Local structure and water cleaning ability of iron oxide nanoparticles prepared by hydro-thermal reaction

Nanoparticles (NPs) of Fe₃O₄ and γFe₂O₃ synthesized by hydrothermal reaction were characterized by X-ray diffractometry (XRD), ⁵⁷Fe-Mössbauer spectroscopy and field emission scanning electron microscopy (FE-SEM). A decrease in concentration of methylene blue (MB) aqueous solution due to bulk Fe⁰-NP γFe₂O₃ mixture with the mass ratio of 3:7 was measured by ultraviolet-visible light absorption spectroscopy (UV-Vis). The Mössbauer spectrum of NP Fe₃O₄ prepared from hydrothermal reaction was composed of two sextets with absorption area (A), isomer shift (δ) and internal magnetic field (H _int) of 56.3 %, 0.34_±0.03 mm s^???1 and 49.0_±0.30 T for tetrahedral (T _d) Fe^III, and 43.7 %, 0.66_±0.11 mm s^???1 and 44.0_±0.71 T for octahedral (O _h) Fe^II?+?III. The Fe^II/Fe^III ratio was determined to be 0.280 for NP Fe₃O₄, giving ‘x’ of 0.124 in Fe_3???xO_4. These results show that NP Fe₃O₄ prepared by hydrothermal reaction was not regular but nonstoichiometric Fe₃O₄. Consistent results were observed for XRD patterns of NP Fe_3???xO₄ indicating sharp intense peaks at 2Θ of 30.2, 35.7 and 43.3° with a large linewidth of 0.44°, yielding the crystallite size of 29–37 nm from the Scherrer’s equation. Iso-thermal annealing of NP Fe_3???xO₄ at 250 °C for 30 min resulted in the precipitation of NP γFe₂O₃ with δ of 0.33_±0.03 mm s^???1 and H _intof 46.4_±0.27 T due to magnetic tetrahedral Fe^III. The Debye temperature of NP Fe_3???xO₄ was respectively estimated to be 267_±5.45 K for Fe $^{\mathrm{III}}(T_{\mathrm{d}})$ and 282_±7.17 K for Fe $^{\mathrm{II+III}}(O_{\mathrm{h}})$ , both of which were smaller than that obtained for bulk Fe₃O₄ of 280_±4.15 K and 307_±5.70 K, indicating that the chemical environment of iron of NPs is less rigid than that of the bulk compounds. A leaching test using methylene blue (MB) and mixture of bulk Fe⁰-NP γFe₂O₃ (3:7) showed a remarkable decrease in MB concentration from 1.90 × 10^???2 to 9.49 × 10^???4 mM for 24 h with the first order rate constant (k _MB) of 2.1 × 10^???3 min^???1. This result verifies that MB decomposing ability is enhanced by using NP γFe₂O₃ compared with the k _MB of 1.1 × 10^???4 min^???1 previously obtained from the leaching test using MB and bulk mixture of Fe⁰???γFe₂O₃ (3:7).     

Electrical conductivity and local structure of lithium iron tungsten vanadate glass

A relationship between physical properties and local structure of 20Li₂O·10Fe₂O₃·xWO₃·(70–x)V₂O₅ glass, abbreviated as xLFWV glass (x?=?0???25 in mol%), was investigated by ⁵⁷Fe-Mössbauer spectroscopy, Fourier transform infrared spectroscopy (FT-IR), differential thermal analysis (DTA), leaching test using 20 vol% HCl and DC two- or four-probe method. ⁵⁷Fe-Mössbauer spectra of xLFWV glass showed an increase of quadrupole splitting (Δ) from 0.67 to 0.73_±0.02 mm s^???1 and a constant isomer shift (δ) of 0.39_±0.01 mm s^???1 with an increase of ‘x’ from 0 to 25. This suggests that Fe^IIIO₄ tetrahedra gradually increase their local distortion along with a substitution of WO₃ for V₂O₅. DTA of xLFWV glass showed an increase in glass transition temperature (T _g) from 252 to 298 $_{\pm 5}^{\circ}$ C with an increase of ‘x’. Composition dependency of T _g and Δ indicates that Fe^III atoms occupy substitutional sites of WO₆ octahedra as network former (NWF), since a large slope of 680 K (mm s^???1)^???1 was obtained in T _g ? Δ plot. Comparable electrical conductivities (σ) of 2.5 × 10^???6, 1.9 × 10^???6, 8.4 × 10^???7 and 2.9 × 10^???6 S cm^???1 obtained for xLFWV glasses with ‘x’ of 0, 10, 20 and 25, respectively increased to 2.4 × 10^???2, 2.4 × 10^???3, 3.5 × 10^???4 and 8.8 × 10^???5 S cm^???1 after annealing at 400 °C for 100 min. Smaller Δ values of 0.58 and 0.67_±0.02 mm s^???1 obtained in annealed xLFWV glasses with ‘x’ of 0 and 10, respectively indicate that structural relaxation occurs in VO₄ units of vanadate glass units, as had been observed in other vanadate glasses.     

Electrical conductivity and local structure of lithium tin iron vanadate glass

A relationship between electrical conductivity (σ) and local structure of 15Li₂O·10Fe₂O₃·xSnO₂·(70–x)V₂O₅·5P₂O₅ glass (x = 0–20 mol%), abbreviated as xLFSVP glass, was investigated by ⁵⁷Fe- and ¹¹⁹Sn-Mössbauer spectroscopies, differential thermal analysis (DTA) and dc-four probe method. A small increase in quadrupole splitting (Δ) for Fe^III was observed from 0.70 to 0.74_{± 0.02} mm s^???1 with an increase of “x”, whereas isomer shift (Δ) values of 0.40_±0.01 mm s^???1 were independent of “x”. This result suggests that local distortion of Fe^IIIO₄ tetrahedra was slightly increased in SnO₂-containing vanadate glasses, which was reflected as an increase in glass transition temperature (T_g) from 266 to 285_±5 °C. A slope of 675 K / (mm s^???1) obtained in ‘T_g vs. Δ plot’ proved that Fe^III occupied the site of network former (NWF). An isothermal annealing of 10LFSVP glass at 500 °C for 100 min resulted in a marked decrease of Δ from 0.72 to 0.56_±0.02 mm s^???1, indicating that local distortion of FeO₄ tetrahedra was reduced by the structural relaxation of 3D-network. In contrast, identical δ and Δ values of 0.07_±0.01 and 0.53_±0.02 mms^???1, respectively, were observed in ¹¹⁹Sn-Mössbauer spectra of 10LFSVP glass before and after the annealing. These results indicate that Sn^IVO₆ octahedra are loosely bound in the glass matrix as a network modifier (NWM). A marked increase in σ from 7.4 × 10^???7 to 9.1 × 10^???3 S cm^???1 was observed in 20LFSVP glass after the isothermal annealing, indicating that structural relaxation of 3D-network evidently causes a marked increase in σ.     

Mössbauer study of new vanadate glass with large charge-discharge capacity

Charge-discharge capacity and cyclicity of lithium ion battery (LIB) was evaluated in which 15Li₂O·10Fe₂O₃·xSnO₂·5P₂O₅·(70–x)V₂O₅ glass (x?=?0 and 20 in mol%, abbreviated as xLFSPV) was used as a cathode. A local structure of xLFSPV glass before and after charging was investigated by ⁵⁷Fe- and ¹¹⁹Sn-Mössbauer spectroscopies. ⁵⁷Fe-Mössbauer spectrum of xLFSPV glass with ‘x’ of 20 was composed of a doublet with isomer shift (δ) of 0.35_±0.02 mm s^???1 and quadrupole splitting (Δ) of 0.88_±0.03 mm s^???1 due to distorted Fe^IIIO₄ tetrahedra. ¹¹⁹Sn-Mössbauer spectrum of this glass consisted of a doublet with δ of 0.08_±0.01 and Δ of 0.52_±0.01 mms^???1 due to distorted Sn^VIO₆ octahedra. After discharging the battery from 4.5 to 1.0 V, larger δ of 0.40_±0.03 mm s^???1 and Δ of 0.94_±0.04 mm s^???1 were obtained, indicating that both iconicity of Fe-O bonds and local distortion of Fe^IIIO₄ tetrahedra were increased. On the contrary, identical δ of 0.09_±0.01 mm s^???1 and Δ of 0.50_±0.01 mm s^???1 were observed in the ¹¹⁹Sn-Mössbauer spectrum of 20LFSPV glass after the discharge, indicating that chemical environment of Sn^IVO₆ octahedra was not affected after the discharge. Charge-discharge curve of LIB containing 20LFSPV glass as a cathode active material recorded under the current density of 8.3 mA g^???1 (0.011 mA cm^???2) between 1.0 and 4.5 V showed a large initial charge capacity of 431.1 mAh g^???1 and discharge capacity of 382.3 mAh g^???1, respectively. These results indicate that 20LFSPV glass could be a new cathode active material for LIB.     

Mössbauer investigation of iron uptake in wheat

Iron uptake and distribution in wheat roots were studied with ⁵⁷Fe Mössbauer spectroscopy. Plants were grown both in iron sufficient and in iron deficient nutrient solutions. Mössbauer spectra of the frozen iron sufficient roots exhibited three iron(III) components with the typical average Mössbauer parameters of δ?= 0.50 mm s^???1, Δ?= 0.43 mm s^???1, δ?= 0.50 mm s^???1, Δ?= 0.75 mm s^???1 and δ?= 0.50 mm s^???1, Δ?= 1.20 mm s^???1 at 80 K. These doublets are very similar to those obtained earlier for cucumber [0], which allows us to suppose that iron is stored in a very similar way in different plants. No ferrous iron could be identified in any case, not even in the iron deficient roots, which confirms the mechanism proposed for iron uptake in the graminaceous plants.     

First observation of K X-rays from pp atoms

K and L series X-rays have been observed from p$\text{p}$ atoms formed in hydrogen gas at NTP in association with annihilations into neutral particles. The total K X-ray yield is (6.5 ± 3.2) × 10^?3 per stopped antiproton. A model-dependent fit of the K X-ray spectrum gives a K_α energy of 8.9±0.3 keV, corresponding to a strong interaction shift of (?0.5±0.3) keV.     

57Fe-Mössbauer study of electrically conducting barium iron vanadate glass after heat treatment

Local structure and thermal durability of semiconducting xBaO·(90?? x)V₂O₅ · 10Fe₂O₃ glasses (x = 20, 30 and 40), NTA glass ^TM, before and after isothermal annealing were investigated by ⁵⁷Fe-Mössbauer spectroscopy and differential thermal analysis (DTA). An identical isomer shift ( $\mathit{\delta}$ ) of 0.39 ± 0.01 mm s^???1 and a systematic increase in the quadrupole splitting (Δ) were observed from 0.70 ± 0.02 to 0.80 ± 0.02 mm s^???1 with an increasing BaO content, showing an increase in the local distortion of Fe^IIIO₄ tetrahedra. From the slope of the straight line in the T _g–Δ plot of NTA glass ^TM, it proved that Fe^III plays a role of network former. Large Debye temperature (Θ _D) values of 1000 and 486 K were respectively obtained for 20BaO · 70V₂O₅ · 10Fe₂O₃ glass before and after isothermal annealing at 400°C for 60 min, respectively. This result also suggests that Fe^III atoms constitute the glass network composed of tetrahedral FeO₄, tetrahedral VO₄ and pyramidal VO₅ units. The electric conductivity of 20BaO · 70V₂O₅ · 10Fe₂O₃ glass increased from 1.6 × 10^???5 to 5.8 × 10^???2 S cm^???1 after isothermal annealing at 450°C for 2,000 min. These results suggest that the drastic increase in the electric conductivity caused by heat treatment is closely related to the structural relaxation of the glass network structure.     

Mössbauer studies of57Fe atoms isolated in CH4 and CO2 matrices

The Mössbauer absorption spectra of matrix isolated⁵⁷Fe atoms have been measured in the inert matrices CH₄ and CO₂ with matrix temperatures between ～3.3 and ～46 K. The isomer shift of the observed resonances is (?0.79±0.02) mm/s and (?0.76±0.05) mm/s with respect to iron metal at 300 K for⁵⁷Fe in CH₄ and for CO₂ respectively. This is within the experimental errors the same isomer shift as that of rare-gas matrix isolated⁵⁷Fe atoms. All spectra show quadrupole doublets due to the noncubic point symmetry of the lattice site occupied by the⁵⁷Fe atoms. The effective Debye temperatures as obtained from the temperature dependence of the resonance absorption areas are (46±4) K for the CH₄ matrix and (121±6) K for the CO₂ matrix annealed at ～20 K.     

Quadrupole interaction of tantalum impurities in bismuth metal

The time differential perturbed angular correlation technique has been used in the measurement of the electric quadrupole interaction of Ta impuritiy in bismuth metal. The interaction frequencies at 293, 400 and 500 K have been observed to be 288±1.5, 266.9±3 and 244.5±4.3 MHz respectively. The electric field gradient at 293 K is 4.75±0.3 × 10¹⁷ V/cm² with the temperature coefficientB=2.2±0.2 × 10⁻⁵ (K)^−3/2.     

Breeding of antideuterons in the AIC at FAIR

We present here a proposal to make use of the antiproton ion collider AIC of FAIR to breed cold antideuterons using the pionic fusion reactions $\overline{pp} \to \overline{d}\pi^{-}$ . An antideuteron yield of 1.4% per pair of antiprotons is reached. With a luminosity L?=?5.2×10²⁸ cm^???2 s^???1 the expected antideuteron production rate is 23 s^???1. Methods for improving the antideuteron yield and production rate are indicated.     

Stiffness matrix and debye temperature of ReO3 from ultrasonic measurements

We have measured the propagation velocities of bulk acoustic waves in the simple cubic transition-metal oxide ReO₃ by ultrasonic pulse propagation. The elastic stiffness constants at 300 K are: C₁₁ = (47.9 ± 1.4) × 10¹¹ dyne/cm²; C₄₄ = (6.1 ± 0.2) × 10¹¹ dyne/cm²; C₁₂ = (?0.7 ± 2.8) × 10¹¹ dyne/cm². These elastic constants indicate a crystal with highly anisotropic shear propagation. The Debye temperature of the compound from these measurements is 528 K. This value is somewhat higher than previous results from specific heat and resistivity determinations.     

Sensitive voltammetric determination of cysteamine using promazine hydrochloride as a mediator and modified multi-wall carbon nanotubes carbon paste electrodes

This paper presents a sensitive electrochemical method for the determination of cysteamine (CA) using promazine hydrochloride-modified multi-wall carbon nanotubes carbon paste electrode (PrH/MWCNTs CPE). Because of the good electrochemical activity of MWCNTs and the acceptable performance of promazine hydrochloride (PrH) as an electrocatalytic mediator, the modified electrode significantly enhanced the sensitivity for the detection of CA in comparison to the bare carbon paste electrode (CPE). All chemical parameters such as pH of solution, concentration of PrH and kinetic parameters of the system were investigated. Linear sweep voltammetric (LSV) method was used to follow the electrocatalytic effect of CA on the current–potential response of PrH. Under optimum conditions, the obtained net peak current ?I _p(I _sample???I _blank) was linear with CA concentrations in two dynamic ranges of 2.0–346.5 μmol l^?1 (?I _p?=?(0.0195?±?0.0043)C _CA?+?(0.7648?±?0.0397) (r ²?=?0.9948)) and 346.5–1,912.5 μmol l^?1 (?I _p?=?(0.0100?±?0.0026)C _CA?+?(3.8981?±?0.0828) (r ²?=?0.9911)) with a detection limit of 0.8 μmol l^?1. Finally, the PrH/MWCNTs CPE was successfully applied for the determination of CA in urine and drug samples with satisfactory results.     

Observation of spin-lattice relaxations of dilute Fe3+ in MgO by Mössbauer spectroscopy

We present a method to describe the temperature dependence of emission Mössbauer spectra showing slow spin-lattice relaxations of Fe^3?+? in MgO single crystals, obtained after implantation of ⁵⁷Mn at ISOLDE/CERN. The analysis is based on the Blume-Tjon model for the line-shape of relaxing paramagnetic sextets with the spin relaxation rate, τ ^???1 as a parameter. The temperature dependent spin relaxation rate of Fe^3?+? in MgO is found to increase to ~10⁸ s^???1 at 647 K by assuming a relaxation rate of τ ^???1?< 10⁶ s^???1 at 77 K. The results are in accordance with those obtained by electron paramagnetic resonance spectroscopy demonstrating the possibility of retrieving spin-lattice relaxation rates of dilute Fe^3?+? from emission Mössbauer spectroscopy of Mn/Fe-implanted oxides.     

Melting curves of argon and methane

The melting curves of argon and of methane have been measured in a diamond-anvil cell from 290 to>700 K. Measurements of argon, fit to the equation P?6.9×10^?5=0.244[(T/83.805)^1.476?1], are in excellent agreement with previously published values up to a temperature of ～ 500 K and thereafter diverge slowly. Measurements of methane, fit to P?1.17×10^?5=0.208[(T/90.6941)^1.698?1], are in serious disagreement with the only previous studies to extend past 400 K.     

Microwave power coupling with electron cyclotron resonance plasma using Langmuir probe

Electron cyclotron resonance (ECR) plasma was produced at 2.45 GHz using 200–750 W microwave power. The plasma was produced from argon gas at a pressure of 2 × 10^???4 mbar. Three water-cooled solenoid coils were used to satisfy the ECR resonant conditions inside the plasma chamber. The basic parameters of plasma, such as electron density, electron temperature, floating potential, and plasma potential, were evaluated using the current–voltage curve using a Langmuir probe. The effect of microwave power coupling to the plasma was studied by varying the microwave power. It was observed that the optimum coupling to the plasma was obtained for ~ 600 W microwave power with an average electron density of ~ 6 × 10¹¹ cm^???3 and average electron temperature of ~ 9 eV.     

Mössbauer spectroscopy of the new iron oxide Fe3B7O13(OH)

In order to investigate the electronic state, the local structure, and the magnetic structure of a new ion oxide Fe₃B₇O₁₃(OH), we have applied ⁵⁷Fe Mössbauer spectroscopy. The room-temperature values of isomer shift and quadrupole splitting are 1.16 mm/s and 3.21 mm/s, respectively, which indicate that the Fe ions are in high spin Fe^2?+? state. The spectrum at 4.2 K is composed of a well-resolved hyperfine sextet with the hyperfine field of 3.6 T. In a trimer, each Fe^2?+? magnetic moment is supposed to be directed from Fe^2?+? to OH^???.     

Experimental estimation of the possible subbarrier penetration of ultracold neutrons through vacuum-tight foils

The probability of subbarrier penetration of ultracold neutrons through 15 μm-thick vacuum-tight beryllium foil (boundary energy for beryllium is E _{lim Be}=249 eV) was measured. It is equal to (?1.2±1.0) × 10^?8 per collision of neutrons with energy lower than ～160 neV.     

Covalent distribution of spin in V2O3:O17 nuclear resonance

O¹⁷ nuclear magnetic resonance has been observed in metallic V₂O₃ with frequency shifts from (?0.10 ± 0.02)-(?0.05 ± 0.02) per cent between 170 and 460°K respectively, a linewidth of 37 ± 5 oe and spin-lattice relaxation rate 1/T₁ ≈ 60 sec^?1 at 296°K. From these quantities, covalency parameters f_s/2S = ? 0.35 × 10^?3 and ?_π/2S ≈ ? 0.07 are calculated. One of the two vanadium 3d electrons in the antiferromagnetic state below the 170°K metal-insulator transition is inferred to lie in a non-magnetic state, while covalent charge transfer augments the spin moment of the other 3d electron to the observed 1.2 μ_B.     

Magnetization behaviour of DyAl2 single crystals

We report the theoretical interpretation of the magnetization and the magnetocrystalline anisotropy of ferromagnetic DyAl₂ single crystals between 4.2 and 60 K and magnetic fields up to 15 T. Good agreement between theory and experiment is obtained by using three temperature independent parameters: the two crystal field parameters B₄ = (?0.50 ± 0.05) × 10^?4 meV, B₆ = ? (0.51 ± 0.05) × 10^?6 meV and the Curie temperature T_c = (62 ± 2) K.