Magnetic Properties of Fe/Cu Codoped ZnO Nanocrystals

Free-standing ZnO nanocrystals simultaneously doped with Fe and Cu with varying Fe/Cu compositions have been synthesized using colloidal methods with a mean size of similar to 7.7 nm. Interestingly, while the Cu-doped ZnO nanocrystal remains diamagnetic and Fe-doped samples show antiferromagnetic interactions between Fe sites without any magnetic ordering down to the lowest temperature investigated, samples doped simultaneously with Fe and Cu show a qualitative departure in exhibiting ferromagnetic interactions, with suggestions of ferromagnetic order at low temperature. XAS measurements establish the presence of Fe2+ and Fe3+ ions, with the concentration of the trivalent species increasing in the presence of Cu doping, providing direct evidence of the Fe2+ + Cu2+ sic Fe3+ + Cu+ redox couple being correlated with the ferromagnetic property. Using DFT, the unexpected ferromagnetic nature of these systems is explained in terms of a double exchange between Fe atoms, mediated by the Cu atom, in agreement with experimental observations.

Magnetocaloric effect and nature of magnetic transition in nanoscale Pr0.5Ca0.5MnO3

Systematic measurements pertinent to the magnetocaloric effect and nature of magnetic transition around the transition temperature are performed in the 10 nm Pr0.5Ca0.5MnO3 nanoparticles (PCMO10). Maxwell's relation is employed to estimate the change in magnetic entropy. At Curie temperature (T-C) similar to 83.5 K, the change in magnetic entropy (-Delta S-M) discloses a typical variation with a value 0.57 J/kg K, and is found to be magnetic field dependent. From the area under the curve (Delta S vs T), the refrigeration capacity is calculated at T-C similar to 83.5K and it is found to be 7.01 J/kg. Arrott plots infer that due to the competition between the ferromagnetic and anti-ferromagnetic interactions, the magnetic phase transition in PCMO10 is broadly spread over both in temperature as well as magnetic field coordinates. Upon tuning the particle size, size distribution, morphology, and relative fraction of magnetic phases, it may be possible to enhance the magnetocalorific effect further in PCMO10. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4759372]

Mechanistic Aspects for the Formation of Copper Dimer Bridged by Phosphonic Acid and Extending Its Dimensionality by Organic and Inorganic Linkers: Synthesis, Structural Characterization, Magnetic Properties, and Theoretical Studies

Six new copper metal complexes with formulas Cu(H2O)(2,2'-bpy) (H2L)](2) center dot H4L center dot 4 H2O (1), {Cu(H2O)(2,2'-bpy)-(H3L)}(2)(H2L)]center dot 2H(2)O (2), Cu(H2O)(1,10-phen)(H2L)](2)center dot 6H(2)O (3), Cu(2,2'-bpy)(H2L)](n)center dot nH(2)O (4), Cu(1,10-phen)(H2L)](n)center dot 3nH(2)O (5), and {Cu(2,2'-bpy)(MoO3)}(2)(L)](n)center dot 2nH(2)O (6) have been synthesized starting from p-xylylenediphosphonic acid (H4L) and 2,2'-bipyridine (2,2'-bpy) or 1,10-phenanthroline (1,10-phen) as secondary linkers and characterized by single crystal X-ray diffraction analysis, IR spectroscopy, and thermogravimetric (TG) analysis. All the complexes were synthesized by hydrothermal methods. A dinuclear motif (Cu-dimer) bridged by phosphonic acid represents a new class of simple building unit (SBU) in the construction of coordination architectures in metal phosphonate chemistry. The initial pH of the reaction mixture induced by the secondary linker plays an important role in the formation of the molecular phosphonates 1, 2, and 3. Temperature dependent hydrothermal synthesis of the compounds 1, 2, and 3 reveals the mechanism of the self assembly of the compounds based on the solubility of the phosphonic acid H4L. Two-dimensional coordination polymers 4, 5, and 6, which are formed by increasing the pH of the reaction mixture, comprise Cu-dimers as nodes, organic (H2L) and inorganic (Mo4O12) ligands as linkers. The void space-areas, created by the (4,4) connected nets in compounds 4 and 5, are occupied by lattice water molecules. Thus compounds 4 and 5 have the potential to accommodate guest species/molecules. Variable temperature magnetic studies of the compounds 3, 4, 5, and 6 reveal the antiferromagnetic interactions between the two Cu(II) ions in the eight membered ring, observed in their crystal structures. A density functional theory (DFT) calculation correlates the conformation of the Cu-dimer ring with the magnitude of the exchange parameter based on the torsion angle of the conformation.

Inversion of moments to retrieve joint probabilities in quantum sequential measurements

A sequence of moments obtained from statistical trials encodes a classical probability distribution. However, it is well known that an incompatible set of moments arises in the quantum scenario, when correlation outcomes associated with measurements on spatially separated entangled states are considered. This feature, viz., the incompatibility of moments with a joint probability distribution, is reflected in the violation of Bell inequalities. Here, we focus on sequential measurements on a single quantum system and investigate if moments and joint probabilities are compatible with each other. By considering sequential measurement of a dichotomic dynamical observable at three different time intervals, we explicitly demonstrate that the moments and the probabilities are inconsistent with each other. Experimental results using a nuclear magnetic resonance system are reported here to corroborate these theoretical observations, viz., the incompatibility of the three-time joint probabilities with those extracted from the moment sequence when sequential measurements on a single-qubit system are considered.

Characterization and magnetic response of multiwall carbon nanotubes filled with iron nanoparticles of different aspect ratios

Three samples of multiwall carbon nanotubes (MWCNT) TF200, TF150 and TF100, where T and F stand for toluene and ferrocene respectively, and numeral denotes the amount (mg) of ferrocene] filled with iron-nanoparticles (Fe-NPs) of different aspect ratios are grown by chemical vapor deposition of toluene-ferrocene mixture. Energy dispersive X-ray analysis shows a systematic variation in the intensities of peak corresponding to Fe, indicating that Fe is present in different amounts in the three MWCNT samples. The lengths of Fe-NPs lie in the range of 200-250; 80-120; and 30-40 nm for TF200, TF150 and TF100, respectively, as estimated statistically from transmission electron microscopy micrographs. However, the diameter of the encapsulated Fe-NPs does not vary significantly for different samples and is 20-30 nm for all samples. Hysteresis loop measurements on these MWCNT samples were done at 10, 150 and 300 K up to an applied field of 1.5 T. At 10 K, values of coercivity are 2584, 2315, and 2251 Oe for TF200, TF150 and TF100 respectively. This is attributed to the strong shape anisotropy of the Fe-NPs and significant dipolar interactions between them. Further, M-H loops reveal that saturation magnetization of TF200 is almost four times that of TF100 at all temperatures.

Interplay of structural distortions, dielectric effects and magnetic order in multiferroic GdMnO3

Multiferroic materials are characterized by simultaneous magnetic and ferroelectric ordering making them good candidates for magneto-electrical applications. We conducted thermal expansion and magnetostriction measurements in magnetic fields up to 14 T on perovskitic GdMnO3 by highresolution capacitive dilatometry in an effort to determine all longitudinal and transversal components of the magnetostriction tensor. Below the ordering temperature T (N) = 42 K, i.e., within the different complex (incommensurate or complex) antiferromagnetic phases, lattice distortions of up to 100 ppm have been found. Although no change of the lattice symmetry occurs, the measurements reveal strong magneto-structural phenomena, especially in the incommensurate sinusoidal antiferromagnetic phase. A strong anisotropy of the magnetoelastic properties was found, in good agreement with the type and propagation vector of the magnetic structure. We demonstrate that our capacitive dilatometry can detect lattice expansion effects and changes of the dielectric permittivity simultaneously because the sample is housed inside the capacitor. A separation of both effects is possible by shielding the sample. Dielectric transitions could be detected by this method and compared to the critical values of H and T in the magnetic phase diagram. Dielectric changes measured at 1 kHz excitation frequency are detected in GdMnO3 at about 180 K, and between 10 K and 25 K in the canted antiferromagnetic structure which is characterized by a complex magnetic order on both the Gd- and Mn-sites.

Physical and magnetic properties of (Co, Ag) doped ZnO nanoparticles

Undoped and (Co, Ag) co-doped ZnO nanostructure powders are synthesized by chemical precipitation method without using any capping agent and annealed in air ambient at 500 A degrees C for 1 h. Here, the Ag concentration is fixed at 5 mol% and Co concentration is increased from 0 to 5 mol%. The X-ray diffraction studies reveal that undoped and doped ZnO powders consist of pure hexagonal structure and nano-sized crystallites. The novel Raman peak at 530 cm(-1) has corroborated with the Co doped ZnO nanoparticles. Moreover, the PL studies reveal that as the Co doping concentration increases and it enters into ZnO lattice as substitutional dopant, it leads to the increase of oxygen vacancies (Vo) and zinc interstitials (Zn-i). From the magnetization measurements, it is noticed that the co-doped ZnO nanostructures exhibit considerably robust ferromagnetism i.e. 4.29 emu g(-1) even at room temperature. These (Co, Ag) co-doped ZnO nanopowders can be used in the fabrication of spintronic and optoelectronic device applications.

Constraining complex aquifer geometry with geophysics (2-D ERT and MRS measurements) for stochastic modelling of groundwater flow

Stochastic modelling is a useful way of simulating complex hard-rock aquifers as hydrological properties (permeability, porosity etc.) can be described using random variables with known statistics. However, very few studies have assessed the influence of topological uncertainty (i.e. the variability of thickness of conductive zones in the aquifer), probably because it is not easy to retrieve accurate statistics of the aquifer geometry, especially in hard rock context. In this paper, we assessed the potential of using geophysical surveys to describe the geometry of a hard rock-aquifer in a stochastic modelling framework. The study site was a small experimental watershed in South India, where the aquifer consisted of a clayey to loamy-sandy zone (regolith) underlain by a conductive fissured rock layer (protolith) and the unweathered gneiss (bedrock) at the bottom. The spatial variability of the thickness of the regolith and fissured layers was estimated by electrical resistivity tomography (ERT) profiles, which were performed along a few cross sections in the watershed. For stochastic analysis using Monte Carlo simulation, the generated random layer thickness was made conditional to the available data from the geophysics. In order to simulate steady state flow in the irregular domain with variable geometry, we used an isoparametric finite element method to discretize the flow equation over an unstructured grid with irregular hexahedral elements. The results indicated that the spatial variability of the layer thickness had a significant effect on reducing the simulated effective steady seepage flux and that using the conditional simulations reduced the uncertainty of the simulated seepage flux. As a conclusion, combining information on the aquifer geometry obtained from geophysical surveys with stochastic modelling is a promising methodology to improve the simulation of groundwater flow in complex hard-rock aquifers. (C) 2013 Elsevier B.V. All rights reserved.

Role of dicarboxylate linkers in Mn-III-salicylaldoximate based extended structures: synthesis, structures, and magnetic behavior

Four new oxo-centered Mn-III-salicylaldoximate triangle-based extended complexes (Mn6O2)-O-III(salox)(6)(EtOH)(4)(phda)](n)(saloxH(2))(n)(2H(2)O)(n) (1), (Mn6O2)-O-III(salox)(6)(MeOH)(5)(5-I-isoph)](n)(3MeOH)(n) (2), (Mn6O2)-O-III(salox)(6)(MeOH)(4)(H2O) (5-N-3-isoph)](n)(4MeOH)(n) (3) and (Mn3NaO)-Na-III(salox)(3)(MeOH)(4)(5-NO2-isoph)](n)(MeOH)(n) (H2O)(n) (4) salox=salicylaldoximate, phda=1,3-phenylenediacetate, isoph=isophthalate] have been synthesized under similar reaction conditions. Single crystal X-ray structures show that in 1, only one type of Mn-6 cluster is arranged in 1D, whereas in 2 and 3 there are two types of clusters, differing in the way the triangle units are joined and assembled. In complex4, however, the basic building structure is heteronuclear and based on Mn-3 units extended in 2D. Susceptibility measurements (dc and ac) over a wide range of temperatures and fields show that the complexes1, 2, and 3 behave as single molecule magnets (SMMs) with S=4ground state, while 4 is dominantly antiferromagnetic with a ground spin state S=2. Density functional theory calculations have been performed on model complexes to provide a qualitative theoretical interpretation for their overall magnetic behavior.

Correspondence between neutron depolarization and higher order magnetic susceptibility to investigate ferromagnetic clusters in phase separated systems

It is a tough task to distinguish a short-range ferromagnetically correlated cluster-glass phase from a canonical spin-glass-like phase in many magnetic oxide systems using conventional magnetometry measurements. As a case study, we investigate the magnetic ground state of La0.85Sr0.15CoO3, which is often debated based on phase separation issues. We report the results of two samples of La0.85Sr0.15CoO3 (S-1 and S-2) prepared under different conditions. Neutron depolarization, higher harmonic ac susceptibility and magnetic relaxation studies were carried out along with conventional magnetometry measurements to differentiate subtle changes at the microscopic level. There is no evidence of ferromagnetic correlation in the sample S-2 attributed to a spin-glass phase, and this is compounded by the lack of existence of a second order component of higher harmonic ac susceptibility and neutron depolarization. A magnetic relaxation experiment at different temperatures complements the spin glass characteristic in S-2. All these signal a sharp variance when we consider the cluster-glass-like phase (phase separated) in S-1, especially when prepared from an improper chemical synthesis process. This shows that the nonlinear ac susceptibility is a viable tool to detect ferromagnetic clusters such as those the neutron depolarization study can reveal.

Characterization, charge transport and magnetic properties of multi-walled carbon nanotube-polyvinyl chloride nanocomposites

Multi-walled carbon nanotube (MWCNT)-polyvinyl chloride (PVC) nanocomposites, with MWCNT loading up to 44.4 weight percent (wt%), were prepared by the solvent mixing and casting method. Electron microscopy indicates high degree of dispersion of MWCNT in PVC matrix, achieved by ultrasonication without using any surfactants. Thermogravimetric analysis showed a significant monotonic enhancement in the thermal stability of nanocomposites by increasing the wt% of MWCNT. Electrical conductivity of nanocomposites followed the classical percolation theory and the conductivity prominently improved from 10(-7) to 9 S/cm as the MWCNT loading increased from 0.1 to 44.4 wt%. Low value of electrical percolation threshold similar to 0.2 wt% is achieved which is attributed to high aspect ratio and homogeneous dispersion of MWCNT in PVC. The analysis of the low temperature electrical resistivity data shows that sample of 1.9 wt% follows three dimensional variable range hopping model whereas higher wt% nanocomposite samples follow power law behavior. The magnetization versus applied field data for both bulk MWCNTs and nanocomposite of 44.4 wt% display ferromagnetic behavior with enhanced coercivities of 1.82 and 1.27 kOe at 10 K, respectively. The enhancement in coercivity is due to strong dipolar interaction and shape anisotropy of rod-shaped iron nanoparticles. (C) 2013 Elsevier B.V. All rights reserved.

Structural, Electrical and Magnetic Behaviour of FeTe0.5Se0.5 Superconductor

We report the synthesis as well as structural and physical properties of the bulk polycrystalline FeTe and FeTe0.5Se0.5 compounds. These samples are synthesised by the solid state-reaction method via vacuum encapsulation. Both studied compounds are crystallized in a tetragonal phase with space group P4/nmm. The parent FeTe compound shows an anomaly in resistivity measurement at around 78 K, which is due to the structural change along with a magnetic phase transition. The superconductivity in the FeTe0.5Se0.5 sample at 13 K is confirmed by the resistivity measurements. DC magnetisation along with an isothermal (M-H) loop shows that FeTe0.5Se0.5 possesses bulk superconductivity. The upper critical field is estimated through resistivity rho (T,H) measurements using Gingzburg-Landau (GL) theory and is above 50 T with 50 % resistivity drop criterion. The origin of the resistive transition broadening under magnetic field is investigated by thermally activated flux flow. The magnetic field dependence of the activation energy of the flux motion is discussed.

Determination of Internal Structures of Heterogeneous Nanocrystals Using Variable-Energy Photoemission Spectroscopy

This article describes the determination of the internal structure of heterogeneous nanoparticle systems including inverted core-shell (CdS core and CdSe shell) and alloyed (CdSeS) quantum dots using depth-resolved, variable-energy X-ray photoelectron spectroscopy (XPS). A unique feature of this work is the combination of photoelectron spectroscopy performed at lower X-ray energies (400-700 eV), to achieve surface sensitivity, with bulk sensitive measurements at high photon energies (>2000 eV), thereby providing detailed information about the whole nanoparticle structure with a great accuracy. The use of high photon energies furthermore allows us to investigate nanoparticles much larger than those studied thus far. This capability is a consequence of the much-increased mean free path of the photoelectron achieved at high excitation energies. Our results show that the actual structures of the synthesized nanoparticles are considerably different from the nominal, targeted structures, which can be post facto rationalized in terms of the reactivity of different constituents.

POLAR NETWORK INDEX AS A MAGNETIC PROXY FOR THE SOLAR CYCLE STUDIES

The Sun has a polar magnetic field which oscillates with the 11 yr sunspot cycle. This polar magnetic field is an important component of the dynamo process which operates in the solar convection zone and produces the sunspot cycle. We have direct systematic measurements of the Sun's polar magnetic field only from about the mid-1970s. There are, however, indirect proxies which give us information about this field at earlier times. The Ca-K spectroheliograms taken at the Kodaikanal Solar Observatory during 1904-2007 have now been digitized with 4k x 4k CCD and have higher resolution (similar to 0.86 arcsec) than the other available historical data sets. From these Ca-K spectroheliograms, we have developed a completely new proxy (polar network index, hereafter PNI) for the Sun's polar magnetic field. We calculate PNI from the digitized images using an automated algorithm and calibrate our measured PNI against the polar field as measured by the Wilcox Solar Observatory for the period 1976-1990. This calibration allows us to estimate the polar fields for the earlier period up to 1904. The dynamo calculations performed with this proxy as input data reproduce reasonably well the Sun's magnetic behavior for the past century.

Graphene Oxide-MnFe2O4 Magnetic Nanohybrids for Efficient Removal of Lead and Arsenic from Water

We show that the hybrids of single-layer graphene oxide with manganese ferrite magnetic nanoparticles have the best adsorption properties for efficient removal of Pb(II), As(III), and As(V) from contaminated water. The nanohybrids prepared by coprecipitation technique were characterized using atomic force and scanning electron microscopies, Fourier transformed infrared spectroscopy, Raman spectroscopy, X-ray diffraction, and surface area measurements. Magnetic character of the nanohybrids was ascertained by a vibrating sample magnetometer. Batch experiments were carried out to quantify the adsorption kinetics and adsorption capacities of the nanohybrids and compared with the bare nanoparticles of MnFe2O4. The adsorption data from our experiments fit the Langmuir isotherm, yielding the maximum adsorption capacity higher than the reported values so far. Temperature-dependent adsorption studies have been done to estimate the free energy and enthalpy of adsorption. Reusability, ease of magnetic separation, high removal efficiency, high surface area, and fast kinetics make these nanohybrids very attractive candidates for low-cost adsorbents for the effective coremoval of heavy metals from contaminated water.