
C
AC
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Time
Immediately after After scale
24 h 168 h 500 h
removal removal
Solution

100-fold
diluted ASW

PT
RI
100-fold
diluted ASW

SC
+
3.7 x 10-4 M
Na2B10O16

100-fold
U
AN
diluted ASW
+
3.7 x 10-3 M
Na2B10O16
M
D

100-fold
diluted ASW
+
TE

3.7 x 10-2 M
Na2B10O16
C EP
AC
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100
ASW dilution ratio

PT
1-fold
10-fold
80
100-fold
1000-fold
Corrosion rate (mdd)

10000-fold

RI
60

SC
40

20

U
AN
0
0 -5
10 10
-4 -3
10 10
-2 -1
10
[Na2B10O16] (Molarity)
M
D
TE
EP
C
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1.5

PT
1
Potential (V vs. SHE)

0.5

RI
0
Epp

SC
-0.5
[Na2B10O16]
3.7x10-4 M

U
-1 3.7x10-3 M
3.7x10-2 M
icrit 1.0x10-1 M
AN
-1.5
-3 -2 -1 0 1 2
10 10 10 10 10 10
Current density (A/m2)
M
D
TE
EP
C
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1.5

PT
1
Potential (V vs. SHE)

0.5

RI
0

SC
-0.5
[NaHCO3]
3.7x10-4 M

U
-1 3.7x10-3 M
3.7x10-2 M
1.0x10-1 M
AN
-1.5
-3 -2 -1 0 1 2
10 10 10 10 10 10
Current density (A/m2)
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

3
10

PT
[Na2B10O16]

10
2 [NaHCO3]

RI
1
10
icrit (A/m2)

SC
0
10

-1
10

U
AN
-2
10
-4 -3 -2 -1 0
10 10 10 10 10
[Na2B10O16] or [NaHCO3] (Molarity)
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

1.5

PT
[Na2B10O16]

1 [NaHCO3]

RI
Epp (V vs. SHE)

0.5

SC
0

-0.5

U
AN
-1
-4 -3 -2 -1 0
10 10 10 10 10
[Na2B10O16] or [NaHCO3] (Molarity)
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

Na2B10O16 may be used for criticality control of fuel debris in the Fukushima Daiichi.

The influence of Na2B10O16 on aqueous corrosion of carbon steel in diluted seawater

PT
The passivation effect of Na2B10O16 and localized corrosion due to aggressive ions

RI
Corrosion form diagram on the water quality map for practical use

U SC
AN
M
D
TE
C EP
AC