A simulation of radiolysis of chloride solutions containing ferrous ion

ABSTRACT

To investigate the effect of dissolved species from steels on the radiolysis processes of Cl^?, radiolysis simulations of solutions containing both Cl^? and Fe²⁺ were carried out. The results showed that the generation of radiolytic products (H₂O₂, O₂ and H₂) increased mainly by the addition of Fe²⁺, and the concentrations of H₂O₂ and O₂ increased with increasing dose rate. Moreover, radiolysis of Fe²⁺ solutions also induced noticeable pH drop due to the hydrolysis of Fe³⁺. This pH drop enhanced the reactivity of Cl^? with ^?OH, which induced additional generation of H₂O₂ and O₂. These results show that low concentrations of Cl^? (1 × 10^?3 mol/dm³ = 35 mg/kg) in the presence of Fe²⁺ could influence the generation of H₂O₂ and O₂ during water radiolysis. On the other hand, it is considered that these effects of Fe²⁺ and Cl^? on water radiolysis are less important for corrosion of steels due to the low concentrations of H₂O₂ and O₂ generated if the concentrations of these additives and dose rate are sufficiently low. The other process, such as dissolution of iron enhanced by FeOOH, might predominantly induce corrosion under the conditions of solutions with low concentrations of H₂O₂ and O₂.     

Effects of hydrazine addition and N2 atmosphere on the corrosion of reactor vessel steels in diluted seawater under gamma-rays irradiation

Seawater was injected into the reactor cores in the Fukushima Daiichi Nuclear Power Station. Corrosion of primary containment vessel (PCV) steel and reactor pressure vessel (RPV) steel is considered to progress until the molten fuel debris is removed. To evaluate durability of the PCV and RPV steels, corrosion tests were conducted in diluted seawater at 50 °C under gamma-rays irradiation of dose rates of 4.4 and 0.2 kGy/h. To evaluate the effect of hydrazine (N₂H₄) as an oxygen scavenger under gamma-rays irradiation, 10 and 100 mg/L N₂H₄ were added to the diluted seawater. Without addition of N₂H₄, weight loss in the PCV and RPV steels irradiated with the 0.2 kGy/h dose rate was comparable with those without irradiation and weight loss in the vessel steels irradiated with the 4.4 kGy/h dose rate was higher than those without irradiation. Under irradiation, weight loss in the PCV and RPV steels in diluted seawater containing N₂H₄ was comparable with that in diluted seawater without N₂H₄. When gas phase in the flask was replaced with N₂, weight loss in the PCV and RPV steels, and O₂ and H₂O₂ concentrations in the diluted seawater decreased.     

Radiation Damage of Organic Extractant in Partitioning of High-Level Liquid Waste, (I)

Di(2-ethylhexyl)phosphoric acid (DEHPA), which is a useful extractant for the treatment of high-level liquid waste, was exposed to ⁶⁰Co γ-rays and the radiolysis products and their yields were determined.

The major radiolytic decomposition process of DEHPA was found to be a stepwise splitting of two alkyl groups resulting in MEHPA and H₃PO₄. 1-Methyl-1-ethylpentyl radical, C₄H₉-C(CH₃)-C₂H₅, was found to form with a large G value in the γ-irradiated DEHPA. Reactions involving 1-methyl-1-ethylpentyl radical were also discussed.     

High dose radiolysis of aqueous solutions of chloromethanes: Importance in the storage of radioactive organic wastes

The radiolysis of aqueous solutions of chloromethanes (dichloromethane, CH₂Cl₂; chloroform, CHCl₃; and carbon tetrachloride, CCl₄) was performed with γ-rays to doses sufficient to completely decompose the solute in order to estimate the effects of radiation on the long-term storage of mixed waste in enclosed containers. One of the main relevant products was the inorganic chloride anion, which increased in concentration with increasing radiation dose due to the reactions of radiolytic decomposition products of water with the chloromethane. The pH of the solutions was observed to decrease with irradiation due to the formation of H₃O⁺ as the counter ion to Cl⁻, i.e. the main radiolytic decomposition product is hydrochloric acid. Polymer formation was observed in aerated solutions as a precipitate while deaerated solutions exhibited a slight turbidity.     

Oxygen concentration measurement and control of lead-bismuth eutectic in a small,static experimental facility

ABSTRACT

Oxygen measurement and control system is critical for minimizing corrosion in nuclear systems. Oxygen measurement and control tools use lead-bismuth eutectic (LBE) and pure lead as a coolant or as a spallation target. Oxygen can be supplied by either gas phase (H₂O or O₂) or solid phase (PbO dissolution); thus, oxygen control includes both gas phase and solid phase methods. This article focuses on oxygen concentration measurement and control of lead-bismuth eutectic in a small, static experimental facility. This facility was developed for oxygen sensor calibration and gas/solid phase control systems test programs. The oxygen sensor with Nano Cu/Cu₂O closely the Nernstian behavior down to 195°C; the oxygen sensor measurement accuracy satisfied the requirements of subsequent experiments. The gas phase control system (verified according to different type of mass transfer, such as air, H₂O, gas injection, and coverage) and the solid phase control system were very successful in small experimental devices. Accurate oxygen concentration control was achieved with both the gas and solid phase control systems.     

Trapping of radiolytic hydrogen by amorphous cobalt oxysulfide

Hydrogen production from the radiolysis of liquid and gaseous hydrocarbons was studied in the presence of several transition metal sulfides. Cobalt oxysulfide obtained by aqueous precipitation was the most efficient admixture to decrease radiolytic production of hydrogen by pure hydrocarbons or mixtures of saturated and unsaturated hydrocarbons. Cobalt oxysulfide was characterized by XRD, scanning and transmission microscopy, and IR spectroscopy. It seems to be amorphous compound with the impurities of lamellar Co(OH)₂ phase. The organic phases were analysed before and after irradiation by γ-rays or protons in order to elucidate the origin of the effect. It has been shown that the solid does not change the composition neither the amount of the organic radiolysis products, neither in liquid nor in gas phase experiments. Therefore the presence of solid does not influence any radiolysis processes in the organics. Amorphous cobalt oxysulfide acts essentially as a trap of hydrogen, being able to absorb considerable amounts of H₂ (up to 0.5 mol H₂/at. Co). The study of the solid-gas interaction showed that slow reaction of cobalt oxysulfide with hydrogen occurs at ambient conditions independently of the irradiation of the system.     

Addition versus radiolytic production effects of hydrogen peroxide on aqueous corrosion of UO2

The effects of hydrogen peroxide, H₂O₂, on UO₂ corrosion is investigated in aerated deionized water in two types of situations. The H₂O₂ species is either added to water or produced by radiolysis at UO₂/H₂O interfaces. The concentrations vary in the range 10⁻⁵–10⁻¹ mol l⁻¹. The radiolysis is induced by irradiating the UO₂/H₂O interfaces with a He²⁺-beam emerging from the UO₂ discs into the solutions. Both the evolution of the aqueous solutions and the UO₂ surfaces are characterised. In both types of experiments, the alteration of UO₂ results in the formation of the same secondary phase, an hydrated uranium peroxide called studtite (UO₂(O)₂ · 4H₂O). However, the uranium release at the interface differs strikingly. It is much higher when H₂O₂ is produced by irradiation than when it is simply added. Furthermore, it varies in opposite direction as a function of the H₂O₂ concentration. This gives evidence that the chemistry at the UO₂ interface under irradiation differs significantly from the chemistry induced by simply adding H₂O₂ to the solution. Rutherford backscattering spectrometry is used to determine the growth rate of the corrosion layer. For H₂O₂ addition, the layer thickness increases with increasing leaching time, although as time increases, the U release tends towards zero. It is possible to establish the first empirical equation relating the corrosion rates to the added H₂O₂ concentrations. For H₂O₂ radiolytic production, the growth is continuous as irradiation time increases but the growth rate seems to decrease as the layer grows and to reach a limit.     

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.     

Water Chemistry in a Crack Tip under Irradiation, (II)

Under neutron and gamma-ray irradiations, radiolytic species are generated directly in the crack tip, which causes higher oxidant concentrations and subsequently influences crack propagation rate.

A crevice radiolysis model was proposed to estimate the oxidant concentrations in the crack tip water under gamma-ray irradiation. Direct generation of radiolytic species in the crevice water, and their secondary generation and disappearance caused by their interaction with the crevice surface as well as species in the crevice water were included in the model. The diffusion of the radiolytic species through the narrow gap from the bulk water to the crack tip and vice versa were also considered.

Calculation results confirmed that the concentrations of H₂O₂, one of the most important oxidants in BWR environments, in both bulk water and crack tip water under irradiation (energy deposition rate: 0.1 W/cm) were high enough to show high local ECP in both regions under NWC, but were high in the bulk water and low in the crack tip water under HWC. A high H₂ diffusion rate from the bulk to the crack tip enhanced the recombination reaction of H₂O₂ and H₂.     

Enrichment of the Uranium Isotopes by Electromigration in a Cation Exchange Membrane

The γ-radiolysis of water subjected to gas bubbling has been studied using a specially desinged gasloop. During the irradiation, N₂ gas was bubbled from the bottom of the irradiation vessel. As the N₂ gas feed rate was raised, the apparent G(H₂) value increased in keeping therewith, from 5 × l0^?3 to 0.26. However in the presence of a sufficient amount of O₂ or H₂O₂, G(H₂) was raised almost to the level of the molecular yield. With reasonable assumptions, it could be concluded that 3～5 × 10^?6 mol/l of H₂O₂ was sufficient to reduce the back reaction of molecular products to less than 10% under the present experimental conditions. It was also found that the G(H₂) value increased with CH₃OH concentration roughly in proportion to log(CH₃OH), and reached 3.1 with 0.1 mol/l CH₃OH.     

Edge Effect in Coolant Radiolysis in a VVÉR Core

Calculations are performed of the concentration of oxidizers of radiolytic origin (O₂, H₂O₂, and O₂ ^–) in a VVÉR first loop with hydrogen water chemistry and a different temporal dropoff law for the absorbed dose rate in the coolant at the core exit. It is shown that a linear or exponential dropoff of the dose rate on the segment of the first loop corresponding to a coolant residence time of 0.1 sec results in a lower concentration of radiolytic oxygen and hydrogen peroxide in the first loop outside the core by at least a factor of 10. 3 figures, 10 references.     

γ辐照联合H_2O_2处理污泥滤液的研究

采用60 Coγ射线辐照处理污泥滤液,通过对比处理前后化学需氧量(COD)、紫外可见吸光度和浑浊度的变化,研究了辐照处理中初始pH、初始H2O2浓度和吸收剂量对污泥滤液处理效果的影响。结果表明:在相同吸收剂量和初始H2O2浓度条件下,酸性条件更利于CODCr的降低;γ辐照联合H2O2处理存在显著协同效应,吸收剂量为18.75kGy、初始H2O2浓度为2mmol/L时,污泥滤液CODcr去除率达70.4%,浑浊度下降94.9%。     

Kinetics of chlorination of uranium–antimony composite oxide for uranium removal from waste catalyst used for acrylonitrile synthesis

For uranium removal from waste catalyst used for acrylonitrile synthesis, kinetics of chlorination of uranium–antimony composite oxide was studied. During the chlorination treatment with hydrogen chloride gas at a partial pressure of 0.6–6.7 kPa and 873–1173 K, the uranium–antimony composite oxide, USb₃O_10, which was contained in the waste catalyst converted to another composite oxide, USbO₅, then changed to uranium oxide. Both reaction rates of the conversions, from USb₃O₁₀ to USbO₅ and from USbO₅ to U₃O₈, were described by a first order function of the fraction of USb₃O₁₀ and USbO₅, and their activation energies under the condition at 1.0 kPa hydrogen chloride gas were almost same values at (8.0 ± 0.4) × 10⁴ J mol^?1.     

1993 National Symposium on Atomic Energy,Tokyo, Japan

A steady-state simulation model of the gas separation system using a hollow-filament type membrane has been proposed. The mass transfer coefficients in the non-porous thin layer, in the porous support layer of the membrane and in the boundary layer of the membrane surface are estimated in the model. The four types of flow patterns: cross flow, mixing flow, concurrent flow and counter current flow, are also considered in the model. The mass transfer through the non-porous thin layer of the membrane controls the overall mass transfer by ~99%. The experimental observations of TPL (Tritium Process Laboratory in JAERI) for N₂–H₂ and Air—H₂ systems agreed with the calculated results of the cross flow under a set of typical conditions (disposal volume of 2.78×10^?3 Nm³/s, feed-side pressure of 3.44×10⁵Pa, and permeated-side pressure of 1.07×10⁴ Pa). The validity of the simulation method was thus proved. For Air-H₂-H₂O system also, the recovery ratios calculated for H₂ are in good agreement with the experimental observations. However, the calculated recovery ratios of water vapor were slightly smaller than the experimental observations. This discrepancy may result from the difference in separation mechanism between H₂ and water vapor, or the construction change of membrane caused by the existence of water vapor.     

Al2O3/Y2O3/ZrO2 Ceramic Composite Properties Investigation by Plasma Focus Device

The Al₂O₃–Y₂O₃–ZrO₂ eutectic composition samples were prepared using the Al₂O₃, Y₂O₃, ZrO₂ powder treated at 900 °C for 30 min, pressed at 5 ton for 15 s and sintered at 1500 °C for 2 h. The locally made dense plasma focus (DPF) system with energy 2.8 kJ was used to surface modification of these samples. The samples, mounted at distance about 2 cm from the anode, were exposed to three shots of the DPF in Ar gas at a pressure of 0.8 mbar. The phase and elemental analysis of the untreated and plasma treated samples were conducted by the Raman and EDX spectroscopy. The Raman spectroscopy showed the formation of new phases (α-Al₂O₃ and c-ZrO₂) in the treated samples. The micro-hardness of the plasma treated samples was increased by about 280 % in comparison with the untreated sample.     

A chemical interpretation of heat generated in “cold fusion”

It is concluded from a thermochemical analysis that the steady-state excess heating observed in calorimetric experiments¹ is attributable to the heat of formation of liquid D₂O resulting from recombination of D₂ and O₂ gases generated in the electrolytic cell. The recombination is catalyzed by both electrodes and the extent of the reaction increases on stirring, especially when D₂ gas sparging is used for this purpose. Thermal effects of stored chemical energy, which include thermal power output exceeding electrical input in the short term and cathode meltdown from total sudden release, arise from storage of D atoms in supersaturated solid solution within the cathode volume. Their recombination to form D₂ builds up high internal pressures, causing multiple fracture. Excess heat is liberated as D atoms and D₂ molecules fall into deep traps created on fresh Pd surfaces, supplemented by D recombination heat. Postulation of unknown nuclear processes to account for the heat is not necessary.     

Numerical simulation on single bubble behavior during Al2O3/H2O nanofluids flow boiling using Moving Particle Simi-implicit method

In this study, regression analysis on the thermal properties of Al₂O₃/H₂O nanofluids was made firstly. The growth and departure of a single bubble behavior in Al₂O₃/H₂O nanofluid and pure water flow boiling process were then numerically simulated by an improved Moving Particle Semi-implicit method in different flow boiling conditions. The results indicate that the bubble in Al₂O₃/H₂O nanofluids grows faster and the bubble departure frequency of Al₂O₃/H₂O nanofluids is greater than that in pure water. The flow boiling heat flux is also improved by dispersing nanoparticles of Al₂O₃/H₂O in pure water. This work initially reveals that nanofluids can enhance flow boiling heat transfer from the point of view of bubble dynamics behavior. The effects of nanoparticle concentrations and diameters of Al₂O₃/H₂O nanofluids on the bubble behavior were also investigated and compared under the same flow conditions. It is found that the increasing of nanoparticle volume concentration may increase the bubble departure frequency and departure diameter, while the increasing rates of departure frequency and departure diameter are lessened with the increasing of nanoparticle volume concentration. It is suggested that the suitable nanoparticle volume concentration of nanofluid for flow boiling heat transfer enhancement should not be too large, especially regarding the negative effect of flow resistance increase due to the increasing of nanoparticle volume concentration. The interesting finding is that in the same nanoparticle volume concentration condition, the bubble departure frequency for the nanofluid with nanoparticle diameter of 29 nm shows a maximum value. The increasing of nanoparticle diameter leads to the decreasing of bubble departure diameter. It is boldly to predict that an optimal nanoparticle diameter range between 20 and 38 nm should be beneficial to flow boiling heat transfer enhancement of Al₂O₃/H₂O nanofluids.     

Recovery of neutron-irradiation-induced defects of Al2O3, Y2O3, and yttrium-aluminum garnet

SiC fiber-reinforced SiC matrix composites (SiC_f/SiC) are considered as one of the candidates for blanket materials in future fusion reactors and as an advanced fuel cladding material for next-generation fission reactors. Generally, the densification of SiC needs sintering additives and oxides such as Al₂O₃, Y₂O₃, and yttrium-aluminum garnet (YAG, Y₃Al₅O₁₂), which are frequently added to SiC. However, the effects of neutron irradiation on sintering additives are still unclear. In this study, we performed the neutron irradiation of Al₂O₃, Y₂O₃, and YAG at fluences up to 2.0–2.5 × 10²⁴ n/m² (E > 0.1 MeV) at 60–90 °C. The isochronal recovery of the macroscopic volume of Al₂O₃ against annealing temperature showed smooth and continuous shrinkage at a temperature of up to 1200 °C, and the volume slightly increased above that temperature. In contrast, the volume of Y₂O₃ showed quick shrinkage at the low temperature range, and slower and smooth recovery was observed up to ～1100 °C. In the case of YAG, the recovery of volume occurred in a step-wise manner at 600–750 °C, and continuous shrinkage occurred at temperatures lower and higher than that temperature range. The activation energies for the macroscopic volume recoveries of three oxides were obtained from the Arrhenius plots of the rate coefficients. Two-stage recovery was observed for Al₂O₃, whereas more complicated recovery processes were suggested for Y₂O₃ and YAG.     

Measurements of Photon Mass Attenuation Coefficients for Ge and BGO Crystals at 10 Me V

The photon mass attenuation coefficients of the important materials for γ-ray detection, Ge and BGO (Bi₄Ge₃O₁₂) crystals, have been measured for 10.0 MeV γ-rays. The measurement system using the laser-Compton backscattering γ-rays and the high-resolution high-energy photon spectrometer has been developed and utilized. The effectiveness of the system achieving the total systematic uncertainties of 0.5% for the measurements of the photon mass attenuation coefficients was demonstrated. It was shown that the measured photon mass attenuation coefficients, 318.1 ± 1.7 [cm²/g] for the Ge crystal and 425.2 ± 2.4 [cm²/g] for the BGO crystal, agree within the achieved experimental uncertainties with the evaluated values including atomic and nuclear processes at 10.0 MeV.     

Deposition of Alumina Films on Si (1 0 0) Substrate Using a Low Energy Dense Plasma Focus Device

A 1.5 kJ pulsed low energy Mather type plasma focus (PF) is used to deposit thin films of alumina (α-Al₂O₃) on Si (1 0 0) substrates. The PF device with its anode made of aluminum was operated with argon-oxygen mixture as the filling gas. The Al₂O₃ thin film samples were prepared using 10, 20 and 30 successive shots with substrates placed at 60 mm from the top of the anode at approximately zero angular position with respect to the anode axis. The crystallography of the as-deposited and annealed samples was studied by X-ray diffractometry (XRD). Raman Spectroscopy studies verified the formation of α-Al₂O₃ phase in the annealed films. Scanning electron micrographs (SEM) of the annealed films present many different sized particulates (50–300 nm) distributed upon the film surface. The cross-sectional SEM micrographs show that the thickness of deposited alumina film is linear with a typical rate of 45 nm/shot at focus storage energy of 850 J.