Pulsed laser reshaping and fragmentation of upconversion nanoparticles — from hexagonal prisms to 1D nanorods through “Medusa”-like structures

One dimensional (1D) nanostructures attract considerable attention, enabling a broad application owing to their unique properties. However, the precise mechanism of 1D morphology attainment remains a matter of debate. In this study, ultrafast picosecond (ps) laser-induced treatment on upconversion nanoparticles (UCNPs) is offered as a tool for 1D-nanostructures formation. Fragmentation, reshaping through recrystallization process and bioadaptation of initially hydrophobic (β-Na_1.5Y_1.5F₆: Yb³⁺, Tm³⁺/β-Na_1.5Y_1.5F₆) core/shell nanoparticles by means of one-step laser treatment in water are demonstrated. “True” 1D nanostructures through “Medusa”-like structures can be obtained, maintaining anti-Stokes luminescence functionalities. A matter of the one-dimensional UCNPs based on direction of energy migration processes is debated. The proposed laser treatment approach is suitable for fast UCNP surface modification and nano-to-nano transformation, that open unique opportunities to expand UCNP applications in industry and biomedicine.

     

Ferroelectric Exchange Bias Affects Interfacial Electronic States

In polar oxide interfaces phenomena such as superconductivity, magnetism, 1D conductivity, and quantum Hall states can emerge at the polar discontinuity. Combining controllable ferroelectricity at such interfaces can affect the superconducting properties and sheds light on the mutual effects between the polar oxide and the ferroelectric oxide. Here, the interface between the polar oxide LaAlO₃ and the ferroelectric Ca-doped SrTiO₃ is studied by means of electrical transport combined with local imaging of the current flow with the use of scanning a superconducting quantum interference device (SQUID). Anomalous behavior of the interface resistivity is observed at low temperatures. The scanning SQUID maps of the current flow suggest that this behavior originates from an intrinsic bias induced by the polar LaAlO₃ layer. Such intrinsic bias combined with ferroelectricity can constrain the possible structural domain tiling near the interface. The use of this intrinsic bias is recommended as a method of controlling and tuning the initial state of ferroelectric materials by the design of the polar structure. The hysteretic dependence of the normal and the superconducting state properties on gate voltage can be utilized in multifaceted controllable memory devices.     

Photon-noise-limited operation of intensified CCD cameras

Intensified CCD cameras are increasingly being used in quantitative applications, which requires not only a greater understanding of their operation but also more detailed modeling to predict their performance more accurately. We have developed a model based on photon-noise-limited operation that incorporates the effects of the point spread function of the intensifier on signal-to-noise ratio. These effects are absent in other models, which renders them inadequate to model the camera performance properly. Calculations of noise-equivalent irradiance with our model are shown to be in good agreement with experimental results presented for two Xybion intensified cameras, Models GEN-III IMC and NIR DCIC intensified cameras.     

Passivity-preserving splitting methods for rigid body systems

A rigid body model for the dynamics of a marine vessel, used in simulations of offshore pipe-lay operations, gives rise to a set of ordinary differential equations with controls. The system is input–output passive. We propose passivity-preserving splitting methods for the numerical solution of a class of problems which includes this system as a special case. We prove the passivity-preservation property for the splitting methods, and we investigate stability and energy behaviour in numerical experiments. Implementation is discussed in detail for a special case where the splitting gives rise to the subsequent integration of two completely integrable flows. The equations for the attitude are reformulated on \(\mathit{SO}(3)\) using rotation matrices rather than local parameterisations with Euler angles.     

Assume,guarantee or repair: a regular framework for non regular properties

We present Assume-Guarantee-Repair (AGR)—a novel framework which verifies that a program satisfies a set of properties and also repairs the program in case the verification fails. We consider communicating programs—these are simple C-like programs, extended with synchronous actions over communication channels. Our method, which consists of a learning-based approach to assume–guarantee reasoning, performs verification and repair simultaneously: in every iteration, AGR either makes another step towards proving that the (current) system satisfies the required properties, or alters the system in a way that brings it closer to satisfying the properties. To handle infinite-state systems we build finite abstractions, for which we check the satisfaction of complex properties that contain first-order constraints, using both syntactic and semantic-aware methods. We implemented AGR and evaluated it on various communication protocols. Our experiments present compact proofs of correctness and quick repairs.

     

Morphological features of porous silicon carbide obtained via a carbothermal method

Samples of porous silicon carbide were obtained using sucrose or carbon and aerosil or silica mesoporous molecular sieves (SBA‐3, SBA‐15, KIT‐6 and MCF). Fibers content in silicon carbide samples is higher when the mesopore surface area of carbon materials derived from carbon‐silica composites is lower. Based on the found correlation between the morphology and porosity of SiC and mesopore surface area of the carbon component in the composites, a templating action of carbon in carbothermal reduction was suggested.     

Intensification of the processes of dehydrogenation and dewaxing of middle distillate fractions by redistribution of hydrogen between the units

The dehydrogenation and dewaxing of hydrocarbons of middle-distillate fractions, which proceed in the hydrogen medium, are of great importance in the petrochemical and oil refining industries. They increase oil refining depth and allow producing gasoline, kerosene, and diesel fractions used in the production of hydrocarbon fuels, polymer materials, synthetic detergents, rubbers, etc. Herewith, in the process of dehydrogenation of hydrocarbons of middle distillate fractions (C₉–C₁₄) hydrogen is formed in the reactions between hydrocarbons, and the excess of hydrogen slows the target reaction of olefin formation and causes the shift of thermodynamic equilibrium to the initial substances. Meanwhile, in the process of hydrodewaxing of hydrocarbons of middle distillate fractions (C₅–C₂₇), conversely, hydrogen is a required reagent in the target reaction of hydrocracking of long-chain paraffins, which ensures required feedstock conversion for production of low-freezing diesel fuels. Therefore, in this study we suggest the approach of intensification of the processes of dehydrogenation and dewaxing of middle distillate fractions by means of redistribution of hydrogen between the two units on the base of the influence of hydrogen on the hydrocarbon transformations using mathematical models. In this study we found that with increasing the temperature from 470 °C to 490 °C and decreasing the hydrogen/feedstock molar ratio in the range of 8.5/1.0 to 6.0/1.0 in the dehydrogenation reactor, the production of olefins increased by 1.45–1.55%wt, which makes it possible to reduce hydrogen consumption by 25,000 Nm³/h. Involvement of this additionally available hydrogen in the amount from 10,000 to 50,000 Nm³/h in the dewaxing reactor allows increasing the depth of hydrocracking of long-chain paraffins of middle distillate fractions, and, consequently improving low-temperature properties of produced diesel fraction. In such a way cloud temperature and freezing temperature of produced diesel fraction decrease by 1–4 °C and 10–25 °C (at the temperature of 300 °C and 340 °C respectively). However, when the molar ratio hydrogen/hydrocarbons decreases from 8.5/1.0 to 6.0/1.0 the yield of side products in the dehydrogenation reactor increases: the yield of diolefins increases by 0.1–0.15%wt, the yield of coke increases by 0.07–0.18%wt depending on the feedstock composition, which is due to decrease in the content of hydrogen, which hydrogenates intermediate products of condensation (the coke of amorphous structure). This effect can be compensated by additional water supply in the dehydrogenation reactor, which oxidizes the intermediate products of condensation, preventing catalyst deactivation by coke. The calculations with the use of the model showed that at the supply of water by increasing portions simultaneously with temperature rise, the content of coke on the catalyst by the end of the production cycle comprises 1.25–1.56%wt depending on the feedstock composition, which is by 0.3–0.6%wt lower that in the regime without water supply.     

Structure and conductivity of yttria and scandia‐doped zirconia crystals grown by skull melting

In this paper a detailed study of the (ZrO₂)_1‐x(Y₂O₃)_x (x=0.025–0.15), (ZrO₂)_1‐x(Sc₂O₃)_x (x = 0.06 – 0.11) and (ZrO₂)_1‐x‐y(Sc₂O₃)_x(Y₂O₃)_y (x=0.07 – 0.11; y=0.01 – 0.04) solid solution crystals grown by skull melting technique is presented. The structure, phase composition, and ion conductivity of the obtained crystals were investigated by X‐ray diffraction, transmission electron microscopy, Raman scattering spectroscopy, and impedance spectroscopy. Maximum conductivity as (ZrO₂)_1‐x(Y₂O₃)_x and (ZrO₂)_1‐x(Sc₂O₃)_x solid solution crystals is observed for the compositions containing 10 mol% stabilizing oxide, and the conductivity of 10ScSZ is ~3 times higher than for 10YSZ. Experiments on crystal growth (ZrO₂)_1‐x‐y(Sc₂O₃)_x(Y₂O₃)_y solid solutions showed that uniform, transparent crystals 7Sc3YSZ, 7Sc4YSZ, 8Sc2YSZ, 8Sc3YSZ, 9Sc2YSZ, 9Sc3YSZ, 10Sc1YSZ, and 10Sc2YSZ are single phase crystal containing t″ phase. It is established that a necessary condition of melt growth of (ZrO₂)_1‐x‐y(Sc₂O₃)_x(Y₂O₃)_y single‐phase crystals is the total concentration of the stabilizing oxides from 10 to 12 mol%. The addition of Y₂O₃ affects the (ZrO₂)_1‐x‐y(Sc₂O₃)_x(Y₂O₃)_y solid solution conductivity different ways and depends on the Sc₂O₃ content in the starting composition. The effects of structure, phase composition, concentration, and type of stabilizing oxides on the electrical characteristics of obtained crystals are discussed.     

Synthesis of 2(E),6(E)-bis(chloromethylidene)-4-thiomorpholinamine-1-oxide and its hydrazones

An efficient method for preparation of earlier unknown S-oxide of 2(E),6(E)-bis(chloromethylidene)-4-thiomorpholinamine by oxidation of 2(E),6(E)-bis(chloromethylidene)-4-thiomorpholinamine hydrochloride with hydrogen peroxide in H₂O or EtOH/H₂O followed by the reaction mixture neutralization with Na₂CO₃ has been described. Interaction of the S-oxide with acetaldehyde, butanal, benzaldehyde, 4-methoxybenzaldehyde and 4-pyridinecarboxaldehyde in EtOH, C₆H₆, in the mixture of acetonitrile and ethanol or ethanol and benzene affords the unknown hydrazones, N-organylmethylidene-2(E),6(E)-bis(chloromethylidene)-4-thiomorpholinamine-1-oxides.