Synthesis and properties of magnetic solid superacid: SO4/ZrO2–B2O3–Fe3O4

A magnetic SO₄²⁻/ZrO₂–B₂O₃–Fe₃O₄ solid superacid catalyst is prepared via a simple chemical co-precipitation approach. The obtained materials were characterized in detailed by X-ray powder diffraction, thermogravimetric analysis–different scanning calorimetry, Fourier transform infrared spectroscopy (FTIR), electron microscopy (SEM and TEM), and Mossbauer spectra. Powder X-ray diffraction patterns show that in this composite oxide the transformation temperature of ZrO₂ from tetragonal to monoclinic phase is higher compared to the pristine SO₄²⁻/ZrO₂ material. The introduction of Fe₃O₄ endows the superacid with a super-paramagnetic property while in a ferromagnetic state after calcination. The superacid exhibits high catalytic activity in forming ethyl acetate by esterification.     

Synthesis and photoluminescence properties of Eu-doped γ-Ca3(PO4)2

Eu³⁺-doped (1% and 3%) γ-Ca₃(PO₄)₂ was synthesized by high-pressure and high-temperature experimental method and the samples were characterized by X-ray diffraction. The luminescence properties of samples were investigated by emission and excitation spectra. The excitation spectra of Eu³⁺-doped γ-Ca₃(PO₄)₂ showed that samples were mainly attributed to Eu³⁺–O²⁻ charge-transfer band at 270 nm, and some sharp lines were also attributed to Eu³⁺ f–f transitions in near-UV regions with the strongest peaks at 395 nm. Under the 395 nm excitation, the intense red emission peak at 611 nm was observed. The strongest line (395 nm) in excitation spectra of those phosphors matched well with the output wavelength of UV InGaN-based light-emitting diodes (LEDs) chip. The luminescent properties suggested that Eu³⁺-doped γ-Ca₃(PO₄)₂ might be regarded as a potential red phosphor candidate for near-UV LEDs.     

Microwave-assisted preparation of Ca6Si6O17(OH)2 and β-CaSiO3 nanobelts

Xonotlite (Ca₆Si₆O₁₇(OH)₂) nanobelts were synthesized by a microwave-assisted hydrothermal method at 180 °C for 90 min independent of the feeding molar ratio of Ca(NO₃)₂·4H₂O to Na₂SiO₃·9H₂O in the range of 0.8-3.0. Crystalline wollastonite (β-CaSiO₃) nanobelts were obtained by microwave thermal transformation of Ca₆Si₆O₁₇(OH)₂ nanobelts at 800 °C for 2 h. Ca₆Si₆O₁₇(OH)₂ nanobelts were used as both the precursor and the template for the preparation of β-CaSiO₃ nanobelts. The morphology and size of Ca₆Si₆O₁₇(OH)₂ nanobelts could be well preserved during the microwave thermal transformation process. The products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and selected area electron diffraction (SAED).     

Microstructures formed during devitrification of Na2O·Al2O3·B2O3·SiO2·Fe2O3 glasses

Soda alumina borosilicate glasses of composition (24-y)Na₂O·yAl₂O₃·14B₂O₃·37SiO₂·25Fe₂O₃, y = 8, 12, 14, 16 mol%, were melted using Fe₂O₃ as raw material. Besides, samples with y = 12 and Fe₂O₃ concentrations of 14.32, 17.8, and 25.0 mol% were prepared from FeC₂O₄·2H₂O as raw material. The X-ray diffraction analyses showed the presence of magnetite for the samples from all the investigated compositions. Transmission electron microscopy (TEM) evidenced that all the samples are phase separated and droplets in the diameter range 100–1000 nm, enriched in iron, are formed. Inside these droplets, numerous small magnetite particles, with size in the 25–40 nm interval, are crystallized.     

Dielectric behaviour of spray dried Pb0.98(La1?x/3Nax)0.02(Zr0.53Ti0.47)0.9950O3 system

Sodium modified PLZT, Pb_0.98(La_{1 – x/3}Na_x)_0.02(Zr_0.53Ti_0.47)_0.9950O₃ (PLNZT) with x = 0.0, 0.5, 1.0, 1.5, 2.0, 2.5, ceramics have been synthesized by spray drying technique. Rhombohedral phases of PLNZT ceramics were confirmed by XRD. Pellets prepared from the calcined powders were sintered at 1100°C. Micro-structural studies show the grains were spherical and homogeneous. Dielectric behaviour of these compounds has been studied as a function of temperature at 10 KHz frequency. Diffusivity of these compounds calculated from -T plots were found to lie between 1 and 2, which suggests that the compounds have diffuse phase transition (DPT). The dielectric constant () as found to increase initially upto x = 1.5 and then to decrease with increasing Na—concentrations.     

Structure and electrical properties of (Bi0.5Na0.5)0.94Ba0.06TiO3–Bi0.5(Na0.82K0.18)0.5TiO3–BiAlO3 lead free piezoelectric ceramics

0.09(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃–(0.01 − x) Bi_0.5(Na_0.82K_0.18)_0.5TiO₃–x BiAlO₃ (BNBKT–xBA) lead-free piezoelectric ceramics were synthesized by conventional solid-state reaction processes. Structure, ferroelectric and piezoelectric properties of BNBKT–xBA ceramics were investigated. X-ray diffraction data shows that BNBKT–xBA ceramics form the pure perovskite phases and the ceramics have the morphotropic phase boundary when x ≤ 0.030. At room temperature, the BNBKT–xBA ceramics at x = 0.030 have better electrical properties, the piezoelectric constant d₃₃ and planar coupling factor k_p of BNBKT–xBA ceramics reaches peak values at x = 0.030: d₃₃ = 217 pC N⁻¹, k_p = 0.308. The remnant polarization P_r, mechanical quality factor Q_m and relative dielectric constant ?_r of BNBKT–xBA ceramics at x = 0.030 attains 33.8 μC cm⁻², 133 and 928 (100 KHz), respectively. As BA content increase, the depolarization temperature T_d shift toward lower temperature, and T_d of BNBKT–xBA ceramics with x = 0.030 decreased to 55 °C.     

Tailored temperature window of CuOx/WOx–ZrO2 for NOx reduction via adjusting the calcination temperature of WOx–ZrO2

WO_x–ZrO₂ support was calcined at various temperatures for obtaining controllable activity of copper catalysts for NO_x reduction by ammonia. The temperature window of copper catalyst for over 80% NO_x conversion shifts from 180–300 to 230–350 °C by elevating the calcination temperature of WO_x–ZrO₂ support from 500 to 600 °C, due to the increased Brønsted acidity and reduced structure and electronic interactions between copper oxides and tungsten oxides arising from the polymerization of WO_x clusters on surface of support. Calcining WO_x–ZrO₂ support at 700 °C leads to the reduced redox property of copper oxides on the Cu–O–W interface and the formation of bulk-like CuO, results in a low activity of catalyst.     

Enhancement of the Current Density J C for Bi2Sr2CaCu2O8 by?Means of Carbon and NbSe2 Nanotubes

Three polycrystalline Bi₂Sr₂CaCu₂O₈, Bi₂Sr₂CaCu₂O₈ with carbon nanotubes, Bi₂Sr₂CaCu₂O₈ with NbSe₂ nanotubes were synthesized by solid state reaction method and studied by scanning electron microscopy, X-ray diffraction, magnetization measurements, and high resolution transmission electron microscopy. The critical temperature T _C for the three compounds was about 85 K. There is an enhancement in the critical current density, J _C for samples with carbon and NbSe₂ nanotubes as compared with pure Bi₂Sr₂CaCu₂O₈. The enhancement provides evidence that wetting exists for the two doped samples investigated.      

Effects of copper and Al2O3 particles on characteristics of Cu–Al2O3 composites

High-energy milling was used for production of Cu–Al₂O₃ composites. The inert gas-atomized prealloyed copper powder containing 2 wt.%Al and the mixture of the different sized electrolytic copper powders with 4 wt.% commercial Al₂O₃ powders served as starting materials. Milling of prealloyed copper powders promotes formation of nano-sized Al₂O₃ particles by internal oxidation with oxygen from air. Hot-pressed compacts of composites obtained from 5 and 20 h milled powders were additionally subjected to the high-temperature exposure in argon at 800 °C for 1 and 5 h. Characterization of processed material was performed by optical and scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), microhardness, as well as density and electrical conductivity measurements. Due to nano-sized Al₂O₃ particles microhardness and thermal stability of composite processed from milled prealloyed powders are higher than corresponding properties of composites processed from the milled powder mixtures. The results were discussed in terms of the effects of different size of starting copper powders and Al₂O₃ particles on the structure, strengthening of copper matrix, thermal stability and electrical conductivity of Cu–Al₂O₃ composites.     

Dielectric and piezoelectric properties of BiMnO3 doped 0.95Na0.5K0.5NbO3–0.05LiSbO3 ceramics

The piezoelectric properties of (1 − x)(0.95K_0.5Na_0.5NbO₃–0.05LiSbO₃)–x BiMnO₃ (x = 0, 0.002, 0.004, 0.006, 0.008, 0.01) lead-free piezoelectric ceramics were investigated as a function of x. These ceramics were fabricated by conventional ceramics sintering processing. BiMnO₃ (BM)-doping was found to increase the Curie temperature, T _c, from 370 °C at x = 0–380 °C at x = 0.002, and clearly increase the d ₃₃, Q _m and k _p values, showing “hard” characteristic. The good piezoelectric and electromechanical properties of d ₃₃ = 226pC/N, k _p = 40.8%, tan θ = 2.60% and T _c = 370 °C appear at x = 0.004.     

Fabrication and structure characterization of MnCO3/α-Fe2O3 nanocrystal heterostructures

Novel MnCO₃/α-Fe₂O₃ nanocrystal heterostructures, with MnCO₃ nanorods 5-10 nm in diameter and 15-50 nm in length, grown onto the surfaces of the α-Fe₂O₃ nanohexahedrons sized around 30-50 nm, were fabricated via a two-step solvothermal route. The coalescent planes of the heterostructure for the MnCO₃ nanorod and the α-Fe₂O₃ nanohexahedron were determined to be (01?4) and (110), respectively. The formation of the MnCO₃ nanorods from the Mn contained amorphous flakes was tracked by transmission electron microscopy observations at various reaction stages, which suggested a rolling-broken-growth process. Evidenced by the comparative experimental result, the α-Fe₂O₃ nanohexahedrons played an important role in inducing the nucleation and growth of the hexagonal MnCO₃ nanorods on their surfaces.     

Optical properties and structure of R2O–Ga2O3–SiO2 and RO–Ga2O3–SiO2 glasses

Refractive index and molar refraction of Li₂O–, Na₂O–, CaO–, and BaO–Ga₂O₃–SiO₂ glasses have been used to test the validity of a structural model of silicate glasses containing Ga₂O₃ glasses. Ga₂O₃ enters these types of glass in a similar manner as Al₂O₃. It is assumed that, for (SiO₂/Ga₂O₃) >1 and (Ga₂O₃/R₂O) ≤1, Ga₂O₃ associates primarily with modifier oxides to form GaO₄ units. The rest of modifier oxide forms silicate units with non-bridging oxygen ions. Silicate structural units have the same factors as found for binary alkali- and alkaline earth silicate glasses. Differences between experimental and model values suggest another structure for (Ga₂O₃/SiO₂) ≥1.     

Crystal structure of uranyl μ3-oxoacetate [(UO2)3(μ3-O)2(OOCCH3)2(H2O)2]

The crystal structure of [(UO₂)₃(₃-O)₂(OOCCH₃)₂(H₂O)₂] consists of uranium coordination polyhedra (CPs) combined via common equatorial edges into ribbons, with ₃-O atoms being common for three CPs. The structure was compared with that of known complexes with ₃-oxo atoms.Translated from Radiokhimiya, Vol. 46, No. 5, 2004, pp. 396–400.Original Russian Text Copyright © 2004 by Charushnikova, Krot, Starikova.     

Structure and electrical properties of Bi0.5Na0.5TiO3–Bi0.5K0.5TiO3–BiCoO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics (1 − x − y)Bi_0.5Na_0.5TiO₃–xBi_0.5K_0.5TiO₃–yBiCoO₃ (x = 0.12–0.24, y = 0–0.04) have been fabricated by a conventional solid-state reaction method, and their structure and electrical properties have been investigated. The XRD analysis shows that samples with y ≤ 0.03 exhibit a pure perovskite phase and very weak impurity reflections can be detected in the sample with y = 0.04. With x increasing from 0.12 to 0.24 and y increasing from 0 to 0.04, the ceramics transform gradually from a rhombohedral phase to a tetragonal phase and rhombohedral–tetragonal phase coexistence to a pseudocubic phase, respectively. The morphotropic phase boundary (MPB) of the system between rhombohedral and tetragonal locates in the range of x = 0.18–0.21, y = 0–0.03. The ceramics near the composition of the MPB have good performances with piezoelectric constant d ₃₃ = 156 pC/N and electromechanical coupling factor k _p = 0.34 at x = 0.21 and y = 0.01, which attains a maximum value in this ternary system. Adding content of BiCoO₃ leads to a disappearance of the response in the curves of dielectric constant-temperature to the ferroelectric–antiferroelectric transition. The temperature dependence of dielectric properties suggests that the ceramics are relaxor ferroelectrics. The results show that (1 − x − y)Bi_0.5Na_0.5TiO₃–xBi_0.5K_0.5TiO₃–yBiCoO₃ ceramics are good candidate for use as lead-free ceramics.     

Structure study of MoO3-ZnO-B2O3 glasses by Raman spectroscopy and formation of α-ZnMoO4 nanocrystals

Molybdenum oxide (MoO₃)-containing glasses of xMoO₃-50ZnO-(50−x)B₂O₃ (x = 10, 20, and 30) are prepared using a conventional melt quenching method, and the glass structure and crystallization behaviour are clarified. It is found that the thermal stability against crystallization of the glasses decreases drastically with increasing MoO₃ content. The main valence of Mo ions in the glasses is found to be Mo⁶⁺ from X-ray photoelectron spectroscopy measurements. The Raman bands observed at ∼860 cm⁻¹ and 950 cm⁻¹ suggest that the coordination state of Mo⁶⁺ ions in the glasses is mainly (MoO₄)²⁻ tetrahedral units. All glasses examined in this study give the formation of α-ZnMoO₄ as the initial crystalline phase. In particular, 30MoO₃-50ZnO-20B₂O₃ glass shows the bulk crystallization of α-ZnMoO₄ nanocrystals with a diameter of ∼5 nm. The crystallized glasses consisting of Eu³⁺-doped ZnMoO₄ crystals are synthesized, and enhanced photoluminescence emissions (i.e., the quantum yield is 9%) due to the 4f transitions ⁵D₀ → ⁷F_J (J = 0-4) of Eu³⁺ ions is observed.     

Al2O3/ZrO2/ZrSiO4复合材料的研究

在Al2O3颗粒补强锆英石陶瓷的研究基础上,探讨了Al2O3与ZrO2共同对锆英石陶瓷的协同补强增韧行为.制备的锆英石基复合材料的室温抗弯强度和断裂韧性分别可达383.31MPa、4.39 MPa·m12.采用XRD分析了复合材料的相组成,采用SEM观察复合材料的断面形貌.结果显示:ZrSiO4为主要晶相,另外还有少量Al2O3和ZrO2存在;第二种增强体ZrO2的最佳引入量为20％(质量分数);确定复合材料的强韧化是由Al2O3和ZrO2颗粒引起的裂纹偏转、微裂纹增韧与ZrO2颗粒引起的相变增韧共同作用而实现的,断裂方式主要为穿晶断裂.     

Elastic and inelastic properties of (Co0.45Fe0.45Zr0.1) x (Al2O3)1 ? x nanocomposites

The elastic (Young’s modulus) and inelastic (internal friction) properties of amorphous (Co₄₅Fe₄₅Zr₁₀) _x (Al₂O₃)_{100 − x} nanocomposites with various relative contents of the metallic and dielectric phases have been studied. In the region of low temperatures, the composites exhibit a peak of the internal friction (at ∼240 K), the intensity of which increases with the content of the metallic phase. For compositions above the percolation threshold, the temperature dependence of the internal friction exhibits exponential growth above 300°C, which is related to the migration of vacancy-like defects in the amorphous structure of the metallic phase.     

Low-temperature sintering of ZrW2O8–SiO2 by spark plasma sintering

Amorphous ZrW₂O₈ powder and amorphous SiO₂ powder were prepared by a sol–gel process as raw materials, and high-density ZrW₂O₈–SiO₂ were successfully prepared at a much lower temperature of 923 K for a much shorter holding time of 10 min by spark plasma sintering (SPS) method rather than by conventional melt-quenching method. The relative densities of 0.85ZrW₂O₈–0.15SiO₂ and 0.70ZrW₂O₈–0.30SiO₂ were 99.4% and 96.6%, respectively. The combined technique of a sol–gel process and SPS should enable us to prepare the varied types of high-density composites of ZrW₂O₈ without severe thermal cracking caused by melt-quenching. The thermal expansion properties and dielectric properties of ZrW₂O₈–SiO₂ were also investigated.     

Magnetoelectric and electrical properties of WO3-doped (Ni0.8Zn0.1Cu0.1)Fe2O4/[Pb(Ni1/3Nb2/3)O3–Pb(Zn1/3Nb2/3)O3–PbTiO3] composites

A total of 5 mol% WO₃-doped (1−x)(Ni_0.8Zn_0.1Cu_0.1)Fe₂O₄/xPb(Ni_1/3Nb_2/3)O₃–Pb(Zn_1/3Nb_2/3)O₃–PbTiO₃ ((1−x)NZCF/xPNN-PZN-PT) magnetoelectric particulate ceramic composites were prepared by conventional solid-state reaction method via low-temperature sintering process. X-ray diffraction (XRD) measurement and scanning electron microscopy (SEM) observation indicate that piezoelectric phase and ferrite phase coexist in the sintered particulate ceramic composites. Dielectric property of the (1−x)NZCF/x0.53PNN–0.02PZN–0.05Pb(Ni_1/2W_1/2)O₃–0.40PT ((1−x)NZCF/xPNN-PZN-PNW-PT, nominal composition) composites is improved greatly as compared to that of the undoped (1−x)NZCF/xPNN-PZN-PT composites. The WO₃-doped (1−x)NZCF/xPNN-PZN-PT composites exhibit typical P–E hysteresis loops at room temperature accompanied by the decrease of saturation polarization (P _s) and remnant polarization (P _r). At the same time, piezoelectric property of the composites deteriorates greatly with the increase of ferrite content. The (1−x)NZCF/xPNN-PZN-PNW-PT composites can be electrically and magnetically poled and exhibit apparent magnetoelectric (ME) effect. A maximum ME voltage coefficient of 13.1 mV/(cm Oe) is obtained in the 0.1NZCF/0.9PNN-PZN-PNW-PT composite at 400 Oe d.c. magnetic bias field superimposed 1 kHz a.c. magnetic field with 5 Oe amplitude. The addition of WO₃ in the piezoelectric phase decreases sintering temperature greatly from 1180 °C to 950 °C and decreases dielectric loss sharply of the composites, thus the ME voltage coefficient increases. Such ceramic processing is valuable for the preparation of magnetoelectric particulate ceramic composites with excellent ME effect.     

Obtainment of the Fe0.70?xCrxAl0.3/Al2O3 nanocomposite by the method of SHS of mechanoactivated Cr2O3 + Fe + Al mixtures

Applying M?ssbauer spectroscopy methods, we have studied the structure of nanocomposites obtained by a technique combining the preliminary mechanical activation of an 8.1 wt % Cr₂O₃ + 65.9 wt % Fe + 25 wt % Al mixture and self-propagating high-temperature synthesis (SHS). It has been found that, at the stage of mechanical activation, an Fe/Al/Cr₂O₃ composite with a low impurity of the Fe₂Al₅ intermetallide is formed. At the stage of SHS, the interaction between activated components of the mixture leads to the formation of the Fe_{0.7 − x} Cr _x Al_0.3 (x = 0 − 0.2)/Al₂O₃ composite. Original Russian Text ? T.Yu. Kiseleva, A.A. Novakova, T.L. Talako, T.F. Grigor’eva, A.N. Falkova, 2009, published in Neorganicheskie Materialy, 2009, Vol. 45, No. 7, pp. 892–896.