Mechanism of Dy3+ and Nd3+ Ions Electrochemical Coreduction with Ni2+, Co2+, and Fe3+ Ions in Chloride Melts

The present paper is devoted to the study of the processes of the mechanism of electrochemical coreduction of Dy3+ and Nd3+ ions with Ni2+, Co2+, and Fe3+ ions in the equimolar NaCl-KCl melt at 973 K and characterization of the synthesized samples. The performed voltammetry analysis of the electrochemical coreduction processes elucidated a significant difference in the values of the extraction potentials of the studied metals. This melt testifies that intermetallic compounds of Dy and Nd with Ni, Co, and Fe may be synthesized in the kinetic regime. The intermetallic phases of Dy and Nd with Ni, Co, and Fe are found to be formed along with the phases of metallic Ni, Co, and Fe either during electrolysis at the cathode current densities exceeding the limiting diffusion current of Ni2+, Co2+, and Fe3+ ions or in the potentiostatic regime at the potentials of the corresponding voltammetry curves. Therefore, the following interrelated key parameters affecting the electrochemical synthesis of Dy and Nd intermetallic compounds with Ni, Co, and Fe were determined: (i) composition of the electrolyte, i.e., concentrations of FeCl3, CoCl2, NiCl2, DyCl3, and NdCl3; (ii) cathode current density or electrolysis potential and (iii) electrolysis time. The obtained samples were characterized by micro-X-ray diffraction analysis, cyclic voltammetry, and scanning electron microscopy methods.

Faceting of Si and Ge crystals grown on deeply patterned Si substrates in the kinetic regime: phase-field modelling and experiments

The development of three-dimensional architectures in semiconductor technology is paving the way to new device concepts for various applications, from quantum computing to single photon avalanche detectors. In most cases, such structures are achievable only under far-from-equilibrium growth conditions. Controlling the shape and morphology of the growing structures, to meet the strict requirements for an application, is far more complex than in close-to-equilibrium cases. The development of predictive simulation tools can be essential to guide the experiments. A versatile phase-field model for kinetic crystal growth is presented and applied to the prototypical case of Ge/Si vertical microcrystals grown on deeply patterned Si substrates. These structures, under development for innovative optoelectronic applications, are characterized by a complex three-dimensional set of facets essentially driven by facet competition. First, the parameters describing the kinetics on the surface of Si and Ge are fitted on a small set of experimental results. To this goal, Si vertical microcrystals have been grown, while for Ge the fitting parameters have been obtained from data from the literature. Once calibrated, the predictive capabilities of the model are demonstrated and exploited for investigating new pattern geometries and crystal morphologies, offering a guideline for the design of new 3D heterostructures. The reported methodology is intended to be a general approach for investigating faceted growth under far-from-equilibrium conditions.

Ammonium nitrate promotes sulfate formation through uptake kinetic regime

Although the anthropogenic emissions of SO2 have decreased significantly in China, the decrease in SO42- in PM2.5 is much smaller than that of SO2. This implies an enhanced formation rate of SO42- in the ambient air, and the mechanism is still under debate. This work investigated the formation mechanism of particulate sulfate based on statistical analysis of long-term observations in Shijiazhuang and Beijing supported with flow tube experiments. Our main finding was that the sulfur oxidation ratio (SOR) was exponentially correlated with ambient RH in Shijiazhuang (SOR = 0.15+0.0032×exp⁡(RH/16.2)) and Beijing (SOR = -0.045+0.12×exp⁡(RH/37.8)). In Shijiazhuang, the SOR is linearly correlated with the ratio of aerosol water content (AWC) in PM2.5 (SOR = 0.15+0.40×AWC/PM2.5). Our results suggest that uptake of SO2 instead of oxidation of S(IV) in the particle phase is the rate-determining step for sulfate formation. NH4NO3 plays an important role in the AWC and the change of particle state, which is a crucial factor determining the uptake kinetics of SO2 and the enhanced SOR during haze days. Our results show that NH3 significantly promoted the uptake of SO2 and subsequently the SOR, while NO2 had little influence on SO2 uptake and SOR in the presence of NH3.

Mechanistic Model and Optimization of the Diclofenac Degradation Kinetic for Ozonation Processes Intensification

This work focused on estimating the rate constants for three ozone-based processes applied in the degradation of diclofenac. The ozonation (Oz) and its intensification with catalysis (COz) and photocatalysis (PCOz) were studied. Three mathematical models were evaluated with a genetic algorithm (GA) to find the optimal values for the kinetics constants. The Theil inequality coefficient (TIC) worked as a criterion to assess the models’ deviation. The diclofenac consumption followed a slow kinetic regime according to the Hatta number (Ha<0.3). However, it strongly contrasted with earlier studies. The obtained values for the volumetric rate of photon absorption (VRPA) corresponding to the PCOz process (1.75×10−6 & 6.54×10−7 Einstein L−1 min−1) were significantly distant from the maximum (2.59×10−5 Einstein L−1 min−1). The computed profiles of chemical species proved that no significant amount of hydroxyl radicals was produced in the Oz, whereas the PCOz achieved the highest production rate. According to this, titanium dioxide significantly contributed to ozone decomposition, especially at low ozone doses. Although the models’ prediction described a good agreement with the experimental data (TIC<0.3), the optimization algorithm was likely to have masked the rate constants as they had highly deviated from already reported values.

A Case for Electron-Astrophysics

The smallest characteristic scales, at which electron dynamics determines the plasma behaviour, are the next frontier in space and astrophysical plasma research. The analysis of astrophysical processes at these scales lies at the heart of the research theme of electron-astrophysics. Electron scales are the ultimate bottleneck for dissipation of plasma turbulence, which is a fundamental process not understood in the electron-kinetic regime. In addition, plasma electrons often play an important role for the spatial transfer of thermal energy due to the high heat flux associated with their velocity distribution. The regulation of this electron heat flux is likewise not understood. By focussing on these and other fundamental electron processes, the research theme of electron-astrophysics links outstanding science questions of great importance to the fields of space physics, astrophysics, and laboratory plasma physics. In this White Paper, submitted to ESA in response to the Voyage 2050 call, we review a selection of these outstanding questions, discuss their importance, and present a roadmap for answering them through novel space-mission concepts.

Fingerprints of nonequilibrium stationary distributions in dispersion relations

Distributions different from those predicted by equilibrium statistical mechanics are commonplace in a number of physical situations, such as plasmas and self-gravitating systems. The best strategy for probing these distributions and unavailing their origins consists in combining theoretical knowledge with experiments, involving both direct and indirect measurements, as those associated with dispersion relations. This paper addresses, in a quite general context, the signature of nonequilibrium distributions in dispersion relations. We consider the very general scenario of distributions corresponding to a superposition of equilibrium distributions, that are well-suited for systems exhibiting only local equilibrium, and discuss the general context of systems obeying the combination of the Schrödinger and Poisson equations, while allowing the Planck’s constant to smoothly go to zero, yielding the classical kinetic regime. Examples of media where this approach is applicable are plasmas, gravitational systems, and optical molasses. We analyse in more depth the case of classical dispersion relations for a pair plasma. We also discuss a possible experimental setup, based on spectroscopic methods, to directly observe these classes of distributions.

Ammonium nitrate promotes sulfate formation through uptake kinetic regime

Although the anthropogenic emissions of SO2 have decreased significantly in China, the decrease in SO42− in PM2.5 is much smaller than that of SO2. This implies an enhanced formation rate of SO42− in the ambient air, and the mechanism is still under debate. This work investigated the formation mechanism of particulate sulfate based on statistical analysis of long-term observations in Shijiazhuang and Beijing supported with flow tube experiments. Our main finding was that the SOR was exponentially correlated with ambient RH in Shijiazhuang (SOR = 0.15 + 0.0032exp(RH/16.2)) and Beijing (SOR = −0.045 + 0.12exp(RH/37.8)). In Shijiazhuang, the SOR is linearly correlated with the ratio of aerosol water content (AWC) in PM2.5 (SOR = 0.15 + 0.40AWC/PM2.5). Kinetics studies suggest that uptake of SO2 instead of oxidation of S(IV) in particle-phase is the rate determining step for sulfate formation. NH4NO3 plays an important role in the AWC and the transition of particle phase, which is a crucial factor determining the uptake kinetics of SO2 and the enhanced SOR during haze days. Our results show that NH3 significantly promoted the uptake of SO2, subsequently, the SOR, while NO2 had little influence on SO2 uptake and SOR in the presence of NH3.