Release behavior of bred tritium from LiAlO2

The release behavior of bred tritium to the blanket purge gas is mainly controlled by such bulk phenomena as tritium forming reaction, diffusion of tritium in grain, interaction of tritium with irradiation defects, and absorption together with such surface phenomena as adsorption, isotope exchange reaction between molecular form hydrogen in purge gas and tritium on grain surface (isotope exchange reaction 1), isotope exchange reaction between water vapor and tritium on grain surface (isotope exchange reaction 2), and water formation reaction at addition of hydrogen. Following the observation of the present authors that the isotope exchange reaction 2 is much faster than the isotope exchange reaction 1, the release curve of bred tritium obtained at purge with humidified gas was used for estimation of the effective diffusivity of bred tritium in LiAlO₂. Then, the effective diffusivity of tritium in grain of LiAlO₂ is obtained as D_T = 2.5 × 10⁻⁷exp(−110 [kJ]/RT) [m²/s]. This equation gives the larger diffusivity than any other diffusivity presented so far because the mass transfer resistance at the grain surface is expected to be eliminated in the estimation procedure of this study.     

Multi-component Adsorption Characteristics of Hydrogen Isotopes on Synthetic Zeolite 5A-type at 77.4K

The pressure swing adsorption (PSA) method, operating rapid desorption, has become applied to medium-massive air-component separation. In this study, with the aim of applying the PSA method to a hydrogen isotope separation process, the multi-component adsorption characteristics of H₂-D₂ or H₂-HD-D₂ on a synthetic zeolite at the liquid nitrogen temperature 77.4 K are investigated by using a volumetric apparatus, where the system effects of thermal transpiration and diffusion are taken into account. The adsorption isotherms for pure H₂ and D₂ are shown in a wide pressure range between 10^-2 and 10⁵Pa. The isotherms are closely approximated by an error functional expression proposed here. The separation factors resulting in adsorption are measured in a wide range of amount adsorbed. The separation factors of D₂/H₂ are estimated in accordance with the ideal adsorbed solution theory using the adsorption isotherms for H₂ and D₂. The behavior of the estimated factors agrees with that of the experimental ones. The result suggests that values around 3 are expectable for the factors of D₂/H₂ at amounts adsorbed roughly between 0.01 and 1 mol/kg.     

Verification of hydrogen isotope separation by pressure swing adsorption process: Successive volume reduction of isotopic gas mixture using SZ-5A column

For the purpose of verifying the applicability of pressure swing adsorption (PSA) process to such as volume reduction of tritiated waste storage, an experimental series was carried out by a PSA apparatus having a zeolite packed column operated at the liquefied nitrogen temperature, where synthetic zeolite 5A was used as a candidate of adsorbents. Experimental results are shown here which were obtained from cyclic operation of isolating a volume of hydrogen decontaminated with its heaver isotope from a mixture of H₂ and D₂ while reducing a volume of this mixture storage. Successive reduction during six cycles is observed in the inventory of this hydrogen mixture in a gas holder. Experimental data are analyzed in order to evaluate the performance of this PSA process operating the hydrogen isotope separation, where several factors are introduced defining efficiencies of decontamination, volumetric reduction, and so on. These factors suggest that the PSA process is available for successive reduction of a tritiated hydrogen storage inventory. A tritium waste management system of PSA process combined with electrolysis is considerable which is aiming at reducing the inventory of tritiated water in storage.     

Surface mediated isotope exchange reactions between water and gaseous deuterium

Maintaining isotopic purity of hydrogen is one of the major tasks in tritium processing systems. The work with multiple isotopes and isotopomers is accompanied by isotope exchanges which is often accelerated by catalysts e.g. surfaces of various materials. In this work, densities of D₂O, HDO produced via isotope exchange reactions in the mixture of D₂, H₂, D₂O, H₂O, HD and HDO contained in a stainless steel (type SS304) vessel were measured as a function of time (40-36 000 s) and pressures near 3.5 × 10² Pa, using mass spectrometry. The derived rates of change of the isotopomers densities are described accurately by a postulated kinetic model.     

Reduction of UO2 by H2

The reactivity of H₂ towards UO₂²⁺ has been studied experimentally using a PEEK coated autoclave where the UO₂²⁺ concentration in aqueous solution containing 2 mM carbonate was measured as a function of time at p_H2∼40 bar. The experiments were performed in the temperature interval 74-100 °C. In addition, the suggested catalytic activity of UO₂ on the reduction of UO₂²⁺ by H₂ was investigated. The results clearly show that H₂ is capable of reducing UO₂²⁺ to UO₂ without the presence of a catalyst. The reaction is of first order with respect to UO₂²⁺. The activation energy for the process is 130 ± 24 kJ mol⁻¹ and the rate constant is k_298K=3.6×10⁻⁹ l mol⁻¹ s⁻¹. The activation enthalpy and entropy for the process was determined to 126 kJ mol⁻¹ and 16.5 J mol⁻¹ K⁻¹, respectively. Traces of oxygen were shown to inhibit the reduction process. Hence, the suggested catalytic activity of freshly precipitated UO₂ on the reduction of UO₂²⁺ by H₂ could not be confirmed.     

The effect of Y2O3 on the dynamics of oxidative dissolution of UO2

In this work, we have studied the impact of Y₂O₃ on the kinetics of oxidative dissolution of UO₂ and the consumption of H₂O₂. The second order kinetics of catalytic consumption of H₂O₂ on Y₂O₃ was investigated in aqueous Y₂O₃ powder suspensions by varying the solid surface area to solution volume ratio. The resulting second order rate constant is 10⁻⁸ m s⁻¹, which is of the same magnitude as for the reaction between H₂O₂ and UO₂. Powder experiments with mixtures of UO₂ and Y₂O₃ show that Y₂O₃ has no effect on the oxidative dissolution of UO₂, whereas the consumption of H₂O₂ seems to be slightly slower in the presence of Y₂O₃ and H₂ respectively. UO₂ pellets with solid inclusions of Y₂O₃ show a decrease in oxidative dissolution by a factor of 3.3 and 5.3 under inert and hydrogen atmosphere, respectively. The rate of H₂O₂ consumption is similar for all cases and is well in line with kinetic data from powder experiments. The effects of H₂ and Y₂O₃ on the oxidative dissolution of UO₂ under gamma irradiation are similar to those found in experiments with H₂O₂. No significant difference in dissolution between inert and reducing atmosphere can be observed for pure UO₂.     

Simulation Procedure for Multistage Water/Hydrogen Exchange Column for Heavy Water Enrichment Accounting for Catalytic and Scrubbing Efficiencies

The present paper gives a simulation procedure for multistage water/hydrogen exchange columns for heavy water enrichment using hydrophobic catalysts. The Murphree-type efficiencies for H₂O, HDO and D₂O are used as the scrubbing efficiencies for sieve trays. The reaction rate of H₂+D₂?HD is assumed to be very rapid and equilibrated at the outlet of the catalyst bed. The catalytic efficiencies defined for H₂O(g) and D₂O(g) are considered for the nonequilibrated exchange reactions: H₂+HDO(g)?HD+H₂O(g) and H₂+D₂O(g)?D₂+H₂O(g). Those efficiencies are treated as input variables for the simulation. The main calculational loop is based on the Newton-Raphson iteration, but the order of the Jacobian matrix is just equal to the number of sieve trays for vapor/hydrogen scrubbing. The procedure is applicable to solution of operating problems in a wide range of input and output specifications.     

Permeability of hydrogen and deuterium of Hastelloy XR

Permeation of hydrogen isotope through a high-temperature alloy used as heat exchanger and steam reformer pipes is an important problem in the hydrogen production system connected to be a high-temperature engineering test reactor (HTTR). An experiment of hydrogen (H₂) and deuterium (D₂) permeation was performed to obtain permeability of H₂ and D₂ of Hastelloy XR, which is adopted as heat transfer pipe of an intermediate heat exchanger of the HTTR. Permeability of H₂ and D₂ of Hastelloy XR were obtained as follows. The activation energy E₀ and pre-exponential factor F₀ of the permeability of H₂ were E₀=67.2±1.2 kJ mol⁻¹ and F₀=(1.0±0.2)×10⁻⁸ m³(STP) m⁻¹ s⁻¹ Pa^−0.5, respectively, in the pipe temperature ranging from 843 K (570 °C) to 1093 K (820 °C). E₀ and F₀ of the permeability of D₂ were respectively E₀=76.6±0.5 kJ mol⁻¹ and F₀=(2.5±0.3)×10⁻⁸ m³(STP) m⁻¹ s⁻¹ Pa^−0.5 in the pipe temperature ranging from 943 K (670 °C) to 1093 K (820 °C).     

Hydrogen Isotope Separation by Plasma-Chemical Method

Deuterium transfer (exchange) reaction as shown in HDO+H₂=H₂O+HD was studied as a case similar to the tritium transfer reaction as shown in DTO+D₂=D₂O+DT, the first step in tritium isotope separation of the tritiated heavy water DTO. The transfer reaction was plasma-chemically catalyzed by allowing a gas mixture such as H₂O/D₂, D₂O/H₂, H₂O/HDO/H₂ or H₂O/D₂O/HDO/H₂ to flow through an atmospheric pressure discharge zone formed in a reaction chamber, the inner temperature of which was maintained just above 100°C. The plasma-chemical reactions diagnosed by infrared and emission spectroscopy revealed that the mixture underwent instantaneous deuterium transfer reactions as it passed the zone. The effectiveness of the method was demonstrated by high deuterium transfer rate, high separation factor of the transfer and a possibility of miniaturizing the separation facility.     

Fabrication of Li2TiO3 pebbles by water-based sol-gel method

Fabrication of Li₂TiO₃ pebbles by wet process received great attention for their convenience to realize mass production and good performances. Li₂TiO₃ pebbles with about 1.4 mm in diameter were prepared by a water-based sol-gel method using Ti(C₄H₉O)₄ and LiNO₃ as raw materials. This process is simple and has not been reported previously. Phase analysis, thermal analysis and morphological observation were carried out with the pebbles. The experimental results showed that a large amount of pores were presented on the surface of the pebbles and the density of the pebbles was sensitive to the sintering temperature. The pebbles sintered at 1200 °C for 10 h reached a density of ∼68%T.D. The shape of the pebbles was favorable with an average sphericity of about 1.08.     

Applicability of CeO2 as a surrogate for PuO2 in a MOX fuel development

The applicability of cerium oxide, as a surrogate for plutonium oxide, was evaluated for the fabrication process of a MOX (mixed oxide) fuel pellet. Sintering behavior, pore former effect and thermal properties of the Ce–MOX were compared with those of Pu–MOX. Compacting parameters of the Pu–MOX powder were optimized by a simulation using Ce–MOX powder. Sintering behavior of Ce–MOX was very similar to that of Pu–MOX, in particular for the oxidative sintering process. The sintered density of both pellets was decreased with the same slope with an increasing DA (dicarbon amide) content. Both the Ce–MOX and Pu–MOX pellets which were fabricated by an admixing of 0.05 wt% DA and sintering in a CO₂ atmosphere had the same average grain size of 11 μm and a density of 95%T.D. The thermal conductivity of the Pu–MOX was a little higher than that of the Ce–MOX at a lower temperature but both conductivities became closer to each other above 900 K. Cerium oxide was found to be a useful surrogate to simulate the Pu behavior in the MOX fuel fabrication.     

Molecular dynamics simulations of C2, C2H, C2H2, C2H3, C2H4, C2H5, and C2H6 bombardment of diamond (1 1 1) surfaces

The sticking and erosion of C₂H_x molecules (where x=0-6), at 300 and 2100 K onto hydrogenated diamond (1 1 1) surfaces was investigated by means of molecular dynamics simulations. We employed both quantum-mechanical and empirical force models. Generally, the sticking probability is observed to somewhat increase when the radical temperature increases and strongly decrease with increasing number of H atoms in the molecule.     

Reactivity of hydrogen peroxide towards Fe3O4, Fe2CoO4 and Fe2NiO4

The kinetics of CRUD oxidation by H₂O₂ has been studied using aqueous suspensions of metal oxide powder. Fe₃O₄, Fe₂CoO₄ and Fe₂NiO₄ were used as model compounds for CRUD. In addition, the activation energies for the reaction between H₂O₂ and the three CRUD models were determined. The rate constants at room temperature were determined to 6.6 (±0.4) × 10⁻⁹, 3.4 (±0.4) × 10⁻⁸ and 1.6 × 10⁻¹⁰ m min⁻¹ for Fe₃O₄, Fe₂CoO₄ and Fe₂NiO₄, respectively. The corresponding activation energies are 52 ± 4, 44 ± 5 and 57 ± 7 kJ mol⁻¹, respectively. The mechanism of the reaction is briefly discussed indicating that the final solid product in all three cases is Fe₂O₃. In addition to the experimental studies, the theoretical grounds for kinetics of reactions in particle suspensions are discussed. The theoretical discussion is also used to explain the somewhat unexpected trends in reactivity observed experimentally.     

Existence states of deuterium irradiated into LiAlO2

The existence states of deuterium in LiAlO₂ were analyzed by in situ IR absorption spectroscopy during irradiation with 3 keV at room temperature. Multiple IR absorption peaks that were related to O-D stretching vibrations were observed, mainly at 2650 cm⁻¹ (O-D_α), 2600 cm⁻¹ (O-D_β), and 2500 cm⁻¹ (O-D_γ). The O-D_α was assigned to the surface O-D. The O-D_β and O-D_γ were interpreted as two distinct O-D states for three candidates: O-D of substitutional D⁺ for Li⁺; O-D of substitutional D⁺ for Al³⁺; and O-D of interstitial D⁺. O-D_β was the dominant O-D state for deuterium irradiated into LiAlO₂, and had higher stability than O-D_γ. Heating after ion irradiation led to the desorption of D₂ and an increase in the intensity of O-D_β, which implies that some of the deuterium irradiated into LiAlO₂ exists in non-O-D states, such as D⁻ captured by F centers.     

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%。     

热处理对LaNi4.25Al0.75/SiO2复合材料储氢特性的影响

采用气相二氧化硅法制备了LaNi_4.25Al_0.75/SiO₂复合材料。研究了该复合材料经不同温度（473～1 073 K）热处理后的相组成、形貌及吸放氢p-C-T曲线、吸氢动力学性能和吸放氢循环性能。结果表明,随着热处理温度的升高,LaNi_4.25Al_0.75/SiO₂复合材料吸氢量减少,平台压升高,平台斜率略有增加,而动力学性能并无显著变化。经60次吸放氢循环后,经不同温度热处理后的样品均未出现粉化现象,且与未循环样品储氢性能基本保持一致。     

Simulations of H2O2 concentration profiles in the water surrounding spent nuclear fuel

A simple mathematical model describing the hydrogen peroxide concentration profile in water surrounding a spent nuclear fuel pellet as a function of time has been developed. The water volume is divided into smaller elements, and the processes that affect hydrogen peroxide concentration are applied to each volume element. The model includes production of H₂O₂ from α-radiolysis, surface reaction between H₂O₂ and UO₂ and diffusion. Simulations show that the surface concentration of H₂O₂ increases fairly rapidly and approaches the steady-state concentration. The time to reach steady-state is sufficiently short to be neglected compared to the times of interest when simulating spent fuel dissolution under deep repository conditions. Consequently, the steady-state approach can be used to estimate the rate for radiation-induced spent nuclear fuel dissolution.     

Mössbauer study and structural characterization of UO2–Gd2O3 sintered compounds

Samples of UO₂and up to 10 wt% of Gd₂O₃ were prepared by solid-state reaction under a reducing atmosphere, in a thermal path comprising ramps and dwell times in the temperature range of 900–1750 °C. The sintered material was analyzed by X-ray diffraction and ¹⁵⁵Gd Mössbauer spectroscopy. The results showed that for samples annealed up to 900 °C, the gadolinium sesquioxide remained unreacted. However, when the temperature was increased to 1300 °C, a solid-state reaction took place forming mixed oxides. For the more severe sintering condition, at 1750 °C, gadolinia left urania partially unreacted producing a material consisting of two compositions, UO₂ (with no dissolved gadolinium) and (U, Gd)O₂. The proposed heating cycle provided pellets free from Gd₂O₃ phase and may be used by the nuclear fuel industry as a suitable sintering process.     

Kinetics of initial stage of sintering of UO2 and UO2 with Nd2O3 addition

The kinetics of initial stage sintering of UO₂ powder were reinvestigated, using Ar-10% H₂ atmosphere. The effect of the addition of neodynium oxide was studied. The results revealed that surface and grain boundary diffusion mechanisms act simultaneously. The values of activation energies were found to be $\text{48.48 ± 3.51 kcal/mole}$ in the temperature range 870–942°C and $\text{89.88 ± 9.87 kcal/mole}$ in the temperature range of 942–1030°C for UO₂, and $\text{115.61 ± 7.77 kcal/mole}$ in the temperature range 1030–1150°C for UO₂ + Nd₂O₃. An important decrease in the calculated diffusion coefficient occurs by the addition of Nd₂O₃.