Preparation of modified MFI (ZSM-5 and silicalite-1) zeolites for potassium extraction from seawater

Modified nanosized MFI (ZSM-5 and silicalite-1) zeolites were successfully synthesized by a hydrothermal method using aluminum isopropoxide and tetraethylorthosilicate as the raw materials. The synthetic zeolites were characterized by X-ray diffraction, energy dispersion spectroscopy, and scanning electron microscopy. The ZSM-5 and silicalite-1 zeolites exhibited ellipse-like and cubic columns, respectively. The K⁺ ion-exchange equilibrium and ion-exchange capacity of the synthetic zeolites in seawater were investigated. The K⁺ ion-exchange of synthetic zeolites was rapid and reached an ion-exchange balance in approximately 20 min. The K⁺ ion-exchange capacity of ZSM-5 and silicalite-1 in seawater was 56.7 and 48.7 mg/g, respectively. The synthetic zeolites have high selectivity toward K⁺, and therefore, they can be used to selectively extract potassium from seawater.     

Potassium sodium tartrate-assisted hydrothermal synthesis of BaLuF5:Yb3+/Er3+ nanocrystals

Highly-dispersed BaLuF₅:Yb³⁺/Er³⁺ nanocrystals were prepared by a facile potassium sodium tartrate-assisted hydrothermal method. The average particle size was approximately 20–25 nm. The formation mechanism is discussed. Potassium sodium tartrate led to form a complex with an approximately three-dimensional network structure, which insured largely concurrent nucleation. As a result, we acquired uniform nanoparticles. The hydrothermal temperature, holding time, and pH value were important factors affecting the formation of the BaLuF₅:Yb³⁺/Er³⁺ nanocrystals. We investigated their influence on the formation and realized the optimal reaction parameters. Remarkably, potassium sodium tartrate also contributed to the biocompatibility and potential biomedical applications of BaLuF₅:Yb³⁺/Er³⁺ nanocrystals by decomposing into small organic groups attached to the nanoparticles.     

Preparation of calcium sulfate whiskers from FGD gypsum via hydrothermal crystallization in the H2SO4–NaCl–H2O system

Little attention has thus far been paid to the potential effect of solution composition on the hydrothermal crystallization of calcium sulfate whiskers prepared from flue-gas desulfurization (FGD) gypsum. When purified FGD gypsum was used as raw material, the morphology and phase structure of the hydrothermal products grown in pure water, H₂SO₄–H₂O, NaCl–H₂O, and H₂SO₄–NaCl–H₂O solutions as well as the solubility of purified FGD gypsum in these solutions were investigated. The results indicate that calcium sulfate whiskers grow favorably in the H₂SO₄–NaCl–H₂O system. When prepared using 10–70 g NaCl/kg gypsum −0.01 M H₂SO₄–H₂O at 130 °C for 60 min, the obtained calcium sulfate whiskers had diameters ranging from 3 to 5 μm and lengths from 200 to 600 μm, and their phase structure was calcium sulfate hemihydrate (HH). Opposing effects of sulfuric acid and sodium chloride on the solubility of the purified FGD gypsum were observed. With the co-presence of sulfuric acid and sodium chloride in the reaction solution, the concentrations of Ca²⁺ and SO₄²⁻ can be kept relatively stable, which implies that the crystallization of the hydrothermal products can be controlled by changing the concentrations of sulfuric acid and sodium chloride.     

Synthesis of potassium sodium niobate powders using an EDTA/citrate complexing sol–gel method

Potassium sodium niobate (KNN) powders were synthesized by a modified sol–gel method, using as starting chemicals potassium carbonate, sodium carbonate, and niobium hydroxide, and, as esterification and chelating agents, respectively, ethylene glycol (EG) and ethylene diamine tetraacetic acid (EDTA)/citrate. The effects of citric acid (CA), EG, and EDTA on the stability of the precursor sol were systemically investigated. The powders and gels were characterized by X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis-differential scanning calorimetry (TGA-DSC). The results indicated that a stable precursor sol was formed when n(CA):n(Mⁿ⁺) = 3:1, n(EDTA):n(NH₄OH) = 1:3.5, and n(CA):n(EG) = 1:2. The xerogel was calcined at 500–950 °C to prepare the KNN powder. Pure KNN perovskite phase with a cube-like structure was synthesized at 850 °C from the precursor sol for a K/Na molar ratio of 1.2. The formation mechanism of the KNN perovskite phase was also discussed.     

Effect of elastic anisotropy on surface pattern evolution of epitaxial thin films

Stress-induced surface instability and evolution of epitaxial thin films leads to formation of a variety of self-assembled surface patterns with feature sizes at micro- and nanoscales. The anisotropy in both the surface and bulk properties of the film and substrate has profound effects on the nonlinear dynamics of surface evolution and pattern formation. Experimentally it has been demonstrated that the effect of anisotropy strongly depends on the crystal orientation of the substrate surface on which the film grows epitaxially. In this paper we develop a nonlinear model for surface evolution of epitaxial thin films on generally anisotropic crystal substrates. Specifically, the effect of bulk elastic anisotropy of the substrate on epitaxial surface pattern evolution is investigated for cubic germanium (Ge) and SiGe films on silicon (Si) substrates with four different surface orientations: Si(0 0 1), Si(1 1 1), Si(1 1 0), and Si(1 1 3). Both linear analysis and nonlinear numerical simulations suggest that, with surface anisotropy neglected, ordered surface patterns form under the influence of the elastic anisotropy, and these surface patterns clearly reflect the symmetry of the underlying crystal structures of the substrate. It is concluded that consideration of anisotropic elasticity reveals a much richer dynamics of surface pattern evolution as compared to isotropic models.     

Hydrothermal synthesis and physicochemical characterization of CuO/ZnO/Al2O3 nanopowder. Part I: Effect of crystallization time

A hydrothermal method was successfully used for synthesis of CuO/ZnO/Al₂O₃ (CZA) nanopowder with atomic ratio of 6:3:1. The effect of crystallization time (3, 6, 9, and 12 h) on physicochemical properties of nanopowder was investigated. Nanopowders were characterized using XRD, FESEM, EDX, FTIR, TG, and BET techniques. The XRD patterns confirmed metal oxides formation and their good crystallinity with average crystallite size of 20 nm as obtained by the Scherrer equation. Relative crystallinity was shown to increase with increasing crystallization time. In agreement with XRD results, FESEM images also illustrated nanosized particles. EDX mapping indicated homogenous dispersion of elements. BET specific surface area analysis showed acceptable surface area for CZA nanopowder. FTIR spectroscopy confirmed metal oxides formation during hydrothermal and calcination processing. TG results illustrated high thermal stability of the synthesized nanopowders. TG-DTG and FTIR analyses were used to propose a reaction mechanism for nanopowder formation during processing. Physicochemical characterization showed optimal crystallization time to be 6 h.     

Flow of drag-reducing surfactant solutions in rough pipes

The paper reports the results of experimental study of the flow of hexadecyltrimethylammonium chloride (CTAC) solutions with addition of sodium salicylate (NaSal) in the rough pipes. Measurements were performed in the range of the surfactant concentration from 200 to 400 ppm at a constant molar ratio CTAC/NaSal of 1:2. Five pipes of the relative roughness k/D varying from 1.2 × 10^?2 to 5.6 × 10^?2, obtained by the covering of inner surface of the pipes with glued silicon carbide particles of different size, were studied. The roughness was observed to increase the drag of flow of CTAC/NaSal solutions already at Reynolds numbers higher than 800. With increasing relative roughness k/D, the critical value of Reynolds number, at which the drag reduction disappears, was found to decrease. However, no influence of the roughness on the critical shear stress was noted. The ratio of the critical Reynolds number for rough pipes to that of hydraulically smooth pipes was independent of the surfactant concentration. The degree of drag reduction by the flow of surfactants was greater in rough pipes than in smooth pipes.     

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.     

Statistical morphological identification of low-dimensional nanomaterials by using TEM

Nanomaterials with low-dimensional morphology display unique properties in catalysis and related fields, which are highly dependent on the structure and aspect ratio. Thus, accurate identification of the structure and morphology is the basis to correlate to the performance. However, the widely adopted techniques such as XRD is incapable to precise identify the aspect ratio of low-dimensional nanomaterials, not even to quantify the morphological uniformity with statistical deviation value. Herein, ZnO nanorod and nanosheet featured with one- and two-dimensional morphology were selected as model materials, which were prepared by the hydrothermal method and statistically characterized by transmission electron microscopy (TEM). The results indicate that ZnO nanorods and nanosheets display rod-like and orthohexagnal morphology, which mainly encapsulated with {100} and {001} planes, respectively. The 7.36 ± 0.20 and 0.39 ± 0.02 aspect ratio (c/a) of ZnO nanorods and nanosheets could be obtained through the integration of the (100) and (002) diffraction rings in selected area electron diffraction (SAED). TEM combining with the SAED is favorable compare with XRD, which not only provides more accurate aspect ratio results with standard deviation values but also requires very small amounts of sample. This work is supposed to provide a convenient and accurate method for the characterization of nanomaterials with low-dimensional morphology through TEM.     

Analytical modeling of synthetic fiber ropes subjected to axial loads. Part I: A new continuum model for multilayered fibrous structures

Synthetic fiber ropes are characterized by a very complex architecture and a hierarchical structure. Considering the fiber rope architecture, to pass from fiber to rope structure behavior, two scale transition models are necessary, used in sequence: one is devoted to an assembly of a large number of twisted components (multilayered), whereas the second is suitable for a structure with a central straight core and six helical wires (1 + 6). The part I of this paper first describes the development of a model for the static behavior of a fibrous structure with a large number of twisted components. Tests were then performed on two different structures subjected to axial loads. Using the model presented here the axial stiffness of the structures has been predicted and good agreement with measured values is obtained. A companion paper (Ghoreishi, S.R. et al., in press. Analytical modeling of synthetic fiber ropes, part II: A linear elastic model for 1 + 6 fibrous structures, International Journal of Solids and Structures, doi:10.1016/j.ijsolstr.2006.08.032) presents the second model to predict the mechanical behavior of a 1 + 6 fibrous structure.     

Phase evolution of （K,Na）NbO3 powder prepared by high temperature mixing under hydrothermal conditions

（Na, K）NbO3 （KNN） powders were successfully prepared by high temperature mixing method （HTMM） under hydrothermal conditions to study the effect of reaction time on the formation of KNN for three K＋/（K＋ ＋Na＋） ratios of 0.6, 0.7 and 0.8. The products were characterized by X-ray diffraction （XRD）, scanning electron microscope （SEM）, transmission electron microscopy （TEM） and selected area electron diffraction （SAED）, to show the change of phase and morphology of the as-prepared particles with the K＋/（K＋ ＋ Na＋） molar ratio in the solution. Pure Na-rich KNN monoclinic phase and pure K-rich KNN orthorhombic phase could be obtained quickly after mixing the solutions at high temperature when the K＋/（K＋ ＋Na＋） molar ratio was either 0.6 or 0.8. When the K＋/（K＋ ＋Na＋） molar ratio was 0.7, however, the K-rich KNN orthorhombic phase grain formed first, followed by the Na-rich KNN monoclinic phase grain, with the two phases coexisting in the final product.     

Experimental pool boiling investigations of FC-72 on silicon with artificial cavities and integrated temperature microsensors

In this experimental study, fluorinert FC-72 is boiled on a silicon chip with artificial cavities and integrated microsensors. The horizontal silicon chip with dimensions of 39.5 × 19 × 0.38 mm is completely immersed in FC-72. The integrated nickel–titanium temperature microsensors on the back of the chip are calibrated individually and exhibit a near-linear increase of electrical resistance with temperature. The applied heat fluxes and the resulting wall superheat at the boiling surface are varied by means of an integral thin-film resistance heater (95% Al, 4% Cu and 1% Si), also on the back of the silicon chip. Artificial cylindrical cavities with a mouth diameter of 10 μm and depths of 40, 80 or 100 μm situated above the microthermometers serve as artificial nucleation sites, due to trapped vapour. Bubble growth rates, frequencies, departure diameters of bubbles and waiting times between bubbles from an isolated cavity for different wall superheats and pressures were obtained by analysing high-speed video images and the simultaneously measured temperature below the artificial cavity.     

Optimization and evaluation of fish oil microcapsules

Fish oil microcapsules were prepared using two natural polysaccharides, alginate and chitosan, as the wall materials. A response surface methodology (RSM) was used to optimize the conditions for fish oil encapsulation efficiency (FOEE). The FOEE was investigated with respect to three key-variables in the RSM: ratio of inner oil phase to aqueous phase (X₁, w/w); concentration of the aqueous phase (X₂, wt%); and ratio of the aqueous phase to outer oil phase (X₃, v/v). The optimal formulation obtained from the RSM model, i.e., 2.7:1 (X₁), 1.6 wt% (X₂), and 11.5:1 (X₃), gave a FOEE of 28%. The model was validated and the fish oil microcapsules prepared under the optimized conditions were characterized in terms of particle size, polydispersity index (PDI), zeta potential, surface morphology, and in vitro release. The average droplet size, PDI, and zeta potential were 915 nm, 0.038, and +5.2 mV, respectively. The fish oil microcapsules were highly uniform microspheres, and had an accumulative release rate of 77.7% in 270 min in a gastrointestinal model, indicating their potential as an alternative carrier for the controlled release of fish oil. In conclusion, formulating optimal microencapsulation conditions by the RSM can be applied to the microencapsulation of various oil-soluble nutrients for food applications.     

Atomistic simulation of crystallization of a polyethylene melt in steady uniaxial extension

We present simulation results of flow-induced crystallization of a dense polymeric liquid subjected to a strong uniaxial elongational flow using a rigorous nonequilibrium Monte Carlo method. A distinct transition between the liquid and the crystalline phases occurred at critical values of flow strength, with an abrupt, discontinuous transition of the overall chain conformation. The flow-induced crystalline phase matched quantitatively the experimental X-ray diffraction data of the real crystals remarkably well, including the sharp Bragg peaks at small wavenumbers, k < 1.5 Å^?1, indicating the existence of a global long-range ordering. We also found that the enthalpy change (ΔH = 225 J/g) during the phase transition was quantitatively very similar to the experimental heat of fusion (276 J/g) of polyethylene crystals under quiescent conditions. Furthermore, a detailed analysis of the configuration-based temperature provided a sound microscopic physical origin for the effective enhancement of the crystallization (or melting) temperature that has been observed in experiments. Simulation results also allow for the deduction of potential nonequilibrium expressions for thermodynamic quantities, such as temperature and heat capacity.     

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.     

In-plane free vibration of a single-crystal silicon ring

In this paper the natural frequencies and the associated mode shapes of in-plane free vibration of a single-crystal silicon ring are analyzed. It is found that the Si(1 1 1) ring is two-dimensionally isotropic in the (1 1 1) plane for elastic constants but three-dimensionally anisotropic, while the Si(1 0 0) ring is fully anisotropic. Hamilton’s principle is used to derive the equations of vibration, which is a set of partial differential equations with coefficients being periodic in polar variable. Expressing the radial and tangential displacements in sinusoidal form with non-predetermined amplitudes, and through the integration with respect to the circumferential variable, the original governing equations in partial differential form can be converted into the amplitude equations in ordinary differential form. The exact expressions for frequencies and mode shapes are obtained. It is found that for Si(1 0 0) rings the frequencies of a pair of modes, which are equal for an isotropic ring, split due to the anisotropic effect only for the second in-plane vibration mode. The phenomena of frequency splitting and degenerate modes can be proved either based on the conservation of averaged mechanical energy or by the concept of crystallographic symmetry groups. When the single-crystal silicon is replaced by the polycrystalline silicon, which is isotropic in elastic constants, the derived equations for frequencies correctly predict the vanishing of the phenomenon of frequency splitting.     

The effect of aspect ratio in counter-current gas-liquid bubble columns: Experimental results and gas holdup correlations

It is generally admitted that the gas holdup is independent of the column dimensions and gas sparger design if three criteria are satisfied: the diameter of the bubble column is larger than 0.15 m, gas sparger openings are larger than 1–2 mm and the aspect ratio is larger than 5. This paper contributes to the existing discussion; in particular, the effect of the aspect ratio (within the range 1–15) in a counter-current gas-liquid bubble column has been experimentally studied and a new gas holdup correlation to estimate the influence of aspect ratio, operation mode and working fluid on the gas holdup has been proposed. The bubble column, equipped with a spider gas sparger, is 5.3 m in height, has an inner diameter of 0.24 m; gas superficial velocities in the range of 0.004–0.23 m/s have been considered, and, for the runs with water moving counter-currently to the gas phase, the liquid has been recirculated at a superficial velocity of −0.0846 m/s. Filtered air has been used as the gaseous phase in all the experiments, while the liquid phase has included tap water and different aqueous solutions of sodium chloride as electrolyte. Gas holdup measurements have been used to investigate the flow regime transitions and the global bubble column hydrodynamics. The counter-current mode has turned out to increase the gas holdup and destabilize the homogeneous flow regime; the presence of electrolytes has resulted in increasing the gas holdup and stabilizing the homogeneous flow regime; the aspect ratio, up to a critical value, has turned out to decrease the gas holdup and destabilize the homogeneous flow regime. The critical value of the aspect ratio ranged between 5 and 10, depending on the bubble column operation (i.e., batch or counter-current modes) and liquid phase properties. Since no correlation has been found in the literature that can correctly predict the gas holdup under the investigated conditions, a new scheme of gas holdup correlation has been proposed. Starting from considerations concerning the flow regime transition, corrective parameters are included in the gas holdup correlation to account for the effect of the changes introduced by the aspect ratio, operation mode and working fluid. The proposed correlation has been found to predict fairly well the present experimental data as well as previously published gas holdup data.     

X-ray spectral measurements and collisional-radiative modeling of hot,gold plasmas at the omega laser

M-Band and L-Band Gold spectra between 3 and 5 keV and 8 and 13 keV, respectively, have been recorded by a photometrically calibrated crystal spectrometer. The spectra were emitted from the plasma in the laser deposition region of a ‘hot hohlraum’. This is a reduced-scale hohlraum heated with ≈9 kJ of 351 nm light in a 1 ns square pulse at the OMEGA laser. The space- and time-integrated spectra included L-Band line emission from Co-like to Ne-like gold. The three L-Band line features were identified to be the 3s → 2p, 3d_5/2 → 2p_3/2 and 3d_3/2 → 2p_1/2 transitions at ≈9 keV, ≈10 keV and ≈13 keV, respectively. M-Band 5f → 3d, 4d → 3p, and 4p → 3s transition features from Fe-like to P-like gold were also recorded between 3 and 5 keV. Modeling from the radiation–hydrodynamics code LASNEX, the collisional-radiative codes FLYCHK and SCRAM, and the atomic structure code FAC were used to model the plasma and generate simulated spectra for comparison with the recorded spectra. Through these comparisons, we have determined the average electron temperature of the emitting plasma to be between 6.0 and 6.5 keV. The electron temperatures predicted by LASNEX appear to be too large by a factor of about 1.5.     

Mixed-solvent thermal synthesis and magnetic properties of flower-like microstructured nickel

Flower-like microstructured nickel was synthesized by a facile mixed-solvent thermal process. The structure, morphology, and magnetic properties of the reaction products were investigated, respectively, by X-ray diffraction (XRD), scanning electron microscopy (SEM), and vibrating sample magnetometry (VSM). The results showed that the products consisted of a face-centered cubic (fcc) structure with lattice constant of α = 3.524 Å. The average diameter of flower-like microstructured nickel was about 5 μm and the thickness of a single flake was about 100 nm. Magnetic measurement showed that these powders exhibited ferromagnetic characteristics.