On-line monitoring of composite nanoparticles synthesized in a pre-industrial laser pyrolysis reactor using Laser-Induced Breakdown Spectroscopy

Laser-Induced Breakdown Spectroscopy (LIBS) was employed for on-line and real time process monitoring during nanoparticle production by laser pyrolysis. Laser pyrolysis has proved to be a reliable and versatile method for nanoparticle production. However, an on-line and real time monitoring system could greatly enhance the process optimization and accordingly improve its performances. For this purpose, experiments aiming at demonstrating the feasibility of an on-line monitoring system for silicon carbide nanoparticle production using the LIBS technique were carried out. Nanosecond laser pulses were focused into a cell through which part of the nanoparticle flux diverted from the production process was flowed for LIBS analysis purposes. The nanoparticles were vaporized within the laser-induced plasma created in argon used as background gas in the process. Temporally-resolved emission spectroscopy measurements were performed in order to monitor nanoparticle stoichiometry. Promising results were obtained and on-line Si/C_x stoichiometry was successfully observed. These results put forward the possibility of real time correction of the nanoparticle stoichiometry during the production process.     

Catalytic Asymmetric Mannich Reactions with Fluorinated Aromatic Ketones: Efficient Access to Chiral β‐Fluoroamines

Reported herein is a Zn/Prophenol‐catalyzed Mannich reaction using fluorinated aromatic ketones as nucleophilic partners for the direct enantio‐ and diastereoselective construction of β‐fluoroamine motifs featuring a fluorinated tetrasubstituted carbon. The reaction can be run on a gram scale with a low catalyst loading without impacting its efficiency. Moreover, a related aldol reaction was also developed. Together, these reactions provide a new approach for the preparation of pharmaceutically relevant products possessing tetrasubstituted C? F centers.     

Surface and grain boundary segregation in 16MND5 steel

An adequate model of quantification when there are many segregating elements is required for industry and research. Hence, for the first time, surface segregation kinetics on industrial 16MND5 steel was studied by XPS spectroscopy at temperatures ranging from 500 to 600 ^oC. From measurements that highlight the competitive segregation of P, S, Sn, Sb, As, and Cu impurities at the surface, a quantification model was developed and successfully used to deduce the surface concentrations during segregation kinetics as well as derive the corresponding diffusion coefficients. We observed that phosphorus and sulfur are the first elements covering the surface, then they are supplanted by others' impurities. This result may reflect impurities segregation behavior at the grain boundaries that impacts mechanical behavior of the material. Indeed, to further the research, 16MND5 samples were aged in the same range of temperatures. Then, Auger spectroscopy measurements at grain boundaries were conducted on broken samples exhibiting intergranular cracking. Results show that phosphorus is the only segregating element present at grain boundaries after 2 months of aging. Importantly, it appears that phosphorus grain boundary segregation kinetics is significantly lower than at surface. Copyright © 2017 John Wiley & Sons, Ltd.     

Toward glasses with better indentation cracking resistance

The microcracking sequence (radial, median, lateral, and ring-like) arising at the glass surface under sharp contact loading and the extent to which these cracks develop is intimately related to the way the material attempts to relax the corresponding stress field. Two processes which are known to occur upon indentation are densification and isochoric shear flow. The contributions of both mechanisms were quantitatively assessed for glasses belonging to different chemical systems in previous papers ,  and . In the present study, indentation cracking maps are provided, which offer guidelines to the design of glasses with better surface damage resistance based on their elastic properties and hardness.     

Atomic-scale simulation of intergranular segregation of H in Al–Mg: implications for H-induced damage

The goal of this work is to make a contribution to the understanding of the microscopic mechanisms of H-induced intergranular damage. We develop an embedded-atom method interatomic potential for H in the Al–Mg system with the main aim of reproducing the current understanding of H trapping to vacancies. This model is used to investigate the effect of the Mg–H affinity on the segregation of H on the Σ =5 (310) [001] grain boundary. Monte Carlo simulations in the grand canonical ensemble are used to estimate equilibrium H concentrations at this boundary at T=300?K. A large structure change, associated with the H enrichment of the grain boundary, is reported. The implications on damage to the interface are discussed.     

Modelling the effect of pressure on the critical shear stress of MgO single crystals

A hierarchical multi-scale model was used to study the effect of high pressure on the critical shear stresses of MgO. The two main slip systems, ½?110?{110} and ½?110?{100}, were considered. Based on a generalised Peierls–Nabarro model, it is shown that the core structure of ½?110? screw dislocations is strongly sensitive to pressure. Mostly planar and spread in {110} at ambient pressure, the core of screw dislocations tends to spread in {100} with increasing pressure. Subsequently, an inversion of the easiest slip systems is observed between 30 and 60?GPa. At high pressure, the plasticity of MgO single crystals is expected to be controlled by ½?110?{100} slip systems, except at high temperature where both slip systems become active. Pressure is also found to increase the critical resolved shear stresses and to shift the athermal temperature toward higher temperatures. Under high pressure, MgO is thus characterised by a significant lattice friction on both slip systems.     

Cyclobutanes in catalysis

The exploitation of ring strain as a driving force to facilitate chemical reactions is a well‐appreciated principle in organic chemistry. The most prominent and most frequently used compound classes in this respect are oxiranes and cyclopropanes. For rather a long time, cyclobutanes lagged behind these three‐membered‐ring compounds in their development as reactive substrates, but during the past decade an increasing number of useful reactions of four‐membered‐ring substrates have emerged. This Minireview examines corresponding catalytic reactions ranging from Lewis or Brønsted acid catalyzed processes to enzymatic reactions. The main focus is placed on transition‐metal‐catalyzed C C bond‐insertion and β‐carbon‐elimination processes, which enable exciting downstream reactions that deliver versatile building blocks.     

Atomistic response of a model silica glass under shear and pressure

The Mechanical Response of a Model Silica Glass is studied extensively at the submicrometer scale, with the help of atomistic simulations. The analysis of the response to a hydrostatic compression is compared to recent experimental results. The irreversible behaviour and the variation of intertetrahedral angles is recovered. It is shown that the atomistic response is homogeneous upon compression, in opposition with the localization along shear bands occuring during shear deformation with constant volume. Moreover, the Bulk Modulus anomaly is interpreted as due to a succession of such homogeneous but irreversible atomic rearrangements.