The master sintering curves for BaTi0.975Sn0.025O3/BaTi0.85Sn0.15O3 functionally graded materials

The most important aim in the design and processing of functionally graded materials (FGMs) is to produce devices free from any deformation. Smart choices of different combination of graded layers, as well as the heating rate during sintering, are important for the fabrication of high-quality FGMs. In this study, BaTi_0.975Sn_0.025O₃/BaTi_0.85Sn_0.15O₃ (noted as BTS2.5 and BTS15, respectively) FGM was used as a model system for the construction of master sintering curves (MSCs) and estimation of the effective activation energies of sintering for different BTS graded layers. The MSCs were constructed, for BTS2.5 and BTS15 graded layers in FGMs, using shrinkage data obtained by a heating microscope during sintering at four constant heating rates, 2, 5, 10 and 20 °/min. The effective activation energies were determined using the concept of MSC; values of 359.5 and 340.5 kJ/mol were obtained for graded layers BTS2.5 and BTS15, respectively. A small difference of the effective activation energies of chosen powders made it possible for us to prepare high-quality FGMs, without delamination, distortion or other forms of defects.     

Nanocrystalline Zn2SnO4/SnO2: Crystal structure and humidity influence on complex impedance

Journal of Electroceramics - Nanocrystalline Zn2SnO4/SnO2 powder was obtained by a solid state reaction of ZnO and SnO2 nanopowders mixed in the molar ratio 1:1. The phase composition of the...     

ZnO micro and nanocrystals with enhanced visible light absorption

In this paper, we investigate the effect of the particle size and morphology on the optical properties of ZnO. A series of ZnO micro and nanocrystals were synthesized by the hydrothermal processing of zinc acetate dihydrate and sodium hydroxide as the starting materials, and polyvinylpyrrolidone (PVP) as the polymer surfactant. The particle size and morphology were tailored by adjusting the reactant molar ratios [Zn²⁺]/[OH⁻], while the reaction temperature and the time remained unchanged. X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and high-resolution TEM (HRTEM) have shown that the micro and nanocrystals have a high crystalline pure wurtzite-type hexagonal structure with nanosized crystallites. The size and morphology of the ZnO micro and nanocrystals were investigated by field emission scanning electron microscopy (FE-SEM), which showed a modification from micro-rods via hexagonal-faceted prismatic morphology to nanospheres, caused by simple adjustment of the reactant molar ratio [Zn²⁺]/[OH⁻] from 1:1 to 1:5. The optical properties of the ZnO micro and nanocrystals, as well as their dependence on the particle size and morphology were investigated by Raman and ultraviolet–visible (UV–vis) diffuse reflectance spectroscopy (DRS). The UV–vis spectra showed that the modification of the particle size and morphology from nanospheres to micro-rods resulted in increased absorption, and a slight red-shift of the absorption edge (0.06 eV). Besides, the band gap energy of the synthesized ZnO micro and nanocrystals showed the red shift (∼0.20 eV) compared to bulk ZnO. According to the results of a Raman spectroscopy, the enhanced visible light absorption of the ZnO micro and nanocrystals is related to two phenomena: (1) the existence of lattice defects (oxygen vacancies and zinc interstitials), and (2) the particle surface sensitization by PVP.     

Electrical properties of barium titanate stannate functionally graded materials

Barium titanate stannate (BTS) functionally graded materials (FGMs) with different tin/titanium concentration gradient were prepared by the powder-stacking method and uniaxially pressing process, followed by sintering. Impedance spectroscopy (IS) was used to determine the electrical characteristics of FGMs and ingredient BTS ceramics, as well as to distinguish the grain-interior and grain boundary resistivity of the ceramics. Activation energies of FGMs and ingredients were calculated. It has been established that for BTS ceramics the activation energy deduced from grain-interior conductivity (0.73–0.75 eV) is defined by chemical composition, while activation energy for grain boundary conductivity (1.07–1.25 eV) is influenced by microstructural development (density and average grain size). Furthermore, for FGMs, activation energy for grain-interior conductivity kept the intrinsic properties (0.74–0.78 eV) and did not depend on tin/titanium concentration gradient, while activation energy (1.03–1.29 eV) for grain boundary was determined by the microstructural gradient. No point dissipation was observed by IS, accordingly, no insulator interfaces (cracks and/or delamination) between graded layers were detected.     

Synthesis of CaOSiO2 compounds and their testing as heterogeneous catalysts for transesterification of sunflower oil

The powder mixtures of calcium oxide (CaO) and silica gel (SiO₂) in molar ratios of 1:1, 1.5:1, 2:1 and 3:1 were mechanochemically treated with the addition of water, and were subsequently calcined with a goal of synthesizing CaSiO_3, Ca₃Si₂O₇, Ca₂SiO₄ compounds and CaO/Ca₂SiO₄ two-phase mixture. The prepared materials were characterized by XRD, FTIR, SEM/EDS, particle size laser diffraction (PSLD), UV–vis diffuse reflectance spectroscopy (DRS), N₂ adsorption/desorption isotherms, Hammett indicator for basic strength and volumetric analysis for free CaO content. The catalytic activity of calcium silicates with different Ca/Si ratios was tested in the transesterification of triacylglycerols (sunflower oil) with methanol. Samples obtained with initial composition 2CaO·SiO₂ and 3CaO·SiO₂ calcined at 700?°C, and 3CaO·SiO₂ calcined at 900?°C had high catalytic activity, resulting with triacylglycerols conversion and fatty acids methyl ester formation (FAME or biodiesel) above 96%. The activity of these samples can be attributed to the existence of free CaO defined by CaO/Ca₂SiO₄ complex mixture. The effect of different amount of catalyst used for transesterification (0.2–2?wt%) was analyzed using the most active catalyst i.e. 3CaO·SiO₂ calcined at 700?°C as well as possibility of its reuse for biodiesel synthesis. It was also found that CaSiO₃, Ca₃Si₂O₇ and Ca₂SiO₄, phases did not possess catalytic activity.     

SERR Spectroelectrochemistry as a Guide for Rational Design of DyP-Based Bioelectronics Devices

Immobilised dye-decolorizing peroxidases (DyPs) are promising biocatalysts for the development of biotechnological devices such as biosensors for the detection of H₂O₂. To this end, these enzymes have to preserve native, solution properties upon immobilisation on the electrode surface. In this work, DyPs from Cellulomonas bogoriensis (CboDyP), Streptomyces coelicolor (ScoDyP) and Thermobifida fusca (TfuDyP) are immobilised on biocompatible silver electrodes functionalized with alkanethiols. Their structural, redox and catalytic properties upon immobilisation are evaluated by surface-enhanced resonance Raman (SERR) spectroelectrochemistry and cyclic voltammetry. Among the studied electrode/DyP constructs, only CboDyP shows preserved native structure upon attachment to the electrode. However, a comparison of the redox potentials of the enzyme in solution and immobilised states reveals a large discrepancy, and the enzyme shows no electrocatalytic activity in the presence of H₂O₂. While some immobilised DyPs outperform existing peroxidase-based biosensors, others fail to fulfil the essential requirements that guarantee their applicability in the immobilised state. The capacity of SERR spectroelectrochemistry for fast screening of the performance of immobilised heme enzymes places it in the front-line of experimental approaches that can advance the search for promising DyP candidates.     

Polymer-Lipid Matrices based on Carboxymethyl Cellulose/Solagum and Liposomes for Controlled Release of Folic Acid

Liposome-encapsulated folic acid is incorporated into the films made from sodium carboxymethyl cellulose (CMC) (2 mas%) and a mixture of CMC and solagum (9:1 w/w) using the film-forming cast solution method. Histidine is used to increase solubility for folic acid in liposomes (1–5 mg mL⁻¹), and propylene glycol is used as a film plasticizer (2.6 mas%). The obtained films (50–60 µm tick) containing 3.12–20.19 mg of folic acid per gram of film are envisaged to be used as patches for transdermal delivery of folic acid. Therefore, some physical, mechanical, release and structural attributes of the films are scrutinized. Folic acid gives yellow color to the films and contributes to stronger chemical bonds which result in improved strength of the film. Liposomes prolong the release of folic acid from films to 24 h without adverse effects on mechanical properties of the films, but degrade homogeneity of the films, which can be ascribed to its agglomeration within the film matrix as revealed by atomic force microscopy. According to the release at pH 5.5, the film formulation based on a blend of CMC and solagum containing 3 mg mL⁻¹ liposome-encapsulated folic acid is recommended. Practical Application: Folic acid is effective in reducing oxidative stress levels in the skin and neutralizing the harmful free radicals and is also essential for various metabolic reactions in the body. However, the limited solubility of folic acid linked with its poor absorption in an organism, low storage stability, short half-life upon oral consumption, specific food preferences of some people, extensive liver metabolism, and pregnancy-induced vomiting point to a large potential in transdermal usage of folic acid. This has motivated us to design new multicomponent polymer-lipid systems as an alternative solution to overcome some of these drawbacks. The results obtained for these multicomponent films pointed to their potential for prolonged release of folic acid to 24 h, which can also be useful for scientists interested in encapsulating similar poorly soluble compounds in CMC patches. The finding can be also valuable information for pharmaceutical manufacturers and scientists worldwide.