Molecular Dynamics and Experimental Study of the Effect of CeF3 and NdF3 Additives on the Physical Properties of FLiNaK.

The paper presents the results, which are consistent within 2%, obtained both in the simulation of molecular dynamics and in the experiment on the study of the kinetic properties of molten FLiNaK with addition of lanthanide fluorides. The parameters of the Born-Huggins-Meier potential for the interaction of CeF3 or NdF3 with FLiNaK components are first calculated using the ab initio approach. The enthalpy of the system with dissolved CeF3 or NdF3 calculated in the model increases by ∼4.4% over the entire temperature range studied (800 ≤ T ≤ 1020 K). The self-diffusion coefficients of the molten salt components are calculated from the Einstein relation and also estimated from the shear viscosity data. The temperature dependences of the shear viscosity of molten FLiNaK as well as FLiNaK with additions of 15 mol % CeF3 or NdF3 are determined experimentally and by calculation. In addition, the dependence of shear viscosity on the concentration of CeF3 and NdF3 in FLiNaK is measured and calculated. The linear growth of the shear viscosity with the CeF3 and NdF3 concentrations is obtained. Experimental dependence is in good agreement with the simulated results in the case of NdF3, and there is the discrepancy while CeF3 addition. An analytical approximation of the temperature and concentration dependences for the viscosity of molten FliNaK and for the calculated self-diffusion coefficients of constituent elements is proposed. Linear approximation of temperature dependence of the self-diffusion coefficients of similar components in the corresponding extended systems is presented.

Synthesis and characterization of chitosan-vermiculite-lignin ternary composite as an adsorbent for effective removal of uranyl ions from aqueous solution: Experimental and theoretical analyses.

Chitosan (Ch), vermiculite (V) and lignin (L) were used as the components of a natural composite adsorbent (Ch-VL) for the removal of the UO22+ ions in aqueous solutions. During the study, we recorded and analyzed the initial UO22+ ion concentration, initial pH, contact time, temperature, and recovery. The recycling performance of the Ch-VL composite was assessed by three sequential adsorption/desorption experiments. Adsorption performance of the Ch-VL composite for UO22+ ions was 600 mg L-1 at pH 4.5 and temperature of 25 °C. Thermodynamic findings, ΔH0:28.1 kJ mol-1, and ΔG0:-14.1 kJ mol-1 showed that adsorption behavior was endothermic and spontaneous. Its maximum adsorption capacity was 0.322 mol kg-1, obtained from the Langmuir isotherm model. The adsorption kinetics indicated that it followed the pseudo-second-order and intraparticle diffusion rate kinetics. The adsorption thermodynamic shown indicated that the UO22+ ion adsorption was both spontaneous and endothermic. The adsorption process was enlightened by FT-IR and SEM-EDX analyses. The study suggested a simple and cost-effective approach for the removal of toxic UO22+ ions from wastewater. To highlight the adsorption mechanism, DFT calculations were performed. Theoretical results are in good agreement with experimental observations.

Development of sensitive and accurate solid-phase microextraction procedure for preconcentration of As(III) ions in real samples.

We synthesized the poly(methyl methacrylate-co-2-aminoethyl methacrylate (PMaema) amphiphilic copolymer in a form of solid phase adsorbent. Then it was used for separation, preconcentration and determination of trace amount of As(III) ions from foods and waters with hydride generation atomic absorption spectrometry. The PMaema was characterized by fourier transform infrared spectrometer and nuclear magnetic resonance spectrometer. The adsorption of As(III) to the PMaema was also supported using computational chemistry studies. The experimental parameters (pH, PMaema amount, adsorption time and ethanol volume) were optimized using a three-level Box-Behnken design with four experimental factors. We observed linear calibration curve for the PMaema amount in the 10-500 ng L-1 range (R2 = 0.9956). Limit of detection, preconcentration factor and sorbent capacity of PMaema were equal to 3.3 ng L-1, 100 and 75.8 mg g-1, respectively. The average recoveries (spiked at 50 ng L-1) changes in the range of 91.5-98.6% with acceptable relative standard deviation less than 4.3%. After validation studies, the method was successfully applied for separation, preconcentration and determination of trace amount of As(III) from foods and waters.

Molecular Hyperdynamics Coupled with the Nonorthogonal Tight-Binding Approach: Implementation and Validation.

We present the molecular hyperdynamics algorithm and its implementation to the nonorthogonal tight-binding model NTBM and the corresponding software. Due to its multiscale structure, the proposed approach provides the long time scale simulations (more than 1 s), unavailable for conventional molecular dynamics. No preliminary information about the system's potential landscape is needed for the use of this technique. The optimal interatomic potential modification is automatically derived from the previous simulation steps. The average time between adjusted potential energy fluctuations provides an accurate evaluation of physical time during the hyperdynamics simulation. The main application of the presented hyperdynamics method is the study of thermal-induced defects arising in the middle-sized or relatively large atomic systems at low temperatures. To validate the presented method, we apply it to the C60 cage and its derivative C60NH2. Hyperdynamics leads to the same results as a conventional molecular dynamics, but the former possesses much higher performance and accuracy due to the wider temperature region. The coefficient of acceleration achieves 107 and more.

A bottom-up approach for controlled deformation of carbon nanotubes through blistering of supporting substrate surface.

Tuning the band structure and, in particular, gap opening in 1D and 2D materials through their deformation is a promising approach for their application in modern semiconductor devices. However, there is an essential breach between existing laboratory scale methods applied for deformation of low-dimensional materials and the needs of large-scale production. In this work, we propose a novel method which is potentially well compatible with high end technological applications: single-walled carbon nanotubes (SWCNTs) first deposited on the flat surface of a supporting wafer, which has been pre-implanted with H+ and He+ ions, are deformed in a controlled and repetitive manner over blisters formed after subsequent thermal annealing. By using resonant Raman spectroscopy, we demonstrate that the SWCNTs clamped by metallic stripes at their ends are deformed over blisters to an average tensile strain of 0.15 ± 0.03%, which is found to be in a good agreement with the value calculated taking into account blister's dimensions. The principle of the technique may be applied to other 1D and 2D materials in perspective.