Kinetic study of isothermal crystallization process of Gd2Ti2O7 precursor's powder prepared through the Pechini synthetic approach

Crystallization process of Gd₂Ti₂O₇ precursor's powder prepared by Pechini-type polymerized complex route has been studied under isothermal experimental conditions in an air atmosphere. It was found that the crystallization proceeds through two-parameter Šesták–Berggren (SB) autocatalytic model, in the operating temperature range of 550 °C≤T≤750 °C. Based on the behavior of SB parameters (M, N), it was found that in the lower operating temperature range, the crystallites with relatively low compactness exist, which probably disclosed low dimensionality of crystal growth from numerous nucleation sites, where the amorphous solid is produced. In the higher operating temperature region (above 750 °C), it was established that a morphological well-defined and high-dimensional particles of the formed pyrochlore phase can be expected. It was found that at T=850 °C, there is a change in the rate-determining reaction step, from autocatalytic into the contracting volume mechanism.     

Electrical relaxation studies of olivine type nanocrystalline LiMPO4 (M=Ni,Mn and Co) materials

The olivine type LiMPO₄ (M=Ni, Mn and Co) materials were synthesized by solution combustion technique using glycine as fuel. The structural characterizations were explored to confirm the phase formation of materials. The scanning electron microscope was used to identify the morphology of olivine materials. The local structure and chemical bonding between MO₆ octahedral and (PO₄)^3- tetrahedral groups were probed by Raman spectroscopy. Grain and grain boundaries were contributed for ion relaxation and dc conduction in olivine materials. Two orders of enhancement in ionic conductivity was observed in these olivine materials than the reported value. Among all the explored olivine samples, LiMnPO₄ showed highest enhancement in conductivity due to weak Li–O bonding and largest unit cell volume.     

Structure refinements of cadmium substituted lead fluoroapatites by powder X-ray pattern fitting

Solid solutions of cadmium and lead fluoroapatite [Pb_(10−x)Cd_x(PO₄)₆F₂ (0?x?5)] were synthesized by a wet process in a basic medium. Replacement of lead by cadmium induces a linear variation of the crystallographic parameters “a” and “c” according to Végard's law. The cadmium content, as obtained from the refinement, is in agreement with the chemical analysis. The distribution of the lead and cadmium ions between two non-equivalent crystallographic sites, M(1) and M(2), was determined by the Rietveld method. The site-occupancy factors of atoms clearly indicate a preference of cadmium for site M(1) in the apatite structure in agreement with its smaller ionic radii. A progressive shift of the F⁻ ion toward the center of the triangles formed by the site M(2) metals has been observed with increasing cadmium content.     

Effect of preparation and metal content on the introduction of Fe in BEA zeolite, studied by DR UV-vis, EPR and Mössbauer spectroscopy

Fe-containing SiBEA zeolites were prepared by a two-step postsynthesis method: creation of vacant T-sites by dealumination of tetraethylammonium BEA zeolite with nitric acid and then impregnation of the resulting SiBEA zeolite with an aqueous solution of Fe(NO₃)₃. X-ray diffraction shows that iron is incorporated in SiBEA at lattice sites. The presence of Fe in its oxidation state +3 and at isolated tetrahedral sites for low metal content, was demonstrated by diffuse reflectance UV-vis, EPR and Mössbauer spectroscopy. For high iron content, diffuse reflectance UV-vis and Mössbauer spectra revealed the additional presence of extra-lattice FeO_x oligomers and superparamagnetic Fe-oxyhydroxide. Mössbauer spectroscopy identified superparamagnetic Fe-oxyhydroxide as the main phase when basic conditions are used for the preparation.     

Electrospinning fabrication and oxygen sensing properties of Cu(I) complex-polystyrene composite microfibrous membranes

In this paper, a phosphorescent Cu(I) complex of [Cu(POP)(ECI-Phen)]BF₄, where POP=bis[2-(diphenylphosphino)phenyl]ether, and ECI-Phen=1-ethyl-2-(N-ethyl-carbazole-yl-4-)imidazo[4,5-f]1,10-phenanthroline, is incorporated into a polystyrene matrix of polystyrene (PS) to form microfibers membranes. The possibility of using the resulted composite microfibrous membranes as an optical oxygen sensor is explored. Good linearity and short response time are obtained with a sensitivity of 9.8. These results suggest that phosphorescent [Cu(POP)(ECI-Phen)]BF₄ is a promising candidate for oxygen-sensors and PS is an excellent matrix for oxygen sensing material because it owns a large surface-area-to-volume ratio and can supply a homogeneous matrix for probe molecules. Further analysis suggests that the molecular structure of diamine ligand in Cu(I) complexes is critical for sensitivity due to the characteristic electronic structure of excited state Cu(I) complexes.     

Thermoelectric properties and electronic structure of Al-doped ZnO

Impure ZnO materials are of great interest for high temperature thermoelectric application. In this work, we present the effects of Al-doping on the thermoelectric properties and electronic structures of a ZnO system. We find that, with increasing Al concentrations, the electrical conductivity increases and the thermal conductivity decreases significantly, whereas, the Seebeck coefficient decreases slightly. Nevertheless, the figure of merit (ZT) increases owing to high electrical conductivity and low thermal conductivity. On the other hand, the electronic band structures show that the position of the Fermi level is moved upwards and the bands split near the valence-band top and conduction-band bottom. This is due to the interaction between the Al3p and Zn4s orbitals, which drive the system towards semimetal. Besides, the Density Of States (DOS) analysis shows that the introduction of Al atom obviously reduces the slope d(DOS)/dE near the Fermi level. Based on the calculated band structures, we are able to explain qualitatively the measured transport properties of the Al-doped ZnO system.     

Multiferroic magnetoelectric coupling and relaxor ferroelectric behavior in 0.7BiFeO3-0.3BaTiO3 nanocrystals

The structural, microstructural, polarization, magnetization, dielectric constant, and relaxor characteristics of 0.7BiFeO₃-0.3BaTiO₃ (BF-BT) nanocrystals have been studied. BF-BT nanocrystals were prepared by a chemical route using polyvinyl alcohol as surfactant. The phase structure is confirmed by X-ray diffraction and average particle size by transmission and scanning electron microscopy. The magnetoelectric coupling is studied by polarization hysteresis loops under the influence of applied magnetic field and the phase transition anomaly. The diffuse phase transition is studied by modified Curie-Weiss law and relaxor characteristics by Vogel-Fulcher relation.     

Rapid reduction of titanium dioxide nano-particles by reduction with a calcium reductant

Micro-, submicron-, and nano-scale titanium dioxide particles were reduced by reduction with a metallic calcium reductant in calcium chloride molten salt at 1173 K, and the reduction mechanism of the oxides by the calcium reductant was explored. These oxide particles, metallic calcium as a reducing agent, and calcium chloride as a molten salt were placed in a titanium crucible and heated under an argon atmosphere. Titanium dioxide was reduced to metallic titanium through a calcium titanate and lower titanium oxide, and the materials were sintered together to form a micro-porous titanium structure in molten salt at high temperature. The reduction rate of titanium dioxide was observed to increase with decreasing particle size; accordingly, the residual oxygen content in the reduced titanium decreases. The obtained micro-porous titanium appeared dark gray in color because of its low surface reflection. Micro-porous metallic titanium with a low oxygen content (0.42 wt%) and a large surface area (1.794 m² g⁻¹) can be successfully obtained by reduction under optimal conditions.     

绿泥石矿物成分与光谱特征关系研究

绿泥石矿物广泛发育于各种岩石和地质环境中,其化学成分的变化,可反映出其形成时的物理化学条件及其光谱特征的变化。为了探索矿物光谱特征与其矿物化学成分间的内在关联性,为利用高光谱技术探测矿物微观信息提供基础依据。通过薄片显微分析,鉴定了岩石样品中的矿物种类及矿物组合特征,圈定出典型的绿泥石矿物颗粒和划分了绿泥石的产状特征;并利用现代电子探针微区分析技术,测定了16件岩石样品中共146个具有典型代表性的绿泥石矿物颗粒的化学成分,据此计算了其n(AlⅣ),n(AlⅥ),n(Fe),n(Mg)与Fe/(Fe+Mg)比值等相关化学参数;此外对测量的岩矿光谱进行分析,提取了岩石样品中绿泥石矿物的特征光谱参量。在以上基础上,对绿泥石矿物的光谱特征参量和其主要晶体化学参数的关系进行分析研究,研究表明绿泥石矿物的诊断性特征吸收波长位置随绿泥石中Fe离子含量的增加而向长波方向移动。研究结果对于利用高光谱遥感技术进行蚀变矿物及造岩矿物种类、成分及结构特征的识别和探测具有重要的指导意义。     

Effects of vitrification suppression on structure morphology, conductivity and dielectric properties of vanadium phosphate glasses

Vitrification suppression in the (V₂O₅)_1−x (P₂O₅)_x glasses where x=0.10, 0.15, 0.20, and 0.25 was controlled by changing the rate of quenching glasses. The structure variations occurring in the glasses were detected by differential thermal analysis and optical microscope. The results implied the separation and growth of V₂O₅ orthorhombic microcrystal in the samples with x=0.10 and 0.15 whereas other samples did not illustrate remarkable changes in their microstructure. However, in temperature range between 300 and 473 K a semiconducting behavior for all samples appears during the study of electrical conductivity-temperature dependence. A decrease in conductivity values accompanied with some variations in activation energies by reducing quenching rate was observed. The conductivity results suggested that the conduction occurs by the phonon assisted hopping of a small polaron between V⁴⁺ and V⁵⁺ states at relatively higher temperature range above θ_D/2. Whereas at relatively low temperatures the conduction may occur by electron jumping between filled and empty states at Fermi level in the disordered matrix besides polaronic conduction. Reasonable values for the density of localized states, carrier concentration and carrier mobility were estimated and discussed. Also, dielectric constant and dielectric loss were studied as a function of frequency at different temperatures confirming the structure variations in the glass system.