Dual Activation of Unsaturated Amides with Schwartz's Reagent: A Diastereoselective Access to Cyclopentanols and N,O-Dimethylcyclopentylhydroxylamines.

The diastereoselective access to cyclopentanols and N,O-dimethylcyclopentylhydroxylamines from 4-pentenoic acid-derived Weinreb amides is described. Based on the concomitant generation of both the nucleophilic and the electrophilic poles by hydrozirconation of the amide and the C=C double bond, the cyclisation may be tuned towards cyclopentanols or N,O-dimethylcyclopentylhydroxylamines depending on the ring-closure promotor. An extension to cis 3-substituted N,O-dimethylcyclohexylhydroxylamines is also presented.

The challenge of acquiring a satisfactory EBSD result of CWSR Zircaloy-4 cladding tube.

This work presents a methodology combining SEM, EDS, conventional EBSD, and transmission-EBSD to analyse a recrystallised Zircaloy-4 sheet and cold-worked stress-relieved (CWSR) Zircaloy-4 cladding in unprecedented detail. Second-phase precipitates (SPPs) in Zircaloy-4 specimens were revealed after chemical polishing using a solution containing hydrofluoric acid (HF). Pitting corrosion of Zircaloy-4 specimens was revealed after electropolishing using an electrolyte containing HClO4 . A zirconium coupon without SPPs was used to confirm the chemical response of SPPs on surface morphology. Intrinsic features of cold-worked Zircaloy-4 such as relatively small grain sizes, high dislocation density, and complex microstructure make it significantly more difficult to collect excellent EBSD results compared to recrystallised Zircaloy-4. The fine hydride structure of as-hydrided CWSR Zircaloy-4 cladding further increases the level of challenge on EBSD analysis. LAY DESCRIPTION: We present a methodology combining multiple microscopic methods to analyse a recrystallised Zircaloy-4 sheet and cold-worked stress-relieved (CWSR) Zircaloy-4 cladding, important alloys of structural materials widely used in nuclear application, and emphasis on the challenge of acquiring a satisfactory electron backscatter diffraction (EBSD) result of CWSR Zircaloy-4 cladding material in great details. EBSD is a powerful technique to characterise the crystallographic distribution and lattice type of conductive crystalline materials, especially for a highly textured material like CWSR Zircaloy-4 alloy. However, zirconium alloys are known to be one of the most difficult materials to prepare for EBSD characterisation. We point out that the configuration of the microstructure of the specimen cause the challenge in the EBSD sample preparations. Moreover, the occurrence of tiny zirconium hydride precipitates in Zircaloy-4 increases the difficulty. We believe that the information of the EBSD sample preparation related results in this paper can provide researchers and scientists in this community a useful reference to speed up the EBSD sample preparation of CWSR Zircaloy-4 cladding material and to expect the corresponding EBSD results.

In situ hydrogen loading on zirconium powder.

For the first time, various hydride phases in a zirconium-hydrogen system have been prepared in a high-energy synchrotron X-ray radiation beamline and their transformation behaviour has been studied in situ. First, the formation and dissolution of hydrides in commercially pure zirconium powder were monitored in real time during hydrogenation and dehydrogenation, then whole pattern crystal structure analysis such as Rietveld and Pawley refinements were performed. All commonly reported low-pressure phases presented in the Zr-H phase diagram are obtained from a single experimental arrangement.

Effects of Hydrogenation on the Corrosion Behavior of Zircaloy-4.

Hydrogen plays an important role in the corrosion of zirconium alloys, and the degree of influence highly depends on the alloy composition and conditions. In this work, the effects of hydrogenation on the corrosion behavior of Zircaloy-4 in water containing 3.5 ppm Li + 1000 ppm B at 360 °C/18.6 MPa were investigated. The results revealed that hydrogenation can shorten the corrosion transition time and increase the corrosion rates of Zircaloy-4. The higher corrosion rates can be ascribed to the larger stress in the oxide film of hydrogenated samples, which can accelerate the evolution of the microstructure of the oxide film. In addition, we also found that hydrogenation has little effect on the t-ZrO2 content in the oxide film and there is no direct correspondence between the t-ZrO2 content and the corrosion resistance of the Zircaloy-4.

Mechanisms of Hydride Nucleation, Growth, Reorientation, and Embrittlement in Zirconium: A Review.

Zirconium (Zr) hydrides threaten the reliability of fuel assembly and have repeatedly induced failures in cladding tubes and pressure vessels. Thus, they attract a broad range of research interests. For example, delayed hydride cracking induced a severe fracture and failure in a Zircaloy-2 pressure tube in 1983, causing the emergency shutdown of the Pickering nuclear reactor. Hydride has high hardness and very low toughness, and it tends to aggregate toward cooler or tensile regions, which initiates localized hydride precipitation and results in delayed hydride cracking. Notably, hydride reorientation under tensile stress substantially decreases the fracture toughness and increases the ductile-to-brittle transition temperature of Zr alloys, which reduces the safety of the long-term storage of spent nuclear fuel. Therefore, improving our knowledge of Zr hydrides is useful for effectively controlling hydride embrittlement in fuel assembly. The aim of this review is to reorganize the mechanisms of hydride nucleation and growth behaviors, hydride reorientation under external stress, and hydride-induced embrittlement. We revisit important examples of progress of research in this field and emphasize the key future aspects of research on Zr hydrides.

First principles calculation for generating new thermal neutron scattering data for Zirconium hydride.

Lattice parameters of materials have the same magnitude as the energy of thermal neutrons in reactors, which directly affects the neutron cross section and its energy. While they are thermalized, incident neutrons can lose or gain energy during their interactions with materials components. Since several decades, methods and models were developed in the aim to generate nuclear data sub-libraries required in correcting neutrons interactions cross sections at thermal energies. However, very few experimental works were dedicated to this field. In this paper we focus our efforts on reviewing the theoretical models and their adequacy in describing thermal scattering events in the aim of proposing new formalisms to calculate the density of states (DOS) and phonon responses of zirconium hydride material, which constitutes an important moderator of neutrons in TRIGA reactors fuel elements. Generally the effects of thermal scattering are provided in nuclear data evaluations by a thermal sub-library ENDF file 7. Data in file 7 are described by the known thermal scattering law S(α,ß) which is a function of momentum transfer and energy transfer parameters α and ß respectively. The thermal scattering law has been used to calculate the double differential cross sections and the corresponding results are presented. Although the comparison with other models shows satisfactory results, no previously personalized use of data may be the raison of its usefulness in some cases and not in others.

Oxidation Behavior Characterization of Zircaloy-4 Cladding with Different Hydrogen Concentrations at 500-800 °C in an Ambient Atmosphere.

This study simulated the after-burned zirconium cladding oxidation in air at temperatures between 500 and 800 °C. The weight changes of Zircaloy-4 cladding with hydrogen contents of 100-1000 ppm continuously measured through thermogravimetric analysis (TGA) during oxidation tests at different temperatures in an air atmosphere. The TGA results indicate a transition of oxidation kinetics from a parabolic rate law to a linear rate law for as-received and hydrided Zircaloy-4 cladding. The hydrogen concentration of Zircaloy-4 had a marked effect on its pre-transition oxidation in air between 500 and 800 °C. For all samples, the linear oxidation (post transition stage) at 650 °C, which is the critical oxidation temperature, displays a similar trend. In addition, scanning electron microscopy and transmission electron micros-copy examinations indicated the presence of a few and numerous discontinuous micro-cracks in the oxide layer in the pre-transition and post-transition stages, respectively.

Hydrogen Permeation Behavior of Zirconium Nitride Film on Zirconium Hydride.

Hydrogen permeation barrier plays an important role in reducing hydrogen loss from zirconium hydride matrix when used as neutron moderator. Here, a composite nitride film was prepared on zirconium hydride by in situ reaction method in nitrogen atmosphere. The phase structure, morphology, element distribution, and valence states of the composite film were investigated by XRD, SEM, AES, and XPS analysis. It was found that the composite nitride film was continuous and dense with about 1.6 µm thickness; the major phase of the film was ZrN, with coexistence of ZrO2, ZrO, and ZrN0.36H0.8; and Zr-C, Zr-O, Zr-N, O-H, and N-H bonds were detected in the film. The existence of ZrN0.36H0.8 phase and the bonds of O-H and N-H revealed that the nitrogen and oxygen in the film could capture hydrogen from the zirconium hydride matrix. The hydrogen permeation performance of nitride film was compared with oxide film by permeation reduction factor (PRF), vacuum thermal dehydrogenation (VTD), and hydrogen permeation rate (HPR) methods, and the results showed that the hydrogen permeation barrier effects of nitride film were better than that of oxide film. The zirconium nitride film would be a potential candidate for hydrogen permeation barrier on the surface of zirconium hydride.

Mechanisms of Growth and Hydrogen Permeation of Zirconium Nitride Film on Zirconium Hydride.

Nitride film as a hydrogen permeation barrier on zirconium hydride has seldom been studied. In this work, the zirconium nitride films were prepared on zirconium hydride in an atmosphere of N2 and N2 + H2 at 500~800 °C, with a holding time of 5 h and 20 h, and the mechanisms of film growth and hydrogen permeation were analyzed. The results showed that the film growth was mostly influenced by the temperature, followed by the reaction atmosphere and the holding time. The hydrogen could increase the nitrogen diffusivity during the formation of zirconium nitride films. The in situ nitriding conditions were optimized as 800 °C, N2 + H2 atmosphere, and 5~20 h. The chemical composition of ZrN-based films was mainly comprised of Zr and N, with a minor content of O. In addition, the film exhibited a major phase of ZrN, accompanied by the coexistence of ZrO2, ZrO, ZrN(NH2), and ZrN0.36H0.8, as well as O-H and N-H bonds based on the XPS analysis. The as-prepared ZrN base films in the present study exhibited superior hydrogen permeation resistance to other ZrO2 films previously reported. The hydrogen permeation resistance of the films could be attributed to the following mechanisms, including the chemical capture of hydrogen by the above-mentioned compounds and bonds; the physical barrier of continuous and dense film incurred from the volume effect of different compounds based on Pilling-Bedworth model and the different nitrogen diffusion coefficients at different temperatures.

Anodizing of Hydrogenated Titanium and Zirconium Films.

Magnetron-sputtered thin films of titanium and zirconium, with a thickness of 150 nm, were hydrogenated at atmospheric pressure and a temperature of 703 K, then anodized in boric, oxalic, and tartaric acid aqueous solutions, in potentiostatic, galvanostatic, potentiodynamic, and combined modes. A study of the thickness distribution of the elements in fully anodized hydrogenated zirconium samples, using Auger electron spectroscopy, indicates the formation of zirconia. The voltage- and current-time responses of hydrogenated titanium anodizing were investigated. In this work, fundamental possibility and some process features of anodizing hydrogenated metals were demonstrated. In the case of potentiodynamic anodizing at 0.6 M tartaric acid, the increase in titanium hydrogenation time, from 30 to 90 min, leads to a decrease in the charge of the oxidizing hydrogenated metal at an anodic voltage sweep rate of 0.2 V·s-1. An anodic voltage sweep rate in the range of 0.05-0.5 V·s-1, with a hydrogenation time of 60 min, increases the anodizing efficiency (charge reduction for the complete oxidation of the hydrogenated metal). The detected radical differences in the time responses and decreased efficiency of the anodic process during the anodizing of the hydrogenated thin films, compared to pure metals, are explained by the presence of hydrogen in the composition of the samples and the increased contribution of side processes, due to the possible features of the formed oxide morphologies.