R. S. Freitas

Magnetic tuning of all-organic binary alloys between two stable radicals

Mixtures of 2-(4,5,6,7-tetrafluorobenzimidazol-2-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (F4BImNN) and 2-(benzimidazol-2-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (BImNN) crystallize as solid solutions (alloys) across a wide range of binary compositions. (F4BImNN)(x)(BImNN)((1-x)) with x < 0.8 gives orthorhombic unit cells, while x ≥ 0.9 gives monoclinic unit cells. In all crystalline samples, the dominant intermolecular packing is controlled by one-dimensional (1D) hydrogen-bonded chains that lead to quasi-1D ferromagnetic behavior. Magnetic analysis over 0.4-300 K indicates ordering with strong 1D ferromagnetic exchange along the chains (J/k = 12-22 K). Interchain exchange is estimated to be 33- to 150-fold weaker, based on antiferromagnetic ordered phase formation below Néel temperatures in the 0.4-1.2 K range for the various compositions. The ordering temperatures of the orthorhombic samples increase linearly as (1 - x) increases from 0.25 to 1.00. The variation is attributed to increased interchain distance corresponding to decreased interchain exchange, when more F4BImNN is added into the orthorhombic lattice. The monoclinic samples are not part of the same trend, due to the different interchain arrangement associated with the phase change.

Guanidine-functionalized Fe3O4 magnetic nanoparticles as basic recyclable catalysts for biodiesel production

Two organic superbases, 1,5,7-triazabicyclo[4,4,0]dec-5-ene (TBD) and 1,1,3,3-tetramethylguanidine (TMG), were anchored onto silica-coated and uncoated iron oxide nanoparticles, resulting in three (MNP–TBD, MNP–TMG and MNP@SiO2–TBD) recoverable basic nanocatalysts. The nanocatalysts were fully characterized by elemental analysis, infrared and Raman spectroscopies, X-ray diffraction, transmission electron microscopy, N2 adsorption/desorption isotherms, thermogravimetric analysis and magnetic measurements. X-ray diffraction indicated the presence of a spinel-structured iron oxide, and Raman spectroscopy revealed both magnetite and maghemite phases in the prepared nanocatalysts. The average particle sizes of the nanocatalysts were in the range of 11 to 12 nm, and they exhibited superparamagnetic behaviour at 300 K. Infrared spectroscopy indicated the presence of the superbases (TBD and TMG) on the surface of the silica-coated and uncoated iron oxide nanoparticles. The performance of the nanocatalysts was tested in the methanolysis reaction of soybean oil under different conditions. At the end of each reaction, the nanocatalysts were magnetically recovered from the medium, and the product was analysed and quantified by high-performance liquid chromatography (HPLC). MNP–TBD exhibited the best catalytic performance in the first cycle (96% biodiesel conversion); however, MNP@SiO2–TBD exhibited the best reusability.

The magnetic behavior of the intermetallic compound NdMn2Ge2 studied by magnetization and hyperfine interactions measurements

The magnetic behavior of the intermetallic compound NdMn2Ge2 was investigated by bulk magnetization measurements and measurements of hyperfine interactions using perturbed γ–γ angular correlation (PAC) spectroscopy. Magnetization measurements indicate the presence of four magnetic transitions associated with the Mn and Nd magnetic sublattices. At high temperatures, magnetic measurements show a change in the slope of the magnetization due to an antiferromagnetic transition around TN ∼ 425 K and a well defined ferromagnetic transition at TC ∼ 320 K. Moreover, at ∼210 K a peak is observed in the magnetization curve, which is assigned to the reorientation of the Mn spin, and at ∼25 K an increase in the magnetic moment is also observed, which is ascribed to the ordering of Nd ions. PAC measurements using 140La(140Ce) and 111In(111Cd) probe nuclei allowed the determination of the temperature dependence of the magnetic hyperfine field (Bhf) at Nd and Mn sites, respectively. PAC results with 111Cd probe nuclei at...

Stable tetragonal phase and magnetic properties of Fe-doped HfO2 nanoparticles

In this paper, the effect in structural and magnetic properties of iron doping with concentration of 20% in hafnium dioxide (HfO2) nanoparticles is investigated. HfO2 is a wide band gap oxide with great potential to be used as high-permittivity gate dielectrics, which can be improved by doping. Nanoparticle samples were prepared by sol-gel chemical method and had their structure, morphology, and magnetic properties, respectively, investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) with electron back scattering diffraction (EBSD), and magnetization measurements. TEM and SEM results show size distribution of particles in the range from 30 nm to 40 nm with small dispersion. Magnetization measurements show the blocking temperature at around 90 K with a strong paramagnetic contribution. XRD results show a major tetragonal phase (94%).In this paper, the effect in structural and magnetic properties of iron doping with concentration of 20% in hafnium dioxide (HfO2) nanoparticles is investigated. HfO2 is a wide band gap oxide with great potential to be used as high-permittivity gate dielectrics, which can be improved by doping. Nanoparticle samples were prepared by sol-gel chemical method and had their structure, morphology, and magnetic properties, respectively, investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) with electron back scattering diffraction (EBSD), and magnetization measurements. TEM and SEM results show size distribution of particles in the range from 30 nm to 40 nm with small dispersion. Magnetization measurements show the blocking temperature at around 90 K with a strong paramagnetic contribution. XRD results show a major tetragonal phase (94%).

Rare earth coordination dinuclear compounds constructed from 3,5-dicarboxypyrazolate and succinate intermetallic bridges

In this paper we describe the synthesis of a new family of rare earth compounds of general formula [RE2(dcpz)2(suc)(H2O)8]·(H2O)1.5, where RE = Y (1), La (2), Ce (3), Pr (4), Nd (5), Sm (6), Gd (7), Tb (8), Dy (9), Ho (10), Er (11), Tm (12) and Yb (13); dcpz = 3,5-dicarboxypyrazolate; suc = succinate. Single crystal X-ray diffraction studies showed that all the complexes are isostructural and crystallize in the triclinic system, space group P. They exist as dinuclear discrete molecules in which the metallic centers are linked together by dcpz and suc bridges. Hydrogen bonds between dimers give rise to a 3D bcu supramolecular network with topology (424·64). Solid-state photoluminescence studies revealed that the ligand-to-metal energy transfer mechanism is responsible for the visible emission of Sm (6), Tb (8) and Dy (9) compounds while for (5), near-infrared (1060 nm) emission was obtained by the direct excitation f orbitals in the Nd3+ ion. Magnetization measurements indicated antiferromagnetic interactions between the RE3+ ions, except Y3+ (1) and La3+ (2).

Properties of Gd2O3 nanoparticles studied by hyperfine interactions and magnetization measurements

The magnetic behavior of Gd2O3 nanoparticles, produced by thermal decomposition method and subsequently annealed at different temperatures, was investigated by magnetization measurements and, at an atomic level, by perturbed γ − γ angular correlation (PAC) spectroscopy measuring hyperfine interactions at 111In(111Cd) probe nuclei. Nanoparticle structure, size and shape were characterized by X-ray diffraction (XRD) and Transmission Electron Microscopy (TEM). Magnetization measurements were carried out to characterize the paramagnetic behavior of the samples. XRD results show that all samples crystallize in the cubic-C form of the bixbyite structure with space group Ia3. TEM images showed that particles annealed at 873 K present particles with highly homogeneous sizes in the range from 5 nm to 10 nm and those annealed at 1273 K show particles with quite different sizes from 5 nm to 100 nm, with a wide size distribution. PAC and magnetization results show that samples annealed at 873 and 1273 K are paramagne...

submitter : Cd and In-doping in thin film SnO2

In this paper, we investigate the effects of doping in the local structure of SnO2 by measuring the hyperfine interactions at impurity nuclei using the Time Differential Perturbed Gamma-Gamma Angular Correlation (TDPAC) method in addition to density functional theory simulations. The hyperfine field parameters have been probed as a function of the temperature in thin film samples. The experimental results reveal that 117Cd/In and 111In/Cd are incorporated and stabilized in the SnO2 lattice replacing the cationic site. Significant differences in the electric field gradient were observed from TDPAC measurements with both the probe nuclei. Furthermore, the absence of strongly damped spectra further indicates that implanted Cd atoms (for 117Cd/In probe nuclei measurements) easily occupy regular substitutional Sn sites with good stability. The simulated value for the electric field gradient obtained with the first oxygen neighbor removed is closer to the experimental value observed for 117Cd, which also indica...

Characterization of magnetic phase transitions in PrMn2Ge2 compound investigated by magnetization and hyperfine field measurements

The magnetic properties of PrMn2Ge2 compound have been investigated by perturbed γ−γ angular correlation (PAC) spectroscopy using 111In(111Cd) as probe nuclei as well as by magnetization measurements. This ternary intermetallic compound exhibits different magnetic structures depending on the temperature. The magnetic ordering is mainly associated with the magnetic moment of 3d-Mn sublattice but at low temperatures a magnetic contribution due to ordering of the magnetic moment from 4f-Pr sublattice appears. PAC results with 111Cd probe nuclei at Mn sites show that the temperature dependence of hyperfine field Bhf(T) follows the expected behavior for the host magnetization, which could be fitted by two Brillouin functions, one for antiferromagnetic phase and the other for ferromagnetic phase, associated with the magnetic ordering of Mn ions. Magnetization measurements showed the magnetic behavior due to Mn ions highlighting the antiferromagnetic to ferromagnetic transition around 326 K and an increase in th...

Synthesis and magnetic characterization of TmCo2B2C

A new quaternary intermetallic borocarbide TmCo2B2C has been synthesized via a rapid-quench of an arc-melted ingot. Elemental and powder-diffraction analyses established its correct stoichiometry and single-phase character. The crystal structure is isomorphous to that of TmNi2B2C(I4/mmm) and is stable over the studied temperature range. Above 7 K, the paramagnetic state follows the modified Curie-Weiss behavior (X=C/(T-theta)+X0 wherein X0=0.008(1) emu/mole and the temperature-dependent term reflecting the paramagnetism of the Tm subsystem: ueff=7.6(2) uB [in agreement with the expected value for a free Tm3+ ion] and theta = -4.5(3) K. Long range ferromagnetic order of the Tm sublattice is observed to develop around ~1 K. No superconductivity is detected in TmCo2B2C down to 20 mK, a feature which is consistent with the general trend in the RCo2B2C series. Finally, the influence of the rapid-quench process on the magnetism (and superconductivity) of TmNi2B2C will be discussed and compared to that of TmCo2B2C.

Synthesis and atomic scale characterization of Er2O3 nanoparticles: enhancement of magnetic properties and changes in the local structure

In the investigation reported in this paper a modified thermal decomposition method was developed to produce very small Er2O3 nanoparticles (NPs). Particles structure, shape and size were characterized by x-ray diffraction and transmission electron microscopy which showed that the synthesis by thermal decomposition under O2 atmosphere produced very small and monodisperse NPs, allowing the investigation of finite-size and surface effects. Results of magnetization measurements showed that the smallest particles present the highest values of susceptibility that decrease as particle size increases. Specific heat measurements indicate that the sample with the smallest NPs (diameter ∼5 nm) has a Néel temperature of 0.54 K. The local structure of particles was investigated by measurements of hyperfine interactions with perturbed angular correlation spectroscopy using 111Cd as probe nuclei replacing the cationic sites. Results showed that the relative population of sites 8b increases in both the core and surface layer of particles.