Effect of intensifying additives on the degradation of thiamethoxam using ultrasound cavitation.

The present study has investigated the degradation of thiamethoxam using ultrasound cavitation (US) operated at a frequency of 20 kHz and its combination with intensifying additives viz. hydrogen peroxide, Fenton and photo-Fenton reagent. At the outset, the performance of US (20 kHz) has been maximised by the optimization of process parameters. Highest rate of degradation of thiamethoxam was observed at the optimum ultrasonic power density of 0.22 W/mL, thiamethoxam concentration of 10 ppm and the pH of 2. The established optimum values of operating parameters were used further in case of combined treatment approaches. The effect of concentration of H2O2 on the rate of degradation of thiamethoxam in the case of US + H2O2 process has confirmed the existence of optimum concentration of H2O2 with the ratio of thiamethoxam: H2O2 as 1:10. US + Fenton process indicated the optimal molar ratio of FeSO4·7H2O:H2O2 as 1:15. The combined processes of US + H2O2, US + Fenton and US + photo-Fenton have resulted in the extent of degradation of 20.47 ± 0.61%, 34.41 ± 1.03% and 85.17 ± 2.56% respectively after 45 min. of operation. These combined processes lead to the synergistic index of 2.04 ± 0.06, 2.26 ± 0.07 and 2.42 ± 0.07 in case of US + H2O2, US + Fenton and US + photo-Fenton processes respectively over only US/stirring treatment with the additive. Additionally, the extent of mineralization and the energy efficiency of individual and combined processes have been compared. US + photo-Fenton process has been found to be the best strategy for effective degradation of thiamethoxam with a significant intensification benefit. The by-products formed during the ultrasonic degradation of thiamethoxam have been identified by using LC-MS/MS analysis.

Cotton based composite fabric reinforced with waste polyester fibers for improved mechanical properties.

With the focus of industries shifting towards sustainable processing methods and the use of sustainable raw materials, reuse and recycling of polyester have gained a lot of momentum. In spite of considerable efforts, the utilization of polyester fiber waste has not yet found a strong foundation in textile processing. In this paper, waste polyester fibers obtained during the melt spinning process has been utilized by first dissolving it in an m-cresol solvent and later by chemical route polyester is regenerated on cotton leading to the preparation of cotton based composite fabric. The presence of polyester was confirmed using XRD, FTIR, and percent add on and SEM. Percent add on of 9.7% along with the doubling of tensile strength and enhanced thermal stability was observed. The results can make a way as one of the possibilities of utilizing polyester fiber waste.

A novel approach for continuous synthesis of calcium carbonate using sequential operation of two sonochemical reactors.

A novel continuous process for the synthesis of calcium carbonate based on precipitation reaction has been developed involving the sequential operation of two sonochemical reactors for the first time. The reactors were also operated as control (conventional approach without ultrasound) to clearly establish the process intensification benefits due to the use of ultrasound. The effect of different operating parameters such as Ca(OH)2 concentration, CO2 flow rate and Ca(OH)2 slurry flow rate on the particle size has been investigated. The obtained calcite particles were characterized using Fourier transform infrared (FTIR), wide angle X-ray diffraction (XRD) and particle size distribution (PSD) analysis. The morphology of the obtained particles was also analyzed using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was established that the average particle size obtained in the presence of ultrasound was smaller with much narrow size distribution as compared to the conventional approach. Further, the average particle size was established to decrease with an increase in the Ca(OH)2 slurry concentration and CO2 flow rate with the optimum conditions giving a particle size of 164nm. The particle size was also influenced by the Ca(OH)2 slurry flow rate and under optimum condition of Ca(OH)2 slurry flow rate as 24mL/min, particle size of 135nm was obtained. Only calcite phase of CaCO3 was observed to be formed as established based on the XRD analysis during both the synthesis approaches confirming the stability of the obtained particles. It was also observed that the shape of the crystals varied with the method of synthesis. Rhombohedral calcite particles were formed in the presence of ultrasound whereas the conventional stirring method resulted in spindle shaped particles. Overall, the utility of the ultrasound assisted approach has been clearly established with novel results based on the use of sonochemical reactors in series.

Investigation of TiO2 photocatalyst performance for decolorization in the presence of hydrodynamic cavitation as hybrid AOP.

In this article, an acoustic cavitation engineered novel approach for the synthesis of TiO2, cerium and Fe doped TiO2 nanophotocatalysts is reported. The prepared TiO2, cerium and Fe doped TiO2 nanophotocatalysts were characterized by XRD and TEM analysis to evaluate its structure and morphology. Photo catalytic performance of undoped TiO2 catalyst was investigated for the decolorization of crystal violet dye in aqueous solution at pH of 6.5 in the presence of hydro dynamic cavitation. Effect of catalyst doping with Fe and Ce was also studied for the decolorization of crystal violet dye. The results shows that, 0.8% of Fe-doped TiO2 exhibits maximum photocatalytic activity in the decolorization study of crystal violet dye due to the presence of Fe in the TiO2 and it may acts as a fenton reagent. Kinetic studies have also been reported for the hybrid AOP (HAOP) that followed the pseudo first-order reaction kinetics.

Intensification of ultrasound-assisted process for the preparation of spindle-shape sodium zinc molybdate nanoparticles.

In the present work, sodium zinc molybdate (SZM) nanoparticles were prepared using conventional and an innovative ultrasound assisted co-precipitation of sodium molybdate, zinc oxide and HNO3 at different temperatures. Prepared product was characterized by XRD, TEM, FT-IR, particle size distribution (PSD), TGA and DTA techniques. TEM analysis shows the spindle-shaped morphology of the formed SZM nanoparticles. The average particle size of SZM nanoparticles is found to be lower in case of sonochemical method (78.3 nm) compared to conventional method (340.2 nm) which is attributed to faster solute transfer rate due to ultrasonic irradiation leading to rapid nucleation and restricted growth of SZM nanoparticles. Further, the kinetics of synthesis of SZM nanoparticles are studied using the sonochemical method at different operating temperature and conventional method at 80°C. It is shown that the rate of reaction is significantly faster at 40°C compared to other temperatures and also conventional method. This can be attributed to intense cavity collapse at lower temperature (low vapour pressure) compared to higher temperature (high vapour pressure) of the reaction mixture.

Synthesis of titanium dioxide by ultrasound assisted sol-gel technique: effect of calcination and sonication time.

Nanostructured titanium dioxide has been synthesized using both conventional and ultrasound assisted sol-gel technique with an objective of understanding the role of cavitational effects in the synthesis process. The experiments were conducted at a constant calcination temperature of 750 °C and the calcination time was varied from 30 min to 3 h to study the effect of calcination time on the properties of the synthesized TiO2. The TiO2 specimens were characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The influence of the sonication time on the phase transformation process from anatase to rutile and also on the crystallite size and percentage crystallinity of the synthesized TiO2 has also been investigated. It was observed that 100% phase transformation occurred after 3 h of calcination for the ultrasound assisted sol-gel synthesized TiO2. The study on the phase transformation via variation of sonication time yielded interesting results. It was observed that as the sonication time increased, an initial increase in the rutile content is obtained and beyond optimum sonication time, the rutile content decreased. In general, the ultrasound assisted process results in synthesis of TiO2 material with higher rutile content as compared to the conventional sol-gel process.

Ultrasound assisted manufacturing of paraffin wax nanoemulsions: process optimization.

This work reports on the process optimization of ultrasound-assisted, paraffin wax in water nanoemulsions, stabilized by modified sodium dodecyl sulfate (SDS). This work focuses on the optimization of major emulsification process variables including sonication time, applied power and surfactant concentration. The effects of these variables were investigated on the basis of mean droplet diameter and stability of the prepared emulsion. It was found that the stable emulsion with droplet diameters about 160.9 nm could be formed with the surfactant concentration of 10 mg/ml and treated at 40% of applied power (power density: 0.61 W/ml) for 15 min. Scanning electron microscopy (SEM) was used to study the morphology of the emulsion droplets. The droplets were solid at room temperature, showing bright spots under polarized light and a spherical shape under SEM. The electrophoretic properties of emulsion droplets showed a negative zeta potential due to the adsorption of head sulfate groups of the SDS surfactant. For the sake of comparison, paraffin wax emulsion was prepared via emulsion inversion point method and was checked its intrinsic stability. Visually, it was found that the emulsion get separated/creamed within 30 min. while the emulsion prepared via ultrasonically is stable for more than 3 months. From this study, it was found that the ultrasound-assisted emulsification process could be successfully used for the preparation of stable paraffin wax nanoemulsions.

Continuous precipitation of calcium carbonate using sonochemical reactor.

The continuous production of calcium carbonate (CaCO3) by precipitation method at room temperature was carried out in a stirred reactor under ultrasonic environment and was compared with the conventional stirring method. The effect of various operating parameters such as Ca(OH)2 slurry concentration, CO2 flow rate and Ca(OH)2 slurry flow rate on the particle size of CaCO3 was investigated. The calcium carbonate particles were characterized by Fourier transform infrared (FTIR), wide angle X-ray diffraction (WXRD) and particle size. The morphology was studied by using scanning electron microscopic (SEM) images. The particle size obtained in the presence of ultrasonic environment was found to be smaller as compared to conventional stirring method. The particle size is found to be reduced with an increase in the concentrations of Ca(OH)2 and increased with increasing CO2 flow rate for both the methods. The slurry flow rate had a major effect on the particle size and the particle size decreased with increased slurry flow rate. Only calcite phase of CaCO3 was predominantly present as confirmed by the characterization techniques for both the preparation methods. In most of the cases rhombohedral calcite particles were observed.

Ultrasound assisted synthesis of doped TiO2 nano-particles: characterization and comparison of effectiveness for photocatalytic oxidation of dyestuff effluent.

The present work deals with the synthesis of titanium dioxide nanoparticles doped with Fe and Ce using sonochemical approach and its comparison with the conventional doping method. The prepared samples have been characterized using X-ray diffraction (XRD), FTIR, transmission electron microscopy (TEM) and UV-visible spectra (UV-vis). The effectiveness of the synthesized catalyst for the photocatalytic degradation of crystal violet dye has also been investigated considering crystal violet degradation as the model reaction. It has been observed that the catalysts prepared by sonochemical method exhibit higher photocatalytic activity as compared to the catalysts prepared by the conventional methods. Also the Ce-doped TiO(2) exhibits maximum photocatalytic activity followed by Fe-doped TiO(2) and the least activity was observed for only TiO(2). The presence of Fe and Ce in the TiO(2) structure results in a significant absorption shift towards the visible region. Detailed investigations on the degradation indicated that an optimal dosage with 0.8 mol% doping of Ce and 1.2 mol% doping of Fe in TiO(2) results in higher extents of degradation. Kinetic studies also established that the photocatalytic degradation followed the pseudo first-order reaction kinetics. Overall it has been established that ultrasound assisted synthesis of doped photocatalyst significantly enhances the photocatalytic activity.

Wet air oxidation as a pretreatment option for selective biodegradability enhancement and biogas generation potential from complex effluent.

This study looks at the possibility of wet air oxidation (WAO) based pretreatment of complex effluent to selectively enhance the biodegradability (without substantial COD destruction) and facilitate biogas generation potential. A lab-scale wet air oxidation reactor with biomethanated distillery wastewater (B-DWW) as a model complex effluent (COD 40,000 mg L(-1)) was used to demonstrate the proof-of-concept. The studies were conducted using a designed set of experiments and reaction temperature (150-200°C), air pressure (6-12 bar) and reaction time (15-120 min) were the main process variables of concern for WAO process optimization. WAO pretreatment of B-DWW enhanced the biodegradability of the complex wastewater by the virtue of enhancing its biodegradability index (BI) from 0.2 to 0.88, which indicate favorable Biochemical Methane Potential (BMP) for biogas generation. The kinetics of COD destruction and BI enhancement has also been reported.

Analysis of semibatch emulsion polymerization: role of ultrasound and initiator.

In this work semibatch miniemulsion was carried out wherein the effect of free radicals produced by ultrasound and an external addition of initiator was examined. Influence of different variables on polymerization rate and polymer particle size has also been investigated. Over a range of 0-4% (by wt) initiator, the polymerization rate was found to increase over a range of 0.56-1.33 g L(-1) min(-1). Similarly monomer concentration range (7.2-15 wt.%) changed the polymerization rate from 1.33 to 2.61 g L(-1) min(-1). Under optimum parametric conditions polymer particle size 50 nm were obtained with a narrow size distribution. Syndiotactic phase of PMMA was observed by controlling the formulation recipe. Although, number of reports could be found in the literature [9,13,17,18,20,22] related to batch emulsion polymerization, this experimental data could be useful for the production of large scale monodispersed PMMA latex as all of the scale-up and design parameters have been qualitatively addressed.

Synthesis of zirconium dioxide by ultrasound assisted precipitation: effect of calcination temperature.

Nanostructured zirconium dioxide was synthesized from zirconyl nitrate using both conventional and ultrasound assisted precipitation in alkaline medium. The synthesized samples were calcinated at temperatures ranging from 400°C to 900°C in steps of 100°C. The ZrO(2) specimens were characterized using X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). The thermal characteristics of the samples were studied via Differential Scanning Calorimetry-Thermo-Gravimetry Analysis (DSC-TGA). The influence of the calcination temperature on the phase transformation process from monoclinic to tetragonal to cubic zirconia and its consequent effect on the crystallite size and % crystallinity of the synthesized ZrO(2) was studied and interpreted. It was observed that the ultrasound assisted technique helped to hasten to the phase transformation and also at some point resulted in phase stabilization of the synthesized zirconia.

Synthesis of chalcone (3-(4-fluorophenyl)-1-(4-methoxyphenyl)prop-2-en-1-one): advantage of sonochemical method over conventional method.

In this work, an attempt was made to synthesize chalcone (3-(4-fluorophenyl)-1-(4-methoxyphenyl)prop-2-en-1-one) by condensation of 4-fluorobenzaldehyde with 1-(4-methoxyphenyl)ethanone under basic conditions by using both conventional (NUS) and sonochemical (US) methods. A simple condensation reaction of 4-fluorobenzaldehyde and 1-(4-methoxyphenyl)ethanone using potassium hydroxide as a base was carried out for the study. The synthesized chalcone derivative was characterized for FTIR, NMR, elemental analyses and studied for XRD, PSM, TGA and SEM properties to evaluate its performance obtained under ultrasonic energy. It was observed that complete conversion to chalcone occurred in 10 min by sonochemical method and in 4h by conventional method. Also it was found that crystallinity of the US synthesized chalcone was found to be increased by 63% than that of NUS synthesized chalcone. Finally, it has been observed that chalcone synthesis using sonochemical method is an energy efficient technique over conventional method (almost 90% of energy saving).

Studies of internal gelation for the production of microspheres: sonication assisted gelation.

Internal gelation studies are carried out with mixed oxides of uranium and plutonium (MOX) and HMUR (i.e. mixture of hexamethylene tetramine (HMTA) and urea in 1:1 proportion). It is necessary to find surrogate of MOX for the detailed experimental work. Hence, the studies have been carried out with aluminium nitrate and magnesium nitrate. Important parameters of gelation such as temperature and concentration of precursors and the effect of sonication and drying on the gelled particles have been studied using these nitrates and HMUR. It has been found that micromixing (sonication) provides narrow and compact size distribution as compared to macromixing (using magnetic stirrer) and temperature of the precursors does not affect the size distribution of the gelled particles. The effect of drying has been studied using IR (infrared) dryer and oven dryer and it was found that IR drying augments the performance as compared to oven drying. Depending on the solubility of the gel in water and its appearance (as pasty mass which is similar to uranyl nitrate gel) aluminium nitrate is chosen as an appropriate surrogate for MOX. FTIR studies have been carried out for characterization of the gel.

Synthesis of titanium dioxide by ultrasound assisted sol-gel technique: effect of amplitude (power density) variation.

Titanium dioxide was successfully synthesized by utilizing sol-gel technique modified by incorporation of ultrasound as a reaction aid. The effect of amplitude of irradiation (power input varied from 19.9 to 80.8 W) on % Rutile, % yield, % crystallinity, crystallite size and morphological (scanning electron microscopy) properties of the obtained nano-TiO(2) was studied. Calcination temperatures of all the samples were kept constant at 750 degrees C. With increasing ultrasonic irradiation amplitude it is observed that the values of % Rutile (after calcination) increased and reached a peak value after which further increase in amplitude resulted in a decrease in the % Rutile. A similar trend was observed in the case of % crystallinity and % yield of the reaction. On the basis of these results an optimum operating ultrasonic irradiation amplitude for the reaction has been suitably established.

Excess cell mass as an internal carbon source for biological denitrification.

Aim of the present work was to examine whether the SCOD (soluble chemical oxygen demand) released after the physical disruption of excess activated sludge can be used as an alternative carbon source for biological denitrification. In the first stage of research, we investigated the potential use of energy efficient hydrodynamic cavitation (HC) technique for the disruption of activated sludge. In a comparative study between ultrasonic cavitation (UC) and HC, it was observed that UC needs five times more energy than that of HC to release the same amount of SCOD. In the second stage of the experimental study, SCOD was successfully used as an alternative carbon source (alternative to sodium acetate) for biological denitrification. The critical weight ratio (SCOD/NO(3)-N) of seven ensured 100% removal of nitrate. Nitrate removal kinetics indicated that denitrification with SCOD as a carbon source gives higher specific denitrification rate (by approximately 200%) as compared to conventional carbon source (sodium acetate).

Phase transformation of nanostructured titanium dioxide from anatase-to-rutile via combined ultrasound assisted sol-gel technique.

An effort was made to synthesize nanostructured TiO(2) via sol-gel technique to obtain a 100% rutile polymorph of nanostructured TiO(2). The sol-gel synthesis technique was suitably modified by incorporating ultrasound to study the effect of cavitation on the phase transformation, crystallite size, crystallinity and morphological (scanning electron microscopy) properties of the obtained nano-TiO(2). It was observed that using ultrasound, yield of the nano-TiO(2) was improved from 86.35% to 95.078%. The phase transformation of anatase-to-rutile of TiO(2) was studied for both (ultrasound assisted and conventional) the processes. Complete phase transformation of the TiO(2) was observed as expected with and without the use of ultrasound but the marked reduction in the required calcination temperature for obtaining 100% phase transformation with ultrasound was the major achievement in the present study, leading to 70% energy savings during calcination.

Effect of dissolved gas on efficacy of sonochemical reactors for microbial cell disruption: Experimental and numerical analysis.

In the present work the effect of dissolved gases on the extent of ultrasonically induced microbial cell disruption has been explored using a mathematical model and it has been validated by experimental data from literature. Degassing experiments are carried out and a degassing kinetics model for horn type ultrasonic device is presented. An overall model combining hydrodynamic and kinetics of cell disruption for horn type reactor is then proposed. The model includes several important operational parameters such as stress generated by the cavity, cell wall strength, dissolved gas concentration, degassing due to sonication, acoustic streaming generated due to sonication and attenuation of ultrasound in water. Model basically realizes in categorizing the volume of sonochemical reactor as active cavitation zone (ACZ) and inactive cavitation zone (ICZ). All the transformations are seen to occur only in ACZ. The two regions, i.e. ACZ and ICZ are assumed to behave as two mixed flow reactor arranged in closed loop. Suggestions have been also made for efficient design and scale up of ultrasonic devices for microbial cell disruption. The same model can be extended for other applications like particle size reduction, nano particle synthesis, leaching, emulsification with the knowledge of critical rate controlling parameter.

Sonocrystallization: effect on lactose recovery and crystal habit.

Sonocrystallization is the use of power ultrasound to control the crystallization process, commonly used during the nucleation phase of crystallization. However, in the present study a different approach has been tried, in which the whole process of lactose crystallization from model reconstituted lactose solutions was completed rapidly with the aid of ultrasound, in the presence of 'ethanol' as an anti-solvent, at temperature of 30+/-2 degrees C (ambient temperature). The lactose recovery and crystal properties from sonicated samples were compared with non-sonicated samples. For optimization of sonocrystallization process for rapid lactose recovery, variations in the time of sonication, lactose concentration, protein concentration and pH were tried. A lactose recovery of 91.48% was obtained in 5 min of sonication time, from a reconstituted lactose solution (17.5% w/v, pH 4.2) as against 14.63% under only stirring. Lactose recovery decreased with lowering of pH from 4.2 to 2.8. The protein showed maximum influence on lactose recovery even at concentration of 0.2% w/v. A rapid process of crystallization gave a better uniformity in crystal size distribution of lactose samples.

Ultrasonic degradation of poly(vinyl alcohol) in aqueous solution.

Solution of poly(vinyl alcohol) in water with different concentrations (by weight 1%, 1.5%, 2%) and different volumes (50, 75 and 100 ml) were subjected to ultrasonic degradation. A method of viscometry was used to study the degradation behavior and kinetic model was developed to estimate the degradation rate constant. The degradation rate constant was correlated with the power input due to ultrasonic irradiation and reaction volume. It was found that rate constant decreases as the reaction volume and concentration increases. The proportionality index of the relation between rate constant, power input and reaction volume was found to be nearly equal for all concentrations studied. The proportionality constant was found to be approximately equal for 1% and 1.5% solution and for 2% solution it was approximately half the value for that of 1% and 1.5% solutions. The decrease in rate constant and proportionality constant is attributed to the fact that at higher concentration and at higher volume, the intensity of cavitation phenomenon is depressed and therefore the extent of polymer chain breaking decreases. The difference in the values of limiting viscosities (constant solution viscosity which does not decrease by further ultrasonic irradiation) for 50, 75 and 100 ml solutions for each of 1% and 1.5% concentration was negligible. But 2% solution at 100 ml volume showed slightly higher value of limiting viscosity than that for 50 and 75 ml.