Phosphate glasses containing monodisperse Fe3−δO4@SiO2 stellate nanoparticles obtained by melt-quenching process

The challenge to obtain stable glasses containing monodisperse magnetic nanoparticles with controlled size and shape is an exciting and almost unexplored field of research. Such new materials can be used in magneto-photonics or ultra-sensitive magnetic sensors. In this work, for the first time, colorless and transparent bulk glasses containing monodisperse 20 nm Fe_3−δO₄ nanoparticles were prepared by a melt-quenching route. Magnetic nanoparticles were synthesized by thermal decomposition and covered with a stellate mesoporous silica shell in order to protect them against dissolution during the glass melting process. The incorporation of nanoparticles into glasses and the ideal parameters obtained for this system are discussed. The new nanocomposite materials were characterized in order to investigate the structure, thermal, and magnetic properties. Such an original approach is a very promising way to incorporate a wide panel of nanoparticles, including metallic, bimetallic and metal oxide nanoparticles, into a variety of glasses providing new properties to these materials.     

Enhanced sintering of Ce0.8Nd0.2O2−δ-La0.8Sr0.2Ga0.8Mg0.2O3−δ using CoO as a sintering aid

Ce_0.8Nd_0.2O_1.9 (NDC) and La_0.8Sr_0.2Ga_0.8Mg_0.2O_3-δ (LSGM) electrolytes were prepared using a sol-gel method. NDC-LSGM composite electrolytes were subsequently prepared by adding 5% (w, mass fraction) precalcined LSGM powders to NDC sols. The electrolyte materials of NDC-Co and NDC-LSGM-Co were obtained by adding 1 mol% CoO to NDC sols and NDC-LSGM composite electrolytes, respectively. The microstructure and phase composition of the pellets were characterized using X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), and energy dispersive X-ray spectroscopy (EDS). The electrical conductivities of the pellets were measured using alternative current (AC) impedance spectroscopy. The results indicate that a single perovskite phase is observed for the LSGM ceramic, while NDC-Co, NDC-LSGM and NDC-LSGM-Co have a cubic fluorite structure similar to that of NDC. As a sintering aid, CoO can further promote grain growth and increase relative density (＞95%) of the NDC-LSGM composite electrolyte. The enhancement of the total conductivity is primarily attributed to the large increase in the conductivity of the grain boundary. However, the slight decrease of the grain boundary conductivity of the NDC-LSGM-Co electrolyte is caused by the presence of trace amounts of impurity phases in the grain boundaries.     

Synthesis,characterization and catalytic properties of La2−x Sr x NiO4−δ

Various compositionsx in the catalyst system La_2–x Sr _x NiO_4– have been prepared by conventional techniques and characterized by X-ray powder diffraction, electron microscopy and BET surface measurements. The catalytic properties of these catalysts have been tested in the propylene oxidation reaction. The catalytic activity can be correlated with the oxygen content and with the strontium substitution.     

Combustion Synthesis of PrBa2Cu3O7−δ and YBa2Cu3O7−δ cuprate materials

PrBaCuO and YBaCuO cuprate materials were prepared from cooper, barium peroxide, and yttrium/praseodymium oxide by SHS and standard solid-state synthesis. SHS reactions were carried out using relatively large cooper particles (< 63 im) to obtain small product samples (13 mm in diameter). High ambient temperature was used to stabilize a combustion front in the ignited pellets. Explored was the effect of cooper particles size, starting density, and ambient temperature on phase evolutions in synthesized materials.     

Lamellar-interpenetrated Al−Si−Mg/Al2O3−ZrO2 composites prepared by freeze casting and pressureless infiltration

Using freeze casting and pressureless infiltration methods, we prepared lamellar Al−Si−Mg/Al₂O₃−ZrO₂ composites with initial ceramic loading of 30 vol% and different Al₂O₃:ZrO₂ weight ratios (Al₂O₃:ZrO₂=1:9, 3:7, 5:5, 7:3 and 9:1). The resultant composites inherited the lamellar structure of the Al₂O₃−ZrO₂ scaffolds, and the thickness of both metal and ceramic layers showed a trend of first increase and then decrease with increasing Al₂O₃ content. During pressureless infiltration, multiple chemical reactions took place between ZrO₂ and the Al−12Si−10Mg alloy and the main reaction products were (Al_1−m, Si_m)₃Zr, Al₂O₃ and ZrSi₂ phases. The degree of the reaction depended on the ZrO₂ content in the ceramic composition. In general, the compressive strength of the composites decreased with increasing Al₂O₃ content, but three-point bending strength showed a first decrease and then increase. When Al₂O₃:ZrO₂=1:9, the compressive and bending strength of the composites reached about 997±60 MPa and 426±10 MPa, respectively. A simple model was proposed to illustrate the fracture mode and toughening mechanism of the composites.     

The effect of Zn addition on the structure and transport properties of BaCe0.9−xZrxY0.1O3−δ

BaCe_0.9−xZr_xY_0.1O_3−δ (0.1 ≤ x ≤ 0.9) are ceramic proton conductors widely investigated for different electrochemical devices, such as Solid Oxide Fuel Cell (SOFC) electrolytes, however, their applications are limited by the high sintering temperatures necessary to achieve densification. Polycrystalline powders of BaCe_0.9−xZr_xY_0.1O_3−δ (BCZ) have been prepared by freeze-drying precursor method at 1000 °C. These powders were mixed with a zinc nitrate solution to decrease the sintering temperature to 1200–1300 °C. The addition of Zn has several effects on the structure and microstructure of BCZ: the densification and grain growth are enhanced at lower temperature and a reduction of the crystallographic symmetry is observed for samples with low Zr-content (x ≤ 0.3). Furthermore, the bulk and specific grain boundary conductivities are only slightly affected by the addition of Zn.     

Ketonization of fatty methyl esters over Sn−Ce−Rh−O catalyst

A mixture of methyl esters of fatty acids obtained by transterification of nonerucic rape oil was ketonized. The starting material, diluted with methanol, was converted at atmospheric pressure over a catalyst that contained Sn, Ce, and Rh oxides in a molar ratio of 90:9:1. At a temperature of 385°C ketones were obtained with a total yield of 63% at the 96% conversion of starting material. The reported experiments prove that catalysts other than iron that are active in ketonization of primary alcohols can be successfully used in ketonization of esters of fatty acids. The kind of diluent used plays a crucial role in the conversion.     

A corrosion mechanism of titanium diboride in KF−AlF3−Al2O3 melt

TiB₂ samples were exposed to molten KF?AlF₃?Al₂O₃: 54.8-42.1-3.1 mol% salt, at 680 °C for 50, 100 and 200 h. The corroded samples of TiB₂ were investigated by SEM-EDX, EBSD, XRD, FT-IR and MAS NMR analysis. Corrosion was noted to occur predominantly as pitting attacks on the surface of the investigated materials. An inter-crystal and trans-crystal corrosion were identified on the cross-sections of the samples. A perturbation of TiB bonds was detected (SEM-EDX and NMR analysis), at which a formation of orthorhombic TiO₂ was also identified (EBSD analysis). The subsequent NMR, XRD and FT-IR analysis of the behaviour of TiB₂ powder in molten KF?AlF₃?Al₂O₃ supports the statement about the formation of orthorhombic TiO₂ and mullite type of aluminium borates.     

Fabrication and phase transition of La2−xLuxZr2O7 transparent ceramics

A series of transparent ceramics with the composition of La_2−xLu_xZr₂O₇ (x = 0−2.0) were prepared by solid-state reactive sintering in vacuum. With the increase of Lu content (x), phase transition from pyrochlore to defective fluorite occurred and a two-phase region existed in the range of x = 0.6−1.2. Grain sizes of the pyrochlore phase dominated samples (x < 0.5) were 11−14 μm, and that of the defective fluorite phase dominated samples were larger than 60 μm. However, grain sizes of the samples in the two-phase region were smaller than 3 μm. The La_0.8Lu_1.2Zr₂O₇ ceramic with the smallest grain size (∼2.5 μm) reached a highest in-line transmittance of 72.4% at 1100 nm among all the samples.     

Electrical,structural and thermal properties of nanoceramic (Bi2O3)1−x−y(Ho2O3)x(Tm2O3)y ternary system

Ho₂O₃ and Tm₂O₃ doped Bi₂O₃ composite electrolyte type materials for solid oxide fuel cells (SOFCs) operating at intermediate-temperature were investigated. The bismuth-based ceramic powders were produced by using conventional solid-state synthesis techniques. The products were characterized by means of scanning electron microscopy (SEM), X-ray powder diffraction (XRD), differential thermal analysis/thermal gravimetry (DTA/TG), and the four-point probe technique (4PPT). XRD and DTA/TG measurements indicate that all of the samples have the stable fluorite type face centered cubic (fcc) δ-phase. 4PPT measurements were performed in the temperature range 150–1000 °C in air and these measurements showed that the electrical conductivity of the samples decrease with increasing amount of Tm₂O₃. This increase in the electrical conductivity of the samples could be attributed to the increase in the numbers of highly polarizable cations and oxide ion vacancies. The highest conductivity value was found as 5.31×10^?1 Ω cm^?1 for the (Bi₂O₃)_1?x?y(Ho₂O₃)_x(Tm₂O₃)_y ternary system (for x=20 and y=5 mol%) at 1000 °C. The activation energies of the samples were calculated from log σ graphics versus 1000/T. These calculated results showed that the translation motion of the charge carriers, oxygen vacancies, and space charge polarizations are responsible for the change in activation energy as a function of temperature.     

Preparation and electrical properties of (1−x)SrBi2Nb2O9−xBiFeO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics, (1−x)SrBi₂Nb₂O₉−xBiFeO₃ [(1−x)SBN−xBFO] (x=0.0, 0.03, 0.05, 0.07, 0.10) were prepared by a conventional solid-state reaction method. The crystal structure, microstructure and electrical properties were systematically investigated. All compositions formed layered perovskite structure without any detectable secondary phases. Plate-like morphology of the grains which is characteristic for layer-structure Aurivillius compounds was clearly observed. The excellent electrical properties (e.g., d₃₃~19 pC/N, 2P_r~18.8 μC/cm²) and a high Curie temperature (e.g., T_c~449 °C) were simultaneously obtained in the ceramics with x=0.05. Additionally, thermal annealing studies indicated that the BFO modified SBN ceramics system possessed stable piezoelectric properties, demonstrating that the modified SBN-based ceramics are the promising candidates for high-temperature applications.     

Microwave dielectric properties of Bi2O3-doped Ca[(Li1/3Nb2/3)1−xTix]O3−δ ceramics

The effect of the additive on the densification, low temperature sintering, and microwave dielectric properties of the Ca[(Li_1/3Nb_2/3)_1−xTi_x]O_3−δ(CLNT) was investigated. Bi₂O₃ addition improved the densification and reduced the sintering temperature from 1150 to 900 °C of CLNT microwave dielectric ceramics. As the Bi₂O₃ content increased, the dielectric constant (ε_r) and bulk density increased. The quality factor (Q·f₀), however, was decreased slightly. The temperature coefficient of resonant frequency (τ_f) shifted to a positive value with increasing Bi₂O₃ content. The dielectric properties (ε_r, Q·f_0, τ_f) of Ca[(Li_1/3Nb_2/3)_0.95Ti_0.05]O_3−δ and Ca[(Li_1/3Nb_2/3)_0.8 Ti_0.2]O_3−δ with 5 wt.% Bi₂O₃ sintered at 900 °C for 3 were 20, 6500 GHz, −4 ppm/°C, and 35, 11,000 GHz, 13 ppm/°, respectively. The relationship between the microstructure and dielectric properties was studied by X-ray diffraction (XRD), and SEM.     

一种合成HgBa2Ca2Cu3O8＋δ超导体的新方法

采用加压烧结工艺在１０－３０ＭＰａ压强下合成了超导化合物ＨｇＢａ２Ｃａ２Ｃｕ３Ｏ８＋δ。样品的ＸＲＤ、磁化率和电阻测量结果表明：这种方法制备的Ｈｇ系超导样品的起始转变温度在１３０Ｋ以上，样品主要由ＨｇＢａ２Ｃａ２Ｃｕ３Ｏ８＋δ（即Ｈｇ－１２２３相）组成。由经验得知：在１０－３０ＭＰａ压强范围内，压力变化对Ｈｇ系超导体伯起始转变温度无明显影响，但烧结过程中的升浊速率对样品制备十分重要。     

Effect of two different dopants (Mg2+ and Ca2+) and processing parameters on γ-phase stabilization and conductivity of Bi4V2O11−δ

Mg²⁺ and Ca²⁺ doped Bi₄V₂O_11−δ systems are synthesized by a melt quench technique followed by heat treatment. The Ca²⁺ doped samples show higher density than Mg²⁺ doped samples. All the quenched samples show γ-phase stabilization irrespective of dopants and their concentration. The γ-phase stabilization takes place at lower dopant concentration than earlier reported systems. The conversion of γ-phase to ordered β-phase is observed with heat treatment for Bi₄V_2−xMg_xO_11−δ (x=0.05, 0.10 and 0.20) and Bi₄V_2−xCa_xO_11−δ (x=0.05 and 0.10). Ca²⁺ doped system, particularly high concentration (x=0.15 and 0.20) did not show γ→γ׳ phase transition. The lowest activation energy; E_a is observed for Bi₄Mg_0.15V_1.85O_11−δ sample ~0.74 eV in the temperature range 570–750 °C.     

Structure and microwave dielectric properties of Ba1−xSrxMg2V2O8 ceramics

The Ba_1−xSr_xMg₂V₂O₈ (0≤x≤0.4) microwave dielectric ceramics were fabricated by a standard solid-state reaction method. The formation of a continuous solid solution within the whole composition range was identified. The ceramic samples could be well densified in the temperature range of 885–975 °C in air for 4 h. The permittivity ε_r was found to increase with increasing ionic polarizabilities. The Q×f values were believed to be closely related with packing fraction and grain refinement. The Sr²⁺ substitution contributed to a monotonous increase of the A-site bond valence, such that the τ_f value experienced a considerable variation from negative to positive values. The optimum microwave dielectric properties of an ε_r of 13.3, a high Qxf of 86,640 GHz (9.6 Hz) and a near-zero τ_f of −6 ppm/°C could be yielded in the x=0.15 sample when sintered at 915 °C for 4 h.     

New catalyst of SO 4 2− /Al2O3–ZrO2 for n-butane isomerization

The catalytic behavior of Al-promoted sulfated zirconia for n-butane isomerization at low temperature in the absence of H₂ and at high temperature in the presence of H₂ was studied. The addition of Al enhances the activity and stability of the catalysts for reaction at 250°C and in the presence of H₂ significantly. After on stream for 120 h, the n-butane conversion of the catalyst containing 3 mol% Al₂O₃ keeps steadily at 88% of its equilibrium conversion and no observable trend of further deactivation has been observed. The difference in behavior of the promoted and unpromoted catalysts at low and high temperature is associated with a change of reaction mechanism from bimolecular to monomolecular. Experimental evidence is presented to show that the promoting effect of Al is different from that of the transition metals. Microcalorimetric measurements of NH₃ adsorption on catalysts reveal that the remarkable activity and stability of the Al-promoted catalysts are caused by an enhancement in the number of acid sites effective for the isomerization reaction. This revised version was published online in June 2006 with corrections to the Cover Date.     

Effect of CeO2 and La2O3 on the Activity of CeO2−La2O3/Al2O3-Supported Pd Catalysts for Steam Reforming of Methane

The effect of the addition of CeO₂ or La₂O₃ on the surface properties and catalytic behaviors of Al₂O₃-supported Pd catalysts was studied in the steam reforming of methane. The FTIR spectroscopy of adsorbed CO and the Pd dispersion suggest the partial coverage of Pd⁰ by ceria or lanthana species. This could lead to the formation of an adduct MPd _x O (M = Ce or La) at the surface of the metal crystallites. The addition of ceria or lanthana resulted in an increase of the turnover rate and specific rate for steam reforming of methane. One possible explanation if that the Pd⁰*Pd^δ+O–M interfacial species (M = Ce or La) are oxidized by H₂O or CO₂, promoting the O* transfer to the metal surface. This could facilitate the removal of C* species from the metal surface, resulting in the increase of specific reaction rate and increase of the accessibility of CH₄ to metal active sites.     

On the Role of Calcination Temperature in Pt-SO 4 2− /ZrO2−Al2O3 Preparation and Catalytic Behaviors During the n-Hexane Hydroisomerization

Effects of calcination temperature for Pt-SO ₄ ^2? /ZrO₂?Al₂O₃ (PSZA) catalysts in n-hexane hydroisomerization were investigated by N₂-adsorption, XRD, TG-DTA, FTIR, XPS and H₂-TPR. An optimum calcination temperature is helpful to complete the crystallization process, resulting in better distribution of alumina into zirconia crystal and producing new acid centers responsible for higher catalytic activity.