Enthalpy measurements of La2Te3O9 and La2Te4O11

Enthalpy increment measurements on La₂Te₃O₉(s) and La₂Te₄O₁₁(s) were carried out using a Calvet micro-calorimeter. The enthalpy values were analyzed using the non-linear curve fitting method. The dependence of enthalpy increments with temperature was given as: H°(T) − H°(298.15 K) (J mol⁻¹) = 360.70T + 0.00409T² + 133.568 × 10⁵/T − 149 923 (373 ? T (K) ? 936) for La₂Te₃O₉ and H°(T) − H°(298.15 K) (J mol⁻¹) = 331.927T + 0.0549T² + 29.3623 × 10⁵/T − 114 587 (373 ? T (K) ? 936) for La₂Te₄O₁₁.     

Swift heavy ion irradiation-induced microstructure modification of two delta-phase oxides: Sc4Zr3O12 and Lu4Zr3O12

Swift gold ions (185 MeV) were used to systematically investigate the radiation damage response of delta phase compounds Sc₄Zr₃O₁₂ and Lu₄Zr₃O₁₂ in the electronic energy loss regime. Ion irradiation-induced microstructural modifications were examined using X-ray diffraction (XRD) and transmission electron microscopy (TEM). XRD investigations indicate a phase transformation from ordered rhombohedral to disordered fluorite (O-D) in both compounds, with the Sc compound transforming at a higher ion fluence compared with the Lu compound. This result is consistent with our previous study on Sc₄Zr₃O₁₂ and Lu₄Zr₃O₁₂ under displacive radiation environment in which the nuclear energy loss is dominant. High resolution TEM revealed that individual ion tracks maintain crystalline structure, while the core region experiences an O-D phase transformation. TEM observations also suggest that for the doses in which the tracks overlap, the O-D phase transformation occurs across the entire ion range.     

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.     

Carbon deposition from a γ-irradiated CO2/CO/CH4/C2H6 gas mixture on the manganese oxides MnO, Mn3O4 and Mn2O3

The composition of oxides formed on steel surfaces within power reactors may influence heat transfer efficiency. Previous studies have indicated that carbon is deposited on spinal-type oxides containing manganese, iron, cobalt, nickel and chromium. In this investigation, characterised manganese oxides have been subjected to γ-irradiation under conditions similar to those experienced in reactors in an effort to understand the catalytic processes involved in deposit initiation and growth. Mn₃O₄ and Mn₂O₃, under the conditions present in the γ-cell, were reduced to MnO during the time of exposure. Relative carbon deposition rates were observed to follow the trend MnO>Mn₃O₄≈Mn₂O₃.     

Helium and xenon behaviour in irradiated Am-containing MgAl2O4 (reactor experiment EFTTRA-T4)

Magnesium aluminate spinel (MgAl₂O₄) containing ²⁴¹Am was irradiated for 358 days in the High Flux Reactor in Petten (NL) with the objective of effectively transmuting this highly radiotoxic actinide. The feasibility of the process was demonstrated; however, a major drawback was observed as material swelling, probably due to the large quantity of helium emitted from formed short-lived actinides. The behaviour of helium and of fission gas in the matrix was investigated by post-irradiation thermal annealing experiments in a Knudsen-cell. The observed gas release was related to the microstructure of the matrix investigated by scanning and transmission electron microscopy. Helium was found to be present in large pores, whereas the less mobile xenon was distributed partly in the same pores and partly in small intragranular bubbles. During post-irradiation thermal annealing, almost complete helium release took place abruptly at a rather high temperature (∼1600 K), whilst only part of the xenon was released during this stage. The release of the remaining xenon was associated with a bulk thermal restructuring of the MgAl₂O₄ target at higher temperatures.     

NHO3氧化去除Np—Pu反萃液中的H2C2O4

研究了用ＮＨＯ３氧化去除ＴＲＰＯ流程反萃Ｎｐ－Ｐｕ的Ｈ２Ｃ２Ｏ４反萃液中Ｈ２Ｃ２Ｏ４的条件。７．５ｍｏｌ．Ｌ＾－１ＨＮＯ３－０．３ｍｏｌ．Ｌ＾－１Ｈ２Ｃ２Ｏ４混合液于９０℃下蒸发１３０ｈ和１００℃下蒸馏回流６ｈ,Ｈ２Ｃ２Ｏ４可完全分解去除;混合液中添加适量催化剂ＭｎＣＯ３,于１００℃下蒸发或蒸馏回流,Ｈ２Ｃ２Ｏ４分解加速,１－１．５ｈ内Ｈ２Ｃ２Ｏ４完全分解。蒸发或蒸馏回流过程中产生的ＨＮＯ２把Ｎｐ     

Structural stability of ZnAl2O4 spinel irradiated by low energy particles

It is now well known that irradiation of metals and alloys can drive materials into complex configurations. Several examples, like the occurrence of order–disorder phase transitions driven by irradiation, are discussed by many authors. To understand the behavior of ceramics under irradiation, several spinels were irradiated. In this paper, experimental results on the irradiation of ZnAl₂O₄ by low-energy particles (4 MeV Au²⁺ ions) are presented. An order–disorder phase transition is observed. The unusual behavior of this spinel under irradiation is discussed within the framework of Martin’s theory of driven alloys under irradiation.     

Thermoluminescence kinetic parameters of Bi4Ge3O12 single crystals

In this work, we present a detailed kinetic study of the thermoluminescence of Bi₄Ge₃O₁₂ (BGO) single crystals grown by the Czochralski technique. A single crystalline phase was confirmed through X-ray diffraction pattern analysis based on the Rietveld profile refinement method. The thermoluminescent (TL) glow curves were induced by UV or beta radiation and measured between 20 °C and 200 °C. The glow curves of BGO crystal presented two peaks at 61 °C and 90 °C for both kinds of radiation. The kinetic parameters, kinetic order (b), activation energy (E) and frequency factor (s), of the TL glow curves have been determined by four different methods. The lifetime of the peaks at room temperature was also determined and used to discuss the stability of the TL peaks at room temperature.     

Plasma-Assisted ALD of an Al2O3 Permeation Barrier Layer on Plastic

Atomic layer deposition(ALD) technique is used in the preparation of organic/inorganic layers,which requires uniform surfaces with their thickness down to several nanometers.For film with such thickness,the growth mode defined as the arrangement of clusters on the surface during the growth is of significance.In this work,Al 2 O 3 thin film was deposited on various interfacial species of pre-treated polyethylene terephthalate(PET,12 μm) by plasma assisted atomic layer deposition(PA-ALD),where trimethyl aluminium was used as the Al precursor and O 2 as the oxygen source.The interfacial species,-NH 3,-OH,and-COOH as well as SiCHO(derived from monomer of HMDSO plasma),were grafted previously by plasma and chemical treatments.The growth mode of PA-ALD Al 2 O 3 was then investigated in detail by combining results from in-situ diagnosis of spectroscopic ellipsometry(SE) and ex-situ characterization of as-deposited layers from the morphologies scanned by atomic force microscopy(AFM).In addition,the oxygen transmission rates(OTR) of the original and treated plastic films were measured.The possible reasons for the dependence of the OTR values on the surface species were explored.     

Interface strain study of thin Lu2O3/Si using HRBS

The interface of thin Lu₂O₃ on silicon has been studied using high-resolution RBS (HRBS) for samples annealed at different temperatures. Thin rare earth metal oxides are of interest as candidates for next generation transistor gate dielectrics, due to their high-k values allowing for equivalent oxide thickness (EOT) of less than 1 nm. Among them, Lu₂O₃ has been found to have the highest lattice energy and largest band gap, making it a good candidate for an alternative high-k gate dielectric. HRBS depth profiling results have shown the existence of a thin (∼2 nm) transitional silicate layer beneath the Lu₂O₃ films. The thicknesses of the Lu₂O₃ films were found to be ∼8 nm and the films were determined to be non-crystalline. Angular scans were performed across the [1 1 0] and [1 1 1] axis along planar channels, and clear shifts in the channeling minimum indicate the presence of Si lattice strain at the silicate/Si interface.     

含TBP-HNO3超临界CO2流体静态络合萃取U3O8

建立了一种快速降低萃取系统压力的静态络合萃取实验装置。在此装置上研究了含TBP-HNO₃超临界CO₂静态络合U₃O₈的快速气化测量方法,探索了含TBP-HNO₃超临界CO₂静态络合萃取U₃O₈的行为规律。     

Characterisation of an oxygen sensor based on In/In2O3 reference electrode

A potentiometric sensor for measuring oxygen activity in LBE has been developed since 2000 until today at ‘Institut Quimic de Sarria’ electrochemistry laboratories. This sensor is based on In/In₂O₃ reference electrode. The last experiments performed with this sensor have been directed to characterise the sensor. For this purpose, the following experiments in stagnant conditions have been performed: effect of the operating temperature from 300 to 500 °C, different covering gases (N₂ + 5% H₂, Ar 99.999%, and N₂ + 10 mg/L O₂) and comparison of different solid electrolytes (ZrO₂/Y₂O₃ and ZrO₂/MgO). Long-term experiments have also been performed to the see the stability of the signal with time.     

Simulation of UAl4 growth in an UAl3/Al diffusion couple

In this work the growth of the UAl₄ phase in an UAl₃/Al diffusion couple is treated as a planar moving boundary problem due to diffusion of Al and U atoms in the direction perpendicular to the interface surface. The diffusion problem was carried out by the DICTRA simulation package which combines data evaluated by Thermo-Calc with a mobility database. A thermodynamic database of the U-Al system, suitable for the Thermo-Calc code, was composed using data from literature. The mobility database was assessed from reported experimental growth of the UAl₄ phase at different temperatures. The Al tracer diffusion coefficient in the UAl₄ phase, is obtained under the assumption that uranium mobility is negligible.     

Investigation of films of YBa2Cu3O7 using Rutherford backscattering spectrometry

Rutherford backscattering spectrometry (RBS) has been applied to films of the high-temperature superconductor YBa₂Cu₃O₇. The films were prepared by rf and dc sputtering and silk-screen printing onto substrates of alumina, sapphire and magnesia. Some of the samples were exposed to various heat treatments in order to promote the superconducting phase. A 2 MeV beam of He⁺ particles from the 3 MV Dynamitron accelerator at Birmingham University's School of Physics and Space Research was employed for the RBS measurements. The composition and the depth profile of the elements in the films were determined by simulating the observed RBS spectra with a simulation software package. The simulations show that the heat treatment causes marked interdiffusion of the film and substrate. The experimental results and the computer simulations shown in this paper illustrate the advantages of using RBS to characterise films of the new superconducting materials.     

掺杂Cr2O3对UO2芯块烧结行为的影响

提高燃料燃耗的一个有效手段是通过增大UO₂晶粒尺寸来减少元件内部气体压力,在大晶粒UO₂芯块中,裂变气体到达晶界表面的距离增加,因而裂变气体的释放速率降低,元件内部气体压力的增高缓慢。本文研究了添加Cr₂O₃对UO₂晶粒尺寸的影响。对纯UO₂、添加0.5% Cr₂O₃及5% Cr₂O₃ 3种配方的芯块进行了试验,在5%H₂Ar保护下,以10 ℃/min和5 ℃/min的升温速率升温至1 700 ℃,然后烧结2 h或4 h,对比纯UO₂芯块与添加Cr₂O₃的芯块发现,添加Cr₂O₃可有效增大晶粒尺寸;较长的烧结时间可促进晶粒长大;较低的升温速率也使晶粒长大。烧结过程产生液相烧结,液相浸润晶粒边界,促进晶粒长大。     

A dilatometric study of the solubility of U4O9 in UO2

Phase relationships in the system UO₂-O₉ were studied using a dilatometei in which the O/U ratio of a UU_2+x specimen could be both controlled and measured. Phase boundary temperatures were indicated by changes in expansion or contraction rate during heating or cooling, respectively. The solubility of U₄O₉ in UO₂ agreed with the results of previous workers using other techniques. The dependence of solubility on temperature is complex, and appears to be influenced by a high-temperature phase transition in U₄0₉.     

Microstructural evolution of Y2O3 and MgAl2O4 ODS EUROFER steels during their elaboration by mechanical milling and hot isostatic pressing

Different ODS EUROFER steels reinforced with Y₂O₃ and MgAl₂O₄ were elaborated by mechanical milling and hot isostatic pressing. Good compromise between strength and ductility could be obtained but the impact properties remain low (especially for the Y₂O₃ ODS steel). The materials were structurally characterized at each step of the elaboration. During milling, the martensite laths of the steel are transformed into nano-metric ferritic grains and the Y₂O₃ oxides dissolve (but not the MgAl₂O₄ spinels). After the HIP, all the ODS steels remain ferritic with micrometric grains, surrounded by nano-metric grains for the Y₂O₃ ODS steels. The mechanisms in the Y₂O₃ ODS steels are complex: the Y₂O₃ oxides re-precipitate as nano-Y₂O₃ particles that impede a complete austenitization during the HIP. The quenchability of the ODS steels is modified by the milling process, the oxide nature and the oxide content. Eventually, the advantages and drawbacks of each oxide type are discussed.     

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.     

Study on effects of swift heavy ion irradiation on the crystal structure in CeO2 doped with Gd2O3

To simulate the effects of Gd₂O₃-doping and high-energy fission products in UO₂, Gd₂O₃-doped CeO₂ pellets were irradiated with 200-MeV Xe¹⁴⁺ ions. Doping and irradiation effects were analyzed using X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS). The lattice constant of CeO₂ decreases and the local structure is disordered with increased doping levels. However, the irradiation induces an expansion of the lattice and a disordering of atomic arrangement near the Gd atoms. The effects of the irradiation become more pronounced with increasing Gd₂O₃-dopant levels. Our results are compared with those of a study involving Er₂O₃-doped CeO₂.