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NaxFe1/2Mn1/2O2 (x = 1 and 2/3) layered oxides were prepared by an improved solid-state synthesis method. The XRD analysis confirmed the high purity of these samples. The Rietveld refinement of the crystalline structure illustrated that the prepared materials crystallize in a hexagonal system in the R3Ìm space group with the P3 structure for x = 1 and in a rhombohedral system with the P63/mmc space group and P2 structure type for x = 2/3. The vibrational study undertaken using IR and Raman spectroscopy techniques yielded the existence of an MO6 group. Their dielectric properties were determined in frequency range 0.1-107 Hz for a temperature range 333-453 K. The permittivity results indicated the presence of two types of polarization, namely dipolar polarization and space charge polarization. The frequency dependence of the conductivity was interpreted in terms of Jonscher's law. The DC conductivity followed the Arrhenius laws either at low or at high temperatures. The temperature dependence of the power law exponent which corresponds to the grain (s2) suggested that the conduction of the P3-NaFe1/2Mn1/2O2 compound is ascribed to the CBH model, while P2-Na2/3Fe1/2Mn1/2O2 can be attributed to the OLPT model.
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The compound NaCu0.2Fe0.3Mn0.5O2 was synthesized using a solid-state method and it crystallized in a hexagonal system with a R3Ìm space group in an O3-type phase. The optical properties were measured using UV-Vis absorption spectrometry to determine the absorption coefficient α and the optical band gap E g. The optical band gap energy of this sample is 2.45 eV, which indicates that it has semiconductor characteristics. Furthermore, the electrical and dielectric properties of the material were investigated using complex impedance spectroscopy between 10-1 Hz and 106 Hz at various temperatures (333-453 K). The permittivity results prove that there are two types of polarization, dipolar polarization and space charge polarization. The Nyquist diagrams show the contribution of the effects of the grain, grain boundary, and electrode properties. The frequency dependence of the conductivity was interpreted in terms of Jonscher's law. The DC conductivity follows both the Mott and Arrhenius laws at low and high temperature, respectively. The temperature dependence of the power law exponent(s) suggests that the overlapping large polaron tunneling (OLPT) model is the dominant transport process in this material. The optimum hopping length of the polaron (4 Å) is large compared with the interatomic spacing (2.384 Å for Na-O and 2.011 Å for Cu, Fe, Mn-O).
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In pharmaceutical applications, the porous particles of organic compounds can improve the efficiency of drug delivery, for example into the pulmonary system. We report on the successful preparation of macroporous spherical granules of mannitol using a spray-drying process using polystyrene (PS) beads of ~340 nm diameter as a sacrificial templating agent. An FDA-approved solvent (ethyl acetate) was used to dissolve the PS beads. A combination of infrared spectroscopy and thermogravimetry analysis proved the efficiency of the etching process, provided that enough PS beads were exposed at the granule surface and formed an interconnected network. Using a lab-scale spray dryer and a constant concentration of PS beads, we observed similar granule sizes (~1-3 microns) and different porosity distributions for the mannitol/PS mass ratio ranging from 10:1 to 1:2. When transferred to a pilot-scale spray dryer, the 1:1 mannitol/PS composition resulted in different distributions of granule size and porosity depending on the atomization configuration (two-fluid or rotary nozzle). In all cases, the presence of PS beads in the spray-drying feedstock was found to favor the formation of the α mannitol polymorph and to lead to a small decrease in the mannitol decomposition temperature when heating in an inert atmosphere.
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Phosphorene is a new two-dimensional material that has recently attracted much attention owing to its fascinating electrical, optical, thermal and chemical properties. Here, we report on high-quality exfoliation of black phosphorus nanosheets, with controllable size produced in large quantities by liquid-phase exfoliation using N-methyl-2-pyrrolidone (NMP) as a solvent under ambient conditions. The as-synthesized few layers show a great potential for solar energy conversion based on the optical results shown in this work.
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The disodium cobalt(ii) orthosilicate material (NCS) has been synthesized using improved solid-state (NCS-SS) and co-precipitation (NCS-CP) methods of synthesis. The Rietveld refinement of the XRD pattern of Na2CoSiO4 has demonstrated an orthorhombic crystal system with the space groups Pna21 and Pbca for NCS-SS and NCS-CP respectively. The elemental mapping of microstructures by scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) showed the porous morphology and the homogenous particles of the Na2CoSiO4 powders. Their dielectric properties were measured in the frequency and temperature ranges of 0.1-106 Hz and 383-613 K respectively. Different dielectric relaxation phenomena associated with the Na+-ion migration through different paths were displayed in relation with the temperature and frequency. The decrease and increase in the dielectric properties were found to be dependent on the formation of short-range ordered structure formed after the migration of Na+-ions. In the present work, an attempt has been made to study the relation between the structural properties and the dielectric process. Thus, interesting insights into the transport behavior of Na+-ions in different chemical environments were obtained. This in turn provides an effective procedure to probe the relationship between the diffusion pathway of Na+-ions and the dielectric response.
RESUMEN
Ba2Mg0.4Co1.6Fe12O22 was prepared in powder form by sonochemical co-precipitation and examined by X-ray diffraction, Mössbauer spectroscopy and magnetization measurements. Careful XRD data analyses revealed the Y-type hexaferrite structure as an almost pure phase with a very small amount of CoFe2O4 as an impurity phase (about 1.4%). No substantial changes were observed in the unit cell parameters of Ba2Mg0.4Co1.6Fe12O22 in comparison with the unsubstituted compound. The Mössbauer parameters for Ba2Mg0.4Co1.6Fe12O22 were close to those previously found (within the limits of uncertainty) for undoped Ba2Mg2Fe12O22. Isomer shifts (0.27-0.38 mm/s) typical for high-spin Fe3+ in various environments were evaluated and no ferrous Fe2+ form was observed. However, despite the indicated lack of changes in the iron oxidation state, the cationic substitution resulted in a significant increase in the magnetization and in a modification of the thermomagnetic curves. The magnetization values at 50 kOe were 34.5 emu/g at 4.2 K and 30.5 emu/g at 300 K. The zero-field-cooled (ZFC) and field-cooled (FC) magnetization curves were measured in magnetic fields of 50 Oe, 100 Oe, 500 Oe and 1000 Oe, and revealed the presence of two magnetic phase transitions. Both transitions are shifted to higher temperatures compared to the undoped compound, while the ferrimagnetic arrangement at room temperature is transformed to a helical spin order at about 195 K, which is considered to be a prerequisite for the material to exhibit multiferroic properties.
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Li2M(WO4)2 (M = Co, Cu or Ni) materials have been synthesized using the solid-state reaction method. X-ray diffraction measurements confirmed the single phase of the synthesized compounds in the triclinic crystal system (space group P1Ì). The SEM analyses revealed nearly spherical morphology with the particle size in the range of 1-10 µm. The IR spectra confirm the presence of all modes of WO4 2-. The impedance spectroscopy measurements showed the presence of grain boundaries and allow determination of the conductivity of the synthesized materials at room temperature. As positive electrode materials for lithium ion batteries, Li2M(WO4)2 (M = Co, Cu or Ni) cathode materials deliver initial discharge capacities of 31, 33 and 30 mA h g-1 for cobalt, nickel, and copper, respectively.
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A hydrothermal synthesis route was used to synthesize iron(III) phosphate hydroxide hydrate-carbon nanotube composites. Carbon nanotubes (CNT) were mixed in solution with Fe1.19(PO4)(OH)0.57(H2O)0.43 (FPHH) precursors for one-pot hydrothermal reaction leading to the FPHH/CNT composite. This produces a highly electronic conductive material to be used as a cathode material for Li-ion battery. The galvanostatic cycling analysis shows that the material delivers a specific capacity of 160 mAh g-1 at 0.2 C (0.2 Li per fu in 1 h), slightly decreasing with increasing current density. A high charge-discharge cyclability is observed, showing that a capacity of 120 mAh g-1 at 1 C is maintained after 500 cycles. This may be attributed to the microspherical morphology of the particles and electronic percolation due to CNT but also to the unusual insertion mechanism resulting from the peculiar structure of FPHH formed by chains of partially occupied FeO6 octahedra connected by PO4 tetrahedra. The mechanism of the first discharge-charge cycle was investigated by combining operando X-ray diffraction and 57Fe Mössbauer spectroscopy. FPHH undergoes a monophasic reaction with up to 10% volume changes based on the Fe3+/Fe2+ redox process. However, the variations of the FPHH lattice parameters and the 57Fe quadrupole splitting distributions during the Li insertion-deinsertion process show a two-step behavior. We propose that such mechanism could be due to the existence of different types of vacant sites in FPHH, including vacant "octahedral" sites (Fe vacancies) that improve diffusion of Li by connecting the one-dimensional channels.
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The performance of electrode materials in lithium-ion (Li-ion), sodium-ion (Na-ion) and related batteries depends not only on their chemical composition but also on their microstructure. The choice of a synthesis method is therefore of paramount importance. Amongst the wide variety of synthesis or shaping routes reported for an ever-increasing panel of compositions, spray-drying stands out as a versatile tool offering demonstrated potential for up-scaling to industrial quantities. In this review, we provide an overview of the rapidly increasing literature including both spray-drying of solutions and spray-drying of suspensions. We focus, in particular, on the chemical aspects of the formulation of the solution/suspension to be spray-dried. We also consider the post-processing of the spray-dried precursors and the resulting morphologies of granules. The review references more than 300 publications in tables where entries are listed based on final compound composition, starting materials, sources of carbon etc.
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To achieve an efficient lung delivery and efficacy, both active ingredient aerosolisation properties and permeability through the lung need to be optimized. To overcome these challenges, the present studies aim to develop cyclodextrin-based spray-dried microparticles containing a therapeutic corticosteroid (budesonide) that could be used to control airway inflammation associated with asthma. The complexation between budesonide and hydroxypropyl-ß-cyclodextrin (HPBCD) has been investigated. Production of inhalation powders was carried out using a bi-fluid nozzle spray dryer and was optimized based on a design of experiments. Spray-dried microparticles display a specific "deflated-ball like shape" associated with an appropriate size for inhalation. Aerodynamic assessment show that the fine particle fraction was increased compared to a classical lactose-based budesonide formulation (44.05 vs 26.24%). Moreover, the budesonide permeability out of the lung was shown to be reduced in the presence of cyclodextrin complexes. The interest of this sustained budesonide release was evaluated in a mouse model of asthma. The anti-inflammatory effect was compared to a non-complexed budesonide formulation at the same concentration and attests the higher anti-inflammatory activity reach with the cyclodextrin-based formulation. This strategy could therefore be of particular interest for improving lung targeting while decreasing systemic side effects associated with high doses of corticosteroids. In conclusion, this works reports that cyclodextrins could be used in powder for inhalation, both for their abilities to improve active ingredient aerosolisation properties and further to their dissolution in lung fluid, to decrease permeability out of the lungs leading to an optimized activity profile.
