Ultrasonic effects on electroorganic processes. Part 17. Product selectivity control in cathodic reduction of acrylonitrile

Product selectivity for adiponitrile, which was formed as the corresponding hydrodimeric product along with propionitrile as the hydromonomeric product in the cathodic reduction of acrylonitrile, was significantly increased under ultrasonic irradiation with an intensity above the ultrasonic cavitation threshold. This ultrasonic effect is rationalized as due to mass transport promotion of acrylonitrile molecules to the cathode surface from the bulk electrolytic solution by high speed jet streams caused by the cavitation. A mechanism for the ultrasonic effect is discussed in detail on the basis of the reaction pathway of the hydrodimerization of acrylonitrile.     

Sonochemical-assisted synthesis of nano-structured lead dioxide

PbO(2) nano-powder was synthesized by the ultrasonic irradiation of an aqueous suspension of dispersed beta-PbO, as precursor, in the presence of ammonium peroxydisulfate as an oxidant. The reaction rate increased with an increase in temperature and ammonium peroxydisulfate concentration. In the presence of ammonium peroxydisulfate, the increased concentration of hydroxyl radical facilitated the oxidation of beta-PbO to PbO(2) under ultrasonic irradiation. The PbO(2) nano-powder was characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). It was found that the applied ultrasonic wave determines the particle size. PbO(2) samples prepared under optimized experimental conditions have lead dioxide particles in the range of 50-100 nm, as shown by SEM. The XRD results reveal that only beta-PbO(2) is formed under optimum conditions. When the reaction mixture was stirred instead of ultrasonically irradiated, only a fraction of the lead oxide was converted to lead dioxide, and lead sulfate was the main reaction product.     

TiO2 treatment using ultrasonication for bubble cavitation generation and efficiency assessment of a dye-sensitized solar cell

In this study, the impacts of different ultrasonic treatments on TiO₂ particles were determined and they were used to manufacture the photoelectrodes of a dye-sensitized solar cell (DSSC). Two methods were used to prepare TiO₂ particles directly sonicated by an ultrasonic horn, and TiO₂ treated indirectly by an ultrasonic cleaner. TEM, XPS analysis was confirmed that cavitation bubbles generated during ultrasonication resulted in defects on the surface of TiO₂ particles, and the defect induced surface activation. To understand the effect of TiO₂ surface activation on energy conversion efficiency of DSSC, ultrasonic horn DSSC and ultrasonic cleaner DSSC were prepared. The UV–vis analysis exhibited that the ultrasonic horn DSSC possessed higher dye adsorption when compared to the ultrasonic cleaner DSSC, and the EIS analysis confirmed that the electron mobility was greatly increased in the ultrasonic horn DSSC. The energy conversion efficiency of the ultrasonic horn DSSC was measured to be 3.35%, which is about 45% increase in comparison to that of the non-ultrasonic treated DSSC (2.35%). In addition to this regard, recombination resistance of ultrasonic horn DSSC was calculated to be 450 Ω·cm², increasing more than two times compared to the non-ultrasonic treated DSSC (200 Ω·cm²). Taken together, these ultrasonic treatments significantly improved the energy conversion efficiency of DSSC, which was not tried in DSSC-related research, and might lead us to develop more efficient practical route in the manufacturing of DSSC.     

A novel ultrasound assisted method in synthesis of NZVI particles

This research is about a novel ultrasound assisted method for synthesis of nano zero valent iron particles (NZVI). The materials were characterized using TEM, FESEM, XRD, BET and acoustic PSA. The effect of ultrasonic power, precursor/reductant concentration (NaBH₄, FeSO₄·7H₂O) and delivery rate of NaBH₄ on NZVI characteristics were investigated. Under high ultrasonic power the morphology of nano particles changed from spherical type to plate and needle type. Also, when high precursor/reductant and high ultrasonic power was used the particle size of NZVI decreased. The surface area of NZVI particles synthesized by ultrasonic method was increased when compared by the other method. From the XRD patterns it was found also the crystallinity of particles was poor.     

Improvement in properties of coal water slurry by combined use of new additive and ultrasonic irradiation

Coal water slurry (CWS) was prepared with a newly developed additive from naphthalene oil. The effects of ultrasonic irradiation on coal particle size distribution (PSD), adsorption behavior of additive in coal particles and the characteristics of CWS were investigated. Results showed that ultrasonic irradiation led to a higher proportion of fine coal in CWS and increased the saturated adsorption amount of additive in coal particles. In addition, the rheological behavior and static stability of CWS irradiated by ultrasonic wave were remarkably improved. The changes on viscosity of CWS containing 1% and 2% additive are qualitatively different with the increasing sonication time studied. The reason for the different effect of sonication time on CWS viscosity is presented in this study.     

Power ultrasound interaction with DC atmospheric pressure electrical discharge

The effect of power ultrasound application on DC hollow needle to plate atmospheric pressure electrical discharge enhanced by the flow of air through the needle electrode was studied experimentally. It was found that applying ultrasound increases discharge volume. In this volume take place plasmachemical processes, used in important ecological applications such as the production of ozone, VOC decomposition and de-NOx processes enhancement. In our experiments we used a negatively biased needle electrode as a cathode and a perpendicularly placed surface of the ultrasonic resonator--horn--as an anode. To demonstrate the effect of ultrasound waves on electrical discharge photographs of the discharge for the needle to the ultrasonic resonator at distances of 4, 6 and 8mm are shown. By varying the distance between needle and the surface of the transducer, we were able to create the node or the antinode at the region around the tip of the needle, where the ionization processes are effective. In our experimental arrangement the amplitude of acoustic pressure at antinode exceeded 10(4) Pa. The photographs reveal that the diameter of the discharge on the surface of the ultrasonic horn is increased when ultrasound is applied. The increase of discharge volume caused by the application of ultrasound can be explained as a combined effect of the change of the reduced electric field E/n (E is electric field strength and n is the neutral particles density), strong turbulence of the particles in the discharge region caused by quick changes of amplitudes of the standing ultrasonic wave and finally by the boundary layer near the ultrasonic transducer perturbations due to vibrations of the transducer surface.     

Ultrasonication an intensifying tool for preparation of stable nanofluids and study the time influence on distinct properties of graphene nanofluids – A systematic overview

Optimum ultrasonication time will lead to the better performance for heat transfer in addition to preparation methods and thermal properties of the nanofluids. Nano particles are dispersed in base fluids like water (water-based fluids), glycols (glycol base fluids) &oils at different mass or volume fraction by using different preparation techniques. Significant preparation technique can enhance the stability, effects various parameters & thermo-physical properties of fluids. Agglomeration of the dispersed nano particles will lead to declined thermal performance, thermal conductivity, and viscosity. For better dispersion and breaking down the clusters, Ultrasonication method is the highly influential approach. Sonication hour is unique for different nano fluids depending on their response to several considerations. In this review, systematic investigations showing effect on various physical and thermal properties based on ultrasonication/ sonication time are illustrated. In this analysis it is found that increased power or time of ideal sonication increases the dispersion, leading to higher stable fluids, decreased particle size, higher thermal conductivity, and lower viscosity values. Employing the ultrasonic probe is substantially more effective than ultrasonic bath devices. Low ultrasonication power and time provides best outcome. Various sonication time periods by various research are summarized with respect to the different thermophysical properties. This is first review explaining sonication period influence on thermophysical properties of graphene nanofluids.     

Ultrasonic effects on electroorganic processes. Part 25. Stereoselectivity control in cathodic debromination of stilbenedibromides

Ultrasonic effects on the cathodic debromination of stilbenedibromides on a platinum cathode was examined. Current efficiency and stereoselectivity for trans-stilbene, which was formed along with cis-stilbene in the cathodic debromination of stilbenedibromides, were significantly increased under ultrasonication with an intensity over the ultrasonic cavitation threshold. This ultrasonic effect is rationalized as due to mass transport promotion in the electrode-electrolytic solution interface. A mechanism for the ultrasonic effect is discussed in detail on the basis of the reaction pathway of the debromination of stilbenedibromides.     

Sonochemical synthesis of polyaniline nanofibers

Conventionally, micro-sized irregular polyaniline (PANI) particles were synthesized by dropwise addition of the ammonium persulfate (APS) solution into the aniline (ANI) solution with mechanical stirring. By replacing the mechanical stirring with an ultrasonic irradiation, PANI nanofibers in diameters of approximately 50 nm and lengths of 200 nm to several micrometers were prepared. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) showed that at the early stage of polymerization, the polymers formed in both the mechanical stirred and ultrasonicated systems are in the form of nanofiber. However, with continuing of the reaction, these primary nanofibers grow and agglomerate into irregular shaped PANI particles in the mechanical stirred system, while in the case of the ultrasonic irradiation, the growth and agglomeration are effectively prevented, preserving thus the PANI nanofibers in the final product. By increasing the APS/ANI molar ratio from 0.5 to 2.5, the aspect ratios of the PANI nanofibers decreased. The PANI nanofibers exhibit higher solubility than the irregular shaped PANI particles. Although the yield, as well as the conductivity of the ultrasonic synthesized PANI nanofibers, was slightly lower than the irregular shaped PANI particles, the ultrasonic synthesis approach is one of the facile and scalable approaches in synthesizing PANI nanofibers in comparison with other ones without use of templates (e.g., the interfacial polymerization and rapid mixing polymerization). UV-Vis and Fourier transformed infrared (FTIR) spectra indicated ultrasound had no significant effect on the chemical structure of the PANI.     

Growth and size control in anti-solvent crystallization of glycine with high frequency ultrasound

Antisolvent crystallization of glycine was performed under ultrasonic irradiation of 1.6 MHz. The irradiation enhanced both the growth of α-glycine crystal and the uniformity in the crystal size. The degree of both enhancement effects increased with increasing ultrasonic power. While under the irradiation of 20 kHz ultrasound, no growth enhancement was observed, but the crystal size reduced as was reported in the literature. To elucidate the mechanism of growth enhancement, another experiment was designed and conducted to avoid the effect of nucleation from the sonocrystallization. The result suggests that the ultrasound enhances the incorporation of microcrystals to larger crystals. Probably, the collision between solid particles is intensified by the disturbance characterized by the high frequency ultrasound. The crystal growth was modeled with an apparent reaction of microcrystal and larger crystal. The result of the growth experiment was successfully predicted with a rate equation for pseudo first order reaction with a single parameter of rate constant. The rate constant linearly increased with the ultrasonic power. The analysis enables quantitative evaluation of the ultrasonic effect on the crystal growth.     

Baeyer-Villiger oxidation of cyclohexanone to epsilon-caprolactone in airlift sonochemical reactor

Baeyer-Villiger oxidation of cyclohexanone to epsilon-caprolactone was studied in a new type reactor--the airlift loop sonochemical reactor. The reactor plays a synergistic effect of sonochemsity and higher oxygen transfer rate. The influences of ultrasound intensity, reaction temperature, the molar ratio of benzaldehyde to cyclohexanone and oxygen gas flow rate on the conversion and selectivity of cyclohexanone were investigated and discussed. Under ultrasound, the amount of benzaldehyde can be reduced from 75% to 67%. Ultrasound not only intensified the rates of reactions but also increased the yield of product. The optimized operation conditions are listed as follows: the reaction temperature is 30 degrees C, the molar ratio of cyclohexanone to benzaldehyde is 1:2, the oxygen gas flow rate is 1.15 cm s(-1), and ultrasonic irradiations 2h at 40 kHz, 2.25 W cm(-2). Under the optimum operation conditions, the average molar yield of epsilon-caprolactone comes up to 87.7%.     

Nanoscale metal oxide particles produced in the plasma discharge in the liquid phase upon exposure to ultrasonic cavitation. 2. Sizes and stability. Dynamic light scattering study

Size distributions of tungsten oxide particles produced in the plasma discharge in the liquid phase upon exposure to ultrasound were studied by the dynamic light scattering method. Particles produced by this method under ultrasonic cavitation (USC), in the absence of cavitation, and without cavitation followed by ultrasonic processing are compared. The behavior of concentrations of particles of various size groups is comparatively estimated by the data on particle sizes and scattering intensity using the Rayleigh-Gans-Debye approximation. It is shown that ultrasonic processing improves the aggregative stability of suspension; in a suspension of particles produced under USC, large aggregates eventually decay into individual small particles.     

Investigation of the influence of humidity on the ultrasonic agglomeration of submicron particles in diesel exhausts

Removing very fine particles in the 0.01-1 micro m range generated in diesel combustion is important for air pollution abatement because of the impact such particles have on the environment. By forming larger particles, acoustic agglomeration of submicron particles is presented as a promising process for enhancing the efficiency of the current filtration systems for particle removal. Nevertheless, some authors have pointed out that acoustic agglomeration is much more efficient for larger particles than for smaller particles. This paper studies the effect of humidity on the acoustic agglomeration of diesel exhausts particles in the nanometer size range at 21 kHz. For the agglomeration tests, the experimental facility basically consists of a pilot scale plant with a diesel engine, an ultrasonic agglomeration chamber a dilution system, a nozzle atomizer, and an aerosol sampling and measuring station. The effect of the ultrasonic treatment, generated by a linear array of four high-power stepped-plate transducers on fumes at flow rates of 900 Nm(3)/h, was a small reduction in the number concentration of particles at the outlet of the chamber. However, the presence of humidity raised the agglomeration rate by decreasing the number particle concentration by up to 56%. A numerical study of the agglomeration process as a linear combination of the orthokinetic and hydrodynamic agglomeration coefficients resulting from mutual radiation pressure also found that acoustic agglomeration was enhanced by humidity. Both results confirm the benefit of using high-power ultrasound together with humidity to enhance the agglomeration of particles much smaller than 1 micro m.     

Effect of ultrasonic treatment on the morphology of casein particles

In this study, the effect of ultrasonic treatment duration on the morphology of self-assembled casein particles was investigated by atomic force microscopy (AFM), low vacuum scanning electron microscopy (SEM) and transmission electron microscopy (TEM). In the case of AFM images, the particle analysis which was carried out by the SPIP program showed that the self-assembled casein particles after being ultrasonically treated for 2 min got smaller in size compared to the casein particles that have not been exposed to any ultrasonic treatment. Surprisingly, however, increasing the ultrasonic time exposure of the particles resulted in an opposite effect where larger particles or aggregates seemed to be present. We show that by comparing the results obtained by AFM, SEM and TEM, the information extracted from the AFM images and analyzed by SPIP program give more detailed insights into particle sizes and morphology at the molecular level compared to SEM and TEM images, respectively.     

Particle Manipulation by Ultrasonic Standing Wave Fields to complement dynamic light scattering experiments

Dynamic light scattering is a widely used technique for the sizing of colloidal suspensions. It is capable of measuring particles across the size range from approximately 1 nm to several microns. However the larger particle sizes tend to pose problems for the interpretation of the scattered light signal either by virtue of their light scattering efficiency relative to the smaller species present or the departure of the scattered light signal from Gaussian statistics. Rapid removal of such particles in-situ could extend the use of dynamic light scattering particularly in on-line analysis or laboratory automated measurement. In this paper a method is demonstrated for the in-situ removal of larger particles in suspension by means of ultrasonic standing waves and concurrent dynamic light scattering measurement. The theory behind ultrasonic particle manipulation and its effect on the motion of the particles is discussed. Data from a scattering cell designed to incorporate the ultrasonic technology is presented showing that dynamic light scattering measurements may be carried out under such conditions. Varying the energy density of the ultrasonic field allows particles greater than a defined cut-off diameter to be removed from the measurement region. Theory shows that the minimum cut-off size may be as small as 100 nm. Results presented here demonstrate complete removal at a lower diameter threshold of approximately 2000 nm.     

Effects of ultrasonic intensity and reactor scale on kinetics of enzymatic saccharification of various waste papers in continuously irradiated stirred tanks

Based on the enzymatic saccharification of the various pulps in the previous 0.8 l ultrasonic stirred tank reactor, the ultrasound-enhanced saccharification of waste papers such as newspaper, carton paper, office paper etc. was carried out in the same reactor as well as larger scale stirred tank reactors of size 3.2 and 6.4 l. The saccharification of each waste paper was less enhanced in the larger reactor at a given ultrasonic intensity. This could be attributed to the decrease in the ultrasonic intensity per reaction volume, i.e., the specific ultrasonic intensity. Most waste papers were more efficiently hydrolyzed with increasing specific ultrasonic intensities, although newspaper was less efficiently done for a too high specific intensity. Such an adverse effect might be due to the fact that some impurities in the newspaper such as lignin were activated by an intensive ultrasonic irradiation to form a rigid and closed network, which inhibited the access and adsorption of cellulase on to the substrate surface. The previous kinetic model was found to be applicable to analyze and simulate the saccharification of each waste paper in the different ultrasonic reactors. The ultimate conversion of a substrate based on the total sugar concentration estimated for an infinite reaction time could be correlated as a function of the ratio of initial substrate to enzyme concentrations at a fixed specific ultrasonic intensity. Either the apparent rate constant or the ultimate conversion increased and tended to approach a constant with an increase in the specific ultrasonic intensity except for the case of newspaper, while neither the apparent Michaelis constant, product inhibition constant nor glucose formation equilibrium constant was influenced by the specific ultrasonic intensity.     

Sonochemical synthesis of zeolite NaP from clinoptilolite

In the present work, natural clinoptilolite was converted to zeolite NaP using ultrasonic energy, in which the transformation time shortened remarkably. The effect of post-synthesis treatment using conventional hydrothermal was also investigated. The synthesized powders were characterized by XRD, TGA/DTA, SEM, and PSD analysis. The results showed that, increasing the sonication time (energy) has no significant effect on the product’s morphology. The crystallinity of the synthesized samples increased slightly with increasing sonication time, but their yield remained relatively unchanged. Furthermore, post-synthesis hydrothermal treatment showed very little influence on properties of the final product. Because the ultrasonic irradiation creates acoustic cavitation cracks on the surface structure of clinoptilolite particulates and increases the concentration of soluble alumino-silicate species, which favors the prevailing super-saturation, crystallization and crystal growth of zeolite NaP happen faster. The particles of zeolite NaP synthesized by ultrasonic irradiation consist of small crystallites of uniform size.     

Ultrasonic pretreatment of spodumene with different size fractions and its influence on flotation

The potential of ultrasonic pretreatment enhancing selective surface dissolution to improve the floatability of spodumene with different size fractions was verified and investigated. For coarse particles of −0.15 + 0.0385 mm, compared with traditional pretreatment methods, ultrasonic pretreatment could optimize the physicochemical properties of the surface, markedly increased the amount of NaOL adsorbed on the mineral surface, and improved the floatability of the spodumene. For fine particles of −0.0385 mm, both pretreatment methods (Ultrasonic and Traditional) could greatly increase the flotation recovery, but ultrasonic pretreatment had no obvious advantage compared with traditional method. ICP combined with XPS analysis were conducted to investigate the dissolution mechanism of spodumene surface in different pretreatment system. Si species on the surface of coarse particles were easily dissolved into the solution under the effect of ultrasound, which increases the relative content of Al and Li species on the surface. This was conducive to the adsorption of the collectors on the surface. However, the selective dissolution of the fine particle surface was weakened by excessive energy intake in the ultrasonic system, which neutralized the advantage brought by the large amount of dissolution, making the results obtained by the two preprocessing methods the same.     

A novel method for the modification of zinc powder by ultrasonic impregnation in cerium nitrate solution

This work is devoted to an extensive study of cerium deposits distributed directly on zinc particles by simple impregnation or ultrasonic impregnation for the modification of zinc powder. Meantime, the characterization of modified zinc powder and the influence of ultrasound parameters in the modification process upon the dendritic growth, the corrosion behavior and the cyclic performance of zinc are investigated using scanning electron microscopy, energy dispersion spectrometry, potentiostatic polarization, potentiodynamic polarization and cyclic voltammetry. Compared with simple impregnation, the assistance of ultrasonic irradiation is found to have a significant effect on the sedimentary state and favorable properties of cerium deposits in a protective way. Besides the cyclic voltammetry measurements display that the application of ultrasound also improves the cyclic performance of zinc electrode containing modified zinc powder mainly because the cerium deposits formed under ultrasonic irradiation can greatly hinder the dissolution and diffusion of the oxidation product of zinc in the electrolyte and effectively favor the capacity maintenance of zinc electrode.     

Ultrasonics in heterogeneous metal catalysis: sonochemical chemo- and enantioselective hydrogenations over supported platinum catalysts

Sonochemical chemo- and enantioselective hydrogenations over supported platinum catalysts are described. We disclose our results with respect to a sonochemical modification of the chemoselective hydrogenation of cinnamaldehyde over supported platinum catalysts, and the asymmetric hydrogenation of ethyl pyruvate promoted by various ultrasonic pretreatments. The ultrasonic pretreatment of the supported platinum catalysts was found to be highly beneficial in almost every case, improving both the catalytic activity and selectivity. The effect of additional experimental variables, such as hydrogen pressure, catalyst support, temperature and the ultrasonic insonation time were also studied. The enantioselectivity of the hydrogenation of ethyl pyruvate increased up to 97.1% ee. In the case of cinnamaldehyde hydrogenation, the selective preparation of cinnamyl alcohol became possible. The theoretical aspects of the working mechanisms in comparison with 'silent' reactions will also be provided.