Solvent effects of ionic liquids: investigation of ferrocenes as electrochemical probes

The redox potentials of ferrocene and decamethylferrocene were determined in a number of molecular and ionic solvents and used as a probe for polarity of room temperature ionic liquids (ILs). No macroscopic solvent property is simply related to redox potentials. Single empirical solvent parameters also are not able to describe the differences in potentials. Instead, Kamlet–Taft multiparameter relationship fits well ferrocenes redox potentials variation, with both molecular solvents and ILs, well describing specific solvent–solute interactions with the two probes. Copyright © 2010 John Wiley & Sons, Ltd.     

A study on the effect of ultrasound on electrochemical phenomena

We have employed microelectrodes in order to resolve single transient cavitation events. High time resolution studies of individual current time transients were shown. Distance and temperature dependencies proved to be in agreement with both the acoustic pressure field generated by the ultrasonic horn and cavitation bubble collapse violence with decreasing vapour pressure within the bubble, respectively. Measurements of electrode kinetics at the point of impact of the transient events were shown for the first time by the employment of sampled voltammetry.     

A comparative study of fracture strength, ultrasonic properties and chemical constituents of kidney stones

Ultrasonic properties of kidney stones were studied with a double-probe-through-transmission technique, the micro hardness was studied using the Viker indentation method and the chemical composition studied using an X-ray technique. The microhardness is found to vary with chemical composition as well as ultrasonic propagation velocity. The comparative results obtained are discussed in detail.     

A comparative study of systems used for dynamic focusing of ultrasound

A comparative study of two methods used for dynamic focusing of ultrasound: the conventional phased arrays and a new method based on time reversal of acoustic signals is carried out. A laboratory model of the focusing system based on time reversal is developed and manufactured. One of the principal elements of the system is a reverberator with several piezoelectric transducers attached to its walls. Experiments are carried out to demonstrate the ability of such a system to generate one focus or several foci and to steer them electronically at considerable distances (50 mm at minimum) off the axis of the focusing system without causing the appearance of any grating lobes or other secondary intensity maxima. The focusing properties of the system are compared with the results of numerical simulation of two-dimensional phased arrays, whose parameters are taken to be typical for the arrays used in extracorporeal surgery. The important role of randomization is demonstrated for both of the aforementioned focusing methods. The prospects of practical application of the two methods are discussed.     

A study on the emulsification of oil by power ultrasound

A commercial ultrasonic probe was used to study emulsification of an o/w system (5 wt% soybean oil stabilised with 1 wt% Tween 80 in water). Two different sets of experiments were performed.

Firstly, we investigated the effect of power, duty cycle and ultrasound time on the production of an oil-in-water emulsion from a coarse pre-emulsion mix. The droplets reached a stable size (0.7 μm) within 5 min independent of the power and duty cycle used.

Secondly, the mechanism of emulsification was studied by observing the emulsification process at an oil–water interface (no pre-mix) with a high-speed camera. Transient cavitation is thought to be responsible for acoustic emulsification; however there have been no measurements to relate the transient cavitation zone to the production of an emulsion. It has already been shown that the transient cavitation in probe systems is directly under the probe tip. High-speed observations showed that an emulsion could only be obtained if the interface was within a few millimetres of the probe tip. These results strongly suggest that the transient cavitation zone is responsible for the acoustic emulsification of oil.     

A comparative study of local quantum Fisher information and local quantum uncertainty in Heisenberg XY model

Recently, it has been shown that the quantum Fisher information via local observables and via local measurements (i.e., local quantum Fisher information (LQFI)) is a central concept in quantum estimation and quantum metrology and captures the quantumness of correlations in multi-component quantum system (Kim et al. (2018) [28]). This new discord-like measure is very similar to the quantum correlations measure called local quantum uncertainty (LQU). In the present study, we have revealed that LQU is bounded by LQFI in the phase estimation protocol. Also, a comparative study between these two quantum correlations quantifiers is addressed for the quantum Heisenberg XY model. Two distinct situations are considered. The first one concerns the anisotropic XY model and the second situation concerns isotropic XY model submitted to an external magnetic field. Our results confirm that LQFI reveals more quantum correlations than LQU.     

Investigation of mass transfer intensification under power ultrasound irradiation using 3D computational simulation: A comparative analysis

This paper aims at investigating the influence of acoustic streaming induced by low-frequency (24 kHz) ultrasound irradiation on mass transfer in a two-phase system. The main objective is to discuss the possible mass transfer improvements under ultrasound irradiation. Three analyses were conducted: i) experimental analysis of mass transfer under ultrasound irradiation; ii) comparative analysis between the results of the ultrasound assisted mass transfer with that obtained from mechanically stirring; and iii) computational analysis of the systems using 3D CFD simulation. In the experimental part, the interactive effects of liquid rheological properties, ultrasound power and superficial gas velocity on mass transfer were investigated in two different sonicators. The results were then compared with that of mechanical stirring. In the computational part, the results were illustrated as a function of acoustic streaming behaviour, fluid flow pattern, gas/liquid volume fraction and turbulence in the two-phase system and finally the mass transfer coefficient was specified. It was found that additional turbulence created by ultrasound played the most important role on intensifying the mass transfer phenomena compared to that in stirred vessel. Furthermore, long residence time which depends on geometrical parameters is another key for mass transfer. The results obtained in the present study would help researchers understand the role of ultrasound as an energy source and acoustic streaming as one of the most important of ultrasound waves on intensifying gas-liquid mass transfer in a two-phase system and can be a breakthrough in the design procedure as no similar studies were found in the existing literature.     

A study on the primary and secondary nucleation of ice by power ultrasound

Several different investigations have been carried out to study the primary and secondary nucleation of ice by sonocrystallisation. Firstly, the primary nucleation of discrete ice crystals in a supercooled sucrose solution has been observed. For increasing concentrations of sucrose solutions from 0 to 45 wt%, the nucleation temperature consistently occurs at a higher nucleation temperature in the presence of ultrasound. The nucleation temperature also increases as the power output and duty cycle of a commercial ultrasonic horn are increased. Snap shot images of the bubble clouds obtained from the ultrasonic horn also show that the number of bubbles appears to increase as the ultrasonic output is increased. This suggests that the nucleation of ice is related to the power output and number of cavitation bubbles. The effect of a single bubble on the sonocrystallisation of ice is discussed. High-speed movies (1120 fps) have shown that the crystallisation appears to occur in the immediate vicinity of the single bubble. In most cases, many crystals are observed and it is not known whether a single ice crystal is being fragmented by the bubble or whether many crystals are being initiated. The bubble appears to undergo a dancing regime, frequently splitting and rejoining and also emitting some small microbubbles. A study on the secondary nucleation of ice in sucrose solutions has been carried out using a unique ultrasonic cold stage device. Images taken using a microscope system show that the pre-existing ice dendrite crystals can be broken up into smaller fragments by an ultrasonic field. Cavitation bubbles appear to be important during the fragmentation process, possibly melting any ice crystals in their path. Flow patterns around cavitation bubbles have also been observed, and these may be responsible for the fragmentation of ice crystals.     

Experimental study of ultrasound-modulated scattering light using different frequencies ultrasound probes

The focused ultrasound plays a role in localization and modulating the scattering light in ultrasound- modulated optical tomography （UOT）. Both the modulation efficiency of the scattering light and the spatial resolution of UOT are determined by ultrasound. The effects of repetition frequency and pulse energy of impulse ultrasound on the modulated scattering light are derived through experiment in this letter. Purthermore, we compare the imaging sensitivity with 1, 2.25, 5, and 10 MHz center frequencies of impulse ultrasound. Experimental results demonstrate that better signal-to-noise ratios and higher sensitivities can be gained by use of more intense ultrasound and lower ultrasound frequencies.     

A preliminary investigation upon the electrochemical behavior of CoO and NiO anodes — comparative study

Among the variety of alternate anode materials being studied, the research on the exploration of 3d-metal oxide anodes gains paramount importance in the recent time, as it is bestowed with an easy preparation method and a less complicated decomposition mechanism. Towards this direction, an attempt to synthesize the compound CoO and to investigate the electrochemical behavior of the same both individually and in comparison with NiO compounds was made with a view to understand the extent to which the chosen candidates, viz., CoO and NiO can be exploited as high capacity anodes. Between the two oxides, CoO exhibited a specific capacity of at least 550 mAh/g, against NiO with an average capacity of ∼330 mAh/g. Also, the magnitude of irreversible capacity loss and the extent of capacity fade upon cycling corresponding to CoO anode were found to be lesser than NiO anodes. The enhanced specific capacity values and the better cycleability properties of CoO anodes are believed to be due to the inherent electrochemical characteristics of the compound. The type and the nature of SEI formed over the electrode surface and the formation of possible progressive agglomeration of the products of decomposition are expected to be the factors responsible for the difference in the electrochemical behavior of CoO and NiO anodes. In short, electrochemical characterization of the individual oxides are studied and probable reasons for the observed difference in the charge-discharge behavior of CoO and NiO anodes are discussed in this communication.     

Bentonite-modified electrochemical sensors: a brief overview of features and applications

Bentonites are promising materials for electrochemical sensing because of their unique physicochemical properties. They have relatively high surface area, good adsorption and ion-exchange ability, highly tunable surface and interlayer composition, non-toxic nature, and excellent biocompatibility. Moreover, they are outstanding substrates for stable immobilization of different functional moieties. The primary focus of this review article is to highlight the applications of bentonite-modified electrodes for the analysis of organic and inorganic analytes in different matrices. A brief summary on the necessity of analysis of different compounds is provided. For the first time, features and applications of bentonite-modified electrodes are critically appraised. The key features of bentonite-modified electrodes that enhance their electrocatalytic activity toward detection of certain target analytes are highlighted. At the end, an account of current status of bentonite-modified electrodes along with future research directions is provided.     

Fluorescence probes of viscosity: A comparative study of the fluorescence anisotropy decay of perylene and 3,9-dibromoperylene in glycerol

The authors compare the results of fluorescence anisotropy decay measurements for glycerol solutions of perylene with those of 3,9-dibromoperylene (DBP). For both molecules a good linear dependence is observed between the glycerol viscosity (varied by temperature) and the longer rotational correlation time obtained as a result of a global (using data obtained at 256- and 430-nm excitation wavelengths) biexponential analysis of the fluorescence anisotropy decay, at least in the range of 7–60 P for perylene and 4–60 P for DBP. This significantly extends the reported range of 0.5 to 150 cP investigated by Williams and Ben-Amotz [1] with the probe BTBP.     

Stopping power of polymers for heavy ions: a comparative study

A comparative study of various stopping power tables and codes for heavy ions in polymers has been made by comparing the computed stopping power values with the corresponding experimental values. The energy loss of different heavy ions (3≤Z ₁≤29) in the energy domain of ～0.19–3.14 MeV/n has been studied in six different polymers mostly used as particle track detectors viz: Mylar (Polyethylene Terephthalate), PEN (Polyethylene Napthalate), Polycarbonate, CR-39 (Polyallyl Diglycol Carbonate), Kapton (Polypyromellitimide) and LR-115 (Cellulose Nitrate). The merits and demerits of the adopted formulations are highlighted. It has been observed that the calculations based on SRIM2003.26 and tables of ICRU-73 provide best agreement with the experimental data for projectiles (3≤Z ₁≤29) and (3≤Z ₁≤18), respectively. The MSTAR3.12 code shows good results for projectiles (3≤Z ₁≤18), except in case of CR-39 for O, Na, and Al projectiles. The statistical analysis on the basis of combined error reveals that the SRIM2003 and ICRU-73 tables are more reliable as compared to the other programs taken in the present study, whereas CasP3.1 is least reliable program in lower energy domain.     

Experimental study of the ultrasound attenuation in chemical reactors

Ultrasound is used in different domains, and in sonochemistry particularly, for different purposes and in various flow configurations: monophasic, two-phase and polyphasic reactors. In order to optimize and to design sonochemical reactors, it is important to describe the ultrasonic intensity space and time distribution. In addition, it is important to study the different parameters influencing the intensity profiles of the ultrasonic wave. In this work, a thermoelectric probe has been used to measure the ultrasonic intensity. This procedure has shown that the ultrasound propagation is influenced by the presence of cavitation bubbles, the flow regime and the presence of solid particles.     

The effects of power ultrasound (24 kHz) on the electrochemical reduction of CO2 on polycrystalline copper electrodes

The electrochemical CO₂ reduction reaction (CO2RR) on polycrystalline copper (Cu) electrode was performed in a CO₂-saturated 0.10 M Na₂CO₃ aqueous solution at 278 K in the absence and presence of low-frequency high-power ultrasound (f = 24 kHz, P_T ~ 1.23 kW/dm³) in a specially and well-characterized sonoelectrochemical reactor. It was found that in the presence of ultrasound, the cathodic current (I_c) for CO₂ reduction increased significantly when compared to that in the absence of ultrasound (silent conditions). It was observed that ultrasound increased the faradaic efficiency of carbon monoxide (CO), methane (CH₄) and ethylene (C₂H₄) formation and decreased the faradaic efficiency of molecular hydrogen (H₂). Under ultrasonication, a ca. 40% increase in faradaic efficiency was obtained for methane formation through the CO2RR. In addition, and interestingly, water-soluble CO₂ reduction products such as formic acid and ethanol were found under ultrasonic conditions whereas under silent conditions, these expected electrochemical CO2RR products were absent. It was also found that power ultrasound increases the formation of smaller hydrocarbons through the CO2RR and may initiate new chemical reaction pathways through the sonolytic di-hydrogen splitting yielding other products, and simultaneously reducing the overall molecular hydrogen gas formation.     

Comparative study of sonochemical reactors with different geometry using thermal and chemical probes

Laboratory scale 20 kHz sonochemical reactors with different geometries have been tested using thermal probes, the kinetics of H(2)O(2) formation, and the kinetics of diphenylmethane (DPhM) sonochemical darkening. Results revealed that the overall sonochemical reaction rates in H(2)O and DPhM are driven by the total absorbed acoustic energy and roughly independent the geometry of the studied reactors. However, the sonochemical efficiency, defined as eta=VG/S, where G is a sonochemical yield of H(2)O(2), V is a volume of sonicated liquid, and S is a surface of the sonotrode, was proved to increase with the decrease of S. This phenomenon was explained by growing of the maximum cavitating bubble size with ultrasonic intensity and its independence towards the specific absorbed acoustic power. For the cleaning bath reactor the kinetics of the sonochemical reactions in H(2)O and DPhM depends strongly on the reaction vessel materials: the reaction rates decreased with the increase of the materials elasticity. Kinetic study of H(2)SO(4) sonolysis using a sonoreactor without direct contact with titanium sonotrode showed that sulphate anion is an effective scavenger of OH() radicals formed during water sonolysis.     

Effect of focused ultrasound stimulation at different ultrasonic power levels on the local field potential power spectrum

Local field potential(LFP) signals of the rat hippocampus were recorded under noninvasive focused ultrasound stimulation(FUS) with different ultrasonic powers. The LFP mean absolute power was calculated with the Welch algorithm at the delta, theta, alpha, beta, and gamma frequency bands. The experimental results demonstrate that the LFP mean absolute power at different frequency bands increases as the ultrasound power increases.     

Magnetism in systems with reduced dimensionality and chemical disorder: The local environment effects

We study influence of the local chemical environment, the so-called local environment effects, on the electronic structure and properties of magnetic systems with reduced dimensionality and chemical disorder, and show that they play a crucial role in a vicinity of magnetic instability. As a model, we consider Fe–Ni Invar. We present results obtained from ab initio calculations of the electronic structure, magnetic moments, and exchange interactions in random fcc Fe–Ni alloy, for a single monolayer alloy film on a Cu (0 0 1) substrate as well as in the bulk. We analyze the difference between the film and the bulk magnetization, which is found to be most pronounced for dilute alloys. We also analyze a sensitivity of the individual magnetic moments and effective exchange parameters to the local chemical environment of the atoms.     

Physical and chemical effects of ultrasound vibration on polymer melt in extrusion

The physical and chemical effects of ultrasound on polypropylene (PP) melts in extrusion were investigated. By applying ultrasound vibration to the entrance of the die, apparent pressure and viscosity of PP can be obviously decreased under the appropriate ultrasound power. Ultrasound has both physical and chemical effects on the polymer melt. In our study with specific polymer and ultrasound system, we determined that the chemical effect makes up 35–40% of the total effect of ultrasound on the apparent viscosity reduction of PP melts at most of the studied intensities. The physical effect plays a more important role in the ultrasound-applied extrusion than the chemical effect. This chemical effect is an irreversible and permanent change in molecule weight and the molecular-weight distribution due to ultrasound. As the ultrasound intensity increases, the molecular weight of PP reduces and its molecular-weight distribution becomes narrower; the orientation of PP molecules along the flow direction reduces (in melt state) and the crystallinity of PP samples (in solid state) decreases by applying the ultrasound vibration. Ultrasound vibration increases the motion of molecular chains and makes them more disorder; it also affects the relaxation process of polymer melts by shortening the relaxation time of chain segments, leading to weakening the elastic effect and decreasing the extruding swell ratios. All the factors discussed above reduce the non-Newtonian flow characteristics of the polymer melt and result in the viscosity drop of the polymer melt in extrusion.