A facile synthesis of nanosheet-structured barium carbonate spheres with a superior adsorption capacity for Cr(VI) removal

A feasible strategy is demonstrated here for low-cost and rapid synthesis of nanosheet-structured BaCO₃ spheres (NSBCs) on a large scale. Experiments reveal that NSBCs were developed from amorphous precursor under the mediation of phosphate. Their nanosheet-composed structures facilitate the rapid removal of contaminant of Cr(VI) within 60 min from aqueous solution, showing an excellent adsorption capacity (q _m,cal = 227 mg/g, T = 298 K). The kinetic and isotherm processes confirmed well to the pseudo-second-order model and Langmuir adsorption model, respectively. Thermodynamic analysis indicated that the adsorption process was spontaneous and endothermic. NSBCs show better Cr(VI) removal behaviour compared with commercial and some synthetic barium carbonate, which may have potential application in water treatment.     

Removal of copper(II) and chromium(VI) from aqueous solution using sorghum roots (<Emphasis Type="Italic">S. bicolor</Emphasis>): a kinetic and thermodynamic study

Biosorption of toxic metal ions from industrial effluents using different plant parts is an important branch of environmental chemistry. Biosorption of copper(II) and chromium(VI) ions from aqueous solution onto sorghum root (SR) powder have been investigated under batch mode. The optimum pH and temperature for biosorption of both the metals was found to be 2 and 20 °C, respectively. The maximum biosorption capacity q _e for Cu(II) and Cr(VI) is 18.6 and 18.39 mg/g, respectively. The Langmuir model gave a better fit than other two models. The kinetic studies indicated that the biosorption process of the metal ions followed well pseudo-second-order model. The thermodynamic parameters were also calculated and the values indicated that the biosorption process was exothermic, spontaneous, and feasible in nature. Desorption experiments with 1 M HCl and 1 M HNO₃ inferred the reusability of biomass. The results showed that SRs have excellent adsorption properties and thus can be used as an effective and low cost biosorbent for the removal of Cu(II) and Cr(VI) ions from aqueous solution.     

Sorption of Mo(VI) on zirconium molybdosilicate gel and potential application as a <Superscript>99</Superscript>Mo/<Superscript>99<Emphasis Type="Italic">m</Emphasis> </Superscript>Tc generator

Sorption of Mo(VI) from aqueous nitrate solutions onto zirconium molybdosilicate (ZrMoSi) gel was studied using ⁹⁹Mo radiotracer. The acid–base titration curve showed that the prepared ZrMoSi gel was an amphoteric material with the point of zero charge (PZC) at pH 2.5. The highest distribution coefficient (600 mL g^–1) of ⁹⁹Mo(VI) on ZrMoSi from nitrate media was achieved at pH 2.1. The sorption kinetics of ⁹⁹Mo(VI) onto ZrMoSi obeyed the pseudo-second-order model. The breakthrough sorption capacity of ZrMoSi gel was found to be 4.25 × 10^–2 [mmol Mo(VI)] g^–1. The prepared ⁹⁹Mo/^99mTc chromatographic column generator showed a good performance: The ^99mTc elution yield was 87.7%, pH of the eluate ranged from 5.6 to 7.2, and the radionuclidic purity of the eluted ^99mTc was >99.99% with a radiochemical purity of 98.31% (as ^99mTcO₄^–).     

Oscillating cylinder in viscous fluid: calculation of flow patterns and forces

Laminar and large-eddy-simulation (LES) calculations with the dynamic Smagorinsky model evaluate the flow and force on an oscillating cylinder of diameter D = 2R in otherwise calm fluid, for β = D ²/νT in the range 197–61400 and Keulegan–Carpenter number K = U _m T/D in the range 0.5–8 (ν kinematic viscosity, T oscillation period, U _m maximal velocity). Calculations resolving the streakline patterns of the Honji instability exemplify the local flow structures in the cylinder boundary layer (β ~ 197–300, K ~ 2) but show that the drag and inertia force are not affected by the instability. The present force calculations conform with the classical Stokes–Wang solution for all cases below flow separation corresponding to K < 2 (with β < 61400). The LES calculations of flow separation and vortical flow resolve the flow physics containing a large range of motion scales; it is shown that the energy in the temporal turbulent fluctuations (in fixed points) are resolved. Accurate calculation of the flow separation occurring for K > 2 has strong implication for the force on the cylinder. Present calculations of the force coefficients for K up to 4 and β = 11240 are in agreement with experiments by Otter (Appl Ocean Res 12:153–155, 1990). Drag coeffients when flow separation occurs are smaller than found in U-tube experiments. Inertia coefficients show strong decline for large K (up to 8) and moderate β = 1035 but is close to unity for K = 4 and β = 11240. The finest grid has 2.2 × 10⁶ cells, finest radial Δr/R = 0.0002, number of points along the cylinder circumference of 180, Δz/R = 0.044 and a time step of 0.0005T.     

Heavy metal removal from simulated wastewater using electrochemical technology: optimization of copper electrodeposition in a membraneless fluidized bed electrode

Heavy metal removal from industrial wastewaters has been intensively studied, since it is well known that they can cause severe problems to human health and aquatic life, even at very low concentrations. In this work, it was demonstrated that electrodeposition in fluidized bed electrode (FBE) can be efficiently employed to remove metal ions from solution, avoid contamination, and recover the metal. Copper electrodeposition from diluted solutions was efficiently performed using a membraneless FBE. The average current efficiency (ACE), average energy consumption (AEC), and space–time yield (AY) was optimized taking into account the operational and process variables. It was noted that for all response variables studied, the raise of supporting electrolyte concentration (C _s) contributed to improvements in the process. The operational conditions current (I) and bed expansion (E) determined the values of CE, Y, and EC under activated control, but the initial copper concentration (C ₀) determined how long the electrodeposition process will work under activated or mass transfer control, thus affecting the average values of CE, Y, and EC. Considering C ₀ of 500 mg L^?1, copper can be optimally recovered with ACE >60 %, AY >38 kg h^?1 m^?3, and AEC <4.0 kWh kg^?1 by applying the lowest I and the highest levels of E and C _s. It was concluded that the electrochemical technology using a membraneless FBE reactor is economically competitive and be applied for the treatment of wastewaters contaminated with copper or other metals.     

Very high thermal stability with excellent dielectric,and non-ohmics properties of Mg-doped CaCu<Subscript>3</Subscript>Ti<Subscript>4.2</Subscript>O<Subscript>12</Subscript> ceramics

In this work, the nominal CaCu_3?xMg_xTi_4.2O₁₂ (0.00, 0.05 and 0.10) ceramics were prepared by sintering pellets of their precursor powders obtained by a polymer pyrolysis solution method at 1100 °C for different sintering time of 8 and 12 h. Very low loss tangent (tanδ)?<?0.009–0.014 and giant dielectric constant (ε′) ～?1.1?×?10⁴–1.8?×?10⁴ with excellent temperature coefficient (Δε′) less than ±?15% in a temperature range of ??60 to 210 °C were achieved. These excellent performances suggested a potent application of the ceramics for high temperature X8R and X9R capacitors. It was found that tanδ values decreased with increasing Mg²⁺ dopants due to the increase of grain boundary resistance (R_gb) caused by the very high density of grain, resulting from the substitution of small ionic radius Mg²⁺ dopants in the structure. In addition, CaCu_3?xMg_xTi_4.2O₁₂ ceramics displayed non-linear characteristics with the significant enhancements of a non-linear coefficient (α) and a breakdown field (E_b) due to Mg²⁺doping. The high values of ε′ (14012), α (13.64) and E_b (5977.02 V/cm) with very low tanδ value (0.009) were obtained in a CaCu_2.90Mg_0.10Ti_4.2O₁₂ ceramic sintered at 1100 °C for 8 h.     

Transport of <Emphasis Type="Italic">E. coli</Emphasis> in saturated and unsaturated porous media: effect of physiological state and substrate availability

Saturated and unsaturated sand and soil column experiments were conducted to study the complex interaction between the effects of biological and hydrological factors on the transport of bacteria through a porous medium. These experiments were conducted with continuous input of bacteria and substrate at the inlet to reflect the groundwater contamination caused by leaking septic tanks and leach pits. Experiments were conducted with metabolically active and inactive Escherichia coli. Cell surface characteristics and batch experimental data for bacterial attachment were correlated with the transport behaviour in continuous column studies. Normalized breakthrough concentration for metabolically inactive cells (C/C ₀ = 0.74 in sand) was higher than that for active cells (C/C ₀ = 0.68 in sand) owing to change in cell surface characteristics. A similar trend was observed in the case of transport through soil columns. There was an increase of 29.5% in the peak C/C ₀ value at the outlet when the flow velocity was increased from 0.0535 cm/h (C/C ₀ = 0.61) to 0.214 cm/h (C/C ₀ = 0.79) in case of sand columns. However, this difference was only 20% in case of soil columns. Peak normalized concentrations at the outlet were less in soil column as compared to those in sand column because of lesser grain size. Unlike the earlier studies with pulse input, present experiments with continuous input of metabolically active bacteria along with substrate indicated that the normalized concentration at the outlet increased with increased concentration at the inlet. It was found that unsaturated conditions led to more retention of bacteria in both sand and soil columns. In case of sand columns, the normalized concentration at the exit reduced to as much as 0.46. It was also found that the existing mathematical models based on macroscopic advection–dispersion–filtration equations could satisfactorily simulate the bacterial transport except in a case where the substrate was added to the bacteria in the column studies.     

Effect of Tb<Superscript>3+</Superscript> ion substitution on structural,optical and magnetic properties of CdS nanoparticles

Cd_1?xTb_xS (x?=?0.00, 0.05, 0.10, 0.15) nanoparticles were synthesized by hydrothermal technique. The effect of Tb-doping on structural, optical and magnetic properties were studied. The X-ray diffraction (XRD) confirmed wurtzite phase without any impurity. HR-TEM micrographs revealed the particle size of ~?18 nm with spherical morphology. Band gap calculated from UV–Visible absorption spectra showed an initial decrease from 2.49 eV (x?=?0) to 2.45 eV (x?=?0.10). Further, increasing Tb-doping to x?=?0.15 band gap increased to 2.54 eV. Photoluminescence emission spectra showed peaks at 430 and 490 nm for x?=?0 and 0.05 which corresponds to blue emission. Further increase in Tb doping, peaks found to be quenched. Peak at 530 nm is due to green emission and shifted to higher wavelength with Tb-doping. Magnetic analysis confirmed ferromagnetism in both undoped and Tb-doped nanoparticles. Saturation magnetization found to decrease upto x?=?0.10 and increased for x?=?0.15.     

Influence of coronene addition on some superconducting properties of bulk MgB<Subscript>2</Subscript>

This study reports the effect of coronene (C₂₄H₁₂) addition on some superconducting properties such as critical temperature (T_c), critical current density (J_c), flux pinning force density (F_p), irreversibility field (H_irr), upper critical magnetic field (H_c2), and activation energy (U₀), of bulk MgB₂ superconductor by means of magnetisation and magnetoresistivity measurements. Disk-shaped polycrystalline MgB₂ samples with varying C₂₄H₁₂ contents of 0, 2, 4, 6, 8, 10 wt%, were produced at 850 °C in Ar atmosphere. The obtained results show an increase in field-J_c values at 10 and 20 K resulting from the strengthened flux pinning, and a decrease in critical temperature (T_c) because of C substitution into MgB₂ lattice, with increasing amount of C₂₄H₁₂ powder. The H_c2(0) and H_irr(0) values are respectively found as 144, 181, 172 kOe, and 128, 161, 145 kOe for pure, 4 wt% and 10 wt% C₂₄H₁₂ added samples. The U₀ depending on the magnetic field curves were plotted using thermally activated flux flow model. The maximum U₀ values are respectively obtained as 0.20, 0.23 and 0.12 eV at 30 kOe for pure, 4 wt% and 10 wt% C₂₄H₁₂ added samples. As a result, the superconducting properties of bulk MgB₂ at high fields was improved using C₂₄H₁₂, active carbon source addition, because of the presence of uniformly dispersed C particles with nanometer order of magnitude, and acting as effective pinning centres in MgB₂ structure.     

Effect of sintering temperature on microstructures and microwave dielectric properties of Ba<Subscript>2</Subscript>MgWO<Subscript>6</Subscript> ceramics

The microwave dielectric properties of Ba₂MgWO₆ ceramics were investigated with a view to the use of such ceramics in mobile communication. Ba₂MgWO₆ ceramics were prepared using the conventional solid-state method with various sintering temperatures. Dielectric constants (? _r ) of 16.8–18.2 and unloaded quality factor (Q _u  × f) of 7000–118,200 GHz were obtained at sintering temperatures in the range 1450–1650 °C for 2 h. A maximum apparent density of 6.76 g/cm³ was obtained for Ba₂MgWO₆ ceramic, sintered at 1650 °C for 2 h. A dielectric constant (? _r ) of 18.4, an unloaded quality factor (Q _u  × f) of 118,200 GHz, and a temperature coefficient of resonant frequency (τ _f ) of ?34 ppm/°C were obtained when Ba₂MgWO₆ ceramics were sintered at 1650 °C for 2 h.     

Synthesis,structure, and properties of the non-centrosymmetric borate Rb<Subscript>2</Subscript>CaB<Subscript>8</Subscript>O<Subscript>26</Subscript>H<Subscript>24</Subscript>

Single crystals of Rb₂CaB₈O₂₆H₂₄, a new non-centrosymmetric borate material, have been grown with sizes up to 8 × 5 × 3 mm³ by the slow evaporation of water solution at room temperature. The structure of the compound was determined by single-crystal X-ray diffraction. It crystallizes in the orthorhombic system, space group P2₁2₁2₁ with a = 11.5288(3) Å, b = 12.6334(4) Å, c = 16.6966(4) Å, Z = 4 and R ₁ = 0.0405, wR ₂ = 0.1043. Ultraviolet (UV)–vis spectrum transmission is performed on the Rb₂CaB₈O₂₆H₂₄, which shows an absorption edge about 195 nm in the UV region. Thermal properties were investigated by TG–DSC analysis. The powder second-harmonic generation (SHG) intensity measured by the Kurtz-Perry method indicates that Rb₂CaB₈O₂₆H₂₄ has about one-third of KDP (KH₂PO₄).The influence of different molar ratios and evaporation speed of water solution on crystal quality and size was also performed on the reported material.     

Structure and electrical properties of MnO doped (Ba<Subscript>0.96</Subscript>Ca<Subscript>0.04</Subscript>)(Ti<Subscript>0.92</Subscript>Sn<Subscript>0.08</Subscript>)O<Subscript>3</Subscript> lead free ceramics

In this work, (Ba_0.96Ca_0.04)(Ti_0.92Sn_0.08)O₃–xmol MnO (BCTS–xMn) lead-free piezoelectric ceramics were fabricated by the conventional solid-state technique. The composition dependence (0 ≤ x ≤ 3.0 %) of the microstructure, phase structure, and electrical properties was systematically investigated. An O–T phase structure was obtained in all ceramics, and the sintering behavior of the BCTS ceramics was gradually improved by doping MnO content. In addition, the relationship between poling temperature and piezoelectric activity was discussed. The ceramics with x = 1.5 % sintering at temperature of 1330 °C demonstrated an optimum electrical behavior: d ₃₃ ~ 475 pC/N, k _p ~ 50 %, ε _r ~ 4060, tanδ ~ 0.4 %, P _r ~ 10.3 μC/cm², E _c ~ 1.35 kV/mm, T _C ~ 82 °C, strain ~0.114 % and \(d_{33}^{*}\) ~ 525 pm/V. As a result, we achieved a preferable electric performance in BaTiO₃-based ceramics with lower sintering temperature, suggesting that the BCTS–xMn material system is a promising candidate for lead-free piezoelectric ceramics.     

Strong up-conversion luminescence and electrical properties of SrBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> multifunctional ceramics by Er<Superscript>3+</Superscript> doping

Novel green-emitting piezoelectric ceramics of SrBi_4?x Er _x Ti₄O₁₅ (SBT-xEr) were prepared. Strong up-conversion with bright green (524 and 548 nm) and a relatively weak red (660 nm) emission bands were obtained under 980 nm excitation at room temperature, which is attributed to the intra 4f–4f electronic transition of (²H_11/2, ⁴S_3/2)–⁴I_15/2 and the transition from ⁴F_9/2 to ⁴I_15/2 of Er³⁺ ions, respectively. Simultaneously, Er³⁺ doping promotes the electrical properties. At 0.8 mol%Er, the optimal electric properties with high Curie temperature of T _c?~527?°C, large remanent polarization of 2P _r?~14.92 μC/cm² and piezoelectric constant of d ₃₃?~17 pC/N was achieved. As a multifunctional material, Er³⁺ doped SBT showed a great potential to be used in 3D-display, bio-imaging, solid state laser and optical temperature sensor.     

Low temperature sintering and microwave dielectric properties of Zn<Subscript>3</Subscript>Mo<Subscript>2</Subscript>O<Subscript>9</Subscript> ceramic

Crystal structure and dielectric properties of Zn₃Mo₂O₉ ceramics prepared through a conventional solid-state reaction method were characterized. XRD and Raman analysis revealed that the Zn₃Mo₂O₉ crystallized in a monoclinic crystal structure and reminded stable up to1020 °C. Dense ceramics with high relative density (~ 92.3%) were obtained when sintered at 1000 °C and possessed good microwave dielectric properties with a relative permittivity (ε _r ) of 8.7, a quality factor (Q?×?f) of 23,400 GHz, and a negative temperature coefficient of resonance frequency (τ _f ) of around ??79 ppm/°C. With 5 wt% B₂O₃ addition, the sintering temperature of Zn₃Mo₂O₉ ceramic was successfully lowered to 900 °C and microwave dielectric properties with ε _r ?=?11.8, Q?×?f?=?20,000 GHz, and τ _f = ??79.5 ppm/°C were achieved.     

Crystal structure,microstructure and microwave dielectric properties of novel MgAl<Subscript>2</Subscript>Ti<Subscript>3</Subscript>O<Subscript>10</Subscript> ceramic

In the present work, a novel MgAl₂Ti₃O₁₀ ceramic was obtained using a traditional solid-state reaction method. X-ray diffraction and energy dispersive spectrometer showed that the main MgAl₂Ti₃O₁₀ phase was formed after sintered at 1300–1450 °C. With rising the sintering temperature from 1300 to 1450 °C, the bulk density (ρ), relative permittivity (ε _r ) and Q?×?f value firstly increased, reached the maximum values (3.61 g/cm³, 14.9, and 26,450 GHz) and then decreased. The temperature coefficient of resonator frequency (τ _f ) showed a slight change at a negative range of ??94.6 to ??83.7 ppm/°C. When the sintering temperature was 1400 °C, MgAl₂Ti₃O₁₀ ceramics exhibited the best microwave dielectric properties with Q?×?f?=?26,450 GHz, ε _r ?=?14.9 and τ _f ?=???83.7 ppm/°C.     

Synthesis of urea-modified MnFe<Subscript>2</Subscript>O<Subscript>4</Subscript> for aromatic micro-pollutants adsorption from wastewater: Mechanism and modeling

Amine-terminated MnFe₂O₄, using urea solution (UMF-MNPs) fabricated by a combined ultrasonic/microwave technique, was characterized and applied as a magnetic adsorbent to remove catechol, phenol, and benzene micro-pollutants from wastewater solutions. The simultaneous effect of solution pH, TDS, micro-pollutants concentrations, UMF-MNPs dose, and temperature was investigated and optimized using D-optimal design in a batch experiment. The quadratic regression, as the best-structured simulated model, predicted the maximum adsorption rates at pH 6.0, TDS 1855 mg/l, UMF-MNPs dose of 0.73 g/l, and temperature 320 K for 50 mg/l micro-pollutant concentrations. Kinetic and isotherm models, through linear and nonlinear regression methods, reflected an excellent correlation (R ² ≈ 0.83 to 1) to simulate the adsorption data. The column breakthrough curves were tested using the equivalent length of the unused bed approach, which well fitted the Thomas model equation. The film diffusion, consequently with Lewis acid–base, is the major rate-controlling adsorption mechanism, and recovered by alkali ethanolic solution.     

Magnetic,magnetocaloric properties,and critical behavior in a layered perovskite La<Subscript>1.4</Subscript>(Sr<Subscript>0.95</Subscript>Ca<Subscript>0.05</Subscript>)<Subscript>1.6</Subscript>Mn<Subscript>2</Subscript>O<Subscript>7</Subscript>

We report the results of magnetic, magnetocaloric properties, and critical behavior investigation of the double-layered perovskite manganite La_1.4(Sr_0.95Ca_0.05)_1.6Mn₂O₇. The compounds exhibits a paramagnetic (PM) to ferromagnetic (FM) transition at the Curie temperature T _C = 248 K, a Neel transition at T _N = 180 K, and a spin glass behavior below 150 K. To probe the magnetic interactions responsible for the magnetic transitions, we performed a critical exponent analysis in the vicinity of the FM–PM transition range. Magnetic entropy change (??S _M) was estimated from isothermal magnetization data. The critical exponents β and γ, determined by analyzing the Arrott plots, are found to be T _C = 248 K, β = 0.594, γ = 1.048, and δ = 2.764. These values for the critical exponents are close to the mean-field values. In order to estimate the spontaneous magnetization M _S(T) at a given temperature, we use a process based on the analysis, in the mean-field theory, of the magnetic entropy change (??S _M) versus the magnetization data. An excellent agreement is found between the spontaneous magnetization determined from the entropy change [(??S _M) vs. M ²] and the classical extrapolation from the Arrott curves (µ₀H/M vs. M ²), thus confirming that the magnetic entropy is a valid approach to estimate the spontaneous magnetization in this system and in other compounds as well.     

Fluctuation induced conductivity of polycrystalline MgB<Subscript>2</Subscript> superconductor

We report fluctuation-induced conductivity (FIC) of the polycrystalline MgB₂ superconductor in the presence of magnetic field. The results are described in terms of the temperature derivative of the resistivity, dρ/dT. The dρ/dT peak temperature observed for H = 0 Tesla at 39 K remains very distinct under applied fields of 6 Tesla and 8 Tesla at 22 and 20 K respectively. Aslamazov and Larkin (AL) equations are used to explain the anisotropic nature of the polycrystalline MgB₂. The effective coherence length, ξ _p (0) determined experimentally is 55.17 Å, which roughly matches with previously reported experimental work.     

Magnetization reversal and tunable exchange bias behavior in Mn-substituted NiCr<Subscript>2</Subscript>O<Subscript>4</Subscript>

Single phase samples of Ni(Cr_1?xMn _x )₂O₄ (x = 0–0.50) were synthesized by using sol–gel route. Investigation of structural, magnetic, exchange bias and magnetization reversal properties was carried out in the bulk samples of Ni(Cr_1?xMn _x )₂O₄. Rietveld refinement of the X-ray diffraction patterns recorded at room temperature reveals the tetragonal structure for x = 0 sample with I4₁/amd space group and cubic structure for x ≥ 0.05 samples with \( {\text{Fd}\bar{3}\text{m}} \) space group. Magnetization measurements show that all samples exhibit ferrimagnetic behavior, and the transition temperature (T_C) is found to increase from 73 K for x = 0 to 138 K for x = 0.50. Mn substitution induces magnetization reversal behavior especially for 30 at% of Mn in NiCr₂O₄ system with a magnetic compensation temperature of 45 K. This magnetization reversal is explained in terms of different site occupation of Mn ions and the different temperature dependence of the magnetic moments of different sublattices. Study of exchange bias behavior in x = 0.10 and 0.30 samples reveals that they exhibit negative and tunable positive and negative exchange bias behavior, respectively. The magnitudes of maximum exchange bias field of these samples are found to be 640 and 5306 Oe, respectively. Exchange bias in x = 0.10 sample originates from the anisotropic exchange interaction between the ferrimagnetic and the antiferromagnetic components of magnetic moment. The tunable exchange bias behavior in x = 0.30 sample is explained in terms of change in domination of one sublattice moment over the other as the temperature is varied.