Morphology,Mineralogy and Mixing of Individual Atmospheric Particles Over Kanpur (IGP): Relevance of Homogeneous Equivalent Sphere Approximation in Radiative Models

Estimation of the direct radiative forcing (DRF) by atmospheric particles is uncertain to a large extent owing to uncertainties in their morphology (shape and size), mixing states, and chemical composition. A region-specific database of the aforementioned physico-chemical properties (at individual particle level) is necessary to improve numerically-estimated optical and radiative properties. Till date, there is no detailed observation of the above mentioned properties over Kanpur in the Indo-Gangetic Plain (IGP). To fill this gap, an experiment was carried out at Kanpur (IITK; 26.52°N, 80.23°E, 142 m msl), India from April to July, 2011. Particle types broadly classified as (a) Cu-rich particles mixed with carbon and sulphur (b) dust and clays mixed with carbonaceous species (c) Fe-rich particles mixed with carbon and sulfur and (d) calcite (CaCO₃) particles aged with nitrate, were observed. The frequency distributions of aspect ratio (AR; indicator of extent of particle non-sphericity) of total 708 particles from April to June reveal that particles with aspect ratio range >1.2 to ≤1.4 were abundant throughout the experiment except during June when it was found to shift to high AR range, >1.4 to ≤1.6 (followed with another peak of AR i.e. >2 to ≤2.4) due to dust storm conditions enhancing the occurrence of more non-spherical particles over the sampling site. The spherical particles (and close to spherical shape; AR range, 1.0 to ≤1.2) were found to be <20% throughout the experiment with a minimum (11.5%) during June. Consideration of Homogeneous Equivalent Sphere Approximation (HESA) in the optical/radiative model over the study region is found to be irrelevant during the campaign.     

Significance of interface barrier at electrode of hematite hydroelectric cell for generating ecopower by water splitting

Recent increase in energy demand and associated environmental degradation concern has triggered more research towards alternative green energy sources. Eco‐friendly energy in facile way has been generated from abundantly available iron oxides using only few microliters of water without any external energy source. Hydroelectric cell (HEC) compatible to environment benign, low cost oxygen‐deficient mesoporous hematite nanoparticles has been used for splitting water molecules spontaneously to generate green electricity. Hematite nanoparticles have been synthesized by coprecipitation method. Chemidissociated hydroxyl group presence on hematite surface has been confirmed by infrared spectroscopy (IR) and X‐ray photoelectron spectroscopy (XPS). Surface oxygen vacancies in nanostructured hematite have been identified by transmission electron microscopy (TEM), XPS, and photoluminescence (PL) measurement. Hematite‐based HEC delivers 30 mA current with 0.92 V emf using approximately 500 μL water. Maximum off‐load output power 27.6 mW delivered by 4.84 cm² area hematite‐based HEC is 3.52 times higher than reported 7.84 mW power generated by Li‐magnesium ferrite HEC. Electrochemistry of HEC in different irreversible polarization loss regions has been estimated by applying empirical modeling on V‐I polarization curve revealing the reaction and charge transport mechanism of cell. Tafel slope 22.7 mV has been calculated by modeling of activation polarization overvoltage region of 0.11 V. Low activation polarization indicated easy charge/ion diffusion and faster reaction kinetics of Ag/Zn electrode owing to lesser energy barrier at interface. Dissociated H₃O⁺ ions diffuse through surface via proton hopping, while OH^? ions migrate through interconnected defective crystallite boundaries resulting into high output cell current.     

Green hydroelectrical energy source based on water dissociation by nanoporous ferrite

Dissociation of water molecule occurs on octahedrally coordinated unsaturated suface cations and oxygen vacancies created by lithium substitution in magnesium ferrite. Lower synthesis temperature of ferrite has generated nanopores in microstructure. Dissociated hydronium and hydroxyl ions are transported through surface and capillary diffusion in porous ferrite network towards attached Zn and Ag electrodes. Water molecule dissociation ability of nanoporous ferrite has been exploited to develop a green electrical energy cell, which is a combination of material science and electrode chemistry. The innovated cell has been nomenclatured as hydroelectric cell (HEC). When HEC is partially dipped in deionized water, spontaneously hydroxide and hydronium ions are produced by water molecule dissociation. Hydronium ions trapped in nanopores develop enough electric field that further dissociates physisorbed water molecules. Thereby, the process of water molecule dissociation is accelerated in a bigger way to increase ionic current in the cell. Oxidation of Zn electrode by hydroxide ion and reduction of H₃O⁺ at Ag electrode develop voltage and electric current in the cell. The HEC cell of a 17 cm² area is able to generate a short circuit current of 82 mA and 920 mV emf with a maximum output power of 74 mW, which is three order higher than reported output power 1.4 μW/cm² produced by water in cement matrix. Hydroelectric cell performance is repetitive, stable and possesses potential to replace traditional ways of generating renewable energy in terms of cost and safety. Copyright © 2016 John Wiley & Sons, Ltd.     

A Novel Approach to Improve Properties of BiFeO3 Nanomultiferroics

In this study we report the synthesis of Bi_1?xIn_xFe_1?yTi_yO₃ (0 ≤ x ≤ 0.1, 0 ≤ y ≤ 0.05) nanoparticles by a simple cost effective solution combustion method. Pure BFO samples shows distorted rhombohedral perovskite structure with space group R3c which is also supported by Fourier transform infrared spectra study. The codoping of In and Ti at A–B sites of BFO (BIFTO) partially distorts the crystal structure, increases the lattice strain, reduces the average particle size (14 nm), and increases the Fe³⁺/Fe²⁺ ratio which significantly affect the observed results. The saturation magnetization increases significantly upon codoping (4.60 emu/gm) by about 12 times than that of pure BFO (0.4 emu/gm). The improved ferromagnetic properties upon codoping is further manifestated in large value of linear magnetoelectric coupling coefficient (4.8 mV/cmOe) which further provides an indirect evidence for the collapse of space modulated spin structure. The activation energy increases with codoping (0.68 eV), although less than 1 eV which indicates that the conduction is still dominated by charged defects.     

Structural development and magnetic phenomenon in Zn–Cr–Fe multi oxide nano-crystals

The Cr³⁺ ions doped multi-oxide ZnFe_2−xCr_xO₄ ferrite nanoparticles have been synthesized by chemical co-precipitation method. Site occupancies of Zn²⁺, Cr³⁺ and Fe³⁺ ions were analyzed using X-ray diffraction data and Buerger's method. The effect of the constituent phase variation on the magnetic hysteresis behavior was examined by saturation magnetization which decreases with the increase in Cr³⁺ content in place of Fe³⁺ ions at octahedral B-site. Typical blocking temperature (T_B) around 90 K was observed by zero field cooling and field cooling magnetization study. Room temperature Mössbauer spectra show two paramagnetic doublets (tetrahedral and octahedral sites). The isomer shifts of both doublets decrease whereas quadrupole splitting and relative area of tetrahedral A-site increases with increasing Cr³⁺ substitution. The dielectric constant (measured on compositions x=0, 0.4, 0.8 and 1.0) increases when the temperature increases as in the semiconductor. This behavior is attributed to the hopping of electrons between Fe²⁺ and Fe³⁺ ions with a thermal activation.     

Study of crystal structure,dielectric, magnetic and magnetoelecrtic properties of xCoFe2O4-(1-x)Na0.5Bi0.5TiO3 composites

Multiferroic composites of spinel ferrite and ferroelectric xCoFe₂O₄ – (1-x)Na_0.5Bi_0.5TiO₃ (with x = 0.10,0.30,0.50) were efficiently prepared by standard solid state reaction mechanism. X-ray diffractometer was used to analyze crystal structure of the prepared composites. The observed XRD patterns of the composites comprise peaks of both the phases i.e. ferrite and ferroelectric, with no sign of secondary peaks. Rietveld refinement of XRD data further confirms the coexistence of these two phases with cubic (Fd3m) and rhombohedral (R3c) symmetry corresponding to ferrite and ferroelectric phase respectively. The 3-dimensional overview of crystal structure of pure CoFe₂O₄ and Na_0.5Bi_0.5TiO₃ and of composite 0.50CoFe₂O₄?0.50Na_0.5Bi_0.5TiO₃ is generated by using refined parameters. The dielectric constant (ε´) and dielectric loss (tanδ) values were recorded as a function of frequency ranging from 100?Hz to 7?MHz and at different temperatures. Both ε´ and tanδ follow dispersion pattern at lower frequencies while show frequency independent behavior at higher frequencies. The magnetic evaluation carried by analyzing M-H hysteresis loop reveals the ferrimagnetic characteristics of these composites. The highest value of magnetic moment is 1.12μ_B observed for composite 0.50CoFe₂O₄ – 0.50Na_0.5Bi_0.5TiO_3. Magnetoelectric (ME) voltage coefficient (α) was also demonstrated to observe the interaction between ferrite and ferroelectric phases. The highest value of α (72.72μV/Oe cm) is obtained for low ferrite composition 0.10CoFe₂O₄ – 0.90Na_0.5Bi_0.5TiO₃, which suggests the dependence of magnetoelectric response on the resistivity of the composites.     

Ascorbic acid-mediated synthesis and characterisation of iron oxide/gold core–shell nanoparticles.

The current article reports on providing surface modification of magnetic nanoparticles with gold to provide stability against aggregation. Gold-coated magnetite nanoparticles were synthesised to combine both magnetic as well as surface plasma resonance (SPR) properties in a single moiety. The nanocomposites were produced by reduction (using ascorbic acid) of gold chloride on to the surface of iron oxide nanoparticles. Ascorbic acid not only acts as a reducing agent, but also the oxidised form of ascorbic acid i.e. Dehydro-ascorbic acid acts as a capping agent to impart stability to as synthesised gold-coated iron oxide nanocomposites. The synthesised nanocomposite was monodispersed with a mean particle size of around 16 nm and polydispersity index of 0.190. X-ray diffraction analysis confirms presence of gold on the surface of magnetite nanoparticles. The synthesised nanocomposites had a total organic content of around 3.2% w/w and also showed a shifted SPR peak at 546 nm as compared to gold nanoparticles (528 nm). Both uncoated and gold-coated magnetite exhibited superparamagnetic behaviour at room temperature. Upon coating with gold shell, saturation magnetisation of iron oxide nanoparticles decreases from 42.806 to 3.54 emu/gram.     

Self-controlled growth of Fe3BO6 crystallites in shape of nanorods from iron-borate glass of small templates

Fe₃BO₆ can be an ideal compound for devising functional magnetic and dielectric properties in a single material for multiple applications such as electrodes, gas sensors, or medical tools. Useful to tailor such properties, here we report on a self-controlled Fe₃BO₆ growth in a specific shape of nanorods from a supercooled liquid precursor (an inorganic polymeric liquid or glass) of an initial composition (100 − x)B₂O₃ − xFe₂O₃, x = 40–50 mol%. B₂O₃ as a strong glass former co-bridges the Fe³⁺ ions in oxygen polygons primarily in a 2-D interconnected polymer network so that it dictates preferably a 1-D directional growth on the reaction Fe³⁺ species in form of a compound Fe₃BO₆, a favorable phase to nucleate and grow when annealing a precursor at 500–800 °C in ambient air. Distinct nanorods with a diameter ∼200 nm and 40–100 μm length have been formed on 10–15 min annealing a sample in microwave at moderate temperature 550 °C. A bonded surface B₂O₃ layer (15–25 nm thickness) has grown on the Fe₃BO₆ of the nanorods in situ in a specific structure. XPS bands in the Fe³⁺, B³⁺ and O²⁻ species confer this model structure. A local BO₃ → BO₄ conversion has incurred in the boroxol (B₃O_4.5)_n, n → ∞, rings in the surface layer, showing three distinct IR bands at 1035, 1215 and 1425 cm⁻¹.     

Magneto-optical properties of barium ferrite sputtered films

Barium ferrite thin films with perpendicular anisotropy were grown on (111) oriented GGG substrate by rf diode sputtering method. Their magnetic properties were measured. Faraday rotation was measured in the wavelength range 460–800 nm for such sputtered thin films. These films were found quite suitable for magneto-optical recording applications.