Treatment of cyanide containing wastewater using cavitation based approach

Industrial wastewater streams containing high concentrations of biorefractory materials like cyanides should ideally be treated at source. In the present work, degradation of potassium ferrocyanide (K₄F_e(CN)₆) as a model pollutant has been investigated using cavitational reactors with possible intensification studies using different approaches. Effect of different operating parameters such as initial concentration, temperature and pH on the extent of degradation using acoustic cavitation has been investigated. For the case of hydrodynamic cavitation, flow characteristics of cavitating device (venturi) have been established initially followed by the effect of inlet pressure and pH on the extent of degradation. Under the optimized set of operating parameters, the addition of hydrogen peroxide (ratio of K₄F_e(CN)₆:H₂O₂ varied from 1:1 to 1:30 mol basis) as process intensifying approach has been investigated. The present work has conclusively established that under the set of optimized operating parameters, cavitation can be effectively used for degradation of potassium ferrocyanide. The comparative study of hydrodynamic cavitation and acoustic cavitation suggested that hydrodynamic cavitation is more energy efficient and gives higher degradation as compared to acoustic cavitation for equivalent power/energy dissipation. The present work is the first one to report comparison of cavitation based treatment schemes for degradation of cyanide containing wastewaters.     

Degradation of diclofenac sodium using combined processes based on hydrodynamic cavitation and heterogeneous photocatalysis

Diclofenac sodium, a widely detected pharmaceutical drug in wastewater samples, has been selected as a model pollutant for degradation using novel combined approach of hydrodynamic cavitation and heterogeneous photocatalysis. A slit venturi has been used as cavitating device in the hydrodynamic cavitation reactor. The effect of various operating parameters such as inlet fluid pressure (2–4 bar) and initial pH of the solution (4–7.5) on the extent of degradation have been studied. The maximum extent of degradation of diclofenac sodium was obtained at inlet fluid pressure of 3 bar and initial pH as 4 using hydrodynamic cavitation alone. The loadings of TiO₂ and H₂O₂ have been optimised to maximise the extent of degradation of diclofenac sodium. Kinetic study revealed that the degradation of diclofenac sodium fitted first order kinetics over the selected range of operating protocols. It has been observed that combination of hydrodynamic cavitation with UV, UV/TiO₂ and UV/TiO₂/H₂O₂ results in enhanced extents of degradation as compared to the individual schemes. The maximum extent of degradation as 95% with 76% reduction in TOC has been observed using hydrodynamic cavitation in conjunction with UV/TiO₂/H₂O₂ under the optimised operating conditions. The diclofenac sodium degradation byproducts have been identified using LC/MS analysis.     

Wastewater treatment: a novel energy efficient hydrodynamic cavitational technique

A novel method of treating a dye solution has been studied by hydrodynamic cavitation using multiple hole orifice plates. The present work deals with the effect of geometry of the multiple hole orifice plates on the degradation of a cationic dye rhodamine B (rhB) solution. The efficiency of this technique has been compared with the cavitation generated by ultrasound and it has been found that there is substantial enhancement in the extent of degradation of this dye solution using hydrodynamic cavitation. Large-scale operation coupled with better energy efficiency makes this technique a viable alternative for conventional cavitational reactors.     

Degradation of imidacloprid using combined advanced oxidation processes based on hydrodynamic cavitation

The harmful effects of wastewaters containing pesticides or insecticides on human and aquatic life impart the need of effectively treating the wastewater streams containing these contaminants. In the present work, hydrodynamic cavitation reactors have been applied for the degradation of imidacloprid with process intensification studies based on different additives and combination with other similar processes. Effect of different operating parameters viz. concentration (20–60 ppm), pressure (1–8 bar), temperature (34 °C, 39 °C and 42 °C) and initial pH (2.5–8.3) has been investigated initially using orifice plate as cavitating device. It has been observed that 23.85% degradation of imidacloprid is obtained at optimized set of operating parameters. The efficacy of different process intensifying approaches based on the use of hydrogen peroxide (20–80 ppm), Fenton’s reagent (H₂O₂:FeSO₄ ratio as 1:1, 1:2, 2:1, 2:2, 4:1 and 4:2), advanced Fenton process (H₂O₂:Iron Powder ratio as 1:1, 2:1 and 4:1) and combination of Na₂S₂O₈ and FeSO₄ (FeSO₄:Na₂S₂O₈ ratio as 1:1, 1:2, 1:3 and 1:4) on the extent of degradation has been investigated. It was observed that near complete degradation of imidacloprid was achieved in all the cases at optimized values of process intensifying parameters. The time required for complete degradation of imidacloprid for approach based on hydrogen peroxide was 120 min where as for the Fenton and advance Fenton process, the required time was only 60 min. To check the effectiveness of hydrodynamic cavitation with different cavitating devices, few experiments were also performed with the help of slit venturi as a cavitating device at already optimized values of parameters. The present work has conclusively established that combined processes based on hydrodynamic cavitation can be effectively used for complete degradation of imidacloprid.     

Degradation of dichlorvos containing wastewaters using sonochemical reactors

The present work deals with application of sonochemical reactors for the degradation of dichlorvos containing wastewaters. The sonochemical reactor used in the work is a simple ultrasonic horn type operating at 20 kHz with a power rating of 270 W. The effect of different operating parameters such as operating pH, temperature and power density on the extent of degradation has been investigated initially followed by intensification studies using additives such as hydrogen peroxide, Fenton's reagent and CCl(4). It has been observed that low frequency sonochemical reactors can be effectively used for treatment of pesticide wastewaters and acidic conditions and optimum values of temperature and power dissipation favors the degradation of dichlorvos. The efficacy of sonochemical reactors can be further enhanced by using different additives at optimized loadings. Complete removal of the pesticide at the given loading has been obtained using an optimized combination of ultrasound and Fenton's chemistry. The controlling mechanism for the sonochemical degradation has been confirmed to be the free radical attack based on the studies involving radical scavengers. The novelty of the present work is clearly established as there have been no earlier studies dealing with degradation of dichlorvos pesticide using sonochemical reactors operating at low frequency which offers distinct advantage in terms of cost and the stability of the reactor.     

Effect of process intensifying parameters on the hydrodynamic cavitation based degradation of commercial pesticide (methomyl) in the aqueous solution

Methomyl, a carbamate pesticide, is classified as a pesticide of category-1 toxicity and hence shows harmful effects on both human and aquatic life. In the present work, the degradation of methomyl has been studied by using hydrodynamic cavitation reactor (HC) and its combination with intensifying agents such as H₂O₂, fenton reagent and ozone (hybrid processes). Initially, the optimization of operating parameters such pH and inlet pressure to the cavitating device (circular venturi) has been carried out for maximizing the efficacy of hydrodynamic cavitation. Further degradation study of methomyl by the application of hybrid processes was carried out at an optimal pH of 2.5 and the optimal inlet pressure of 5 bar. Significant synergetic effect has been observed in case of all the hybrid processes studied. Synergetic coefficient of 5.8, 13.41 and 47.6 has been obtained by combining hydrodynamic cavitation with H₂O₂, fenton process and ozone respectively. Efficacy of individual and hybrid processes has also been obtained in terms of energy efficiency and extent of mineralization. HC + Ozone process has proved to be the most effective process having highest synergetic coefficient, energy efficiency and the extent of mineralization. The study has also encompassed the identification of intermediate by-products generated during the degradation and has proposed the probable degradation pathway. It has been conclusively established that hydrodynamic cavitation in the presence of intensifying agents can effectively be used for complete degradation of methomyl.     

Mineralisation of 2,4-dichlorophenoxyacetic acid by acoustic or hydrodynamic cavitation in conjunction with the advanced Fenton process

The mineralisation of 2,4-dichlorophenoxyacetic acid (2,4-D) in the presence of zero-valent iron and hydrogen peroxide (the advanced Fenton process--AFP) whilst being subjected to acoustic or hydrodynamic cavitation is reported. If the reaction is merely stirred then there is 57% removal of TOC whilst on irradiation the figure is 64% although the latter reaction is more rapid. Use of ultrasound alone results in only 11% TOC removal in 60 min of treatment time. Addition of iron powder marginally enhances the extent of degradation but an appreciable increase is observed in the presence of hydrogen peroxide which acts as a source for hydroxyl radicals by Fenton chemistry as well as by dissociation in the presence of ultrasound. The use of hydrodynamic cavitation in conjunction with the advanced Fenton process has also been found to be a useful tool for continuous remediation of water contaminated with 2,4-D. After 20 min of treatment the residual TOC is reduced to 30% and this probably represents the remaining highly recalcitrant small organic molecules.     

Investigation of in-plane orientation characteristics for Bi-2212/MgO thin films fabricated by the MOD method

We investigated the characteristics of in-plane orientation for c-axis-oriented Bi-2212 thin films on MgO substrates, fabricated by the metal–organic decomposition (MOD) method. Bi-2212/MgO films were annealed using a 2-step heat treatment. The dominant rotation angle of the Bi-2212 film was 45° ([1 0 0] of Bi-2212 // [1 1 0] of MgO) for a precursor film fabricated at 500 °C and fired at 840 °C for 0 min or 30 min. However, after firing for 1 h the ?-scanning signal indicating the 45° angle became smaller and the signal representing an angle of about ±12° ([1 0 0] of Bi-2212 // [5 1 0] of MgO) became larger. After firing for 3 h, this ±12° signal became dominant. The extent of the 45° angle’s shift to ±12° increased with increasing firing time. On the other hand, when the precursor film was fabricated at 430 °C, signals indicating angles of 0°, ∼±12°, and 45° were observed after firing for 30 min. The rotation angle depended on the precursor-fabrication temperature when the precursor film was fired at 840 °C for 0 min or 30 min.     

Electrical- and magneto-resistance control for magnetite nanoparticle sinter by regulation of heat treatment temperature

We investigated electrical- and magneto-resistance control in magnetite (Fe₃O₄) nanoparticle sinter (MNPS) by the regulation of heat treatment (HT) temperature. MNPS was produced from hematite (α-Fe₂O₃) nanoparticles (HNP’s) using a deoxidization reaction. The average size of HNP was 30 nm, and HT was carried out between 400 and 800 °C. X-ray diffraction, magnetization, electrical resistivity (ER), and magneto-resistivity (MR) measurements were performed at temperatures ranging from 5 to 300 K. The ER and MR behaviors were considerably different at HT temperatures above and below ∼600 °C. After HT below ∼600 °C, ER followed the Mott-type variable-range-hopping conduction, and MR showed large values over a wide temperature range. After HT above ∼600 °C, ER indicated a Verwey transition near 110 K and MR showed small values, except in the vicinity of the Verwey transition temperature. Changing the HT temperature altered the coupling between adjacent magnetite nanoparticles (MNPs) and affected the crystallinity of MNPS. Below ∼600 °C, ER and MR were dominated by grain-boundary conduction, while above ∼600 °C they were determined by inter-grain conduction. The application of a magnetic field to the grain-boundary region, which had random localized spins, caused a large enhancement in MR.     

Thermodynamic and kinetic aspects on the selective surface oxidation of binary, ternary and quarternary model alloys

Segregation and selective oxidation phenomena of minor alloying elements during annealing of steel sheets lead to the formation of bare spots after hot dip galvanizing. In order to understand the influence of common alloying elements on the surface chemistry after annealing, model alloys of binary (Fe-2Si, Fe-2Mn and Fe-0.8Cr), ternary (Fe-2Mn-2Si, Fe-2Mn-0.8Cr and Fe-2Si-0.8Cr) and quarternary (Fe-2Mn-2Si-0.8Cr) systems were investigated. The specimens were annealed for 60 s at 820 °C in N₂-5% H₂ gas atmospheres with different dew points −80 and −40 °C, respectively. Surface chemistry of the annealed specimens was obtained by using X-ray photoelectron spectroscopy (XPS). The field emission scanning electron microscopy (FE-SEM) was used to view surface morphology. At low dew point −80 °C, apart from the thermodynamical calculations such as solubility product of oxides and their critical solute concentrations, kinetics play a decisive role on the selective oxidation, i.e. oxygen competition. As expected, the amount of external selective oxidation of alloying elements are well pronounced at higher dew point −40 °C. An attempt has been made to explain the dominant process of Si and Mn on Cr-oxidation and segregation. It is observed that annealing of quarternary system at higher dew point shifts the Cr-oxidation from external to internal.     

Analysis of temperature dependence for a ratiometric wavelength measurement system using SMS fiber structure based edge filters

Temperature dependence of an edge filter based on singlemode-multimode-singlemode (SMS) fiber structure is investigated numerically and experimentally. The experimental results and numerical results are in good agreement within an operational temperature range from 10 °C to 40 °C. It is found that the thermo-optic coefficient (TOC) has a more significant effect on the temperature dependence of an SMS edge filter compared to the thermal expansion coefficient (TEC). In the ratiometric wavelength measurement using two SMS edge filters, a small temperature variation can induce the ratio variation and in turn the wavelength measurement error. It is found the SMS edge filter’s response to both wavelength and temperature is linear. It is proposed that self-monitoring of temperature can be carried out using an updated ratiometric scheme. Self-monitoring of the temperature reduces temperature induced wavelength error to ±0.7 pm at 1545 nm, regardless of the ambient temperature variation.     

Degradation of benzene present in wastewater using hydrodynamic cavitation in combination with air

The degradation of benzene present in wastewater using hydrodynamic cavitation (HC) alone as well as in combination with air has been studied using nozzles as cavitating device of HC reactor. Initially, the energy efficiency of the HC reactor operated at different inlet pressures was determined using the calorimetric studies. Maximum energy efficiency of 53.4% was obtained at an inlet pressure of 3.9 bar. The treatment processes were compared under adiabatic as well as isothermal conditions and it was observed that under the adiabatic condition, the extent of degradation is higher as compared to isothermal condition. Studies related to the understanding the effect of inlet pressure (range of 1.8–3.9 bar) revealed that the maximum degradation as 98.9% was obtained at 2.4 bar pressure using the individual operation of HC under adiabatic conditions and in 70 min of treatment. The combination of HC with air was investigated at different air flow rates with best results for maximum degradation of benzene achieved at air flow rate of 60 mL/sec. A novel approach of using cavitation for a limited fraction of total treatment time was also demonstrated to be beneficial in terms of the extent of degradation as well as energy requirements and cost of operation. Based on the cavitational intensity, the resonant radius of aggregates of cavitation bubbles was also determined for distilled water as well as for aqueous solution of benzene. Overall, significant benefits of using HC combined with air have been demonstrated for degradation of benzene along with fundamental understanding into cavitation effects.     

Ni–Zn nanoferrite for radar-absorbing material

Nanoparticles of nickel–zinc ferrite have been prepared by using the citrate precursor method. According to scanning electron microscopy (SEM), the particle size is nanometric for the powder calcined at 350 °C/3.5 h. The phase formation has been studied by applying different calcining atmospheres, such as air and argon. Pure Ni–Zn ferrite has been observed when calcined in argon at the temperature of 350 °C. Hysteresis analyses have been done with magnetization of 53.01 emu/g at 350 °C and obtaining 84.62 emu/g at 1100 °C due to an optimization of domains formation at high temperature. Measures of reflectivity of Ni–Zn ferrite/epoxy composite have been obtained below 21% at 350 °C and above 96% at 1100 °C with a coercive field of 26.61 Oe. Low value of coercive field increased the mobilization of domains wall and increased the radiation absorption.     

Decolourization of Rhodamine B: A swirling jet-induced cavitation combined with NaOCl

A hydrodynamic cavitation reactor (Ecowirl) based on swirling jet-induced cavitation has been used in order to allow the degradation of a waste dye aqueous solution (Rhodamine B, RhB). Cavitation generated by Ecowirl reactor was directly compared with cavitation generated by using multiple hole orifice plates. The effects of operating conditions and parameters such as pressure, pH of dye solution, initial concentration of RhB and geometry of the cavitating devices on the degradation rate of RhB were discussed. In similar operative conditions, higher extents of degradation (ED) were obtained using Ecowirl reactor rather than orifice plate. An increase in the ED from 8.6% to 14.7% was observed moving from hole orifice plates to Ecowirl reactor. Intensification in ED of RhB by using hydrodynamic cavitation in presence of NaOCl as additive has been studied. It was found that the decolourization was most efficient for the combination of hydrodynamic cavitation and chemical oxidation as compared to chemical oxidation and hydrodynamic cavitation alone. The value of ED of 83.4% was reached in 37 min using Ecowirl combined with NaOCl (4.0 mg L⁻¹) as compared to the 100 min needed by only mixing NaOCl at the same concentration. At last, the energetic consumptions of the cavitation devices have been evaluated. Increasing the ED and reducing the treatment time, Ecowirl reactor resulted to be more energy efficient as compared to hole orifice plates, Venturi and other swirling jet-induced cavitation devices, as reported in literature.     

Degradation of 2,4-dinitrophenol using a combination of hydrodynamic cavitation,chemical and advanced oxidation processes

In the present work, degradation of 2,4-dinitrophenol (DNP), a persistent organic contaminant with high toxicity and very low biodegradability has been investigated using combination of hydrodynamic cavitation (HC) and chemical/advanced oxidation. The cavitating conditions have been generated using orifice plate as a cavitating device. Initially, the optimization of basic operating parameters have been done by performing experiments over varying inlet pressure (over the range of 3–6 bar), temperature (30 °C, 35 °C and 40 °C) and solution pH (over the range of 3–11). Subsequently, combined treatment strategies have been investigated for process intensification of the degradation process. The effect of HC combined with chemical oxidation processes such as hydrogen peroxide (HC/H₂O₂), ferrous activated persulfate (HC/Na₂S₂O₈/FeSO₄) and HC coupled with advanced oxidation processes such as conventional Fenton (HC/FeSO₄/H₂O₂), advanced Fenton (HC/Fe/H₂O₂) and Fenton-like process (HC/CuO/H₂O₂) on the extent of degradation of DNP have also been investigated at optimized conditions of pH 4, temperature of 35 °C and inlet pressure of 4 bar. Kinetic study revealed that degradation of DNP fitted first order kinetics for all the approaches under investigation. Complete degradation with maximum rate of DNP degradation has been observed for the combined HC/Fenton process. The energy consumption analysis for hydrodynamic cavitation based process has been done on the basis of cavitational yield. Degradation intermediates have also been identified and quantified in the current work. The synergistic index calculated for all the combined processes indicates HC/Fenton process is more feasible than the combination of HC with other Fenton like processes.     

Oscillation characteristics of a laser-induced cavitation bubble in water at different temperatures

Comprehensive numerical and experimental analyses of the effect of temperature on cavitation oscillations are performed. In the experimental study, the oscillation of a laser-generated single cavitation bubble near a rigid boundary is obtained using a fiber-optic diagnostic technique based on optical beam detection (OBD). The maximum and minimum bubble radii as well as the oscillation times for each oscillation cycle are determined according to the characteristic signals. And cavitation bubble tests are performed using water at different temperatures, and its temperature ranges from freezing point (0 °C) to near boiling. Furthermore, a modified Rayleigh-Plesset equation is derived for calculating the temporal development of the bubble radius at different temperatures. Both the experimental and the numerical results show that the maximum bubble radius and bubble lifetime both increase as temperature increases. The mechanism behind it has also been discussed.     

Evidence of formation of tetravacancies in uniformly oxygen irradiated n-type silicon

High purity n-type silicon single crystal with resistivity in the order of 4000 Ω cm has been irradiated with high-energy oxygen ions at room temperature up to a fluence of 5E15 ions/cm². The energy of the beam was varied from 3 to 140 MeV using a rotating degrader to achieve a depthwise near-uniform implantation profile. Radiation induced defects and their dynamics have been studied using positron annihilation spectroscopy along with isochronal annealing up to 700 °C in steps of 50 °C for 30 min. After annealing the sample at 200 °C for 30 min, formation of silicon tetravacancies has been noticed. The formation of the tetravacancies was found to be due to agglomeration of divacancies present in the irradiated sample. An experimentally obtained positron lifetime value of 338±10 ps has been reported for silicon tetravacancies, which has a very close agreement with the value obtained from recent theoretical calculations. The tetravacancies were found to dissociate into trivacancy clusters upon further annealing. The trivacancies thus obtained were observed to agglomerate beyond 400 °C to form larger defect clusters. Finally, all the defects were found to anneal out after annealing the sample at 650 °C.     

Annealing and surface conduction on Hydrogen peroxide treated bulk melt-grown,single crystal ZnO

We report on the studies carried out on hydrogen peroxide treated melt-grown, bulk single crystal ZnO samples. Results show the existence of two shallow donors in the as-received ZnO samples with energy levels (37.8±0.3) meV that has been suggested as Zn_i related and possibly H-complex related and (54.5±0.9) meV, which has been assigned to an Al-related donor. Annealing studies performed on the hydrogen peroxide treated samples reveal the existence of a conductive channel in the samples in which new energy levels have been observed, Zn vacancies, related to the Group I elements, X_Zn. The surface donor volume concentration of the conductive channel was calculated from a theory developed by Look (2007) [1]. Results indicate an increase in the surface volume concentration with increasing annealing temperature from 60×10¹⁷ cm⁻³ at 200 °C to 4.37×10¹⁸ cm^-3 at 800 °C.     

Influence of a controlled oxidation at moderate temperatures on the surface chemistry of nitinol wire

Commercial nitinol wire is oxidised at 480-530 °C/10 min in air. Surface morphology and chemistry is studied in detail using scanning electron microscopy, energy dispersive spectrometry, X-ray diffraction, Raman spectrometry and X-ray photoelectron spectroscopy. It is found that the main oxidation product at both temperatures is rutile containing a few at.% Ni. Beneath the rutile layer, there are titanium sub-oxides, showing characteristic maxima in depth profiles. Nickel in an oxidised state is present on the surface, whereas in a sub-surface region of scales, there is only metallic nickel. Thickness of the total oxide layers is 70 and 140 nm after oxidation at 480 and 530 °C, respectively. The preferential oxidation of titanium causes the formation of a Ni-enriched and Ti-depleted zone, suggesting the presence of Ni₃Ti phase. XRD reveals that the presence of cubic B2 NiTi phase in the base alloy is not affected by oxidation at 480-530 °C/10 min.     

Interaction of ultrasonic waves with domain walls on nanocrystalline YIG

The nanocrystalline YIG samples with different particle sizes (20–40 nm) has been prepared using microwave–hydrothermal method. As synthesized powders were characterized using XRD and TEM. The powders were pressed and sintered at three different temperatures i.e., 700 °C/30 min, 800 °C/30 min, 900 °C/30 min, using microwave furnace. The sintered samples were characterized using XRD and TEM. The sintered samples are monophasic in nature with average grain size ranging in between 72 nm and 90 nm. The thermal variation of ultrasonic velocities [longitudinal (V_l) and transverse (V_S)] and longitudinal attenuation (α_l) has been measured on sintered samples by the pulse transmissionmethod at 1 MHz, in the temperature range of 300–600 K. The room temperature velocity is found to be grain size dependent and decreases with increasing temperature, except near the Curie temperature, T_C, where a small anomaly is observed. The longitudinal attenuation (α₁) at room temperature is also found to be more sample dependent. The temperature variation of ultrasonic longitudinal attenuation exhibits a sharp maximum just below Curie temperature (T_C). The above observations were carried on in the demagnetized state, on the application of a saturation field of 380 mT, the anomaly observed in the thermal variation of velocities (longitudinal and transverse) and attenuation is found to disappears. The observed interaction of ultrasonic velocity with domain walls has been qualitatively explained with the help oftemperature variation of magneto-crystalline anisotropy constant (k₁) and Landau’s theory.