Sonochemical removal of trihalomethanes from aqueous solutions

In this research, ultrasound irradiation was employed to degrade the trihalomethanes, THMs: CHCl₃, CHBrCl₂, CHBr₂Cl, CHBr₃, and CHI₃. The kinetics reaction rates and removal efficiencies of the THMs compounds, as a sole component in the aqueous solutions, were studied. Batch experiments were conducted at an ultrasonic frequency of 20 kHz and acoustic intensity of 3.75 W/cm². The first-order degradation rate constants and the sonolysis efficiencies followed the decreasing order of CHCl₃ > CHBrCl₂ > CHBr₂Cl > CHBr₃ > CHI₃. Up to 100% of the CHCl₃ was removed, while only 60% of the CHI₃ was sonodegraded, after 180 min sonication. The THMs vapor pressure was found to be the most important parameter affecting the sonodegradation kinetics and efficiency, while the bond dissociation energy and hydrophilic/hydrophobic characteristics of the THMs compounds were found to be of secondary importance.     

Ultrasonic and viscometric studies of molecular interactions in binary mixtures of formamide with ethanol, 1-propanol, 1,2-ethanediol and 1,2-propanediol at different temperatures

The ultrasonic speeds, u and viscosities, η of binary mixtures of formamide (FA) with ethanol, 1-propanol, 1,2-ethanediol, and 1,2-propanediol, including those of pure liquids, over the entire composition range were measured at 293.15, 298.15, 303.15, 308.15, 313.15, and 318.15 K. From the experimental values of u and η, the deviations in isentropic compressibility, Δk_s, in ultrasonic speed, Δu, and in viscosity, Δη were calculated. The variation of these parameters with composition and temperature of the mixtures are discussed in terms of molecular interaction in these mixtures. The observed trends in Δk_s values indicate the presence of specific interactions between FA and alkanol molecules. The Δk_s values follow the order: ethanol < 1-propanol < 1,2-propanediol < 1,2-ethanediol. It is observed that the Δk_s values depend upon the number of hydroxyl groups and alkyl chain length in these alkanol molecules. Furthermore, the free energies, ΔG, enthalpies, ΔH and entropies, ΔS of activation of viscous flow have also been obtained by using Eyring viscosity equation and their dependence on composition of the mixtures have been discussed.     

Structural and optical properties of thermally evaporated Bi2Te3 films

Bi₂Te₃ films were prepared by thermal evaporation technique. X-ray diffraction analysis for as-deposited and annealed films in vacuum at 150 °C were polycrystalline with rhombohedral structure. The crystallite size is found to increase as the film thickness increases and has values in the range 67–162 nm. The optical constants (the refractive index, n, and absorption index, k) were determined using transmittance and reflectance data in the spectral range 2.5–10 μm for Bi₂Te₃ films with different thicknesses (25–99.5 nm). Both n and k are independent on the film thickness in the investigated range. It was also found that Bi₂Te₃ is a high refractive index material (n has values of 4.7–8.8 in the wavelength range 2.5–10 μm). The allowed optical transitions were found to be direct optical transitions with energy gap  eV. The optical conductivities σ₁ = ƒ(hν) and σ₂ = f(hν) show distinct peaks at about 0.13 and 0.3 eV, respectively. These two peaks can be attributed to optical interband transitions.     

Using low intensity ultrasound to improve the efficiency of biological phosphorus removal

Low intensity ultrasound can produce various effects on biological materials, such as stimulating enzyme activity, cell growth, biosynthesis, etc., which may improve the efficiency of enhanced biological phosphorus removal (EBPR). We adopt total phosphorus (TP) and dehydrogenase activity (DHA) as indicators to confirm the feasibility of applying low intensity ultrasound in EBPR. Single-factor experiments and orthogonal test were conducted in batch anaerobic/oxic (A/O) process simulation to study the influence of ultrasonic intensity and exposure time in the EBPR process. The results showed that the optimal ultrasonic parameters were 0.2 W/cm² and 10 min under which condition the TP concentration in the effluent was 35–50% lower than that of the control (without ultrasonic irradiation). Changes of sludge activities after ultrasonic irradiation were examined. The improvement of sludge activity by ultrasound took 4 h after irradiation to reach the peak level, when an increase above 50% of DHA has been achieved by ultrasonic irradiation, and the enhancing effects induced by ultrasound disappeared in 16 h after irradiation. A tentative mechanism of biological phosphorus removal enhancement stimulated by ultrasound was discussed based on these phenomena.     

Study on degradation of dimethoate solution in ultrasonic airlift loop reactor

In this work, the degradation of dimethoate solution in ultrasonic airlift loop reactor (UALR) assisted with advanced oxidation processes was studied. The effects of O₃ flow rate, ultrasonic intensity, pH value and reaction temperature on the degradation rate were investigated. UALR imposed a synergistic effect combining sonochemical merit with high O₃ transfer rate. Under the optimal operation conditions: ultrasonic irradiation time was 4 h, O₃ flow rate was 0.41 m³ h⁻¹, ultrasonic intensity was 4.64 W cm⁻², pH value was 10.0, reaction temperature was 25 °C, and initial concentration of dimethoate was 20 mg L⁻¹, degradation rate of dimethoate increased to 90.8%. The experimental results indicated that the method of UALR degradation of organic pollutants in the presence of gas could reduce reaction time and improve degradation rate. UALR was an advisable choice for treating organic waste waters and this device could be easily scale up. Thus this process has wide application prospect in industry.     

Sonochemical degradation of triclosan in water and wastewater

The sonochemical degradation of 5 μg l⁻¹ triclosan, a priority micro-pollutant, in various environmental samples (seawater, urban runoff and influent domestic wastewater) as well as in model solutions (pure and saline water) was investigated. Experiments were conducted with a horn-type sonicator operating at 80 kHz frequency and a nominal applied power of 135 W, while solid-phase microextraction coupled with gas chromatography–electron capture detector (SPME/GC–ECD) was employed to monitor triclosan degradation. The latter followed pseudo-first order kinetics with the rate constant being (min⁻¹): 0.2284 for seawater > 0.1051 for 3.5% NaCl in deionised water > 0.0597 for centrifuged urban runoff  0.0523 for untreated urban runoff > 0.0272 for deionised water > 0.0063 for wastewater influent. SPME/GC–ECD and SPME coupled with gas chromatography–mass spectrometry (SPME/GC–MS) were also used to check for the formation of chlorinated and other toxic by-products; at the conditions in question, the presence of such compounds was not confirmed.     

27Al NMR study in ZrNiAl

We have studied the microscopic properties of the hexagonal ZrNiAl, a model compound for a wide family of intermetallic compounds crystallizing in this type of structure, by using ²⁷Al NMR spectroscopy. We have investigated the lineshape of static and MAS NMR spectra as a function of magnetic field strength (4.7–9.4 T) and temperature (5–300 K). Our data indicate that the ²⁷Al NMR spectra result from a combined effect of quadrupole and anisotropic shift interactions. The ²⁷Al nuclei are in an environment characterized by the quadrupole coupling constant e²qQ/h of 3.3 MHz, asymmetry parameter η_Q of 0.42, isotropic shift δ_iso of 393 ppm, shift anisotropy δ_anis = δ_zz − (δ_xx + δ_yy)/2 of 150 ppm, and asymmetry factor η_S of 0.5. They are found to be temperature independent. The spin–lattice relaxation rate measured at 7.05 T is proportional to the temperature with T₁T = 135 s K. The mechanisms responsible for observed values of δ_iso, δ_anis, T₁T, and the enhanced Korringa constant are discussed.     

Sonolytic degradation of hazardous organic compounds in aqueous solution

Benzene, chlorobenzene, 1,2-, 1,3-, 1,4-dichlorobenzene, biphenyl, and polychlorinated biphenyls such as 2-, 4-chlorobiphenyl and 2,2′-dichlorobiphenyl in aqueous solutions have been subjected to sonolysis with 200 kHz ultrasound at an intensity of 6 W cm⁻² under an argon atmosphere. 80–90% of initial amount of these compounds were degraded by 30–60 min of sonication when the initial concentrations were 10–100 μmol l⁻¹. The degradation rate of these compounds increased with increase in their vapor pressures. In all cases of sonolysis of chlorinated organic compounds, an appreciable amount of liberated chloride ion was observed.     

Radiative and non radiative spectroscopic properties of Er ion in tellurite glass

We have investigated in detail the mechanism of infrared emission and upconversion emission of Er³⁺ in tellurite glass as a function of the dopant concentration. Both the infrared and upconversion emissions are competing processes and the efficiency of infrared emission at 1534 nm is 100% at the lowest Er content (0.5 mol%) and reduces to 50% at higher dopant concentration (>2 mol%). The green upconversion emission at 548 nm is mainly due to the excited state absorption (ESA) from ⁴I_11/2, which populate the ⁴F_7/2 level. In addition to this, the possible energy transfer (ET) through Er³⁺(⁴I_11/2) + Er³⁺(⁴I_11/2) → Er³⁺(⁴F_7/2) + Er³⁺(⁴I_15/2) can also results in the green emission as is noticed from the concentration dependent efficiency change of the green emission. The fluorescence quenching of green emission with Er concentration may be related with the cross relaxation (CR) process ²H_11/2 + ⁴I_15/2 → ⁴I_9/2 + ⁴I_13/2. The red emission is due to the combined effect of the ESA from level ⁴I_13/2 to ⁴F_9/2, the energy transfer process described by Er³⁺(⁴I_13/2) + Er³⁺(⁴I_11/2) → Er³⁺(⁴F_9/2) + Er³⁺(⁴I_15/2) and the cross relaxation process.     

Comparison of enhancement of pentachlorophenol sonolysis at 20 kHz by dual-frequency sonication

The comparison of enhancement effect of pentachlorophenol sonolysis at 20 kHz by different dual-frequency ultrasonic irradiations has been investigated. Dual-frequency (20 kHz/40 kHz, 20 kHz/530 kHz, 20 kHz/800 kHz and 20 kHz/1040 kHz) ultrasounds have been used. It has been found that the rate of pentachlorophenol degradation at dual-frequency ultrasonic irradiation is the highest compared to mono-frequency ultrasonic systems. The combination of dual-frequency systems has synergistic effect and the enhancement effect of sonochemical degradation of pentachlorophenol at 20 kHz by dual-frequency systems appears to be remarkable frequency sensitive. The order of contribution to the enhancement effect of sonochemical degradation of pentachlorophenol at 20 kHz is as follows: 530 kHz > 800 kHz > 40 kHz > 1040 kHz.     

Excess molar heat capacity of isobutyric acid–water binary liquid mixtures near and far away from the critical temperature

The heat capacity of the liquid–liquid mixture isobutyric acid–water has been measured for the first time near and far away from its critical point using an adiabatic calorimeter. The measurements were performed at atmospheric pressure, in the one phase region as a function of three temperatures: (1) T − T_C = 0.055 °C, (2) T − T_C = 3.055 °C, (3) T − T_C = 8.055 °C and of the composition X in acid (IA). The heat capacity C_p decreases rapidly when X increases at the used temperatures. Near the critical composition, C_p is not affected by the correlation of the concentration fluctuations.

The molar excess heat capacity of the system under investigation was analysed along the phase diagram and considered as a structural transformation effect.     

Superconductivity and pseudogap states studied by microwave conductivity measurements of λ-(BEDT-TSF)2GaCl4

We have investigated the microwave response at 45 GHz in an organic superconductor λ-(BEDT-TSF)₂GaCl₄ with T_c = 4.8 K. We determine the μ₀H_c2–T phase diagram from microwave loss and find that the superconducting state is in the pure limit (l/ξ_GL  10). Although the real part of the complex conductivity (=σ₁ + iσ₂) does not show a coherence peak just below T_c, the London penetration depth completely saturates at low temperatures down to T/T_c = 0.2, which may provide an evidence for a conventional s-wave pairing. In the metallic state below about 50 K, (parallel to the c-axis) deviates downward from , while σ₂, which should be zero in a conventional metal, increases exponentially toward T_c. In spite of the fact that the Hagen–Rubens limit is well satisfied as far as the dc conductivity is concerned, a Drude model is unable to explain the large positive σ₂. In order to explain such anomalies in the metallic state, we propose a possible existence of so-called a pseudogap near a Fermi level. The anomalous increase of the positive σ₂ may be attributed to an appearance of pre-formed electron pairs in the pseudogap state. This appearance can be regarded as a precursor to the superconducting transition. Such a precursory phenomenon has been observed also in the isostructural FeCl₄ salt with the anomalous metallic states, which shows a negative σ₂ in contrast to the GaCl₄ salt. Just the opposite of ground states in between the GaCl₄ and FeCl₄ salts may result in the contrasting anomalous metallic states with different precursory phenomena with opposite signs of σ₂.     

27Al NMR study in UNiAl

The ternary compound UNiAl exhibiting an antiferromagnetic order below T_N = 19.3 K has been studied in the paramagnetic state using the ²⁷Al NMR technique and different magnetically oriented samples. The quadrupole coupling constant e²qQ/h = 1.56 MHz is temperature independent. The dominant, longitudinal component of the Knight shift with respect to the hexagonal c axis, K, is positive and increases upon lowering the temperature down to 50 K. Much smaller in magnitude, the transverse component, K_±, is also positive and only slightly temperature dependent. The plots of the Knight shift vs magnetic susceptibility K(χ) and K_±(χ_±) form the same line, which implies that the transferred hyperfine field of 9.2 kOe/μB for ²⁷Al nuclei should be considered isotropic.     

Gas Cotton-Mouton constant measurement by extrapolation in dissolved binary liquid solutions

The magneto-optic Cotton-Mouton effect constant C, light refraction index n and density ρ of binary solutions of toluene in carbon tetrachloride, -picoline and β-picoline in 1,4-dioxane have been measured at different concentrations. The results have been used for the calculation of the molar C^M constants of the solutions. By extrapolating the values C^M = C^M(f₂) for the concentration f₂ → 0, the constant _∞C₂^M = _gasC₂^M of the dipolar component of the solution has been found, which is interpreted as the Cotton-Mouton gas constant. For all solutions, the reduction factors of the dissolved component have been calculated and their linear dependence on the solution concentration has been found.     

The beneficial influence of ultrasound in the polymerization of epsilon-caprolactam to polyamide-6 (Nylon 6). Part II: additional experiment to understand the "pre-sonication effect"

Ultrasound (US) “pre-sonication effect” is the beneficial effect of US in the hydrolytic polymerization of ε-caprolactam (CL) mixtures with very low water concentrations (about 0.1–1 wt%). It appears after a mild initial treatment of the mixtures with US [17.5–20 kHz, short times (5–15 min), low temperatures (70–110 °C)] followed by heating at 220–260 °C. An explanation is proposed on the basis of the formation in mild conditions (100 °C) of low concentrations of cyclic oligomers never detected in the literature at those conditions. These, under US irradiation, produce linear amino acid oligomers, which are strong activators of polymerization when the mixture of CL and water, after US irradiation, is heated at the suitable polymerization temperature indicated above.     

Gas source MBE grown wavelength extended 2.2 and 2.5 μm InGaAs PIN photodetectors

Using homo-junction structure and relative thin linear graded In_xGa_1−xAs as the buffer layer, extended wavelength InGaAs PIN photodetectors with cut-off wavelength of 2.2 and 2.5 μm at room temperature have been grown by using GSMBE, and their performance over a wide temperature range have been extensively investigated. For those 2.2 or 2.5 μm detectors with 100 μm diameter, the typical dark current (V_R = 10 mV) and R₀A are 57 nA/10.3 Ω cm² or 67 nA/12.7 Ω cm² at 290 K, and 84 pA/4.70 kΩ cm² or 161 pA/3.12 kΩ cm² at 210 K respectively. The thermal activation energies of the dark current are 0.447 eV or 0.404 eV for 2.2 or 2.5 μm detectors respectively.     

Crosstalk between two-photon and two-color (two-photon) excitation in optical beam induced current generation with two confocal excitation beams

We analyze the influence of residual two-photon excitation (2PE) in two-color (two-photon) optical beam induced current (2CE-OBIC) generation in wide band gap semiconductor samples. 2CE-OBIC generation is accomplished with two confocal excitation beams of separation angle θ and wavelengths λ₁ and λ₂ where , λ_e = hc/E_b, h is the Planck’s constant, c is speed of light in vacuum, and E_b is the energy band gap. Because the conduction band of the sample is a continuum, at least one excitation beam would also contribute an undesirable 2PE-OBIC signal that degrades the signal-to-noise ratio of the measured 2CE-OBIC response and broadens the effective OBIC distribution in the sample particularly when θ ≠ 0 or π. We show that the deleterious effects of crosstalk are reduced by a careful selection of λ₁ and λ₂ and the relative excitation beam intensities. λ₁ and λ₂ should be chosen to minimize the ratio of the two-photon absorption coefficients (β₁, β₂) to the 2CE absorption coefficient β₁₂ or at least satisfy the constraint: β₁ + β₂  β₁₂. Keeping the two excitation intensities equal is beneficial only when β₁ = β₂. Otherwise, it is advantageous to bias the intensity ratio towards the wavelength with a lower 2PE absorption coefficient.     

Population lensing effect in Cr:LiSAF probed by Z-scan technique

An experiment has been performed for measuring a nonlinear refractive index that is due to the polarizability difference Δ_P between excited (⁴T₂) and ground (⁴A₂) states in a Cr³⁺:LiSAF crystal at λ = 647 nm. The latter one is responsible for a population lensing effect which has been monitored by using the eclipsing Z-scan technique. We have performed a data analysis that allows to distinguish between thermal and population contributions to the lensing effect. We have found Δ_P = 4.6 × 10⁻²⁵ cm³ which is in a good agreement with our previous measurements with a different technique.     

On the origin of 1.5 μm luminescence in porous silicon coated with sol–gel derived erbium-doped Fe2O3 films

Sol–gel derived Fe₂O₃ films containing about 10 wt% of Er₂O₃ were deposited on porous silicon by dipping or by a spin-on technique followed by thermal processing at 1073 K for 15 min. The samples were characterized by means of PL, SEM and X-ray diffraction analyses. They exhibit strong room-temperature luminescence at 1.5 μm related to erbium in the sol–gel derived host. The luminescence intensity increases by a factor of 1000 when the samples are cooled from 300 to 4.2 K. After complete removal of the erbium-doped film by etching and partial etching the porous silicon, the erbium-related luminescence disappears. Following this, luminescence at 1.5 μm originating from optically active dislocations (“D-lines”) in porous silicon was detected. The influence of the conditions of synthesis on luminescence at 1.5 μm is discussed.