Preparation of La0.7Ca0.3-xSrxMnO3 Manganites by Four Synthesis Methods and Their Influence on the Magnetic Properties and Relative Cooling Power.

Manganites of the family La0.7Ca0.3-xSrxMnO3 were fabricated by four preparation methods: (a) the microwave-assisted sol-gel Pechini method; (b) sol-gel Pechini chemical synthesis; (c) solid-state reaction with a planetary mill; and (d) solid-state reaction with an attritor mill, in order to study the effect of the preparation route used on its magnetocaloric and magnetic properties. In addition, the manganites manufactured by the Pechini sol-gel method were compacted using Spark Plasma Sintering (SPS) to determine how the consolidation process influences its magnetocaloric properties. The Curie temperatures of manganites prepared by the different methods were determined in ~295 K, with the exception of those prepared by a solid-state reaction with an attritor mill which was 301 K, so there is no correlation between the particle size and the Curie temperature. All samples gave a positive slope in the Arrot plots, which implies that the samples underwent a second order Ferromagnetic (FM)⁻Paramagnetic (PM) phase transition. Pechini sol-gel manganite presents higher values of Relative Cooling Power (RCP) than the solid-state reaction manganite, because its entropy change curves are smaller, but wider, associated to the particle size obtained by the preparation method. The SPS technique proved to be easier and faster in producing consolidated solids for applications in active magnetic regenerative refrigeration compared with other compaction methods.

First Order Reversal Curve Study of SmFe2 Melt-Spun Ribbons.

First-order reversal curves (FORC) and the FORC distribution provide a detailed characterization of the relative proportions of reversible and irreversible components of the magnetization of a material, revealing the dominant interactions in the system. Alloys with the nominal composition SmFe2 were obtained by melt-spinning with a cooper wheel velocity of 30 m/s. X-ray powder diffraction analysis showed a greater part consisting of an amorphous phase and a very small amount of SmFe2 crystalline phase with an average crystallite size of 8 nm. A constant acceleration Mössbauer spectrum, measured at room temperature in transmission mode, was fitted to a continuous distribution of effective fields at the nucleus of the amorphous phase (about 84% of the total area), plus two sextets for the non-equivalent sites of Fe in the SmFe2 crystalline phase. 91 first-order reversal curves were collected in a Quantum Design PPMS-VSM with reversal fields from ⁻800 mT to +800 mT and using a calibration field of 850 mT. The obtained FORC diagrams showed a combined effect of a local interaction field and a mean interaction field, and showed that the reversible magnetization is a function of both, the applied magnetic field and the irreversible magnetization.

Effect of Native Defects on Transport Properties in Non-Stoichiometric CoSb3.

The effect of native defects originated by a non-stoichiometric variation of composition in CoSb3 on I-V curves and Hall effect was investigated. Hysteretic and a non-linear behavior of the  I-V curves at cryogenic temperatures were observed; the non-linear behavior originated from the Poole-Frenkel effect, a field-dependent ionization mechanism that lowers Coulomb barriers and increases emission of charge carriers, and the hysteresis was attributed to the drastic decrease of specific heat which produces Joule heating at cryogenic temperatures. CoSb3 is a narrow gap semiconductor and slight variation in the synthesis process can lead to either n- or p-type conduction. The Sb-deficient CoSb3 presented an n-type conduction. Using a single parabolic model and assuming only acoustic-phonon scattering the charge transport properties were calculated at 300 K. From this model, a carrier concentration of 1.18 × 1018 cm-3 and a Hall factor of 1.18 were calculated. The low mobility of charge carriers, 19.11 cm²/V·s, and the high effective mass of the electrons, 0.66 m0, caused a high resistivity value of 2.75 × 10-3 Ω·m. The calculated Lorenz factor was 1.50 × 10-8 V²/K², which represents a decrease of 38% over the degenerate limit value (2.44 × 10-8 V²/K²).

Role of vanadium ions, oxygen vacancies, and interstitial zinc in room temperature ferromagnetism on ZnO-V2O5 nanoparticles.

In this work, we present the role of vanadium ions (V+5 and V+3), oxygen vacancies (VO), and interstitial zinc (Zni) to the contribution of specific magnetization for a mixture of ZnO-V2O5 nanoparticles (NPs). Samples were obtained by mechanical milling of dry powders and ethanol-assisted milling for 1 h with a fixed atomic ratio V/Zn?=?5% at. For comparison, pure ZnO samples were also prepared. All samples exhibit a room temperature magnetization ranging from 1.18?×?10-3 to 3.5?×?10-3 emu/gr. Pure ZnO powders (1.34?×?10-3 emu/gr) milled with ethanol exhibit slight increase in magnetization attributed to formation of Zni, while dry milled ZnO powders exhibit a decrease of magnetization due to a reduction of VO concentration. For the ZnO-V2O5 system, dry milled and thermally treated samples under reducing atmosphere exhibit a large paramagnetic component associated to the formation of V2O3 and secondary phases containing V+3 ions; at the same time, an increase of VO is observed with an abrupt fall of magnetization to σ?~?0.7?×?10-3 emu/gr due to segregation of V oxides and formation of secondary phases. As mechanical milling is an aggressive synthesis method, high disorder is induced at the surface of the ZnO NPs, including VO and Zni depending on the chemical environment. Thermal treatment restores partially structural order at the surface of the NPs, thus reducing the amount of Zni at the same time that V2O5 NPs segregate reducing the direct contact with the surface of ZnO NPs. Additional samples were milled for longer time up to 24 h to study the effect of milling on the magnetization; 1-h milled samples have the highest magnetizations. Structural characterization was carried out using X-ray diffraction and transmission electron microscopy. Identification of VO and Zni was carried out with Raman spectra, and energy-dispersive X-ray spectroscopy was used to verify that V did not diffuse into ZnO NPs as well to quantify O/Zn ratios.

Removal of total organic carbon from sewage wastewater using poly(ethylenimine)-functionalized magnetic nanoparticles.

The increased levels of organic carbon in sewage wastewater during recent years impose a great challenge to the existing wastewater treatment process (WWTP). Technological innovations are therefore sought that can reduce the release of organic carbon into lakes and seas. In the present study, magnetic nanoparticles (NPs) were synthesized, functionalized with poly(ethylenimine) (PEI), and characterized using TEM (transmission electron microscopy), X-ray diffraction (XRD), FTIR (Fourier transform infrared spectroscopy), CCS (confocal correlation spectroscopy), SICS (scattering interference correlation spectroscopy), magnetism studies, and thermogravimetric analysis (TGA). The removal of total organic carbon (TOC) and other contaminants using PEI-coated magnetic nanoparticles (PEI-NPs) was tested in wastewater obtained from the Hammarby Sjöstadsverk sewage plant, Sweden. The synthesized NPs were about 12 nm in diameter and showed a homogeneous particle size distribution in dispersion by TEM and CCS analyses, respectively. The magnetization curve reveals superparamagnetic behavior, and the NPs do not reach saturation because of surface anisotropy effects. A 50% reduction in TOC was obtained in 60 min when using 20 mg/L PEI-NPs in 0.5 L of wastewater. Along with TOC, other contaminants such as turbidity (89%), color (86%), total nitrogen (24%), and microbial content (90%) were also removed without significant changes in the mineral ion composition of wastewater. We conclude that the application of PEI-NPs has the potential to reduce the processing time, complexity, sludge production, and use of additional chemicals in the WWTP.