An alternative method to study the cooling of glasses from melt to solid phase

The aim of this preliminary work was to present a novel method, suitable to investigate the glass cooling, from melt to solid state, based on a fast, non-usual and easy microwave method. The following glass system xBaO · (100?x)B₂O₃ (x = 0% and 40%) was selected as an example for this study. The melt was poured inside a piece of waveguide and then, its cooling was monitored by the microwave signal as a function of time. The variations in the signal can provide valuable informations about some structural changes that take place during the cooling stages, such as relaxation processes. This method can be useful to investigate the cooling and heating of other materials, opening new possibilities for investigation of dielectric behavior of materials under high temperatures.     

Preparation of 3D micro/nanostructured CeO2: Influence of organic/inorganic acids

CeO₂ is an important porous material with a wide range of applications in the abatement of volatile organic compounds (VOCs). In this paper, we prepared a series of novel three-dimensional (3D) micro/nanostructured CeO₂ materials via a solvothermal method. Organic acid-assisted synthesis and inorganic acid post-treatment were used to adjust the CeO₂ microstructures. The size of the 3D micro/nanostructures could be controlled in the range from 180 nm to 1.5 μm and the surface morphology changed from rough to smooth with the use of different organic acids. The CeO₂ synthesized with acetic acid featured a hierarchical porosity and showed good performance for toluene catalytic combustion: a T₅₀ of 187 °C and a T₉₀ of 195 °C. Moreover, the crystallite size, textural properties, and surface chemical states could be tuned by inorganic acid modification. After treatment with HNO₃, the modified CeO₂ materials exhibited improved catalytic activity, with a T₅₀ of ∼175 °C and a T₉₀ of ∼187 °C. We concluded that the toluene combustion activity is related to the porosity and the amount of surface active oxygen of the CeO₂. Both these features can be tuned by the co-work of organic and inorganic acids.     

Flow evolution of a turbulent submerged two-dimensional rectangular free jet of air. Average Particle Image Velocimetry (PIV) visualizations and measurements

The paper presents average flow visualizations and measurements, obtained with the Particle Image Velocimetry (PIV) technique, of a submerged rectangular free jet of air in the range of Reynolds numbers from Re = 35,300 to Re = 2200, where the Reynolds number is defined according to the hydraulic diameter of a rectangular slot of height H. According to the literature, just after the exit of the jet there is a zone of flow, called zone of flow establishment, containing the region of mixing fluid, at the border with the stagnant fluid, and the potential core, where velocity on the centerline maintains a value almost equal to the exit one. After this zone is present the zone of established flow or fully developed region. The goal of the paper is to show, with average PIV visualizations and measurements, that, before the zone of flow establishment is present a region of flow, never mentioned by the literature and called undisturbed region of flow, with a length, L_U, which decreases with the increase of the Reynolds number. The main characteristics of the undisturbed region is the fact that the velocity profile maintains almost equal to the exit one, and can also be identified by a constant height of the average PIV visualizations, with length, L_CH, or by a constant turbulence on the centerline, with length L_CT. The average PIV velocity and turbulence measurements are compared to those performed with the Hot Film Anemometry (HFA) technique. The average PIV visualizations show that the region of constant height has a length L_CH which increases from L_CH = H at Re = 35,300 to L_CH = 4–5H at Re = 2200. The PIV measurements on the centerline of the jet show that turbulence remains constant at the level of the exit for a length, L_CT, which increases from L_CT = H at Re = 35,300 to L_CT = 4–5H at Re = 2200. The PIV measurements show that velocity remains constant at the exit level for a length, L_U, which increases from L_U = H at Re = 35,300 to L_U = 6H at Re = 2200 and is called undisturbed region of flow. In turbulent flow the length L_U is almost equal to the lengths of the regions of constant height, L_CH, and constant turbulence, L_CT. In laminar flow, Re = 2200, the length of the undisturbed region of flow, L_U, is greater than the lengths of the regions of constant height and turbulence, L_CT = L_CH = 4–5H. The average PIV and HFA velocity measurements confirm that the length of potential core, L_P, increases from L_P = 4–5H at Re = 35,300 to L_P = 7–8H at Re = 2200, and are compared to the previous experimental and theoretical results of the literature in the zone of mixing fluid and in the fully developed region with a good agreement.     

Mesoporous composite of LiFePO4 and carbon microspheres as positive-electrode materials for lithium-ion batteries

Mesoporous LiFePO₄/C microspheres consisting of LiFePO₄ nanoparticles are successfully fabricated by an eco-friendly hydrothermal approach combined with high-temperature calcinations using cost-effective LiOH and Fe³⁺ salts as raw materials. In this strategy, pure mesoporous LiFePO₄ microspheres, which are composed of LiFePO₄ nanoparticles, were uniformly coated with carbon (∼1.5 nm). Benefiting from this unique architecture, these mesoporous LiFePO₄/C microspheres can be closely packed, having high tap density. The initial discharge capacity of LiFePO₄/C microspheres as positive-electrode materials for lithium-ion batteries could reach 165.3 mAh/g at 0.1 C rate, which is notably close to the theoretical capacity of LiFePO₄ due to the large BET surface area, which provides for a large electrochemically available surface for the active material and electrolyte. The material also exhibits high rate capability (∼100 mAh/g at 8 C) and good cycling stability (capacity retention of 92.2% after 400 cycles at 8 C rate).     

Fabrication of nano-sized Ca(OH)2 with excellent adsorption ability for N2O4

Uniform nano-sized calcium hydroxide (Ca(OH)₂) monocrystal powder was synthesized from calcium oxide in a surfactant solution via a digestion method by decreasing the surface tension of the reaction system to control the growth of crystalline Ca(OH)₂. The Ca(OH)₂ monocrystal powder samples were characterized by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), and Fourier transform-infrared spectroscopy (FT-IR). The NO_x adsorption ability of the samples was evaluated, and the influence of various types and concentrations of surfactants on powder agglomeration and then the specific surface area in the precipitation process were studied. The specific surface area of the samples was found as high as 58 m²/g and 92 m²/g and the particle size, 300–400 nm and 200–300 nm in the presence of 10 wt% PEG600 and 0.086 mL/L SDS at a reaction time of 5 h, respectively. The product has an exceptionally strong adsorption ability for NO_x, which makes it a highly promising adsorbent for emission control and air purification.     

Dry modification of electrode materials by roller vibration milling at room temperature

For the first time dry roller vibration milling at room temperature was used to prepare active carbon （AC） nano-particles and to modify MnO2 powder as electrode materials. In 30 min AC was milled to a mean particle size of 30-50 nm with increased crystallinity and higher specific surface area, predominantly mesoporous and with improved pore diameter distribution. Then, AC nano-particles were incorporated with MnO2 or bismuth-doped MnO2 nano-particles synthesized by sol-gel methods to prepare nano-composite electrode materials for studying their electrochemical performance. The AC nano-particles combined with 10 wt.% bismuth-doped MnO2 nano-particles were found to possess excellent electrochemical property with specific capacitance up to 308 F/g and without obvious attenuation with increasing current. Our method seems to ooen a new way to imorove AC based electrode materials used for clean energy such as suner capacitors.     

Solid-state synthesis of Li[Li0.2Mn0.56Ni0.16Co0.08]O2 cathode materials for lithium-ion batteries

Layered Li[Li_0.2Mn_0.56Ni_0.16Co_0.08]O₂ cathode materials were synthesized via a solid-state reaction for Li-ion batteries, in which lithium hydroxide monohydrate, manganese dioxide, nickel monoxide, and cobalt monoxide were employed as metal precursors. To uncover the relationship between the structure and electrochemical properties of the materials, synthesis conditions such as calcination temperature and time as well as quenching methods were investigated. For the synthesized Li[Li_0.2Mn_0.56Ni_0.16Co_0.08]O₂ materials, the metal components were found to be in the form of Mn⁴⁺, Ni²⁺, and Co³⁺, and their molar ratio was in good agreement with stoichiometric ratio of 0.56:0.16:0.08. Among them, the one synthesized at 800 °C for 12 h and subsequently quenched in air showed the best electrochemical performances, which had an initial discharge specific capacity and coulombic efficiency of 265.6 mAh/g and 84.0%, respectively, and when cycled at 0.5, 1, and 2 C, the corresponding discharge specific capacities were 237.3, 212.6, and 178.6 mAh/g, respectively. After recovered to 0.1 C rate, the discharge specific capacity became 259.5 mAh/g and the capacity loss was only 2.3% of the initial value at 0.1 C. This work suggests that the solid-state synthesis route is easy for preparing high performance Li[Li_0.2Mn_0.56Ni_0.16Co_0.08]O₂ cathode materials for Li-ion batteries.     

Microwave-assisted polyol synthesis of LiMnPO4/C and its use as a cathode material in lithium-ion batteries

We synthesized LiMnPO₄/C with an ordered olivine structure by using a microwave-assisted polyol process in 2:15 (v/v) water–diethylene glycol mixed solvents at 130 °C for 30 min. We also studied how three surfactants—hexadecyltrimethylammonium bromide, polyvinylpyrrolidone k30 (PVPk30), and polyvinylpyrrolidone k90 (PVPk90)—affected the structure, morphology, and performance of the prepared samples, characterizing them by using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, charge/discharge tests, and electrochemical impedance spectroscopy. All the samples prepared with or without surfactant had orthorhombic structures with the Pnmb space group. Surfactant molecules may have acted as crystal-face inhibitors to adjust the oriented growth, morphology, and particle size of LiMnPO₄. The microwave effects could accelerate the reaction and nucleation rates of LiMnPO₄ at a lower reaction temperature. The LiMnPO₄/C sample prepared with PVPk30 exhibited a flaky structure coated with a carbon layer (∼2 nm thick), and it delivered a discharge capacity of 126 mAh/g with a capacity retention ratio of ∼99.9% after 50 cycles at 1C. Even at 5C, this sample still had a high discharge capacity of 110 mAh/g, demonstrating good rate performance and cycle performance. The improved performance of LiMnPO₄ likely came from its nanoflake structure and the thin carbon layer coating its LiMnPO₄ particles. Compared with the conventional polyol method, the microwave-assisted polyol method had a much lower reaction time.     

Controllable hydrothermal synthesis of star-shaped Sr3Fe2(OH)12 assemblies and their thermal decomposition and magnetic properties

Pure phase star-shaped hydrogarnet Sr₃Fe₂(OH)₁₂ assemblies were synthesized by a mild hydrothermal method (210 °C, 12 h), and the effects of the preparation conditions on the phase composition of the product were investigated. It was found that the impurity phases could be decreased or eliminated by increasing the molar ratio of Sr²⁺ to Fe³⁺, and that high temperatures favored the formation of Sr₃Fe₂(OH)₁₂ and reduced the concentration of CO₃^2–-containing byproducts. The thermal decomposition of the star-shaped Sr₃Fe₂(OH)₁₂ assemblies was examined, and the results showed that the dehydration process at higher temperatures is accompanied by the formation of SrFeO_3–δ. Above 655 °C, a solid state reaction between the SrFeO_3–δ and Sr(OH)₂ or SrCO₃ results in the formation of Sr₄Fe₃O_10–δ.The magnetic properties of the as-synthesized Sr₃Fe₂(OH)₁₂ and of samples calcined at different temperatures were assessed. A sample calcined at 575 °C exhibited greatly enhanced ferromagnetic properties, with a remanent magnetization of 1.28 emu/g and a coercivity of 4522.1 Oe at room temperature.     

Fabrication of magnetic nanosized γ-FeNi-coated ceramic core–shell microspheres by heterogeneous precipitation and thermal reduction

Precursors with NiCO₃·2Ni(OH)₂·2H₂O- and Fe₂O₃·nH₂O-coated alumina, graphite and cenosphere were synthesized by precipitation using ferrous sulfate, nickel sulfate, ammonium bicarbonate, alumina, graphite and cenosphere as the main starting materials. Magnetic γ-FeNi-coated alumina, graphite and cenosphere core–shell structural microspheres were subsequently prepared by thermal reduction of the as-prepared precursors at 600 °C for 2 h. Precipitation parameters, e.g. concentration of ceramic micropowders (10 g/L), sulfate solution (0.2 mol/L), rate of adding reactants (3 mL/min) and pH value were optimized by a trial-and-error method. Powders of the precursors and the resulting coating of γ-FeNi with grain size below 40 nm on alumina, graphite and cenosphere microspheres were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). The magnetic properties of the nanosize γ-FeNi-coated alumina, graphite and cenosphere microspheres were measured by vibrating sample magnetometer (VSM). The results show that the core–shell structural γ-FeNi-coated ceramic microspheres exhibited higher coercivity than pure γ-FeNi powders, indicating that these materials can be used for high-performance functional materials and devices.     

Hydrothermal preparation of nanocrystalline ZnO2

A green hydrothermal method was proposed for the synthesis of nanocrystalline ZnO₂, using Zn₅(CO₃)₂(OH)₆ powder and 6 vol% H₂O₂ aqueous solution as the starting materials. Characterization results from X-ray diffraction, Raman, high resolution transmission electron microscopy and selected area electron diffraction revealed that the products synthesized at 80–120 °C for 6–18 h were pure cubic phase ZnO₂ nanocrystals. Room temperature photoluminescence spectra of the as-synthesized ZnO₂ nanocrystals displayed a wide and strong emission band in the visible region of about 525–570 nm upon laser excitation at 325 nm, which may have originated from their surface state and other crystal defects.     

Mass and isotopic concentrations of water-insoluble refractory carbon in total suspended particulates at Mt. Waliguan Observatory (China)

Mass concentration and isotopic values δ¹³C and ¹⁴C are presented for the water-insoluble refractory carbon (WIRC) component of total suspended particulates (TSP), collected weekly during 2003, as well as from October 2005 to May 2006 at the WMO-GAW Mt. Waliguan (WLG) site. The overall average WIRC mass concentration was (1183 ± 120) ng/m³ (n = 79), while seasonal averages were 2081 ± 1707 (spring), 454 ± 205 (summer), 650 ± 411 (autumn), and 1019 ± 703 (winter) ng/m³. Seasonal variations in WIRC mass concentrations were consistent with black carbon measurements from an aethalometer, although WIRC concentrations were typically higher, especially in winter and spring. The δ¹³C PDB value (−25.3 ± 0.8)‰ determined for WIRC suggests that its sources are C₃ biomass or fossil fuel combustion. No seasonal change in δ¹³C PDB was evident. The average percent Modern Carbon (pMC) for ¹⁴C in WIRC for winter and spring was (67.2 ± 7.7)% (n = 29). Lower pMC values were associated with air masses transported from the area east of WLG, while higher pMC values were associated with air masses from the Tibetan Plateau, southwest of WLG. Elevated pMC values with abnormally high mass concentrations of TSP and WIRC were measured during a dust storm event.     

Magnetic and electrochemical behavior of rhombohedral α-Fe2O3 nanoparticles with (1 0 4) dominant facets

Uniform rhombohedral α-Fe₂O₃ nanoparticles, ～60 nm in size, were synthesized via a triphenylphosphine-assisted hydrothermal method. Scanning electron micrograph (SEM) and transmission electron micrograph (TEM) analyses showed that the as-synthesized rhombohedral nanoparticles were enclosed by six (1 0 4) planes. The concentration of triphenylphosphine played an important role in morphological evolution of the α-Fe₂O₃ nanoparticles. The as-prepared rhombohedral nanoparticles possessed remanent magnetization M_r of 2.6 × 10^?3 emu/g and coercivity H_C of 2.05 Oe, both lower than those of other α-Fe₂O₃ particles with similar size, indicating their potential applications as superparamagnetic precursor materials. Furthermore, these rhombohedral α-Fe₂O₃ nanoparticles exhibited good sensor capability toward H₂O₂ with a linear response in the concentration range of 2–20 mM.     

Surface responses induced by point load or uniform traction moving steadily on an anisotropic half-plane

Surface responses induced by point load or uniform traction moving steadily with subsonic speed on an anisotropic half-plane boundary are investigated. It is found that the effects of the material constant on surface displacements are through matrices L^?1(v) and S(v)L^?1(v), while those on surface stress components are through matrices Ω(v) and Γ(v). Explicit expressions for the elements of these four matrices are expressed in terms of elastic stiffness for general anisotropic materials. The special cases of monoclinic materials with symmetry plane at x₁ = 0, x₂ = 0 and x₃ = 0, and the case for orthotropic materials are all deduced. Results for isotropic material may be recovered from present results. For monoclinic materials with a plane of symmetry at x₃ = 0, two of the elements of matrix Ω(v) are found to be independent of subsonic speed.     

Microwave-hydrothermal preparation of a graphene/hierarchy structure MnO2 composite for a supercapacitor

Graphene/hierarchy structure manganese dioxide (GN/MnO₂) composites were synthesized using a simple microwave-hydrothermal method. The properties of the prepared composites were analyzed using field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) measurements. The electrochemical performances of the composites were analyzed using cyclic voltammetry, electrochemical impedance spectrometry (EIS), and chronopotentiometry. The results showed that GN/MnO₂ (10 wt% graphene) displayed a specific capacitance of 244 F/g at a current density of 100 mA/g. An excellent cyclic stability was obtained with a capacity retention of approximately 94.3% after 500 cycles in a 1 mol/L Li₂SO₄ solution. The improved electrochemical performance is attributed to the hierarchy structure of the manganese dioxide, which can enlarge the interface between the active materials and the electrolyte. The preparation route provides a new approach for hierarchy structure graphene composites; this work could be readily extended to the preparation of other graphene-based composites with different structures for use in energy storage devices.     

Synthesis and phase evolution of LiNb0.6Ti0.5O3 powder via a sol–gel method

A simple sol–gel route was demonstrated for the synthesis of LiNb_0.6Ti_0.5O₃ (M-phase) powder, using cheap and manageable starting materials at a relatively low temperature. The phase transitions in both chemical and solid-state processes were studied by X-ray diffraction (XRD) in detail. The results showed that in the sol–gel process the anatase TiO₂ phase first appeared at 400 °C and then LiNbO₃ solid solution (LiNbO₃ ss) emerged at 500 °C. When calcined to 600 °C, the M-phase started to appear along with the decrease of TiO₂ and LiNbO₃ ss. Single M-phase could be formed at 700 °C, which is 300 °C lower than that by the traditional solid-state method. A plausible evolution mechanism of the as-synthesized powder in calcination was proposed. The produced powder has potential applications in microelectronics systems.     

Evolution of planetary boundary layer under different weather conditions,and its impact on aerosol concentrations

A field experiment was conducted in Tianjin, China from September 9–30, 2010, focused on the evolution of Planetary Boundary Layer (PBL) and its impact on surface air pollutants. The experiment used three remote sensing instruments, wind profile radar (WPR), microwave radiometer (MWR) and micro-pulse lidar (MPL), to detect the vertical profiles of winds, temperature, and aerosol backscattering coefficient and to measure the vertical profiles of surface pollutants (aerosol, CO, SO₂, NO_x), and also collected sonic anemometers data from a 255-m meteorological tower. Based on these measurements, the evolution of the PBL was estimated. The averaged PBL height was about 1000–1300 m during noon/afternoon-time, and 200–300 m during night-time. The PBL height and the aerosol concentrations were anti-correlated during clear and haze conditions. The averaged maximum PBL heights were 1.08 and 1.70 km while the averaged aerosol concentrations were 52 and 17 μg/m³ under haze and clear sky conditions, respectively. The influence of aerosols and clouds on solar radiation was observed based on sonic anemometers data collected from the 255-m meteorological tower. The heat flux was found significantly decreased by haze (heavy pollution) or cloud, which tended to depress the development of PBL, while the repressed structure of PBL further weakened the diffusion of pollutants, leading to heavy pollution. This possible positive feedback cycle (more aerosols → lower PBL height → more aerosols) would induce an acceleration process for heavy ground pollution in megacities.     

Minimum spouting velocity of flat-base spouted fluid bed

Experiments were performed on spout characteristics of a cylindrical spout-fluidized bed (I.D. = 10 cm) with different static heights and two materials (Al₂O₃ and high density polyethylene). Results of minimum spouting velocity obtained in this study were compared with reported correlations for both spouted and spout-fluidized beds. Considerable discrepancies were found between the values obtained using different model equations as well as with respect to experimental results. Based on the Mathur–Gishler correlation, a new correlation is proposed for calculating the minimum spouting velocity that introduces the ratio U/U_mf. It was found that the minimum spouting velocity decreases with increasing fluidizing gas velocity (U/U_mf). The pressure drop at the point of minimum spouting velocity is also correlated using this dimensionless group and is presented in this work. This investigation demonstrates that the use of correlations reported in the literature that focus primarily on conical bottom spouted beds are not applicable to flat-bottom spouted and spout-fluidized beds.     

Experimental investigation on flow asymmetry in solid entrance region of a square circulating fluidized bed

To study the influence of back feeding particles on gas-solid flow in the riser, this paper investigated the flow asymmetry in the solid entrance region of a fluidized bed by particle concentration/velocity measurements in a cold square circulating fluidized beds （CFB）. The pressure drop distribution along the riser and the saturation carrying capacity of gas for Geldart-B type particles were first analyzed. Under the condition of u0 = 4 m/s and Gs = 21 kg/（m^2 s）, the back feeding particles were found to penetrate the lean gas-solid flow near the entrance （rear） wall before reaching the opposite （front） wall, thus leading to a relatively denser region near the front wall in the bottom bed. Higher solid circulation rate （u0 =4 m/s, Gs = 33 kg/（m^2 s）） resulted in a higher particle concentration in the riser. However the back feeding particles with higher momentum increased the asymmetry of the particle concentration/velocity profile in the solid entrance region. Lower air velocity （u0 =3.2 m/s） and Gs =21 kg/（m2 s）, beyond the saturation carrying capacity of gas, induced an S-shaped axial solid distribution with a denser bottom zone. This limited the penetration of the back feeding particles and forced the flnidizing air to flow in the central region, thus leading to a higher solid holdup near the rear wall. Under the conditions of uo = 4 m/s and Gs = 21 kg/（m^2 s）, addition of coarse particles （dp= 1145 μm） into the bed made the radial distribution of solids more symmetrical.     

Metallic iron nanoparticles: Flame synthesis,characterization and magnetic properties

Metallic iron (Fe) nanoparticles (NPs) with a typical core–shell structure have been prepared by a simple and continuous flame spray pyrolysis (FSP) method, which are stabilized by the corresponding Fe₃O₄ shell with a thickness of 4–6 nm. The size of metallic Fe cores is about 30–80 nm. The core–shell structured iron NPs show an air stability as long as one month as a result of the protection of oxide shell. Through the control of the residence time of materials in flame and flame atmosphere, metallic Fe and iron oxides are obtained, showing a better external magnetic field responsibility. It is concluded that the evolution of morphology and composition of flame-made magnetic NPs could be attributed to the competition mechanism between reduction and oxidation reactions of in situ flame combustion, which offers more choices and better effective design strategy for the synthesis of advanced functional materials via FSP techniques.