Surface spin disorder in nickel ferrite nanomagnets studied by in-field Mossbauer spectroscopy

The magnetic structure of NiFe(2)O(4) nanoparticles has been investigated by means of Mossbauer spectra at T=4.2 K in applied fields up to 12 T. Four samples were studied, with mean particle diameters ranging from 4.3 to 8.9 nm. All spectra could be decomposed into three sextets, two corresponding to the ferrimagnetic sublattices of Fe ions in the spinel structure (core) and the third one to randomly frozen spins near the particle surface (shell). The shell thickness, calculated from the fraction of disordered spins, was found to be about one-third of the particle radius at H (app)=e0 and to decrease with the applied field toward a common limit of similar to 0.4 nm. The mean canting angle relative to the field was also found to decrease for increasing fields, at a rate inversely correlated to the particle size.

Magnetic characterization of ferrihydrite nanoparticles synthesized by hydrolysis of Fe metal-organic precursor

We investigate the formation of ferrihydrite nanoparticles (NPs) by hydrolysis of the Fe(III) alkoxide Fe(O(t)Bu)(3). Controlled amounts of water, up to 3.0 vol%, were added to the precursor solution yielding a series of hydrolyzed samples ranging from P0.0 (the unreacted precursor) to P3.0. X-ray diffraction (XRD) analysis evidenced the formation of high-crystalline ferrihydrite NP in sample P3.0, with grain size estimate of about 3.2 nm. The transition from the molecular precursor to the formation of crystalline magnetic NPs was followed through magnetization measurements M(T) and M(H), as well as Mossbauer spectroscopy (MS). M(T) measurements indicate a paramagnetic (PM) behavior for sample P0.0, characteristic of binuclear Fe-O-Fe units, which evolves to a superparamagnetic (SPM) behavior, with an energy barrier for the blocking process estimated for sample P3.0 as E(a) = 4.9 x 10(-21) J (E(a)/k(B) = 355 K), resulting in a high effective anisotropy constant K(eff) = 290 kJ/m(3). Magnetization loops at 5 K progressively change from PM-like to ferromagnetic-like shape upon increasing the hydrolysis process, although hysteresis (H(c) approximate to 500 Oe) only is apparent for P2.0 and higher. MS spectra at room temperature are PM/SPM doublets for all samples, while the MS spectra at T = 4.2 K reveal increasingly well-defined magnetic ordering as hydrolysis of the precursor stepwise progresses until well-crystallized ferrihydrite particles are formed. (C) 2008 Elsevier B.V. All rights reserved.

Magnetic hysteresis loop shift in NiFe(2)O(4) nanocrystalline powder with large grain boundary fraction

Magnetic properties of nanocrystalline NiFe(2)O(4) spinel mechanically processed for 350 h have been studied using temperature dependent from both zero-field and in-field (57)Fe Mossbauer spectrometry and magnetization measurements. The hyperfine structure allows us to distinguish two main magnetic contributions: one attributed to the crystalline grain core, which has magnetic properties similar to the NiFe(2)O(4) spinel-like structure (n-NiFe(2)O(4)) and the other one due to the disordered grain boundary region, which presents topological and chemical disorder features(d-NiFe(2)O(4)). Mossbauer spectrometry determines a large fraction for the d-NiFe(2)O(4) region(62% of total area) and also suggests a speromagnet-like structure for it. Under applied magnetic field, the n-NiFe(2)O(4) spins are canted with angle dependent on the applied field magnitude. Mossbauer data also show that even under 120 kOe no magnetic saturation is observed for the two magnetic phases. In addition, the hysteresis loops, recorded for scan field of 50 kOe, are shifted in both field and magnetization axes, for temperatures below about 50 K. The hysteresis loop shifts may be due to two main contributions: the exchange bias field at the d-NiFe(2)O(4)/n-NiFe(2)O(4) interfaces and the minor loop effect caused by a high magnetic anisotropy of the d-NiFe(2)O(4) phase. It has also been shown that the spin configuration of the spin-glass like phase is modified by the consecutive field cycles, consequently the n-NiFe(2)O(4)/d-NiFe(2)O(4) magnetic interaction is also affected in this process. (C) 2010 Elsevier B.V. All rights reserved.

Synthesis and characterization of glass-ceramic microspheres for thermotherapy

Glass microspheres containing radionuclides are used to treat liver cancer. A promising alternative therapy is being developed based on the magnetic hyperthermia which is related to the heat supplied by a magnetic material under an alternating current magnetic field. The advantage of this option is that most of killed cells are cancer cells which are more susceptible to the temperature raise. In the present work aluminum iron silicate glasses containing minor glass modifiers and nucleating agents were synthesized as irregular shape particles which were further transformed in microspheres by using a petrol liquefied gas-oxygen torch. The optimized processing parameters which lead to microspheres that give a response to the magnetic field were determined. The dissolution rate in water at 90 degrees C was determined to be 3 x 10(-8) g cm(-2) min(-1). The microsphere size distribution was determined by laser scattering. The crystalline phase responsible for the ferromagnetic response was identified as magnetite. Since this phase has a high saturation magnetization and high Curie temperature, it is potentially useful for biomedical applications. The hysteresis magnetic loop was measured for materials produced in different conditions, and some of them showed to be appropriated for thermotherapy. The ratio Fe(3+)/Fe(total) was determined by Mossbauer spectroscopy. (C) 2010 Elsevier B.V. All rights reserved.

Geochemistry of iron and manganese in soils and sediments of a mangrove system, Island of Pai Matos (Cananeia - SP, Brazil)

Five zones along a transect of 180 m were selected for study on the Island of Pai Matos (Sao Paulo, Brazil). Four of the zones are colonised by vascular plants (Spartina SP, Laguncularia LG, Avicennia AV and Rhizophora RH) and were denominated soils, and the other zone, which lacks vegetation, was denominated sediment (SD). The geochemical conditions differed significantly in soils and sediment and also at different depths. The soils were oxic (Eh > 350 mV) or suboxic (Eh: 350-100 mV) at the surface and anoxic (Eh < 100 mV) at depth, whereas in the sediment anoxic conditions prevailed at all depths, but with a lower concentration of sulphides in the pore water and pyrite in the solid fraction. Under these geochemical conditions Fe is retained in the soils, while the Mn tends to be mobilized and lost. The most abundant form of iron oxyhydroxide was lepidocrocite (mean concentration for all sites and depths, 45 +/- 19 mu mol g(-1)), followed by goethite (30 19 mu mol g(-1))and ferrihydrite (19 +/- 11 mu mol g(-1)),with significant differences among the mean concentrations. There was a significant decrease with depth in all the types of Fe oxyhydroxides measured, particularly the poorly crystalline forms. The pyrite fraction was an important component of the free Fe pool (non-silicate Fe) in all soils as well as in the sediment, especially below 20 cm depth (mean concentration for all sites and depths, 60 +/- 54 mu mol CI). Furthermore, the mean concentration of Fe-pyrite for all sites and depths was higher than that obtained for any of the three Fe oxyhydroxides measured. The Fe-AVS was a minor fraction, indicating that the high concentrations of dissolved Fe in the soils in the upper area of the transect result from the oxidation of Fe sulphides during low tide. Mossbauer spectroscopy also revealed that most of the Fe (III) was associated with silicates, in this case nontronite. The presence of crystals of pyrite associated with phyllosilicates in samples from the upper layer of the soils may indicate that pyritization of this form of Fe(III) is more rapid than usually reported for ocean bed sediments. The sequential extraction of Mn did not reveal any clearly dominant fraction, with the Mn-carbonate fraction being the most prevalent, followed by exchangeable Mn and oxides of Mn, whereas pyrite-Mn and Mn associated with crystalline Fe-oxides were present at significantly lower concentrations. The high concentration of dissolved Mn found in the soils in the lower part of the transect is consistent with the fact that the solubility is determined by the carbonate fraction. Unlike for Fe, in the soils in the higher zone, which are subject to intense drainage during low tide, there was loss of Mn, as reflected by the concentration of total Mn. (C) 2008 Elsevier B.V. All rights reserved.

Effect of Ti-C and Cr Additions on Magnetic Properties of Nanocrystalline (Pr,Nd)-Fe-B Alloys

The addition of both Ti-C and Cr as grain refiners in Nd-Fe-B nanocomposites substantially increases the coercive field Hc. This motived our investigation of the effect of Ti-C and Cr on Pr-Fe-B nanocomposites. Melt-spun ribbons of composition (Pr(9.5)Fe(84.5)B(6))(0.97-x)Cr(x)(TiC)(0.03)(x = 0; 0.25; 0.5; 0.75; 1) and (Nd(9.5)Fe(84.5)B(6))(0.97-x)Cr(x)(TiC)(0.03)(x = 0.5 and 1) were produced for study. For a Pr nanocomposite with 1% Cr, Hc = 12.5 kOe. However, the energy product was limited to 13.6 MGOe by the remanence value. Rietveld analysis of X-ray spectra showed the ribbons to consist of predominantly hard (similar to 70 wt%) R(2)Fe(14)B, the soft phase being (similar to 30 wt%) alpha-Fe. Mossbauer measurements at 300 K are consistent with a reduced hyperfine field for the hard magnetic phase due to the Cr addition. Analysis of transmission electron microscopy images showed the Pr nanocomposite with 1% Cr to have an increased average grain size.

Heterobimetallic compounds [Ru(eta(5)-Cp)(dppf)X] (X = Cl, Br, I and N(3)): synthesis, electrochemical analysis, and the crystal structure of [Ru(eta(5)-Cp)(dppf)I] [dppf=1,1`-bis(diphenylphosphino)ferrocene]

A series of new ruthenium-iron based derivatives [Ru(eta(5)-Cp)(dppf)Cl] (1), [Ru(eta(5)-Cp)(dppf)Br] (2), [Ru(eta(5)-Cp)(dppf)I] (3) and [Ru(eta(5)-Cp)(dppf)N(3)] (4) were obtained by reactions of [Ru(eta(5)-Cp)(PPh(3))(2)Cl] with 1,1`-bis(diphenylphosphino) ferrocene (dppf) and characterized by IR, NMR ((1)H, (13)C and (31)P), (57)Fe Mossbauer spectroscopy and cyclic voltammetry. Additionally, the compound (3) was structurally characterized by X-ray crystallography, and the results were as follows: orthorhombic, Pbca, a = 18.2458(10), b = 20.9192(11), c = 34.4138(19) a""<<, alpha = beta = gamma = 90A degrees, V = 13135.3(12) a""<<(3) and Z = 16.

Synthesis and Crystal Structures of Octahedral Sn(IV) Complexes Prepared from SnCl(2)center dot 2H(2)O and 2-Hydroxyacetophenone (S-benzydithiocarbazate) Ligand (H(2)L)

Two coordination octahedral Sn(IV) complexes [Sn(L)(2)] and cis-[SnCl(2)(L)(dmso)], where H(2)L is 2-hydroxyacetophenone (S-benzydithiocarbazate), were prepared and characterized by elemental analysis, IR, NMR ((1)H, (13)C), (119)Sn Mossbauer spectroscopies and X-ray diffraction techniques to investigate their structural properties. Both crystallize in the Monoclinic system, with parameters: a = 8.1905(3), b = 30.8811(15), c = 12.8959(7) angstrom, beta = 94.465(3)degrees and Z = 4 for [Sn(L)(2)] and a = 8.5247(2), b = 21.5445(7), c = 12.3706(3) angstrom, beta = 96.932(2)degrees and Z = 4 for cis-[SnCl(2)(L)(dmso)]. In both complexes, the Sn(IV) central atom is coordinated in a distorted octahedral geometry with the thiolate ligand (L(2-)) coordinated via O, N and S atoms. The (119)Sn Mossbauer spectroscopy of the complexes were studied and the results revealed that both complexes posses isomer shift (delta) and quadrupole splitting (Delta), which are almost the same.

Tectonic fabric revealed by AARM of the proterozoic mafic dike swarm in the Salvador city (Bahia state): Sao Francisco Craton, NE Brazil

Magnetic fabric and rock magnetism studies were performed on 25 unmetamorphosed mafic dikes of the Meso-Late Proterozoic (similar to 1.02 Ga) dike swarm from Salvador (Bahia State, NE Brazil). This area lies in the north-eastern part of the Sao Francisco Craton, which was dominantly formed/reworked during the Transamazonian orogeny (2.14-1.94 Ga). The dikes crop out along the beaches and in quarries around Salvador city, and cut across both amphibolite dikes and granulites. Their widths range from a few centimeters up to 30 m with an average of similar to 4 m, and show two main trends N 140-190 and N 100-120 with vertical dips. Magnetic fabrics were determined using both anisotropy of low-field magnetic susceptibility (AMS) and anisotropy of anhysteretic remanent magnetization (AARM). The magnetic mineralogy was investigated by many experiments including remanent magnetization measurements at variable low temperatures (10-300 K), Mossbauer spectroscopy, high temperature magnetization curves (25-700 degrees C) and scanning electron microscopy (SEM). The rock magnetism study suggests pseudo-single-domain magnetite grains carrying the bulk magnetic susceptibility and AARM fabrics. The magnetite grains found in these dikes are large and we discard the presence of single-domain grains. Its composition is close to stoichiometric with low Ti substitution, and its Verwey transition occurs around 120 K. The main AMS fabric recognized in the swarm is so-called normal, in which the K(max)-K(int) plane is parallel to the dike plane and the magnetic foliation pole K(min)) is perpendicular to it. This fabric is interpreted as due to magma flow, and analysis of the K m inclination permitted to infer that approximately 80% of the dikes were fed by horizontal or sub-horizontal flows (K(max) < 30 degrees). This interpretation is supported by structural field evidence found in five dikes. In addition, based on the plunge of K(max), two mantle sources could be inferred; one of them which fed about 80% of the swarm would be located in the southern part of the region, and the other underlied the Valeria quarry. However, for all dikes the AARM tensors are not coaxial with AMS fabrics and show a magnetic lineation (AARM(max)) oriented to N30-60E, suggesting that magnetite grains were rotated clockwise from dike plane. The orientation of AARM lineation is similar to the orientation of a system of faults in which the Salvador normal fault is the most important. These faults were formed during Cretaceous rifting in the Reconcavo-Tucano-jatoba assemblage that corresponds to an aborted intra-continental rift formed during the opening of the South Atlantic. Therefore, the AARM fabric found for the Salvador dikes is probably tectonic in origin and suggests that the dike swarm was affected by the important tectonic event responsible for the break-up of the Gondwanaland. (C) 2008 Elsevier B.V. All rights reserved.