Study on the optically linear birefringence and dichroism properties of Fe3O4 magnetic nanoparticles

We adopt an improved co-precipitation method to prepare the Fe₃O₄ magnetic nanoparticles (MNPs). Influence factors such as the reaction temperature, the pH value of the solution, and the Fe³⁺/Fe²⁺ molar concentration are considered. Via the transmission electronic microscope and X-ray diffractometry, we characterize the dispersibility and size of the products. The reaction temperature and the pH value of the solution have a great influence in the dispersibility and size of MNPs. The diameter of Fe₃O₄ MNP, produced under Fe³⁺/Fe²⁺ molar concentration of 0.25 mole/l and molar ratio of 1.9:1, the reaction temperature is 80 °C, and the pH value reaches 9, is close to 11 nm. Above all, considering the variation of molar concentrations in Fe³⁺/Fe²⁺, the linear birefringence and dichroism of the kerosene-based ferrofluids are investigated by a Stokes polarimeter.     

Sono-enhanced degradation of dye pollutants with the use of H2O2 activated by Fe3O4 magnetic nanoparticles as peroxidase mimetic

Sono-enhanced degradation of a dye pollutant Rhodamine B (RhB) was investigated by using H₂O₂ as a green oxidant and Fe₃O₄ magnetic nanoparticles (MNPs) as a peroxidase mimetic. It was found that Fe₃O₄ MNPs could catalyze the break of H₂O₂ to remove RhB in a wide pH range from 3.0 to 9.0 and its peroxidase-like activity was significantly enhanced by the ultrasound irradiation. At pH 5.0 and temperature 55 °C, the ultrasound-assisted H₂O₂–Fe₃O₄ catalysis removed about 95% of RhB (0.02 mmol L⁻¹) in 15 min with a apparent rate constant of 0.15 min⁻¹ for the degradation of RhB, being 6.5 and 37.6 folds of that in the simple catalytic H₂O₂–Fe₃O₄ system, and the simple ultrasonic US-H₂O₂ systems, respectively. The beneficial synergistic behavior between Fe₃O₄ catalysis and ultrasonic was demonstrated to be dependent on Fe₃O₄ dosage, H₂O₂ concentration, pH value and temperature. As a tentative explanation, the observed significant synergistic effects was attributed to the positive interaction between cavitation effect accelerating the catalytic breakdown of H₂O₂ over Fe₃O₄ nanoparticles, and the function of Fe₃O₄ MNPs providing more nucleation sites for the cavitation inception.     

Sonochemical fabrication of Fe3O4 nanoparticles on reduced graphene oxide for biosensors

This study synthesized Fe₃O₄ nanoparticles of 30–40 nm by a sonochemical method, and these particles were uniformly dispersed on the reduced graphene oxide sheets (Fe₃O₄/RGO). The superparamagnetic property of Fe₃O₄/RGO was evidenced from a saturated magnetization of 30 emu/g tested by a sample-vibrating magnetometer. Based on the testing results, we proposed a mechanism of ultrasonic waves to explain the formation and dispersion of Fe₃O₄ nanoparticles on RGO. A biosensor was fabricated by modifying a glassy carbon electrode with the combination of Fe₃O₄/RGO and hemoglobin. The biosensor showed an excellent electrocatalytic reduction toward H₂O₂ at a wide, linear range from 4 × 10^?6 to 1 × 10^?3 M (R² = 0.994) as examined by amperometry, and with a detection limit of 2 × 10^?6 M. The high performance of H₂O₂ detection is attributed to the synergistic effect of the combination of Fe₃O₄ nanoparticles and RGO, promoting the electron transfer between the peroxide and electrode surface.     

Conductivity of SnP2O7 and In-doped SnP2O7 prepared by an aqueous solution method

SnP₂O₇ and In-doped SnP₂O₇ have been prepared by an aqueous solution method using (NH₄)₂HPO₄ as phosphorous source. It was found that the solid solution limit in Sn_1 ? xIn_x(P₂O₇)_1 ? δ was at least x = 0.12. All pyrophosphates in the Sn_1 ? xIn_x(P₂O₇)_1 ? δ (x ≤ 0.12) series exhibit 3 × 3 × 3 superlattice structures. The conductivities of Sn_0.92In_0.08(P₂O₇)_1 ? δ in air are 6.5 × 10^? 6 and 8.0 × 10^? 9 S/cm at 900 and 400 °C, respectively, when prepared by an aqueous solution method and annealed at 1000 °C. The conductivity of undoped SnP₂O₇ is slightly lower. However, it was also found that the low-temperature conductivities of pyrophosphates annealed only at 650 °C are several orders of magnitude higher than those annealed at 1000 °C, which could be related to a trace amount of an amorphous secondary phase. The peak conductivity was in this case observed at around 250 °C, which is the same temperature as previously observed in In-doped SnP₂O₇ although the conductivity is still three orders of magnitude lower in the present study. These differences can be related to large differences in particle size and morphology, and all in all, the conductivities of SnP₂O₇-based materials are very sensitive to the synthetic history.     

Oxygen diffusion studies on (Y2O3)2(Sc2O3)9(ZrO2)89

The oxygen tracer diffusion coefficient (D?) has been measured for 9 mol% scandia 2 mol% yttria co-doped zirconia solid solution, (Y₂O₃)₂(Sc₂O₃)₉(ZrO₂)₈₉, using isotopic exchange and line scanning by Secondary Ion Mass Spectrometry, as a function of temperature. The values of the tracer diffusion coefficient are in the range of 10^? 8–10^? 7 cm² s^? 1 and the Arrhenius activation energy was calculated to be 0.9 eV; both valid in the temperature range of 600–900 °C. Electrical conductivity measurements were carried out using 2-probe and 4-probe AC impedance spectroscopy, and a 4-point DC method at various temperatures. There is a good agreement between the measured tracer diffusion coefficients (D?, Ea = 0.9 eV) and the diffusion coefficients calculated from the DC total conductivity data (D_σ, Ea = 1.0 eV), the latter calculated using the Nernst–Einstein relationship.     

Effect of Sr2+-doping on structure and luminescence properties of BaAl2Si2O8:Eu2+ phosphors

Sr²⁺ doped BaAl₂Si₂O₈:Eu²⁺ phosphor was synthesized by chemical co-precipitation method. With the increase of Sr²⁺ concentration, the phase structure of (Ba_0.965 ? xSr_xEu_0.035)Al₂Si₂O₈ changes from hexagonal phase to monoclinic phase owing to large activation energy in SrAl₂Si₂O₈ system. (Ba_0.965 ? xSr_xEu_0.035)Al₂Si₂O₈ phosphor exhibits a broad blue band peaking at 425 nm due to the 4f⁶5d–4f⁷(⁸S_7/2) transition of Eu²⁺ ions. The emission intensity increases, accompanied by the blue shift of emission maximum from 459 to 417 nm with the Sr²⁺ doping concentration increasing. The optimal concentration of Sr²⁺ ion is 40%, and the phosphor shows high color stability in CIE chromaticity diagram. The result indicates that Sr²⁺ doped phosphor not only can enhance the relative intensity but also can adjust the chromaticity coordinate.     

On the rate constants of OH + HO2 and HO2 + HO2: A comprehensive study of H2O2 thermal decomposition using multi-species laser absorption

Hydrogen peroxide (H₂O₂) and hydroperoxy (HO₂) reactions present in the H₂O₂ thermal decomposition system are important in combustion kinetics. H₂O₂ thermal decomposition has been studied behind reflected shock waves using H₂O and OH diagnostics in previous studies (Hong et al. (2009) [9] and Hong et al. (2010) [6,8]) to determine the rate constants of two major reactions: H₂O₂ + M → 2OH + M (k₁) and OH + H₂O₂ → H₂O + HO₂ (k₂). With the addition of a third diagnostic for HO₂ at 227 nm, the H₂O₂ thermal decomposition system can be comprehensively characterized for the first time. Specifically, the rate constants of two remaining major reactions in the system, OH + HO₂ → H₂O + O₂ (k₃) and HO₂ + HO₂ → H₂O₂ + O₂ (k₄) can be determined with high-fidelity.No strong temperature dependency was found between 1072 and 1283 K for the rate constant of OH + HO₂ → H₂O + O₂, which can be expressed by the combination of two Arrhenius forms: k₃ = 7.0 × 10¹² exp(550/T) + 4.5 × 10¹⁴ exp(?5500/T) [cm³ mol^?1 s^?1]. The rate constants of reaction HO₂ + HO₂ → H₂O₂ + O₂ determined agree very well with those reported by Kappel et al. (2002) [5]; the recommendation therefore remains unchanged: k₄ = 1.0 × 10¹⁴ exp(?5556/T) + 1.9 × 10¹¹⁺exp(709/T) [cm³ mol^?1 s^?1]. All the tests were performed near 1.7 atm.     

Polymorphic phase transition and thermal stability in squaric acid (H2C4O4)

Phase transformations in squaric acid (H₂C₄O₄) have been investigated by thermogravimetry and differential scanning calorimetry with different heating rates β. The mass loss in TG apparently begins at onset temperatures T_di=245±5 °C (β=5 °C min^?1), 262±5 °C (β=10 °C min^?1), and 275±5 °C (β=20 °C min^?1). A polymorphic phase transition was recognized as a weak endothermic peak in DSC around 101 °C (T_c⁺). Further heating with β=10 °C min^?1 in DSC revealed deviation of the baseline around 310 °C (T_i), and a large unusual exothermic peak around 355 °C (T_p), which are interpreted as an onset and a peak temperature of thermal decomposition, respectively. The activation energy of the thermal decomposition was obtained by employing relevant models. Thermal decomposition was recognized as a carbonization process, resulting in amorphous carbon.     

Enhanced sonocatalytic degradation of organic dyes from aqueous solutions by novel synthesis of mesoporous Fe3O4-graphene/ZnO@SiO2 nanocomposites

Fe₃O₄-graphene/ZnO@mesoporous-SiO₂ (MGZ@SiO₂) nanocomposites was synthesized via a simple one pot hydrothermal method. The as-obtained samples were investigated using various techniques, as follows: scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and specific surface area (BET) vibrating sample magnetometer (VSM), among others. The sonocatalytic activities of the catalysts were tested according to the oxidation for the removal of methylene blue (MB), methyl orange (MO), and rhodamine B (RhB) under ultrasonic irradiation. The optimal conditions including the irradiation time, pH, dye concentration, catalyst dosage, and ultrasonic intensity are 60 min, 11, 50 mg/L, 1.00 g/L, and 40 W/m², respectively. The MGZ@SiO₂ showed the higher enhanced sonocatalytic degradation from among the three dyes; furthermore, the sonocatalytic-degradation mechanism is discussed. This study shows that the MGZ@SiO₂ can be applied as a novel-design catalyst for the removal of organic pollutants from aqueous solutions.     

Ultrasound assisted co-precipitation synthesis and catalytic performance of mesoporous nanocrystalline NiO-Al2O3 powders

Mesoporous nanocrystalline NiO-Al₂O₃ powders with high surface area were synthesized via ultrasound assisted co-precipitation method and the potential of the selected samples as catalyst was investigated in dry reforming reaction for preparation of synthesis gas. The prepared samples were characterized by N₂ adsorption (BET), X-ray diffraction (XRD), Temperature programmed reduction and oxidation (TPR, TPO) and scanning electron microscopy (SEM) techniques. The effects of pH, power of ultrasound irradiation, aging time and calcination temperature on the textural properties of the catalysts were studied. The sample prepared under specified conditions (pH10, 70 W, without aging time and calcined at 600 °C) exhibited the highest surface area (249.7 m² g⁻¹). This catalyst was calcined at different temperature and employed in dry reforming of methane and the catalytic results were compared with those obtained over the catalysts prepared by impregnation and co-precipitation methods. The results showed that the catalyst prepared by ultrasound assisted co-precipitation method exhibited higher activity and stability with lower degree of carbon formation compared to catalysts prepared by co-precipitation and impregnation methods.     

Electrical conductivity and thermal expansion of the oxy-cuspidine Gd4Al2O9 substituted with Ca and Sr

The series of Gd_4 ? xM_xAl₂O_9 ? x/2 (M = Ca, Sr) with x = 0, 0.01, 0.05, 0.10 and 0.25 was prepared by the citrate complexation method. Both Gd_4 ? xCa_xAl₂O_9 ? x/2 and Gd_4 ? xSr_xAl₂O_9 ? x/2 show the monoclinic cuspidine structure with space group of P2₁/c up to 0.05–0.1 and 0.01–0.05 mol for Ca and Sr, respectively. Beyond the substitution limit of Gd₄Al₂O₉, GdAlO₃ and SrGd₂Al₂O₇ appear as additional phases. The highest electrical conductivity obtained at 900 °C yielded σ = 1.49 × 10^? 4 S/cm for Gd_3.95Ca_0.05Al₂O_8.98. In comparison, the conductivity of pure Gd₄Al₂O₉ was σ = 1.73 × 10^? 5 S/cm. The conductivities determined are in a similar range as those of other cuspidine materials investigated previously. The thermal expansion coefficient of Gd₄Al₂O₉ at 1000 °C was 7.4 × 10^? 6 K^? 1. The phase transition between 1100 and 1200 °C reported earlier changes with increasing substitution of Ca and Sr.     

Antiferromagnetic phase transition in garnet-type AgCa2Mn2V3O12 and NaPb2Mn2V3O12

Ferrimagnetism has been extensively studied in garnets, whereas it is rare to find the antiferromagnet. Present work will demonstrate antiferromagnetism in the two Mn–V-garnets. Antiferromagnetic phase transition in AgCa₂Mn₂V₃O₁₂ and NaPb₂Mn₂V₃O₁₂ has been found, where the magnetic Mn²⁺ ions locate only on octahedral A site. The heat capacity shows sharp peak due to antiferromagnetic order with the Néel temperature T_N=23.8 K for AgCa₂Mn₂V₃O₁₂ and T_N=14.2 K for NaPb₂Mn₂V₃O₁₂. The magnetic entropy change over a temperature range 0–50 K is 13.9 J K^?1 mol-Mn²⁺-ions^?1 for AgCa₂Mn₂V₃O₁₂ and 13.6 J K^?1 mol-Mn²⁺-ions^?1 for NaPb₂Mn₂V₃O₁₂, which are in good agreement with calculated value of Mn²⁺ ion with spin S=5/2. The magnetic susceptibility shows the Curie–Weiss behavior over the range 29–350 K. The effective magnetic moment μ_eff and the Weiss constant θ are μ_eff=6.20 μ_B Mn²⁺-ion^?1 and θ=?34.1 K (antiferromagnetic sign) for AgCa₂Mn₂V₃O₁₂ and μ_eff=6.02 μ_B Mn²⁺-ion^?1 and θ=?20.8 K for NaPb₂Mn₂V₃O₁₂.     

Synthesis and crystallographic studies of garnet-related lithium-ion conductors Li6CaLa2Ta2O12 and Li6BaLa2Ta2O12

High-purity specimens of Li₆CaLa₂Ta₂O₁₂ and Li₆BaLa₂Ta₂O₁₂ have been successfully synthesized by solid-state reactions. The analytical chemical compositions of these samples were in good agreement with the nominal compositions of Li₆CaLa₂Ta₂O₁₂ and Li₆BaLa₂Ta₂O₁₂. The Rietveld refinements verified that these compounds have the garnet-type framework structure with the lattice constants of a = 12.725(2) Å for Li₆CaLa₂Ta₂O₁₂ and a = 13.001(4) Å for Li₆BaLa₂Ta₂O₁₂. All of the diffraction peaks of X-ray powder diffraction patterns were well indexed on the basis of cubic symmetry with space group Ia-3d. To make a search for Li sites, the electron density distributions were precisely examined by using the maximum entropy method. Li⁺ ions occupy partially two types of crystallographic site in these compounds: (i) tetrahedral 24d sites, and (ii) distorted octahedral 96h sites, the latter of which are the vacant sites of the ideal garnet-type structure. The present Li₆CaLa₂Ta₂O₁₂ and Li₆BaLa₂Ta₂O₁₂ samples exhibit the conductivity σ = 2.2 × 10^? 6 S cm^? 1 at 27 °C (E_a = 0.50 eV) and σ = 1.3 × 10^? 5 S cm^? 1 at 25 °C (E_a = 0.44 eV), respectively.     

Ce0.8Sm0.2O1.9 synthesis for solid oxide fuel cell electrolyte by ultrasound assisted co-precipitation method

In this study, the synthesis of Ce_0.8Sm_0.2O_1.9 (SDC) solid electrolyte by the ultrasound assisted co-precipitation method was accomplished to explore the effects of ultrasound power, ultrasound pulse ratio and probe type upon the ionic conductivity of SDC as well as the lattice parameter, the microstructure and the density. Fine powders of uniform crystallite sizes (average 11.70 ± 0.62 nm) were obtained, needing lower sintering temperature. The SDC powders were successfully sintered to a relative density of over 95% at 1200 °C (5 °C min^?1) for 6 h. The micrograph of SDC pellets showed non-agglomerated and well-developed grains with average size of about 200 nm. X-ray diffraction analysis showed that the lattice parameter increased with increasing acoustic intensity and reached a maximum for the 14.94 W cm^?2. Further, a linear relationship was detected between the lattice parameter and the ionic conductivity, inspiring a dopant like effect of US on the electrolyte properties. The highest ionic conductivity as σ_800°C = 3.07 × 10^?2 S cm^?1 with an activation energy E_a = 0.871 kJ mol^?1 was obtained with pulsed ultrasound for an acoustic intensity of 14.94 W cm^?2, using 19 mm probe and 8:2 pulse ratio.     

Conductivity and oxygen permeability of a novel oxide Pr2Ni0.8 − x Cu0.2FexO4 and its application to partial oxidation of CH4

Iron-doped Pr₂Ni_0.8Cu_0.2O₄ was studied as a new mixed electronic and oxide-ionic conductor for use as an oxygen-permeating membrane. An X-ray diffraction analysis suggested that a single phase K₂NiF₄-type structure was obtained in the composition range from x = 0 to 0.05 in Pr₂Ni_0.8 − xCu_0.2Fe_xO₄. It is considered that the doped Fe is partially substituted at the Ni position in Pr₂NiO₄. The prepared Pr₂NiO₄-based oxide exhibited a dominant hole conduction in the P_O2 range from 1 to 10^− 21 atm. The electrical conductivity of Pr₂Ni_0.8−xCu_0.2Fe_xO₄ is as high as 10² S cm^− 1 in the temperature range of 873–1223 K and it gradually decreased with the increasing amount of Fe substituted for Ni. The oxygen permeation rate was significantly enhanced by the Fe doping and it was found that the highest oxygen permeation rate (60 μmol min^− 1 cm^− 2) from air to He was achieved for x = 0.05 in Pr₂Ni_0.8 − xCu_0.2Fe_xO₄. Since the chemical stability of the Pr₂NiO₄-based oxide is high, Pr₂Ni_0.75Cu_0.2Fe_0.05O₄ can be used as the oxygen-separating membrane for the partial oxidation of CH₄. It was observed that the oxygen permeation rate was significantly improved by changing from He to CH₄ and the observed permeation rate reached a value of 225 μmol min^− 1 cm^− 2 at 1273 K for the CH₄ partial oxidation.     

Sonochemical assisted synthesis of SrFe12O19 nanoparticles

We present the synthesis of M-type strontium hexaferrite by sonochemistry and annealing. The effects of the sonication time and thermal energy on the crystal structure and magnetic properties of the obtained powders are presented. Strontium hexagonal ferrite (SrFe₁₂O₁₉) was successfully prepared by the ultrasonic cavitation (sonochemistry) of a complexed polyol solution of metallic acetates and diethylene glycol. The obtained materials were subsequently annealed at temperatures from 300 to 900 °C. X-ray diffraction analysis shows that the sonochemical process yields an amorphous phase containing Fe³⁺, Fe²⁺ and Sr²⁺ ions. This amorphous phase transforms into an intermediate phase of maghemite (γ-Fe₂O₃) at 300 °C. At 500 °C, the intermediate species is converted to hematite (α-Fe₂O₃) by a topotactic transition. The final product of strontium hexaferrite (SrFe₁₂O₁₉) is generated at 800 °C. The obtained strontium hexaferrite shows a magnetization of 62.3 emu/g, which is consistent with pure hexaferrite obtained by other methods, and a coercivity of 6.25 kOe, which is higher than expected for this hexaferrite. The powder morphology is composed of aggregates of rounded particles with an average particle size of 60 nm.     

High-pressure dielectric studies of a novel hydrogen-bonded ferroelectric (NH4)2H2P2O6

The hydrostatic pressure effect on the dielectric properties of (NH₄)₂H₂P₂O₆ ferroelectric crystal was studied for pressures from 0.1 MPa to 360 MPa and for temperatures from 100 to 190 K. The pressure–temperature phase diagram obtained is linear with increasing pressure. The paraelectric–ferroelectric phase transition temperature decreases with increasing pressure with the pressure coefficient dT_c/dp=?5.16×10^?2 K MPa^?1. Additionally, the pressure dependences of Curie–Weiss constants for the crystal in paraelectric (C₊) and ferroelectric (C_?) phases are evaluated and discussed. The possible mechanism of paraelectric–ferroelectric phase transition is also discussed.     

A time-resolved luminescence spectroscopy study of non-linear optical crystals K2Al2B2O7

We report the results of complex study of luminescence and dynamics of electronic excitations in K₂Al₂B₂O₇ (KABO) crystals obtained using low-temperature luminescence-optical vacuum ultraviolet spectroscopy with sub-nanosecond time resolution under selective photoexcitation with synchrotron radiation. The paper discusses the decay kinetics of photoluminescence (PL), the time-resolved PL emission spectra (1.2–6.2 eV), the time-resolved PL excitation spectra and the reflection spectra (3.7–21 eV) measured at 7 K. On the basis of the obtained results three absorption peaks at 4.7, 5.8 and 6.5 eV were detected and assigned to charge-transfer absorption from O^2? to Fe³⁺ ions; the intrinsic PL band at 3.28 eV was revealed and attributed to radiative annihilation of self-trapped excitons, the defect luminescence bands at 2.68 and 3.54 eV were separated; the strong PL band at 1.72 eV was revealed and attributed to a radiative transition in Fe³⁺ ion.     

Effect of Fe doping on the room temperature ferromagnetism in chemically synthesized (In1−xFex)2O3 (0 ⩽ x ⩽ 0.07) magnetic semiconductors

Observation of room temperature ferromagnetism in Fe doped In₂O₃ samples (In_1−xFe_x)₂O₃ (0 ⩽ x ⩽ 0.07) prepared by co-precipitation technique is reported. Lattice parameter obtained from powder X software shows distinct shrinkage of the lattice constant indicating an actual incorporation of Fe ions into the In₂O₃ lattice. X-ray diffraction data measurements show that the entire sample exhibits single phase polycrystalline behavior. SEM micrographs showed the prepared powder was in the range 25–36 nm. SEM EDS mapping showed the presence of Fe and In ions in the Fe doped In₂O₃ sample. The highest remanence magnetization moment (6.624 × 10⁻⁴ emu/g) is reached in the sample with x = 0.03.     

High surface area monodispersed Fe3O4 nanoparticles alone and on physical exfoliated graphite for improved supercapacitors

Highly conductive, unsophisticated and easy to be obtained physical exfoliated graphite (PHG) supporting well dispersed magnetite, Fe₃O₄/PHG nanocomposite, has been prepared by a one-step chemical strategy and physico-chemical characterized. The nanocomposite, favoured by the a-polar nanoparticles (NPs) capping, results in a self-assembled monolayer of monodispersed Fe₃O₄, covering perfectly the hydrophobic surfaces of PHG. The nanocomposite as an electrode material was fabricated into a supercapacitor and characterized by cyclic voltammetry (CV) and galvanostatic charge–discharge measurements. It shows, after a suitable annealing, significant electrochemical properties (capacitance value of 787 F/g at 0.5 A g⁻¹ and a Fe₃O₄/PHG weight ratio of 0.31) and good cycling stability (retention 91% after 30,000 cycles). Highly monodispersed very fine Fe₃O₄ NPs, covered by organic chains, have been also synthesized. The high surface area Fe₃O₄ NPs, after washing to leave a low content of organic chains able to avoid aggregation without excessively affecting the electrical properties of the material, exhibit remarkable pseudocapacitive activities, including the highest specific capacitance over reported for Fe₃O₄ (300 F/g at 0.5 A g⁻¹).