Effect of LiNO3 on Corrosion Prevention of Aluminum Wastes after Their Land Disposal

After their land disposal, LiNO₃ added to cement solidified miscellaneous wastes inhibits hydrogen gas generation due to alkaline corrosion of aluminum contained in the wastes. We considered the presence of an Li-Al preservation film prevents hydrogen gas generation, and then, we assumed a scenario in which the amount of LiNO₃ included in the waste packages is lowered by underground water penetration, resulting in dissolution of the Li-Al preservation film. This dissolution allows the alkaline underground water to reach and corrode the aluminum materials. The loss of Na₂O and K₂O in cement by underground water penetration lowers the pH, so that the aluminum corrosion in the waste packages with LiNO₃, expected when the Li-Al preservation film dissolves, is less than that without LiNO₃.

To test this scenario, we measured solubility of the Li-Al preservation film, Li⁺ ion concentration, pH variation by underground water penetration, and aluminum corrosion when the Li-Al preservation film had dissolved. The measured solubility of the Li-Al preservation film was 3 × 10^?4 _M at 283 K. At that time, pH was lowered from 12.9—13.0 to 12.2—12.3. As a result, with LiNO₃ addition the aluminum corrosion amount was reduced to 10% of that without LiNO₃ addition, because of the pH decrease.     

LiNO3 Addition to Prevent Hydrogen Gas Generation from Cement-Solidified Aluminum Wastes

LiNO₃ addition to the cement solidified miscellaneous wastes has been proposed for preventing hydrogen ges generation caused by the corrosion of aluminum materials contained in the wastes. To determine an additive among alkaline metal ions, galvanic current was measured in 0.1 M alkaline metal hydroxide solution between aluminum and platinum electrodes. The volume of hydrogen gas generated from an aluminum specimen was measured in a KOH solution with LiNO₃, LiCl, LiBr, Li₂CO₃ or Li₂SO₄ to decide the best additive. Applicability of the chosen additive to cement was confirmed by hydrogen gas generation measurement from an aluminum specimen in cement paste. The prevention mechanism was analyzed by X-ray diffraction, SEM and SIMS.

The current measured in LiOH solution decreased with time, then reached 0 μA/mm², while the current was detected in other alkaline metal hydroxide solutions. The least volume of hydrogen gas generation was measured in a KOH solution with LiNO₃. The volume of generated hydrogen gas in cement paste with LiNO₃ was less than 10% of that without LiNO₃. The results of analyses showed that an insoluble film of LiH(AlO₂)₂5H₂O was formed on the aluminum surface.

These results suggested that LiNO₃ addition to cement is effective to prevent hydrogn gas generation by formation of the insoluble film on aluminum.     

Extraction of Lithium from Sea Water with Metallic Aluminum

Extraction of lithium from sea water was investigated. It was found that a corrosion product of metallic aluminum immersed in sea water extracts lithium from it selectively. Effects of the temperature and the pH of sea water, and of the initial concentration of lithium in it were examined. On the basis of the analysis of the surface deposit on aluminum, which is a corrosion product of aluminum, the selectivity coefficients were calculated. For the extraction of lithium from natural sea water, the values of K ^Li _Na ^Li _MgK ^Li _Ca and ^Li _K were 9.9 × 10², 1.1×10, 4.5×10 and 4.4 × 10², respectively.     

Lithium nitrate as a fusion reactor coolant fluid?: A thermochemical assessment

In connection with possible application as a coolant fluid in fusion reactors, molten LiNO₃ and LiNO₃/LiNO₂ mixtures, and their mixtures with Na/K nitrates, have been evaluated with respect to their high temperature stability, their ability to reversibly dissolve and release tritium and, in a very limited sense, their corrosiveness toward structural alloys. The results of the primarily thermochemical evaluation indicate that with respect to thermal/radiolytic decomposition and corrosivity LiNO₃/LiNO₂ may be suitable for application up to R 700^°K; however, with respect to reversibility/irreversibility of tritium release, it appears unsuitable at all likely operating temperatures (R 675–800°K).     

Effects of Hydrogen Peroxide on Intergranular Stress Corrosion Cracking of Stainless Steel in High Temperature Water, (III)

The stress corrosion cracking (SCC) of structural materials used in boiling water reactors has been studied at relatively low hydrogen peroxide (H₂O₂) concentrations, around lOppb, which was assumed to be representative of the corrosion environment formed in hydrogen water chemistry (HWC). The 1/4T compact tension specimen was used for measurement of crack growth rates (CGRs) of sensitized type 304 stainless steel in high temperature and high purity water. Crack length was monitored by a reversing direct current potential drop method. Since H2O2 is easily decomposed thermally, a polytetrafluoroethylene-lined autoclave was used to minimize its decomposition on the autoclave surface. The CGR in the H₂O₂ environment differed from that in the O₂ environment even though the electrochemical corrosion potential (ECP) for both conditions was the same. The data implied that the ECP could not be used as a common environmental deterministic parameter for SCC behavior at higher potentials for different oxidant conditions. The corrosion current density was found to play an important role as an environmental index for SCC, which was given as just the current density at the ECP at a specific oxidant concentration. The CGRs were found to be written as CGR = (3.8±0.6)xl0^-3 _icor +(l-5±1.6) x 10^-8mm/s using the calculated corrosion current density i_corbelow 10^-4 A-cm^-2.     

Online measurement of the atmosphere around geopolymers under gamma irradiation

ABSTRACT

The gas production of wasteforms is a major safety concern for encapsulating active nuclear wastes. For geopolymers and cements, the H₂ produced by radiolytic processes is a key factor because of the large amount of water present in their porous structure. Herein, the gas composition evolution around geopolymers was monitored online under ⁶⁰Co gamma irradiation. The transient evolution of the hydrogen release yield was measured for samples with different formulations. Its evolution and the final values are consistent with the presence of a pseudo-first-order chemical reaction consuming hydrogen in the samples. The results show that this phenomenon can significantly reduce the hydrogen source term of geopolymer wasteform provided their diffusion coefficient remains low. Lower hydrogen production rates and faster kinetics were observed with geopolymer formulations in which pore water pH was higher. Besides hydrogen release, a steady oxygen consumption was observed for all geopolymer samples. The oxygen consumption rates are proportional to the diffusion coefficients estimated in the modelization of hydrogen recombination by a pseudo-first-order reaction.     

Development of a suppression method for deposition of radioactive cobalt after chemical decontamination: (III) the suppression mechanism with preoxidized ferrite film for deposition of radioactive cobalt

The Hitachi ferrite coating film process (Hi-F) has been developed to lower recontamination after chemical decontamination. In this process, the chemical decontamination process is carried out, and a fine Fe₃O₄ coating film is formed on the surface of stainless steel piping in an aqueous solution. In order to improve the suppression of ⁶⁰Co deposition further, we combined the original Hi-F with a preoxidation step. We found the deposited amount of ⁶⁰Co with preoxidized Hi-F coating film (OHi-FC) was 1/10 of that for non-coated specimens. In this study, we investigated the suppression mechanism of ⁶⁰Co for the OHi-FC. The composition of OHi-FC was changed from Fe₃O₄ to Fe₂O₃ and then the crystals in the OHi-FC grew three times larger than those of the original Hi-F coating film. Consequently the corrosion amount of the stainless steel base metal was reduced by getting larger grains in the coating film. Because ⁶⁰Co was incorporated into the corrosion oxide, the suppression effect of ⁶⁰Co deposition by preoxidation was attributed to the suppression of the formation of the corrosion oxide by the OHi-FC.     

Intergranular stress corrosion cracking susceptibility of sensitized type 304 steel in 561 K pure water under γ-ray irradiation

Intergranular stress corrosion cracking (IGSCC) of sensitized type 304 stainless steel has been investigated in 561 K water under γ-ray irradiation at a flux of 2.6 × 10³ C kg⁻¹ h⁻¹ by slow-strain-rate tensile tests. The IGSCC susceptibility was enhanced by γ-ray irradiation in water containing 8 ppm dissolved oxygen (DO). The DO dependence of the IGSCC susceptibility was observed in the water under γ-irradiation. Although slight IGSCC susceptibility was observed even in deaerated water (less than 1 ppb DO) under γ-ray irradiation, the susceptibility was completely suppressed by injection of hydrogen into the water. The enhancement of IGSCC susceptibility seems to be related to the formation of H₂O₂ in high temperature water by radiolysis under γ-ray irradiation and the H₂O₂ formation rate is markedly decreased by hydrogen injection.     

Effects of seawater components on radiolysis of water at elevated temperature and subsequent integrity of fuel materials

Effects of seawater components on radiolysis of water at elevated temperature have been studied with a radiolysis model and a corrosion test under gamma-ray irradiation conditions to evaluate the subsequent influence on integrity of fuel materials used in an advanced boiling water reactor. In 2011, seawater flowed into the nuclear power plant system of the Hamaoka Nuclear Power Station Reactor No. 5 during the plant shutdown operation. The reactor water temperature was 250 °C and its maximum Cl^? concentration was ca. 450 ppm when seawater was mixed with reactor water. The radiolysis model predicted that the main radiolytic species were hydrogen, oxygen and hydrogen peroxide. Concentrations of radiolytic products originating from Cl^? and other seawater components were found to be rather low. The dominant product among them was ClO₃^? and its concentration was found to be below 0.01 ppm for a 10⁵ s irradiation period. No significant corrosion of zircaloy-2 and 316L stainless steel was found in the corrosion test. These results led to the conclusion that the harmful influence of radiolytic products originating from seawater components on integrity of fuel materials must be smaller than that of Cl^? which is the main ionic species in seawater.     

Effect of Metallographic Factor on Hydrogen Pick-up Properties of Zircaloy-2

Zirconium alloy sheets were prepared with varying Fe, Cr and Ni systematically. The corrosion and hydrogen pickup property were estimated in steam at 673 K, in water at 633 K and in super critical water at 673 K. The effect of the SPP and the oxide film on the hydrogen pick-up was studied from the hydrogen pick-up route using D₂O and the microstructure of the oxide film and secondary phase particle (SPP) in the oxide film. The hydrogen pick-up ratio decreased with increase of Fe and decrease of Ni. It was affected by Fe/Ni ratio of the matrix. The hydrogen pickup was not related to SPP but was related to the oxide film when the oxide film was relatively thick. The tetragonal ZrO₂ is considered to act as a barrier for hydrogen pick-up.     

Radionuclide release from high burnup spent fuel during corrosion in salt brine in the presence of hydrogen overpressure

In the case of a contact between groundwater and Fe-based spent fuel disposal containers in a repository large amounts of hydrogen will be produced by the corrosion of iron, which may result in significant hydrogen pressures. To quantify to what extent the hydrogen overpressure may counteract radiolysis enhanced matrix dissolution, related experimental work has been performed. High burnup spent fuel was corroded in 5.6 mol (kg H₂O)⁻¹ NaCl solution applying H₂ overpressures (experimental set 1) <0.17 bar by radiolysis, (experimental set 2) 2.8 bar by Fe corrosion, (experimental set 3) 3.2 bar by external H₂ gas. In the absence of Fe (experimental set 3) the UO₂ matrix dissolution rate decreased by a factor of about 10. In this test the concentrations of U, Np, Tc in solution were found to be decreasing by at least two orders of magnitude, and ranging within the same level as in the presence of Fe powder (experimental set 2). However, Pu and Am concentrations (experimental set 3) were less affected, due to the high sorption capacity for these radioelements onto Fe corrosion products.     

In situ measurement of corrosion of type 316L stainless steel in 553 K pure water via the electrical resistance of a thin wire

A system for the in situ monitoring of corrosion depth via electrical resistance measurements was applied to study the corrosion rate of type 316L stainless steel at 553 K in pure water. Corrosion depth was measured using a 50 μm diameter wire probe mounted axially in the tube. Measurements were in good agreement with literature data for both the hydrogen water chemistry (HWC) condition and the normal water chemistry (NWC) condition. Oxide film analyses by scanning electron microscopy and laser Raman spectroscopy on the wire probe and the tube showed no effects from shape of the test specimens or the application of electric current. Corrosion kinetics was evaluated by fitting equations to the measurements. Data for the HWC condition could be fitted by a two-step logarithmic–parabolic law. A single-step logarithmic law fitted data for the NWC condition. Changes in corrosion rate by the water chemistry changes were readily detected with the technique. Corrosion depth change could be observed for the water chemistry change from the NWC condition to the HWC condition with electrochemical corrosion potential (ECP) of ?0.56 V vs. standard hydrogen electrode, which is lower than the ECP that the phase of iron oxide changes from α-Fe₂O₃ to Fe₃O₄.     

Hafnium corrosion behavior in high-temperature steam

Corrosion properties for three kinds of hafnium have been examined in 10.5 MPa steam at 773 K. Nuclear grade hafnium formed a shiny black film with a few white nodules, which were found to be monoclinic HfO₂. Hydrogen pick-up fraction during the corrosion amounted to ca. 40% to produce hydrogen dissolved in the hafnium matrix with evolving the remaining 60% hydrogen as H₂ gas. Sponge and crystal bar hafnium were also examined and they showed superior and inferior corrosion resistance, respectively, to nuclear grade hafnium. The corrosion resistance for hafnium increased with increasing the iron content involved in hafnium for these three kinds of hafnium and, correspondingly related to the density of iron-containing second phase particles, which were characterized to be face centered cubic Hf₂Fe.The corrosion mechanism, which was previously proposed for Zircaloy nodular corrosion, was adopted with making minor alterations, to explain the hafnium corrosion properties.     

Vitrification of a simulator of Savannah River site (USA) wastes with high iron and aluminum content on bench and commercial facilities with a cold crucible

Bench and commercial-facility experiments have been performed on cold-crucible vitrification of a simulator of high-level wastes from the Savannah River site (USA). The wastes contained up to 29 mass% Fe₂O₃ and 26 mass% Al₂O₃. The specific product flow reached 1700 and 2450 kg/(m²·day) with specific energy consumption 14–16 and 9–10 kW·h/kg, respectively. The crucibles did not undergo any appreciable corrosion during the period of the work performed and are reusable. The product consisted of a borosilicate matrix, containing up to 10 vol.% crystalline phase of spinel. The method of induction melting in a cold crucible is especially effective for crucibles with a large diameter, since the specific productivity increases and the specific energy consumption on the vitrification of high-level wastes decreases. __________ Translated from Atomnaya énergiya, Vol. 104, No. 5, pp. 291–295, May, 2008.     

Hydrogen generation by water radiolysis with immersion of oxidation products of Zircaloy-4

In order to predict the hydrogen gas generation from seawater or water in which debris would be included by the severe accident of nuclear power plant, we investigated the effect of ZrO₂ and the oxidation products of Zircaloy-4 on hydrogen gas generation by radiolysis of water since the radiolytic generation could be affected by materials immersed in water. Powders of well-characterized oxides and oxidation products were immersed in either seawater or distilled water, and irradiated by gamma ray from a Co-60 source. The observed hydrogen yield, G(H₂), was measured as a function of the weight fraction of oxide in water up to 50 wt%. The enhancement of the hydrogen generation by radiolysis of water with the commercial oxides and the oxidation products of Zircaloy-4 was quite small or absent in seawater. But the enhancement was observed in the presence of the oxides or the oxidation products at low weight fraction in distilled water. This enhancement in distilled water seemed to be dependent on specific surface area or particle size, but its dependence on the crystal structure was not apparent in the experimental results. The enhancement was saturated at higher ZrO₂ weight fractions and it was not apparent in the seawater.     

核级不锈钢焊接接头钝化膜耐蚀性能和半导体特性研究

采用电化学阻抗谱(EIS)、场发射扫描电子显微镜(SEM)、Auger扫描能谱仪(AES)以及容抗测试技术(M-S曲线),研究了316LN/316L不锈钢焊接接头在模拟压水堆一回路高温高压水中形成的钝化膜的耐蚀性能和半导体特性。结果表明,焊缝区、热影响区和母材区形成的钝化膜的耐蚀性能不同,热影响区钝化膜开路电位及电化学阻抗等均低于其他区域,说明热影响区钝化膜的耐蚀性能最差,这主要与钝化膜的致密程度、厚度及Cr氧化物的含量有关。M-S曲线表明,母材区钝化膜平带电位为-0.7V,较其他区域(-0.4V)负移,表明有BO-3等阴离子在钝化膜表面吸附,加之具有较低的施主和受主浓度,可排斥侵蚀离子的腐蚀,使之较其他区域有更强的耐蚀性能。     

Inconel690在ETA/NH_3水化学环境中的均匀腐蚀行为研究

本文在模拟压水堆二回路的高温高压水化学环境下,研究了蒸汽发生器传热管材料镍基合金Inconel690试样在乙醇胺(ETA)和氨(NH3)水化学环境中的均匀腐蚀行为。结果显示:在5 000h均匀腐蚀试验后,ETA水化学环境下试样的均匀腐蚀速率为0.21mg/(m2·h),NH3水化学环境下试样的均匀腐蚀速率为0.50mg/(m2·h);在ETA水化学环境下试样表面形成的氧化膜中铬含量更高,氧化膜的保护性更好。以上结果表明,Inconel690在ETA水化学环境下的耐蚀性强于NH3水化学环境。     

Effect of Oxygen Partial Pressure on Oxidation of Iron at 573 K

The oxidation of iron was investigated by Rutherford backscattering spectroscopy at 573 K under the oxygen partial pressure from 10^?1 to 10⁵ Pa for 3~24 h. In the first stage of oxidation, thickness of the oxide film reached the maximum around 1 Pa. In the second stage the oxidation obeyed the parabolic rate law. From 10^?1 to 10^?0.5 Pa the parabolic rate constant increased with increasing oxygen partial pressure due to the growth of magnetite, whereas from 1 to 10^0.5 Pa hematite covered magnetite but the parabolic rate constants were kept still high values possibly due to the presence of grain boundaries. Between 10 and 10^4.3 Pa the protective hematite coverage over magnetite kept the parabolic rate constants low regardless of oxygen partial pressure. At 10⁵ Pa a sharp increase of the parabolic rate constant was observed due to the simultaneous growth of hematite and magnetite. The oxygen concentration in water for the inhibition of the corrosion may correspond to the oxygen partial pressure for the formation of protective film in gas phase around 573 K.     

Characterization and storage of radioactive zeolite waste

For the safe storage of zeolite wastes generated by the treatment of radioactive saline water at the Fukushima Daiichi Nuclear Power Station, this study investigated the fundamental properties of herschelite adsorbent and evaluated its adsorption vessel for hydrogen production and corrosion. The hydrogen produced by the herschelite sample is oxidized by radicals as it diffuses to the water surface and thus depends on the sample's water level and dissolved species. The hydrogen production rate of herschelite submerged in seawater or pure water may be evaluated by accounting for the water depth. From the obtained fundamental properties, the hydrogen concentration of a reference vessel (decay heat = 504 W) with or without residual pure water was evaluated by thermal–hydraulic analysis. The maximum hydrogen concentration was below the lower explosive limit (4%). The steady-state corrosion potential of a stainless steel 316L increased with the absorbed dose rate, but the increase was repressed in the presence of herschelite. The temperature and absorbed dose at the bottom of the 504 W vessel were determined as 60 °C and 750 Gy/h, respectively. Under these conditions, localized corrosion of a herschelite-contacted 316L vessel would not immediately occur at Cl^? concentrations of 20,000 ppm.     

Depth profiling of hydrogen under an atmospheric pressure

Nuclear reaction analysis of hydrogen with a use of the ¹H(¹⁵N,αγ)¹²C reaction was performed under a atmospheric condition. A 100 nm-thick silicon nitride membrane coated with gold of 10 nm was used for the extraction of the ¹⁵N beam into the sample chamber filled with gas molecules. Hydrogen contained in a Y film with a thickness of 80 nm was detected in N₂ of 10⁵ Pa. This nuclear reaction analysis (NRA) setup was also applied to H₂ gas, and the yield curve revealed a plateau feature. The plateau level was, furthermore, found to be constant independent of the H₂ pressure. We show that this plateau intensity can be used to obtain the detection efficiency of a NRA setup.