Template‐Free Fabrication of Mesoporous Alumina Nanospheres Using Post‐Synthesis Water‐Ethanol Treatment of Monodispersed Aluminium Glycerate Nanospheres for Molybdenum Adsorption

This work reports the template‐free fabrication of mesoporous Al₂O₃ nanospheres with greatly enhanced textural characteristics through a newly developed post‐synthesis “water‐ethanol” treatment of aluminium glycerate nanospheres followed by high temperature calcination. The proposed “water‐ethanol” treatment is highly advantageous as the resulting mesoporous Al₂O₃ nanospheres exhibit 2–4 times higher surface area (up to 251 m² g^?1), narrower pore size distribution, and significantly lower crystallization temperature than those obtained without any post‐synthesis treatment. To demonstrate the generality of the proposed strategy, a nearly identical post‐synthesis “water treatment” method is successfully used to prepare mesoporous monometallic (e.g., manganese oxide (MnO₂)) and bimetallic oxide (e.g., CuCo₂O₄ and MnCo₂O₄) nanospheres assembled of nanosheets or nanoplates with highly enhanced textural characteristics from the corresponding monometallic and bimetallic glycerate nanospheres, respectively. When evaluated as molybdenum (Mo) adsorbents for potential use in molybdenum‐99/technetium‐99m (⁹⁹Mo/^99mTc) generators, the treated mesoporous Al₂O₃ nanospheres display higher molybdenum adsorption performance than non‐treated Al₂O₃ nanospheres and commercial Al₂O₃, thereby suggesting the effectiveness of the proposed strategy for improving the functional performance of oxide materials. It is expected that the proposed method can be utilized to prepare other mesoporous metal oxides with enhanced textural characteristics and functional performance.     

Electric field–temperature phase diagram of sodium bismuth titanate-based relaxor ferroelectrics

The electric field–temperature phase diagrams of three bismuth sodium titanate-based relaxor ferroelectrics are reported, namely 0.94(Na_1/2Bi_1/2TiO₃)–0.06(BaTiO₃), 0.80(Na_1/2Bi_1/2TiO₃)–0.20(K_1/2Bi_1/2TiO₃) and 0.75(Na_1/2Bi_1/2TiO₃)–0.25(SrTiO₃). Relaxor behavior is demonstrated by temperature-dependent dielectric permittivity measurements in the unpoled and poled states, as well as by the field-induced phase transition into a ferroelectric phase from the relaxor phase. From temperature-dependent thermometry measurements, we identified the threshold electric field to induce the ferroelectric phase and obtained the released latent heat of the phase transition. We determined the nonergodic and ergodic relaxor phase temperature range based on the absence or presence of reversibility of the relaxor to ferroelectric transition. For all three compositions, the electric field–temperature phase diagram was constructed and a critical point was identified. The constructed electric field–temperature phase diagrams are useful to find optimum operational ranges of ferroelectrics and relaxors for electromechanical and electrocaloric applications.     

One-step route to a hybrid TiO2/TixW1?xN nanocomposite by in situ selective carbothermal nitridation

Metal oxide/nitride nanocomposites have many existing and potential applications, e.g. in energy conversion or ammonia synthesis. Here, a hybrid oxide/nitride nanocomposite (anatase/Ti_xW_1−xN) was synthesized by an ammonia-free sol–gel route. Synchrotron x-ray diffraction, complemented with electron microscopy and thermogravimetric analysis, was used to study the structure, composition and mechanism of formation of the nanocomposite. The nanocomposite contained nanoparticles (<5 nm diameter) of two highly intermixed phases. This was found to arise from controlled nucleation and growth of a single oxide intermediate from the gel precursor, followed by phase separation and in situ selective carbothermal nitridation. Depending on the preparation conditions, the composition varied from anatase/Ti_xW_1−xN at low W content to an isostructural mixture of Ti-rich and W-rich Ti_xW_1−xN at high W content. In situ selective carbothermal nitridation offers a facile route to the synthesis of nitride-oxide nanocomposites. This conceptually new approach is a significant advance from previous methods, which generally require ammonolysis of a pre-synthesized oxide.     

Use of Ponkan mandarin peels as biosorbent for toxic metals uptake from aqueous solutions

Waste Ponkan mandarin (Citrus reticulata) peel was used as biosorbent to extract Ni(II), Co(II) and Cu(II) from aqueous solutions at room temperature. To achieve the best adsorption conditions the influence of pH and contact time were investigated. The isotherms of adsorption were fitted to the Langmuir equation. Based on the capacity of adsorption of the natural biosorbent to interact with the metallic ions, the following results were obtained 1.92, 1.37 and 1.31 mmol g(-1) for Ni(II), Co(II) and Cu(II), respectively, reflecting a maximum adsorption order of Ni(II)>Co(II)>Cu(II). The quick adsorption process reached the equilibrium before 5, 10 and 15 min for Ni(II), Co(II) and Cu(II), respectively, with maximum adsorptions at pH 4.8. In order to evaluate the Ponkan mandarin peel a biosorbent in dynamic system, a glass column was fulfilled with 1.00 g of this natural adsorbent, and it was fed with 5.00 x 10(-4)mol l(-1) of Ni(II) or Co(II) or Cu(II) at pH 4.8 and 3.5 ml min(-1). The lower breakpoints (BP(1)) were attained at concentrations of effluent of the column attained the maximum limit allowed of these elements in waters (>0.1 mg l(-1)) which were: 110, 100 and 130 bed volumes (V(effluent)/V(adsorbent)), for Ni(II), Co(II) and Cu(II), respectively. The higher breakpoints (BP(2)) were attained when the complete saturation of the natural adsorbent occurred, and the values obtained were: 740, 540 and 520 bed volumes for Ni(II), Co(II) and Cu(II), respectively.     

Enhanced capacitance of composite anodic ZrO₂ films comprising high permittivity oxide nanocrystals and highly resistive amorphous oxide matrix

Anodic oxide films with nanocrystalline tetragonal ZrO(2) precipitated in an amorphous oxide matrix were formed on Zr-Si and Zr-Al alloys and had significantly enhanced capacitance in comparison with those formed on zirconium metal. The capacitance enhancement was associated with the formation of a high-temperature stable tetragonal ZrO(2) phase with high relative permittivity as well as increased ionic resistivity, which reduces the thickness of anodic oxide films at a certain formation voltage. However, there is a general empirical trend that single-phase materials with higher permittivity have lower ionic resistivity. This study presents a novel material design based on a nanocrystalline-amorphous composite anodic oxide film for capacitor applications.     

Synthesis and Characterization of Tetravalent Cerium Complexes with p-Tert-butylcalix[ n ] arenes （ n = 4, 6, 8）

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Experimental Study of Macro- and Microbehavior of Natural Diatomite

Diatomite is widely deposited in Oita prefecture of Japan. It has high natural water content but its consolidation yield stress is much higher than the overburden pressure. Oedometer and triaxial consolidated undrained shear tests were performed in this study to investigate its macrobehavior in terms of compressibility and strength. The test results indicate that the compressibility and undrained shear strength of diatomite in the preyield state (i.e., the consolidation stress lower than the yield stress) are independent of the consolidation stress level. When the consolidation stress is higher than the yield stress, however, like virtually all soils, the compressibility of the diatomite increases dramatically. Similarly, the undrained shear strength of the diatomite depends on the confining stress when the confining stress is higher than the transitional stress. Both mercury intrusion porosimetry analysis and scanning electron microscopy were performed to investigate the change of the microstructure of the natural diatomite with the consolidation stress. The test results indicate that the microstructure of the diatomite remains unchanged in the preyield state, but it changes significantly in the vicinity of the yield stress. This unchanged microstructure is attributed to the unchanged macrobehavior within the preyield state. The breakage of diatoms particles and the compression of interparticle pores between the diatom particles in the postyield state contribute to the high compressibility of the diatomite.     

Defect structure and electrical conductivity in rapidly-quenched and slowly-cooled rhombohedral solid solutions of the system Bi2O3-BaO

The solid solubility limit, grain orientation, defect structure and electrical conductivity of solidified rhombohedral specimens in the Bi₂O₃-BaO system are described. The c-axes (in hexagonal notation) of solidified specimens were almost entirely oriented along the platelet/film thickness. Slow-cooling (∼ 10⁻²° Csec⁻¹) of the system gave solid solutions with substitutional type of 2BaO → 2Ba_Bi′ + 20+ V ₀ ^.. for 12 to 32 mol % BaO. High-temperature modification of slowly-cooled sample (16 mol % BaO) showed a conductivity of 8.8×10⁻¹ Ω⁻¹ cm ⁻¹ at 600° C along the conduction plane (perpendicular to the c-axis). Rapid quenching (∼ 10⁵° C sec⁻¹) produced solid solutions for 8 to 20 mol % BaO introducing interstitial Ba²⁺ (10–12 mol % BaO) and Schottky type defects such as V_Bi‴ and V _Bi ^‴ and V ₀ ^.. (16 to 20 mol % BaO), however the high-temperature modification of the rhombohedral structure could not be frozen.     

On-chip cell sorting system using laser-induced heating of a thermoreversible gelation polymer to control flow

We have developed a microfabricated fluorescence-activated cell sorter system using a thermoreversible gelation polymer (TGP) as a switching valve. The glass sorter chip has Y-shaped microchannels with one inlet and two outlets. A biological specimen containing fluorescently labeled cells is mixed with a solution containing a thermoreversible sol-gel polymer. The mixed solution is then introduced into the sorter chip through the inlet. The sol-gel transformation was locally induced by site-directed infrared laser irradiation to plug one of the outlets. The fluorescently labeled target cells were detected with sensitive fluorescence microscopy. In the absence of a fluorescence signal, the collection channel is plugged through laser irradiation of the TGP and the specimens are directed to the waste channel. Upon detection of a fluorescence signal from the target cells, the laser beam is then used to plug the waste channel, allowing the fluorescent cells to be channeled into the collection reservoir. The response time of the sol-gel transformation was 3 ms, and a flow switching time of 120 ms was achieved. Using this system, we have demonstrated the sorting of fluorescent microspheres and Escherichia coli cells expressing fluorescent proteins. These cells were found to be viable after extraction from the sorting system, indicating no damage to the cells.     

Calculations for the availability of photoneutron using synchrotron radiation

The availability of the neutrons due to photonuclear reactions has been discussed by using synchrotron radiation with the beryllium targets. The superconducting wiggler with the magnetic field of approximately 10 T, which is installed into an 8 GeV class storage ring, can emit intense and high-energy photons to produce neutrons. By using MCNPX, the simulations were performed for the conceptual design of the neutron beamline to estimate the available intensity and to investigate the shield conditions. The results were discussed in comparison with other research reactors.